WO2013157643A1 - Polysiloxane composition having radical-crosslinkable group - Google Patents
Polysiloxane composition having radical-crosslinkable group Download PDFInfo
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- WO2013157643A1 WO2013157643A1 PCT/JP2013/061674 JP2013061674W WO2013157643A1 WO 2013157643 A1 WO2013157643 A1 WO 2013157643A1 JP 2013061674 W JP2013061674 W JP 2013061674W WO 2013157643 A1 WO2013157643 A1 WO 2013157643A1
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- 0 CC(C)(CC(CC1(C)C)O*)N1O Chemical compound CC(C)(CC(CC1(C)C)O*)N1O 0.000 description 13
- SWJMGACCJPXARK-UHFFFAOYSA-N CC(C)(CC(C1(C)C)C#N)N1O Chemical compound CC(C)(CC(C1(C)C)C#N)N1O SWJMGACCJPXARK-UHFFFAOYSA-N 0.000 description 1
- CLKPVQZFNYXFCY-UHFFFAOYSA-N CC(C)(CC(C1(C)C)C(O)=O)N1O Chemical compound CC(C)(CC(C1(C)C)C(O)=O)N1O CLKPVQZFNYXFCY-UHFFFAOYSA-N 0.000 description 1
- USGBLEMQARVRDC-UHFFFAOYSA-N CC(C)(CC(C1(C)C)N)N1O Chemical compound CC(C)(CC(C1(C)C)N)N1O USGBLEMQARVRDC-UHFFFAOYSA-N 0.000 description 1
- KVTOSAMSZMXLKB-UHFFFAOYSA-N CC(C)(CC(CC1(C)C)C#N)N1O Chemical compound CC(C)(CC(CC1(C)C)C#N)N1O KVTOSAMSZMXLKB-UHFFFAOYSA-N 0.000 description 1
- GVQKWFQBWZOJHV-UHFFFAOYSA-N CC(C)(CC(CC1(C)C)C(O)=O)N1O Chemical compound CC(C)(CC(CC1(C)C)C(O)=O)N1O GVQKWFQBWZOJHV-UHFFFAOYSA-N 0.000 description 1
- AYSOUYKQIUYGFR-UHFFFAOYSA-N CC(C)(CC(CC1(C)C)N)N1O Chemical compound CC(C)(CC(CC1(C)C)N)N1O AYSOUYKQIUYGFR-UHFFFAOYSA-N 0.000 description 1
- CSGAUKGQUCHWDP-UHFFFAOYSA-N CC(C)(CC(CC1(C)C)O)N1O Chemical compound CC(C)(CC(CC1(C)C)O)N1O CSGAUKGQUCHWDP-UHFFFAOYSA-N 0.000 description 1
- VUZNLSBZRVZGIK-UHFFFAOYSA-O CC(C)(CCCC1(C)C)N1[OH2+] Chemical compound CC(C)(CCCC1(C)C)N1[OH2+] VUZNLSBZRVZGIK-UHFFFAOYSA-O 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/32—Compounds containing nitrogen bound to oxygen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- the present invention relates to the formation of a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, etc. in a semiconductor device as an insulating material suitably used for a display device, and a semiconductor device equipped with an image sensor, micromachine, or microactuator
- the present invention relates to a polysiloxane composition having a radically crosslinkable group that is preferably used for, for example, a cured product obtained by curing the polysiloxane composition, or a transparent insulating film.
- Polyimide resins having excellent heat resistance, electrical properties, and mechanical properties are widely used for insulating materials for electronic parts and surface protection films, interlayer insulation films, and ⁇ -ray shielding films for semiconductor devices.
- Such a polyimide resin is usually provided in the form of a photosensitive polyimide precursor composition, which is applied to a substrate, soft baked, irradiated with actinic rays (exposure) through a desired patterning mask, and developed. And it has the characteristic that the hardening relief pattern which consists of heat resistant polyimide resin can be formed easily by performing a thermosetting process (for example, refer the following patent documents 1).
- polyimide having excellent characteristics as described above has absorption derived from the polyimide ring in the vicinity of 500 nm to 400 nm and is not suitable for applications requiring high transparency such as display devices or optical system materials.
- the lower limit of the curing treatment temperature is 300 ° C. Before and after.
- Patent Document 2 discloses a photosensitive siloxane-based material that can be cured at a low temperature.
- the patterned resin When forming a display device or optical material, the patterned resin is exposed to high temperature several times, and after it becomes a final product, it is exposed to temperature shocks due to changes in the surrounding environment, so it has high crack resistance is required.
- Patent Document 2 when the technique disclosed in Patent Document 2 is used, it has been found that there is room for improvement in crack resistance in the required thick film.
- area which requires high transparency and low temperature curability like a display apparatus or an optical system material the photosensitive film-forming material which satisfy
- the problem to be solved by the present invention is a radically crosslinkable group capable of obtaining a cured product having high transparency and excellent crack resistance due to thermal shock, and capable of being cured at low temperature.
- the present inventors have unexpectedly discovered that the above problems can be solved by using a polysiloxane composition having a specific radical crosslinkable group.
- the present invention has been completed. That is, the present invention is as follows.
- the g value is 2.034.
- a radical crosslinkable group having a peak of ⁇ 1.984 and containing a radical of 0.1 ⁇ 10 ⁇ 6 mol / g to 120 ⁇ 10 ⁇ 6 mol / g with respect to 100 parts by mass of the total solid content in the composition A polysiloxane composition.
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
- R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
- a polysiloxane composition further comprising a photoradical initiator.
- the (C) nitroxy compound has the following general formula: ⁇ Wherein R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
- R 6 represents a divalent or trivalent organic group
- n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
- n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2
- n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
- l is an integer of 2 or 3.
- polysiloxane according to any one of [1] to [6], wherein the polysiloxane having a radical crosslinkable group (A) is a polysiloxane having a (meth) acryloyl group and / or a styryl group. Composition.
- the above-mentioned [F] further comprises an alkali-soluble resin having an acid value of 10 to 200 mg KOH / g of 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
- the polysiloxane composition according to any one of [9].
- the polysiloxane having a radical crosslinkable group (A) has the following general formula: ⁇ In the formula, Ph represents a phenyl group. ⁇
- the following structure ⁇ Wherein R 1 , R 2 , R 3 and R 4 each independently represent a hydrogen atom and / or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 4 3 and R 4 may be bonded to each other to form a ring structure.
- a polysiloxane composition further comprising (B) a photoradical initiator.
- the (C) nitroxy compound has the following general formula: ⁇ Wherein R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
- R 6 represents a divalent or trivalent organic group
- n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
- n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2
- n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
- l is an integer of 2 or 3.
- composition [20] The above [14] to [14], further comprising (D) a compound having a photopolymerizable double bond in an amount of 5 to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
- the polysiloxane fat composition according to any one of [19].
- the alkali-soluble resin further comprising (F) an acid value of 10 to 200 mgKOH / g of 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
- the polysiloxane having a radical crosslinkable group (A) has the following general formula: ⁇ In the formula, Ph represents a phenyl group.
- the polysiloxane composition according to any one of [14] to [22] which has a structure represented by: [24] A cured product obtained by curing the polysiloxane composition according to any one of [14] to [22].
- a polysiloxane composition having a radical crosslinkable group capable of being cured at low temperature which can obtain a cured product having high transparency and excellent resistance to cracking due to temperature shock.
- ESR measurement results of electron spin resonance (ESR) measurement of acetone ESR measurement result of 4-hydroxy-TEMPO. The figure explaining the calculation method of g value in ESR.
- the ESR measurement result of the polysiloxane composition of Example 19 The ESR measurement result of the polysiloxane composition of Example 10.
- the ESR measurement result of the polysiloxane composition of Example 11 The ESR measurement result of the polysiloxane composition of Example 12.
- the polysiloxane composition having a radical crosslinkable group includes the following components: (A) polysiloxane having a radical crosslinkable group, and (B) a photoradical initiator, Optionally, other ingredients are included.
- the polysiloxane having a radical crosslinkable group (A) can be composed of a polysiloxane having a radical crosslinkable group and (C) a nitroxy compound as described below.
- a cured product obtained by curing a polysiloxane composition having a radical crosslinkable group will be described.
- the nitroxy compound is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., atmospheric pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus.
- ESR electron spin resonance
- the polysiloxane having a radical crosslinkable group is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., normal pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus. And a group capable of generating a radical having a peak with a g value of 2.034 to 1.984 when measured.
- the polysilosan simple substance has the predetermined peak.
- a polysiloxane composition having a radical crosslinkable group having a peak of ⁇ 1.984 means that the polysiloxane simple substance having a radical crosslinkable group has the radical generating group, and the polysiloxane simple substance having a radical crosslinkable group is Although it does not have the radical generating group, for example, it includes both in the case of a mixed state of a polysiloxane simple substance, a radical, and a polysiloxane simple substance, a radical and a combination thereof generated when coexisting with a nitroxy compound .
- the polysiloxane composition having a radical crosslinkable group further has an alkali-soluble group means that the polysiloxane itself has an alkali-soluble group and the composition containing the polysiloxane has an alkali As a result of including a soluble resin, both the case where the polysiloxane composition includes an alkali-soluble group are included.
- a radical having a peak with a g value of 2.034 to 1.984 when measured using a spin resonance (ESR) apparatus is preferably contained in an amount of 0.1 ⁇ 10 ⁇ 6 mol or more with respect to 1 g of the solid content in the composition. More preferably, it is 0.15 ⁇ 10 ⁇ 6 mol or more.
- the total solid content in the polysiloxane composition having a radical crosslinkable group can be measured, for example, using a TGA (thermogravimetric apparatus).
- the amount of radicals can be measured using an ESR (electron spin resonance apparatus).
- 4-hydroxy TEMPO was prepared as a standard having 1 mole of radical per mole, a calibration curve was created, the amount of radicals in the composition was measured, and the composition was combined with the solid content measured by TGA. It is possible to calculate the radical content contained per gram of solid content.
- 0.0017 parts by mass of the nitroxy compound corresponds to a radical amount of 0.1 ⁇ 10 ⁇ 6 mol / g
- the nitroxy compound 0.005 The mass part corresponds to a radical amount of 0.29 ⁇ 10 ⁇ 6 mol / g
- the nitroxy compound 0.009 part by mass corresponds to a radical amount of 0.523 ⁇ 10 ⁇ 6 mol / g
- the nitroxy compound 1 part by mass corresponds to a radical amount of 58 ⁇ 10 ⁇ 6 mol / g
- 2 parts by weight of the nitroxy compound corresponded to a radical amount of 116 ⁇ 10 ⁇ 6 mol / g.
- the polysiloxane having a radical crosslinkable group has a group that can be crosslinked by radicals in the polysiloxane, and can dramatically improve the hardness of the cured film.
- the radical crosslinkable group may be a group containing a photopolymerizable unsaturated bond (for example, a double bond). Although it does not restrict
- the polysiloxane having a radical crosslinkable group may contain two or more of these groups. Further, (A) the polysiloxane having a radical crosslinkable group preferably has at least a (meth) acryloyl group and / or a styryl group from the viewpoint of curability. (A) The molar concentration of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group is preferably 0.01 mmol / g or more from the viewpoint of pattern adhesion, film hardness, and crack resistance. More preferably, it is 0.1 mmol / g or more, and still more preferably 0.5 mmol / g or more.
- the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and still more preferably 5.0 mmol / g or less.
- the content of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group can be calculated by measuring the iodine value of the obtained polymer.
- the polysiloxane having a radical crosslinkable group preferably contains an alkali-soluble group in one molecule.
- the alkali-soluble group is not particularly limited.
- a carboxyl group, a dicarboxylic acid anhydride group, or a residue of a dicarboxylic acid anhydride group improves the alkali solubility of the polysiloxane and is a residue after development. It is preferable from the viewpoint of suppressing the occurrence of the above.
- the content of the carboxyl group, dicarboxylic acid anhydride group, or dicarboxylic acid anhydride group residue in the polysiloxane having a radical crosslinkable group is such that (A) the polysiloxane having a radical crosslinkable group is Although it is not particularly limited as long as it has a group, the acid value of the polysiloxane having a radical crosslinkable group (A) is 10 mgKOH / g from the viewpoint of reduction of residues after development and crack resistance of a cured film. The above is preferable, more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more.
- the acid value is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / gmol or less, and still more preferably 180 mgKOH / g or less.
- the polysiloxane composition having a radical crosslinkable group contains a polysiloxane having two or more types of (A) radical crosslinkable groups, at least one of them has an acid value within the range described above. It is preferable that it contains the residue of a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride group in such a content that it has.
- the acid value means the number of milligrams of potassium hydroxide necessary to neutralize the carboxyl group in 1 g of a sample.
- An example of a method for measuring the acid value is as follows: A 3 g sample is accurately weighed and dissolved in 20 ml of ethanol. Stir the resulting solution at room temperature, add another 5 g of purified water and stir for an additional hour at room temperature. Thereafter, several drops of a phenolphthalein methanol solution are added as an indicator, neutralized with a 1/2 N aqueous potassium hydroxide solution, and the acid value is calculated from the amount of the aqueous potassium hydroxide solution used.
- the polysiloxane having a radical crosslinkable group is represented by the following general formula (I): R 7 R 8 a1 Si (R 9 ) 3-a1 ⁇
- R 7 represents a monovalent organic group having 2 to 20 carbon atoms including a photopolymerizable unsaturated bond group (for example, a double bond group), and each R 8 independently represents a substituent.
- R 9 is a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a phenoxy group, an alkylcarbonyloxy group, chlorine (Cl) or bromine (Br).
- at least one monovalent group selected from the group consisting of: a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group, and from the viewpoint of reactivity, a hydroxyl group, a methoxy group, or an ethoxy group. Groups are more preferred.
- R 7 is preferably a monovalent organic group having 2 to 17 carbon atoms having an unsaturated bond (for example, a double bond), specifically, for example, a vinyl group, styryl.
- R 7 is preferably a monovalent organic group having 2 to 17 carbon atoms having an unsaturated bond (for example, a double bond), specifically, for example, a vinyl group, styryl.
- a styryl group or a 3- (meth) acryloxypropyl group is preferable.
- (meth) acryl shows an acryl group and a methacryl group.
- the polysiloxane having a radical crosslinkable group may contain an alkali-soluble group, at least one silane compound represented by the above general formula (I) and the following general formula Formula (II): R 10 R 11 a2 Si (R 9 ) 3-a2 ⁇
- R 9 is as defined in the above general formula (I)
- R 10 represents an alkali-soluble group
- each R 11 independently represents the number of carbon atoms that may have a substituent.
- 1 to 20 represents a linear or branched organic group, aryl group, or alkylaryl group
- a2 is an integer of 0 to 2.
- R 10 is not particularly limited as long as it has a carboxyl group, a dicarboxylic anhydride group, or a dicarboxylic anhydride group residue. It is preferably selected from the group consisting of monovalent organic groups represented by II-1).
- Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms
- Ry and Rz are each independently a methyl group, an ethyl group, a propyl group, or an isopropyl group.
- Ra is a linear, branched or cyclic divalent group having 2 to 16 carbon atoms.
- Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms
- Rt is a linear group having 1 to 18 carbon atoms
- a branched or cyclic divalent organic group, and Ru and Rv are each independently a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or It is a monovalent organic group represented by the general formula (II-2).
- Rw is a linear, branched or cyclic divalent organic group having 1 to 16 carbon atoms
- Rb is a linear or branched chain having 1 to 20 carbon atoms.
- Rc is a group represented by the following general formula (II-3) or a hydrogen atom is there.
- Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms.
- R 10 preferred examples of the organic group contained in R 10 include succinic anhydride group (R 10 -1), cyclohexanedicarboxylic anhydride group (R 10 -2), 4-methyl- Cyclohexanedicarboxylic anhydride group (R 10 -3), 5-methyl-cyclohexanedicarboxylic anhydride group (R 10 -4), bicycloheptane dicarboxylic anhydride group (R 10 -5), 7-oxa-bicycloheptane Dicarboxylic anhydride group (R 10 -6), phthalic anhydride group (R 10 -7), succinic acid group or its half ester group (R 10 -8), cyclohexane dicarboxylic acid group or its half ester group (R 10-9), 4-methyl - cyclohexane dicarboxylic acid group or a half ester group (R 10 -10), 5-methyl - cyclohexane Carboxylic acid group
- Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms.
- Rx is preferably a hydrocarbon group.
- the hydrocarbon group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, A tert-pentylene group may be mentioned.
- These groups may contain a double bond and / or a triple bond, and may be used alone or in combination of two or more.
- a propylene group is the most preferable.
- a group having an amide bond (R 10 -15) is obtained by reaction of an amino group with a dicarboxylic acid anhydride, a group containing a carboxyl group.
- Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms.
- the dicarboxylic acid anhydride represented by the general formula (II-1) include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and 5-methyl-cyclohexane dicarboxylic acid.
- the group having an isocyanuric skeleton (R 10 -16) is a hydroxyl group generated from an isocyanuric skeleton having a glycidyl group via a ring-opening reaction of glycidyl by a reaction with a carboxyl group or a hydroxyl group. It is a group containing a carboxyl group obtained by reacting with a dicarboxylic acid anhydride.
- R 10 is a propyl succinic anhydride group (R 10 -1), a propyl succinic acid group, or a half methyl ester group thereof, or a half ethyl ester group thereof (R 10 -8).
- the polysiloxane having a radical crosslinkable group is at least one silane compound represented by the above general formula (I) and at least one kind represented by the above general formula (II).
- the silane compound the following general formula (III): R 12 a3 Si (R 9 ) 4-a3 ⁇ Wherein R 9 is as defined in the above general formula (I), and each R 12 is independently a linear or branched chain having 1 to 20 carbon atoms which may have a substituent.
- a3 is an integer of 0 to 3.
- silane compound represented by the general formula (I) examples include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, and 3- (meth) acrylic.
- the most preferable compound among the alkoxysilane compounds containing a carboxyl group, a dicarboxylic anhydride group, or a half ester group of a dicarboxylic anhydride group is (3- (Trimethoxysilylpropyl) succinic anhydride, (3-triethoxysilylpropyl) succinic anhydride, (3-trimethoxysilylpropyl) succinic acid, (3-triethoxysilylpropyl) succinic acid, (3-trimethoxy (Silylpropyl) succinic acid half methyl ester, (3-triethoxysilylpropyl) succinic acid half methyl ester, (3-trimethoxysilylpropyl) succinic acid half ethyl ester, and (3-triethoxysilylpropyl) succinic acid It is a half ethyl ester of an acid.
- examples of the compound having a polymerizable cyclic ether bond group include 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxy.
- Silane 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methyldiethoxysilane, and the like.
- silane compound represented by the general formula (III) other than the compound having a polymerizable cyclic ether bond group include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxylane, dimethyldiethoxysilane, Ethyltrimethoxysilane, ethyltriethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, Phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, dicyclopentyldimethoxysilane, dicyclopentyldiethoxysilane
- the polysiloxane having a radical crosslinkable group can be synthesized by any method.
- the silane compound represented by the general formula (I) and the silane compound represented by the general formula (II) And the silane compound represented by the general formula (III) can be obtained by adding water and a catalyst and then condensing the obtained hydrolyzate in the presence or absence of a solvent. .
- the hydrolysis reaction is carried out by adding an acidic catalyst and water over 1 minute to 180 minutes to the silane compound in the solvent.
- the temperature in the process of obtaining a hydrolyzate is preferably 10 ° C. or higher, more preferably 20 ° C. or higher from the viewpoint of hydrolysis reactivity, while 150 ° C.
- the reaction time in the process of obtaining the hydrolyzed monster is preferably 0.1 hour or more from the viewpoint of hydrolysis reactivity, more preferably 0.5 hour or more, while 10 hours from the viewpoint of protecting the functional group. The following is preferable, and more preferably 5 hours or less.
- the hydrolysis reaction is preferably performed in the presence of an acidic catalyst.
- an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid is preferable.
- the preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of hydrolysis reactivity with respect to all silane compounds used during the hydrolysis reaction, and 10 mol% or less from the viewpoint of functional group protection. Is preferred.
- the reaction solution is preferably heated as it is at 50 ° C. or higher and below the boiling point of the solvent used for 1 hour to 100 hours to carry out the condensation reaction.
- the solvent used for the hydrolysis reaction of the silane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. Further, these reactions may be carried out by combining two or more solvents or without solvent. Specific examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol, diacetone alcohol, ethylene glycol, propylene glycol and the like.
- Glycols ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and other ethers, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, Such as methyl isobutyl ketone and cyclopentanone Tons, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetates such as methyl lactate, ethyl lactate, butyl lactate, ⁇ -butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, etc. be able to.
- a solvent When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the hydrolysis reaction. Moreover, according to the use of a resin composition, after hydrolysis, an appropriate amount, such as produced
- the amount of the solvent used for the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of all silane compounds.
- the water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but is preferably in the range of 1.0 mol to 4.0 mol with respect to 1 mol of the silane compound used in the hydrolysis reaction.
- Silanol (residual silanol) present in the polysiloxane having a radical crosslinkable group and not involved in the condensation is reduced in shrinkage due to condensation during baking, water generated by condensation, and degassing reduction of alcohol. From the viewpoint, a small amount is preferable, and it is preferable that the amount is almost eliminated.
- the polysiloxane having a radical crosslinkable group preferably has little or no residual silanol.
- the cycloalkyl groups may be the same or different from each other, and may be linked to each other via a covalent bond.
- examples of R 13 include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group.
- silane diol compound represented by the general formula (IV) examples include diphenyl silane diol, di-p-toluyl silane diol, dixyl silane diol, ditrimethyl phenyl silane diol, di-p-styryl silane diol, Examples include dinaphthyl silane diol, dicyclopentyl silane diol, cyclohexyl methyl silane diol, and the like, and diphenyl silane diol, dicyclopentyl silane diol, and cyclohexyl methyl silane diol are particularly preferable from the viewpoint of copolymerization and heat resistance.
- the temperature of the reaction for performing condensation without positively adding water is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, while from the viewpoint of protecting functional groups. 150 ° C. or lower is preferable, and 130 ° C. or lower is more preferable.
- the reaction time for performing the condensation without positively adding water is preferably 0.5 hours or more, more preferably 1 hour or more, while from the viewpoint of protecting the functional group. 48 hours or less is preferable, and 30 hours or less is more preferable.
- a catalyst is used and water is not positively added.
- the catalyst a basic catalyst or an acidic catalyst can be used.
- basic catalyst a trivalent or tetravalent metal alkoxide can be used.
- basic catalysts include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, tri-iso-propoxyaluminum, tri-n-butoxyaluminum, tri-iso-butoxyaluminum, tri-sec.
- Alkali metal hydroxides or alkaline earth metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide, calcium hydroxide, and magnesium hydroxide are used as basic catalysts. May be.
- NH 4 F ammonium fluoride
- barium hydroxide, sodium hydroxide, strontium hydroxide, tetra-tert-butoxy titanium, and tetra-iso-propoxy titanium are preferable.
- the basic catalyst is preferably liquid in the reaction temperature range.
- the preferable content of these basic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
- an organic acidic catalyst containing no water can be used. Specifically, as the acidic catalyst, acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid, or a half ester thereof, And (3-triethoxysilylpropyl) succinic acid or a half ester thereof.
- the preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
- a polymerization inhibitor may be added during synthesis from the viewpoint of protecting the crosslinkable group.
- the polysiloxane having a radical crosslinkable group has the following structure: ⁇ In the formula, Ph represents a phenyl group. ⁇ It is also preferable from the viewpoint of heat resistance.
- the ratio of the silicon atom of the polysiloxane having a radical crosslinkable group having the above structure is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, still more preferably 40 mol% to 60 mol%. %.
- the content of (A) the polysiloxane having a radical crosslinkable group is not particularly limited and can be arbitrarily selected depending on the desired film thickness or application, but from the viewpoint of heat-resistant transparency.
- 1 part by mass or more is preferable with respect to 100 parts by mass of the total solid content in the photosensitive resin composition, more preferably 10 parts by mass or more, and further preferably 15 parts by mass or more. From a viewpoint of property, 99 mass parts or less are preferable, More preferably, it is 90 mass parts or less, More preferably, 85 mass parts or less are preferable.
- (B) Photoradical (polymerization) initiator It is important that the (B) photoradical initiator is added to the polysiloxane composition in order to impart a formability of a photosensitive pattern to the polysiloxane composition.
- Examples of the (B) photoradical initiator include the following photoradical initiators (1) to (10):
- Benzophenone derivatives for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, fluorenone
- Acetophenone derivatives For example, 2,2′-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by BASF, IRGACURE651) ), 1-hydroxycyclohexyl phenyl ketone (manufactured by BASF, IRGACURE 184), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF, IRGACURE 907), 2- Hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] -phenyl ⁇ -2-methylpropan-1-one (manufactured by BASF, IRGACURE127), methyl phenylglyoxylate
- Thioxanthone derivatives for example, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, diethylthioxanthone
- Benzyl derivatives for example, benzyl, benzyldimethyl ketal, benzyl- ⁇ -methoxyethyl acetal
- Benzoin derivatives for example, benzoin, benzoin methyl ether, 2-hydroxy-2-methyl-1phenylpropan-1-one (manufactured by BASF, DAROCURE 1173)
- Oxime compounds for example, 1-phenyl-1,2-butanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-benzoyl) oxime, 1,3-diphenylpropanetrione-2 -(O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrione-2- (O-benzoyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyl) Oxime)] (manufactured by BASF, IRGACURE OXE01), ethanone, 1- [9-ethyl-6- (2-methylb
- ⁇ -hydroxy ketone compounds for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl -1-propan-1-one, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methylpropionyl) -benzyl] phenyl ⁇ -2-methylpropane
- ⁇ -aminoalkylphenone compounds for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by BASF, IRGACURE 369), 2-dimethylamino-2- (4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) butan-1-one (manufactured by BASF, IRGACURE 379)
- Phosphine oxide compounds for example, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, IRGACURE 819), bis (2,6-dimethoxybenzoyl) -2,4,4 -Trimethyl-pentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (BASF, Lucirin TPO)
- Titanocene compound for example, bis ( ⁇ 5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium (manufactured by BASF) , IRGACURE 784)
- the photo radical initiators (1) to (10) may be used alone or in combination of two or more.
- benzoin derivatives or (9) phosphine oxide compounds are more preferable, particularly from the viewpoint of improving photosensitivity and transparency.
- the content of the photo radical initiator is preferably 0.01 parts by mass or more, more preferably 0. 0 parts by mass from the viewpoint of obtaining sufficient sensitivity with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From the viewpoint of sufficiently curing the bottom portion of the photosensitive resin layer, it is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less.
- the nitroxy compound has the following general formula (V): ⁇ Wherein R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms, and R 1 and R 2 , or R 3 and R 4 4 may be bonded to each other to form a ring structure. ⁇ It is a compound containing the structure represented by this. R 1 , R 2 , R 3 and R 4 are preferably monovalent organic groups having 1 to 10 carbon atoms.
- the polysiloxane composition of this embodiment is excellent in crack resistance after being cured in a nitrogen atmosphere by containing (C) a nitroxy compound.
- R 1 , R 2 , R 3 and R 4 may each independently be an alkyl group or an alkyl group substituted with a hetero atom.
- alkyl group a methyl group, an ethyl group, a propyl group and the like are preferable, and as the hetero atom, a halogen, oxygen, sulfur, nitrogen and the like are preferable.
- Examples of the (C) nitroxy compound used in the present embodiment include di-tert-butyl nitroxide, di-1,1-dimethylpropyl nitroxide, di-1,2-dimethylpropyl nitroxide, di-2,2-dimethyl.
- Propyl nitroxide and a compound represented by the following general formula (VI), (VII) or (VIII) are preferred.
- a compound represented by the following general formula (VI), (VII) or (VIII) is more preferable.
- R 5 is bonded through a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a hydroxyl group, an amino group, a carboxylic acid group, a cyano group, a heteroatom-substituted alkyl, or an ether, ester, amide or urethane bond.
- R 6 represents a divalent or trivalent organic group
- n 1 and m 1 are integers satisfying 1 ⁇ n 1 + m 1 ⁇ 2
- n 2 and m 2 are 1 ⁇ n 2 + m 2 ⁇ 2 is satisfied
- n 3 and m 3 are integers satisfying 1 ⁇ n 3 + m 3 ⁇ 2
- l is an integer of 2 or 3.
- each R 20 independently represents a linear or branched alkyl group having 1 to 20 carbon atoms, an aromatic group, or an alicyclic group; and R 20 represents another substituent. You may have. ⁇
- More preferable (C) nitroxy compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1 from the viewpoint of crack resistance.
- -Oxyl free radical 4-amino-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-carboxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-cyano -2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-methacrylic acid-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acrylic acid-2,2,6 , 6-Tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethyl Piperidine 1-oxyl free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4
- a nitroxy compound may be used independently and may be used in combination of 2 or more types.
- the nitroxy compound may be contained even in a trace amount in the polysiloxane composition, but from the viewpoint of crack resistance, the content of (C) the nitroxy compound is 100 mass of the total solid content in the polysiloxane composition. Is preferably 0.005 parts by mass or more, more preferably 0.009 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less from the viewpoint of transparency. .
- the polysiloxane composition further includes (D) a compound having a photopolymerizable double bond.
- the compound having a photopolymerizable double bond is a polymerizable monomer containing at least one photopolymerizable double bond group in one molecule.
- Examples of the compound (D) having a photopolymerizable double bond include polyethylene glycol di (meth) acrylate [number of ethylene glycol units 2 to 20], poly (1,2-propylene glycol) di (meth) acrylate [ 1,2-propylene glycol units 2-20], polytetramethylene glycol di (meth) acrylate [tetramethylene glycol units 2-10], tri-2-hydroxyethyl isocyanurate tri (meth) acrylate, methylenebisacrylamide , Ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, N, N′-bis (2 -Methacryloy Of (Ruoxyethyl) urea succinic acid modified pentaerythritol tri (meth) acrylate, phthal
- the compound having a photopolymerizable double bond may further contain a carboxyl group.
- the compound (D) having a photopolymerizable double bond further containing a carboxylic acid include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxy Examples thereof include ethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, and 2,2,2-triacryloyloxymethyl ethyl succinic acid. These may be used alone or in combination of two or more.
- the content of the compound having a photopolymerizable double bond is from the viewpoint of sufficiently cross-linking each component with respect to 100 parts by mass of the total solid content in the polysiloxane composition and exhibiting adhesion to the substrate. 5 mass parts or more is preferable, More preferably, it is 10 mass parts or more, On the other hand, from a viewpoint of the residue reduction after image development, 45 mass parts or less are preferable, More preferably, it is 40 mass parts or less.
- ⁇ (E) UV absorber> in order to improve the light resistance of the polysiloxane composition and reduce residues during development, it is preferable to include (E) an ultraviolet absorber in the polysiloxane composition. Further, it is preferable to use (E) an ultraviolet absorber in combination with (C) a nitroxy compound because the resolution of the polysiloxane composition can be greatly improved.
- an ultraviolet absorber a benzotriazole type compound, a benzophenone type compound, etc. can be mentioned, for example.
- UV absorbers include, for example, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and ( Reaction product of 2-ethylhexyl) -glycidic acid ester (TINUVIN 405 manufactured by BASF), 2- (2Hbenzotriazol-2-yl) phenol, 2- (2Hbenzotriazol-2-yl) -4,6-t- Pentylphenol, 2- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2Hbenzotriazol-2-yl) -6-dodecyl-4- Methylphenol, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzof Such as non, and the like.
- the content of the (E) ultraviolet absorber is to prevent curing of the unexposed portion with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From a viewpoint, 0.01 mass part or more is preferable, More preferably, it is 0.1 mass part or more, On the other hand, 10 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation
- the polysiloxane composition further includes (F) an alkali-soluble resin.
- (F) an alkali-soluble resin is added to the polysiloxane composition. It is preferable to do.
- the (F) alkali-soluble resin refers to an alkali-soluble resin having an alkali-soluble group and having an acid value of 10 to 200 mgKOH / g.
- the acid value of the alkali-soluble resin is preferably close to (A) a polysiloxane having a radical crosslinkable group from the viewpoint of compatibility, and is preferably 10 mgKOH / g or more from the viewpoint of residue reduction during development. Preferably, it is 20 mgKOH / g or more. On the other hand, from the viewpoint of the adhesiveness of the pattern, 200 mgKOH / g or less is preferable, and more preferably 190 mgKOH / g or less.
- the alkali-soluble resin is not particularly limited as long as it has an alkali-soluble group and has an acid value of 10 to 200 mgKOH / g.
- a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride is contained in one molecule. It preferably has a group residue. Since the polysiloxane composition has a carboxyl group in the (F) alkali-soluble resin, the polysiloxane composition exhibits alkali solubility while maintaining heat-resistant transparency, and good film properties can be obtained.
- (F) There is no restriction
- the amount is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more.
- 50 parts by mass or less is preferable, and more preferably 45 parts by mass. Part or less, preferably 40 parts by weight or less.
- the alkali-soluble resin has an alkali-soluble group, and (1) to (5) below: (1) a vinyl polymer composed mainly of a reactant of a polymerizable double bond, (2) an epoxy polymer mainly composed of an addition reaction product of an epoxy group and a hydroxyl group, (3) an aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde, (4) At least one selected from the group consisting of urethane polymers composed mainly of reactants of dialcohol and diisocyanate, and (5) ester polymers composed mainly of reactants of dicarboxylic acid and diepoxide.
- the polymer is preferably.
- the main component means that the component is contained in an amount of 70 mol% or more in the molecule.
- Vinyl polymer mainly composed of a reaction product of a polymerizable double bond For example, a carboxyl group-containing vinyl polymer represented by the following general formula (4) or the following general formula (6) may be mentioned.
- Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms
- Re is represented by the following general formula (5):
- Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group
- Rc is the following general formula (3): (In the formula, Ra is a linear, branched or cyclic divalent organic group having 2 to 16 carbon atoms) or hydrogen.
- Rf is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, and Rh is independently , A methyl group or hydrogen, m is an integer selected from 1 to 500, and n is an integer selected from 10 to 1,000.
- Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group; Is a group represented by the general formula (5) or hydrogen, and Rd is a linear, branched or cyclic divalent organic group having 0 to 20 carbon atoms, or a photopolymerizable divalent group.
- Rf is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, and Rh is a methyl group or hydrogen; M is an integer selected from 1 to 500, and n is an integer selected from 10 to 1,000.
- Examples of the method for obtaining the carboxyl group-containing vinyl polymer include the following three methods: (I) at least one compound (a) selected from ⁇ , ⁇ -unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide and hydrogen on the nitrogen thereof.
- Examples of the compound (a) used for the preparation of the carboxy-containing vinyl polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, and 2- (meth) acrylate. ) Acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid half ester, etc. Is mentioned. These may be used alone or in combination of two or more.
- Examples of the compound (b) used for the preparation of the carboxyl group-containing vinyl polymer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meta ) Acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone (meth) Acrylate, nonylphenoxy polypropylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylamide, N-meth Roll acrylamide, N-butoxymethyl acrylamide, styrene, ⁇ -methyl
- the compound (c) used for the preparation of the carboxyl group-containing vinyl polymer is an epoxy (meth) acrylate obtained by reacting an epoxy resin having two epoxy groups with (meth) acrylic acid by a conventional method. If it is a half ester, it will not specifically limit.
- examples of the compound (c) include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, vinylcyclohexene monooxide, hydroquinone diglycidyl ether.
- Examples of the compound (d) used for the preparation of the carboxyl group-containing vinyl polymer include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and 5-methyl-cyclohexane dicarboxylic acid anhydride.
- Bicycloheptane dicarboxylic anhydride Bicycloheptane dicarboxylic anhydride, 7-oxabicycloheptane dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipic anhydride, phthalic anhydride, (3-trimethoxy And polybasic acid anhydrides such as (silylpropyl) succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.
- the vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a conventional method, and known methods such as solution polymerization, suspension polymerization method and emulsion polymerization method are possible. Polymerization is preferred.
- the polymerization initiator that can be used in this case those having a 10-hour half-life temperature in the range of 60 ° C. to 120 ° C. are preferable. Examples of such polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyl).
- Esters such as t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, bis-3,5,5-trimethylhexanoyl peroxide, octa Diacyl peroxides such as noyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, t- Dialkyl peroxides such as chill cumyl peroxide, and the like. These may be used alone or in combination of two or more.
- the addition reaction between a carboxyl group and a compound having an epoxy group and a (meth) acryl group is preferably performed in a solvent using a polymerization inhibitor and a catalyst.
- the temperature is preferably 50 to 120 ° C.
- reaction solvent examples include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether , Glycol ethers such as diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether; ethyl acetate, butyl acetate, ethylene glycol monoethyl Teracetate, ethylene glycol monobutyl ether Acetates such as acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propyl
- reaction catalyst for the preparation of the carboxyl group-containing vinyl polymer examples include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, Examples thereof include phosphorus compounds such as triphenylphosphine, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octoenoic acid. These may be used alone or in combination of two or more.
- Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine. These may be used alone or in combination of two or more. Further, although the dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 to 120 ° C.
- a novolak type phenol polymer represented by the following general formula (9) may be mentioned.
- Rb is a linear, branched or cyclic monovalent organic group having 1 to 20 carbon atoms, or a monovalent organic group having a photopolymerizable double bond group
- Rc is
- Rj is a methyl group, a hydroxyl group or hydrogen
- Rk is the above general formula (5) or the following general formula (8):
- m is an integer selected from 0 to 100
- n is an integer selected from 4 to 1,000.
- the novolak type phenol polymer used in the present embodiment is obtained by reacting an epihalohydrin with a condensation reaction product of phenol and formaldehyde. Furthermore, an epoxy group of the reaction product may be subjected to an addition reaction between a carboxyl group or a (meth) acrylate compound having a hydroxyl group, and the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride.
- the phenol used for the preparation of the novolak type phenol polymer include phenol, cresol, xylenol, trimethylphenol and the like. These may be used alone or in combination of two or more.
- Examples of the epihalohydrin used in the novolac type phenol polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.
- Examples of the compound having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of the novolak type phenol polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, Carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, croton Examples include acids, itaconic acid, and maleic acid half esters. These may be used alone or in combination of two or more.
- Examples of the hydroxyl group and (meth) acrylate compound used in the preparation of the novolak type phenol polymer in one molecule include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol methacrylate acrylate, Examples include pentaerythritol tri (meth) acrylate and caprolactone adducts of these monomers.
- epoxy (meth) acrylate compounds in which an epoxy group is (meth) acrylate-modified include epoxy (meth) acrylates of phenyl diglycidyl ethers such as hydroquinone diglycidyl ether, catechol diglycidyl ether, resorcinol diglycidyl ether, and bisphenol.
- Epoxy (meth) acrylates of bisphenol type epoxy compounds such as hydrogenated bisphenol-A type epoxy resin, hydrogenated bisphenol-F type epoxy resin, hydrogenated bisphenol-S type epoxy resin, hydrogenated 2,2- (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane epoxy compound, etc.
- Epoxy (meth) acrylates of aliphatic diglycidyl ether compounds such as epoxy (meth) acrylates of alicyclic diglycidyl ether compounds, 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, diethylene glycol diglycidyl ether, etc. ) Acrylate and the like.
- Dicarboxylic acid anhydrides used for the preparation of novolak type phenol polymers include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid.
- Acid anhydride 7-oxabicycloheptanedicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, adipic acid anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinate
- polybasic acid anhydrides such as acid anhydride and (3-triethoxysilylpropyl) succinic acid anhydride. These may be used alone or in combination of two or more.
- an acid catalyst When performing the condensation reaction of phenol and formaldehyde in the preparation of the novolak type phenol polymer, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, Acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable.
- the condensation reaction of phenol and formaldehyde can be performed in the absence of a solvent or in the presence of an organic solvent.
- organic solvent include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone and the like.
- the amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged.
- the reaction temperature is usually 40 ° C. to 180 ° C., and the reaction time is usually 1 hour to 10 hours. These solvents may be used alone or in combination of two or more.
- water washing treatment is performed until the pH value of the water washing liquid of the reaction mixture becomes 3 to 7, preferably 5 to 7.
- alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
- alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide
- ammonia sodium dihydrogen phosphate, diethylenetriamine
- You may process using various basic substances, such as organic amines, such as ethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent.
- organic amines such as ethylenetetramine, aniline, and phenylenediamine
- An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to the dissolved mixture of the phenol-formaldehyde condensate obtained in the above reaction and epihalohydrin such as epichlorohydrin, epibromohydrin or the like.
- An epoxy resin can be obtained by reacting at ⁇ 120 ° C. for 1 to 10 hours. After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin or other added solvent is removed under reduced pressure by heating at 110 ° C. to 250 ° C. and a pressure of 10 mmHg or less.
- the obtained epoxy resin is again dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved.
- Further reaction can be performed by adding an aqueous solution to ensure ring closure.
- the reaction temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.
- the produced salt is removed by filtration, washing with water, and the solvent of toluene, methyl isobutyl ketone and the like is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.
- the addition reaction between the epoxy group and the compound having a carboxyl group or a hydroxyl group and a (meth) acryl group in the preparation of the novolak type phenol polymer is preferably carried out in a solvent using a polymerization inhibitor and a catalyst,
- the reaction temperature is preferably 50 to 120 ° C.
- the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each described in (1)
- Preparation of a vinyl polymer mainly composed of a reactant of a polymerizable unsaturated double bond can be used.
- dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, but the reaction temperature is preferably 50 ° C. to 120 ° C.
- the alkali-soluble resin is mainly composed of a vinyl polymer composed mainly of a polymerizable unsaturated double bond reactant and an addition product of an epoxy group and a hydroxyl group from the viewpoint of heat resistance of the reactant composed mainly of the polymer.
- a seed polymer is preferred.
- Ratio of acid value (A) (mgKOH / g) of polysiloxane having radical crosslinkable group and acid value (F) (mgKOH / g) of alkali-soluble resin that is, acid value (A) / acid value (F) Is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of compatibility by polarity between (A) a polysiloxane having a radical crosslinkable group and (F) an alkali-soluble resin. More preferably, it is 0.3 or more. On the other hand, this ratio is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.0 or less.
- a silane coupling agent can be added to the polysiloxane composition in order to improve the adhesion between the cured film after exposure and development of the polysiloxane composition and the substrate.
- a silane coupling agent can be added to the polysiloxane composition in order to improve the adhesion between the cured film after exposure and development of the polysiloxane composition and the substrate.
- the content of the silane coupling agent in the case of adding the silane coupling agent to the polysiloxane composition is such that the adhesiveness with the substrate is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
- 0.1 mass part or more is preferable, More preferably, it is 0.5 mass part or more.
- 20 mass parts or less are preferable, More preferably, 15 mass parts or less It is.
- Suitable solvents include the following solvents (1) to (6): (1) Aliphatic alcohols: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octan
- Aromatic alcohol benzyl alcohol, (2-hydroxyphenyl) methanol, (methoxyphenyl) methanol, (3,4-dihydroxyphenyl) methanol, 4- (hydroxymethyl) benzene-1,2-diol, (4 -Hydroxy-3-methoxyphenyl) methanol, (3,4-dimethoxyphenyl) methanol, (4-isopropylphenyl) methanol, 2-phenylethanol, 1-phenylethanol, 2-phenyl-1-propanol, p-tolyl alcohol 2- (4-hydroxy-3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1-ol, 3-phenylpropan-1-ol, 2-phenylpropane-2 -All, cinnamyl alcohol, 3- (4-H Loxy-3-methoxyphenyl) prop-2-en-1-ol, 3- (4-hydroxy-3,5-
- Glycol or derivatives thereof for example, ethylene glycol, ethylene glycol monoalkyl (1 to 8 carbon atoms) ether, ethylene glycol monovinyl ether, ethylene glycol monophenyl ether, dioxane, diethylene glycol monoalkyl (1 to 6 carbon atoms) ) Ether, diethylene glycol monovinyl ether, diethylene glycol monophenyl ether, triethylene glycol monoalkyl (1 to 3 carbon atoms) ether, triethylene glycol monovinyl ether, triethylene glycol monophenyl ether, tetraethylene glycol monophenyl ether, propylene glycol, Propylene glycol monoalkyl (1 to 4 carbon atoms) ether, propylene glycol monophenyl Ether, dipropylene glycol monoalkyl (1-3 carbon atoms) ether, ethylene glycol monoacetate, propylene glycol monoacrylate, propylene glycol monoacetate
- Ketone compounds acetone, methyl ethyl ketone, 3-butyn-2-one, methyl-n-propyl ketone, methyl isopropyl ketone, 3-pentyn-2-one, methyl isopropenyl ketone, methyl n-butyl ketone, methyl isobutyl Ketone, mesityl oxide, 4-hydroxy-4-methyl-2-pentanone, methyl-n-amyl ketone, methyl isoamyl ketone, ethyl-n-butyl ketone, di-n-propyl ketone, diisopropyl ketone, 2-octanone, 3- Octanone, 5-methyl-3-heptanone, 5-nonanone, diisobutylketone, trimethylnonanone, 2,4-pentanedione, 2,5-hexanedione, cyclopentanone, cyclohexanone, methylcycl
- propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable from the viewpoint of heating the coating film and evaporating the solvent.
- These solvents can be appropriately added to the polysiloxane composition depending on the coating film thickness and viscosity, but are 50 to 1,000 parts by mass with respect to 100 parts by mass of all solid components in the polysiloxane composition. It is preferable to use in the range.
- a surfactant may be contained in the polysiloxane composition in order to ensure applicability of the polysiloxane composition and film smoothness after drying.
- the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, or polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether.
- Polyoxyethylene arylalkyl ethers, or polyoxyethylene dialkyl esters such as polyoxyethylene ethylene dilaurate and polyoxyethylene distearate, MegaFac F171, 172, 173 (Dainippon Ink), Florard FC430, 431 (Sumitomo) 3M), Asahi Guard AG710, Surflon S-382, SC-101,102,103,104,105 (Asahi Glass) Active agents, such as DBE-712, DBE821 (manufactured by DAICEL-CYTEC Co., Ltd.) silicone surfactants, and the like.
- the content of these surfactants is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, from the viewpoint of coating suitability and residue reduction with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From the viewpoint of pattern adhesion after development, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
- the polysiloxane composition may contain a polymerization inhibitor (for example, a radical polymerization inhibitor).
- a polymerization inhibitor for example, a radical polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium
- the content of the polymerization inhibitor causes the polymerization inhibiting effect of the photopolymerizable double bond to be expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition.
- 0.001 mass part or more is preferable, More preferably, 0.01 mass part or more is preferable,
- 5 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation
- an antioxidant can be added to the polysiloxane composition in order to improve the thermal stability of the polysiloxane composition in the presence of oxygen.
- antioxidants include hindered phenols, phosphoruss, lactones, vitamin Es, and sulfurs.
- the antioxidant is not limited, but is triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Corporation).
- IRGANOX 245) 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (IRGANOX 259 manufactured by BASF), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX565 manufactured by BASF), pentaerythrityl tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate) (IRGANOX1010 manufactured by BASF), 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX1035 manufactured by BASF), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IR
- the antioxidant is not limited, but is 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy. ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (SUMILIZER GA-80, manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis (6-t-butyl) -4-methylphenol) (SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4′-butylidenebis (6-t-butyl-3-methylphenol) (SUMILIZER BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4, 4 ′ -Thiobis (6-tert-butyl-3-methylphenol) (SUMIZER WX-R manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl-te
- antioxidants can be used alone or as a mixture of two or more.
- the content of the antioxidant in the case of adding an antioxidant to the polysiloxane composition is such that the heat stability effect in the presence of oxygen is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more.
- the amount is preferably at most 10 parts by mass, more preferably at most 10 parts by mass, even more preferably at most 5 parts by mass.
- the polysiloxane composition may contain additives such as a plasticizer as necessary.
- additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether.
- the content of the plasticizer when adding the plasticizer to the polysiloxane composition is 0.1 parts by mass or more from the viewpoint of increasing the flexibility of the film with respect to 100 parts by mass of the total solid content in the polysiloxane composition. Is more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more. On the other hand, from the viewpoint of the glass transition temperature, 10 parts by mass or less is preferable, and more preferably 8 parts by mass or less. More preferably, it is 5 parts by mass or less.
- the acid value of the polysiloxane composition used in the present embodiment is preferably 0.1 mgKOH / g or more, more preferably 1 mgKOH / g or more, further from the viewpoint of reduction of residues after development and crack resistance of the cured film. Preferably, it is 5 mgKOH / g or more. On the other hand, from the viewpoint of pattern adhesion, it is preferably 200 mgKOH / g or less, more preferably 170 mgKOH / gmol or less, and further preferably 150 mgKOH / g or less.
- the transmittance of light at a wavelength of 400 nm after baking at 220 ° C. for 3 hours in the atmosphere of the cured product having a thickness of 10 ⁇ m It is preferable that it is 70% or more. It is also preferable to obtain a transparent insulating film by curing the polysiloxane composition used in the present invention.
- the radical content in the cured product is preferably contained in an amount of 0.1 ⁇ 10 ⁇ 6 mol or more, more preferably 0.15 ⁇ 10 ⁇ 6 mol or more with respect to 1 g of the cured product.
- preferably 120 ⁇ 10 -6 mol or less from the viewpoint of pattern formation more preferably 60 ⁇ 10 - is 6 mol or less.
- the method for measuring the radical content in the cured product is the same as that described above for the polysiloxane composition.
- a method for forming a cured relief pattern includes a first step of applying a polysiloxane composition on a substrate, a second step of irradiating actinic rays, a third step of removing uncured portions with a developer, A fourth step of heat curing is included.
- the polysiloxane composition is applied on various desired substrates such as a silicon wafer, a ceramic substrate, and an aluminum substrate.
- a spin coater As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used.
- the coated substrate is soft baked at 80 ° C. to 200 ° C. for 1 to 15 minutes, and then irradiated with actinic rays through a desired photomask using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. .
- X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used as the actinic rays. In the present invention, those having a wavelength of 200 nm to 500 nm are preferably used.
- the light source wavelength is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferred as the exposure projection apparatus. Thereafter, for the purpose of improving the photosensitivity, etc., any combination of temperature and time is used as necessary (preferably, the temperature is 40 ° C. to 200 ° C., and the time is 10 seconds to 360 seconds).
- Post-exposure baking (PEB) or pre-development baking may be performed.
- a developer an organic solvent or an alkaline developer is preferable.
- the good solvent of the composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
- suitable alkali developers include ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like.
- amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine.
- carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine are contained in an amount of 0.05 to 10% by mass.
- Development is preferably performed at a temperature of 20 ° C. to 35 ° C. using a weakly alkaline aqueous solution.
- organic solvent developers include glycols such as ethylene glycol and propylene glycol.
- glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol.
- An example is monoethyl ether.
- Other organic solvent developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, ⁇ -acetyl- Examples thereof include gamma butyrolactone, cyclopentanone, and cyclohexanone.
- the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern.
- a rinse solution As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like can be used alone, or appropriately mixed, or used in a stepwise combination.
- the relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 ° C. to 250 ° C., which is much lower than the conventional polyimide precursor composition.
- This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven that can set a temperature program, and the like. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary.
- the above-described cured relief pattern is applied to, for example, a silicon wafer, glass, a film, a surface protection film of a semiconductor device formed on a base material such as a base material on which one or more kinds of metals are sputtered, an interlayer insulating film, an ⁇ -ray shielding. It is used as one selected from the group consisting of a film and a support (partition) between a microstructure such as a microlens array and its packaging material, and a known semiconductor device manufacturing method is applied to other processes. As a result, various display devices and semiconductor devices including optical elements such as a touch panel and a CMOS image sensor can be manufactured. Moreover, an electronic component or a semiconductor device having a coating film made of a resin obtained by curing the polysiloxane composition can be obtained.
- ⁇ Calculation method of g value> Among the six peaks of Mn 2+, the third peak counted from the low magnetic field side is used as the standard peak.
- the absorption magnetic field of the standard peak is H s
- the g s value is 2.034
- the absorption magnetic field of the measurement sample is H 0 .
- Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5 Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds ⁇ 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen. (About Example 15) Following exposure, PGMEA (propylene glycol monomethyl ether acetate) was used and developed under the conditions of 23 ° C.
- PGMEA propylene glycol monomethyl ether acetate
- resolution range is wider than 420mJ / cm 2 ⁇ : the resolution range is wider than 300mJ / cm 2 ⁇ : wider than the resolution range is 120mJ / cm 2 ⁇ : resolution range is 120mJ / cm 2 or less
- the polysiloxane composition was applied to an aluminum-sputtered silicon substrate so that the film thickness after baking was 15 ⁇ m, and baked on a hot plate at 95 ° C. for 4 minutes.
- the substrate having the coating film was exposed to 400 mJ / cm 2 using an i-line stepper through a reticle with a test pattern. Exposure was performed in air and the focus was set to -15.
- Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5 Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds ⁇ 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen. (About Example 15) Following exposure, PGMEA was used and developed under the conditions of 23 ° C. and 30 seconds ⁇ 2 times to remove the unexposed portion of the coating film.
- an alkali developer developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution
- the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
- the patterned substrates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were further baked at 300 ° C. for 30 minutes in an oven purged with nitrogen, and subsequently -40 ° C. at 15 ° C. using a thermal shock tester. Minute, 120 ° C. and 15 minutes once were repeated 100 times, then visually and observed with an optical microscope, and evaluated according to the following criteria.
- ⁇ : No cracks confirmed in 5 substrates ⁇ : 1-5 cracks occurred in 5 substrates
- the substrate developed above was baked at 220 ° C. for 6 hours in an atmosphere using an oven.
- a spectrophotometer UV-1600PC manufactured by Shimadzu Corporation
- a glass substrate without a coating film was placed on the reference portion, and the light transmittance at 800 nm to 300 nm was measured to confirm the light transmittance at 400 nm.
- Example 2 to 27 and Comparative Examples 1 to 5 For Examples 2 to 27 and Comparative Examples 1 to 5, the same as in Example 1 except that the components described in Table 1, Table 2, and Table 3 below were used in the ratios described in the same table. A siloxane composition or a resin composition was obtained.
- ⁇ (C) component> c-1 The following formula: 4-Hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) c-2: The following formula: TEMPO having a structure represented by (manufactured by Tokyo Chemical Industry Co., Ltd.) c-3: The following formula: 4-oxo-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) having the structure represented by c-4: The following formula: 3-Carboxy-proxyl-free radical having a structure represented by (Tokyo Chemical Industry Co., Ltd.)
- Examples 1 to 27 The crack resistance of Examples 1 to 27 was evaluated using a Mo-sputtered silicon wafer. As a result, in Examples 1 to 20 and Examples 24 to 27, the pattern was not peeled off and no cracks were generated. However, in Examples 21 to 23, the pattern peeled off. Comparative Example 5 could not be evaluated because exposure and development did not leave a film.
- the polysiloxane composition having an alkali-soluble group of the present invention is used as an insulating material for a display device, for forming a surface protective film, an interlayer insulating film, an ⁇ -ray shielding film, etc. in a semiconductor device, and for an image sensor, a micromachine, or a microactuator. It can be suitably used for a semiconductor device or the like on which is mounted.
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Abstract
Description
をさらに含む、ポリシロキサン組成物。 (B) A polysiloxane composition further comprising a photoradical initiator.
[14]下記構造:
[15]アルカリ可溶性基をさらに有する、前記[14]に記載のラジカル架橋性基を有するポリシロキサン組成物。
[16] (B)光ラジカル開始剤
をさらに含む、ポリシロキサン組成物。
[17]前記ポリシロキサン組成物中の全固形分100質量部に対して、(A)1質量部~99質量部のラジカル架橋性基を有するポリシロキサン、0.01質量部~15質量部の(B)光ラジカル開始剤、及び0.005質量部~2質量部の(C)ニトロキシ化合物を含む、前記[16]に記載のポリシロキサン組成物。
[18]前記(C)ニトロキシ化合物は、下記一般式:
[19]前記(A)ラジカル架橋性基を有するポリシロキサンは、(メタ)アクリロイル基及び/又はスチリル基を有するポリシロキサンである、前記[14]~[18]のいずれかに記載のポリシロキサン組成物。
[20]前記ポリシロキサン組成物中の全固形分100質量部に対して、5質量部~45質量部の(D)光重合性二重結合を有する化合物をさらに含む、前記[14]~[19]のいずれかに記載のポリシロキサン脂組成物。
[21]前記ポリシロキサン組成物中の全固形分100質量部に対して、0.01質量部~10質量部の(E)紫外線吸収剤をさらに含む、前記[14]~[20]のいずれかに記載のポリシロキサン組成物。
[22]前記ポリシロキサン組成物中の全固形分100質量部に対して、1質量部~50質量部の(F)酸価が10~200mgKOH/gであるアルカリ可溶性樹脂をさらに含む、前記[14]~[21]のいずれかに記載のポリシロキサン組成物。
[23]前記(A)ラジカル架橋性基を有するポリシロキサンは、下記一般式:
[24]前記[14]~[22]のいずれかに記載のポリシロキサン組成物を硬化して得られる硬化物。
[25]前記[14]~[22]のいずれかに記載のポリシロキサン組成物を硬化して得られる透明絶縁膜。 [13] A transparent insulating film obtained by curing the polysiloxane composition according to any one of [1] to [11].
[14] The following structure:
[15] The polysiloxane composition having a radical crosslinkable group according to [14], further including an alkali-soluble group.
[16] A polysiloxane composition further comprising (B) a photoradical initiator.
[17] (A) 1 to 99 parts by mass of a polysiloxane having a radical crosslinkable group, 0.01 to 15 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition (B) The polysiloxane composition according to the above [16], comprising a photo radical initiator and 0.005 to 2 parts by mass of (C) a nitroxy compound.
[18] The (C) nitroxy compound has the following general formula:
[19] The polysiloxane according to any one of [14] to [18], wherein the polysiloxane having a radical crosslinkable group (A) is a polysiloxane having a (meth) acryloyl group and / or a styryl group. Composition.
[20] The above [14] to [14], further comprising (D) a compound having a photopolymerizable double bond in an amount of 5 to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition. [19] The polysiloxane fat composition according to any one of [19].
[21] Any of [14] to [20], further comprising 0.01 to 10 parts by mass of (E) an ultraviolet absorber with respect to 100 parts by mass of the total solid content in the polysiloxane composition. A polysiloxane composition according to
[22] The alkali-soluble resin further comprising (F) an acid value of 10 to 200 mgKOH / g of 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition. The polysiloxane composition according to any one of 14] to [21].
[23] The polysiloxane having a radical crosslinkable group (A) has the following general formula:
[24] A cured product obtained by curing the polysiloxane composition according to any one of [14] to [22].
[25] A transparent insulating film obtained by curing the polysiloxane composition according to any one of [14] to [22].
本実施形態に係るラジカル架橋性基を有するポリシロキサン組成物は、具体的には、以下の成分:
(A)ラジカル架橋性基を有するポリシロキサン、及び
(B)光ラジカル開始剤、
所望により、その他の成分
を含む。前記(A)ラジカル架橋性基を有するポリシロキサンは、以下に説明するように、ラジカル架橋性基を有するポリシロキサンと(C)ニトロキシ化合物からなるもであることができる。
以下、ラジカル架橋性基を有するポリシロキサン組成物を硬化することにより得られる硬化物などについて説明する。
但し、本実施形態において、ニトロキシ化合物は、大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるとき、g値2.034~1.984のピークを持つラジカル構造を提供するものの例示であり、本発明は、これに限定されることを意図していない。
すなわち、以下に説明する(A)ラジカル架橋性基を有するポリシロキサンと、例えば、(C)成分であるニトロキシ化合物が共存した状態で、これらを加熱した場合、該ポリシロキサン(A)成分と該(C)成分の一部が結合するが、その際、ラジカル架橋性基を有するポリシロキサン単体と、大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるときg値2.034~1.984のピークを持つラジカルと、該ポリシロキサンとラジカルが結合したものとの、混合状態が存在することになる。本発明においては、かかる混合状態を、「大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるとき、g値2.034~1.984のピークを持つ、ラジカル架橋性基を有するポリシロキサン組成物」と表現する。あるいは、ラジカル架橋性基を有するポリシロキサンは、大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるときg値2.034~1.984のピークを持つラジカルを発生する基をさらに有することができる。この場合には、ポリシロシサン単体が前記所定のピークを有することになる。すなわち、「大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるとき、g値2.034~1.984のピークを持つ、ラジカル架橋性基を有するポリシロキサン組成物」とは、ラジカル架橋性基を有するポリシロキサン単体が前記ラジカル発生基を有する場合と、ラジカル架橋性基を有するポリシロキサン単体は前記ラジカル発生基を有しないが、例えば、ニトロキシ化合物と共存したときに生じる、ポリシロキサン単体と、ラジカルと、ポリシロキサン単体とラジカルとそれらが結合したものとの混合状態の場合の両者を包含する。
尚、同様に、「前記ラジカル架橋性基を有するポリシロキサン組成物がアルカリ可溶性基をさらに有する」とは、該ポリシロキサン自体がアルカリ可溶性基を有する場合と、該ポリシロシサンを含む組成物が、アルカリ可溶性樹脂を含む結果、該ポリシロキサン組成物がアルカリ可溶性基を含む場合の両者を包含する。 <Polysiloxane composition having radical crosslinkable group>
Specifically, the polysiloxane composition having a radical crosslinkable group according to the present embodiment includes the following components:
(A) polysiloxane having a radical crosslinkable group, and (B) a photoradical initiator,
Optionally, other ingredients are included. The polysiloxane having a radical crosslinkable group (A) can be composed of a polysiloxane having a radical crosslinkable group and (C) a nitroxy compound as described below.
Hereinafter, a cured product obtained by curing a polysiloxane composition having a radical crosslinkable group will be described.
However, in the present embodiment, the nitroxy compound is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., atmospheric pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus. When measured, this is an illustration of what provides a radical structure having a peak with a g value of 2.034 to 1.984, and the present invention is not intended to be limited thereto.
That is, when (A) a polysiloxane having a radical crosslinkable group described below and, for example, a nitroxy compound as the component (C) are coexisting, when heated, the polysiloxane (A) component and the polysiloxane (A) A part of the component (C) is bonded, and at that time, the polysiloxane alone having a radical crosslinkable group, and 24 hours at 24 ° C. under atmospheric pressure and light with a wavelength of 400 nm or less are shielded from light for 24 hours. After being allowed to stand, there is a mixed state of a radical having a peak with a g value of 2.034 to 1.984 when measured using an electron spin resonance (ESR) apparatus and a combination of the polysiloxane and the radical. Become. In the present invention, such a mixed state is expressed as “under atmospheric conditions at 24 ° C., normal pressure, and under a condition where light of a wavelength of 400 nm or less is shielded for 24 hours, and then using an electron spin resonance (ESR) apparatus. When measured, it is expressed as a “polysiloxane composition having radical crosslinkable groups having a peak of g value of 2.034 to 1.984”. Alternatively, the polysiloxane having a radical crosslinkable group is allowed to stand for 24 hours in the atmosphere under the condition of shielding light having a wavelength of 24 ° C., normal pressure, and 400 nm or less, and then using an electron spin resonance (ESR) apparatus. And a group capable of generating a radical having a peak with a g value of 2.034 to 1.984 when measured. In this case, the polysilosan simple substance has the predetermined peak. That is, “g value 2.034 when measured using an electron spin resonance (ESR) apparatus after standing for 24 hours under the condition of shielding light of a wavelength of 400 nm or less in the atmosphere at 24 ° C., normal pressure,” A polysiloxane composition having a radical crosslinkable group having a peak of ˜1.984 ”means that the polysiloxane simple substance having a radical crosslinkable group has the radical generating group, and the polysiloxane simple substance having a radical crosslinkable group is Although it does not have the radical generating group, for example, it includes both in the case of a mixed state of a polysiloxane simple substance, a radical, and a polysiloxane simple substance, a radical and a combination thereof generated when coexisting with a nitroxy compound .
Similarly, “the polysiloxane composition having a radical crosslinkable group further has an alkali-soluble group” means that the polysiloxane itself has an alkali-soluble group and the composition containing the polysiloxane has an alkali As a result of including a soluble resin, both the case where the polysiloxane composition includes an alkali-soluble group are included.
本実施形態で温度衝撃によるクラック耐性に優れた硬化物を得るためには、大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるときg値2.034~1.984のピークを持つラジカルが、組成物中の固形分1gに対し、0.1×10-6モル以上含まれることが好ましく、さらに好ましくは0.15×10-6モル以上である。一方で、パターン形成の観点から120×10-6モル以下が好ましく、さらに好ましくは60×10-6モル以下である。
ラジカル架橋性基を有するポリシロキサン組成物中の全固形分量は、例えば、TGA(熱重量測定装置)を用いて測定することができる。
ラジカル量は、ESR(電子スピン共鳴装置)を用い測定することができる。4-ヒドロキシTEMPOを、1モルあたり1モルのラジカルを持つ標品として、検量線を作成することで、組成物中のラジカル量を測定し、TGAで測定した固形分量と合わせることで、組成物中の固形分1g当たりに含まれるラジカル含有量を算出することができる。
尚、以下に説明するが、本実施態様に係るポリシロキサン組成物においては、ニトロキシ化合物0.0017質量部は、ラジカル量0.1×10-6モル/gに相当し、ニトロキシ化合物0.005質量部は、ラジカル量0.29×10-6モル/gに相当し、ニトロキシ化合物0.009質量部は、ラジカル量0.523×10-6モル/gに相当し、ニトロキシ化合物1質量部は、ラジカル量58×10-6モル/gに相当し、そしてニトロキシ化合物2質量部は、ラジカル量116×10-6モル/gに相当した。 <Radical content>
In order to obtain a cured product having excellent resistance to cracking due to temperature shock in the present embodiment, after standing for 24 hours under the condition of shielding light at a temperature of 24 ° C., normal pressure, and a wavelength of 400 nm or less in the atmosphere, A radical having a peak with a g value of 2.034 to 1.984 when measured using a spin resonance (ESR) apparatus is preferably contained in an amount of 0.1 × 10 −6 mol or more with respect to 1 g of the solid content in the composition. More preferably, it is 0.15 × 10 −6 mol or more. On the other hand, from the viewpoint of pattern formation, it is preferably 120 × 10 −6 mol or less, and more preferably 60 × 10 −6 mol or less.
The total solid content in the polysiloxane composition having a radical crosslinkable group can be measured, for example, using a TGA (thermogravimetric apparatus).
The amount of radicals can be measured using an ESR (electron spin resonance apparatus). 4-hydroxy TEMPO was prepared as a standard having 1 mole of radical per mole, a calibration curve was created, the amount of radicals in the composition was measured, and the composition was combined with the solid content measured by TGA. It is possible to calculate the radical content contained per gram of solid content.
As will be described below, in the polysiloxane composition according to this embodiment, 0.0017 parts by mass of the nitroxy compound corresponds to a radical amount of 0.1 × 10 −6 mol / g, and the nitroxy compound 0.005 The mass part corresponds to a radical amount of 0.29 × 10 −6 mol / g, the nitroxy compound 0.009 part by mass corresponds to a radical amount of 0.523 × 10 −6 mol / g, and the
(A)ラジカル架橋性基を有するポリシロキサンは、ポリシロキサン中にラジカルによって架橋できる基を有しており、硬化膜の硬度を飛躍的に向上させることができる。
ラジカル架橋性基は、光重合性不飽和結合(例えば、二重結合)を含む基でよい。光重合性不飽和結合を含む基としては、特に制限されないが、例えば、ビニル基、スチリル基、(メタ)アクリロイル基などが、架橋性の観点から好ましい。(A)ラジカル架橋性基を有するポリシロキサンは、これらの基を二種類以上含有してもよい。また、(A)ラジカル架橋性基を有するポリシロキサンとしては、硬化性の観点から、少なくとも(メタ)アクリロイル基及び/又はスチリル基を有することがより好ましい。
(A)ラジカル架橋性基を有するポリシロキサン中の光重合性不飽和結合基のモル濃度は、パターンの密着性、膜の硬度、及び耐クラック性の観点から、0.01mmol/g以上が好ましく、より好ましくは0.1mmol/g以上、さらに好ましくは0.5mmol/g以上である。一方で、現像時の残渣低減の観点から、このモル濃度は、10.0mmol/g以下が好ましく、より好ましくは7.5mmol/g以下、さらに好ましくは5.0mmol/g以下である。
(A)ラジカル架橋性基を有するポリシロキサン中の光重合性不飽和結合基の含有量は、得られたポリマーのヨウ素価を測定することで算出することができる。
(A)ラジカル架橋性基を有するポリシロキサンは、1分子内にアルカリ可溶性基を含むことが好ましい。アルカリ可溶性基としては、特に制限はされないが、例えば、カルボキシル基、ジカルボン酸無水物基、又はジカルボン酸無水物基の残基などが、ポリシロキサンのアルカリ溶解性を向上させ、かつ現像後の残渣の発生を抑制するという観点から好ましい。 <(A) Polysiloxane having radical crosslinkable group>
(A) The polysiloxane having a radical crosslinkable group has a group that can be crosslinked by radicals in the polysiloxane, and can dramatically improve the hardness of the cured film.
The radical crosslinkable group may be a group containing a photopolymerizable unsaturated bond (for example, a double bond). Although it does not restrict | limit especially as group containing a photopolymerizable unsaturated bond, For example, a vinyl group, a styryl group, a (meth) acryloyl group etc. are preferable from a crosslinkable viewpoint. (A) The polysiloxane having a radical crosslinkable group may contain two or more of these groups. Further, (A) the polysiloxane having a radical crosslinkable group preferably has at least a (meth) acryloyl group and / or a styryl group from the viewpoint of curability.
(A) The molar concentration of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group is preferably 0.01 mmol / g or more from the viewpoint of pattern adhesion, film hardness, and crack resistance. More preferably, it is 0.1 mmol / g or more, and still more preferably 0.5 mmol / g or more. On the other hand, from the viewpoint of reducing residues during development, the molar concentration is preferably 10.0 mmol / g or less, more preferably 7.5 mmol / g or less, and still more preferably 5.0 mmol / g or less.
(A) The content of the photopolymerizable unsaturated bond group in the polysiloxane having a radical crosslinkable group can be calculated by measuring the iodine value of the obtained polymer.
(A) The polysiloxane having a radical crosslinkable group preferably contains an alkali-soluble group in one molecule. The alkali-soluble group is not particularly limited. For example, a carboxyl group, a dicarboxylic acid anhydride group, or a residue of a dicarboxylic acid anhydride group improves the alkali solubility of the polysiloxane and is a residue after development. It is preferable from the viewpoint of suppressing the occurrence of the above.
また、ラジカル架橋性基を有するポリシロキサン組成物が、2種以上の(A)ラジカル架橋性基を有するポリシロキサンを含有する場合には、少なくとも1種が、上記で説明した範囲内の酸価を有するような含有量で、カルボキシル基、ジカルボン酸無水物基、又はジカルボン酸無水物基の残基を含むことが好ましい。
なお、本明細書では、酸価とは、試料1g中のカルボキシル基を中和するのに必要な水酸化カリウムのミリグラム数をいう。
酸価を測定する方法の一例は下記の通りである:
3gの試料を精密に秤量し、エタノール20mlに溶解する。得られた溶液を室温で撹拌し、更に5gの精製水を加え更に1時間室温で撹拌する。その後、指示薬としてフェノールフタレインのメタノール溶液を数滴添加し、1/2規定の水酸化カリウム水溶液で中和滴定し、使用した水酸化カリウム水溶液量から酸価を算出する。 (A) The content of the carboxyl group, dicarboxylic acid anhydride group, or dicarboxylic acid anhydride group residue in the polysiloxane having a radical crosslinkable group is such that (A) the polysiloxane having a radical crosslinkable group is Although it is not particularly limited as long as it has a group, the acid value of the polysiloxane having a radical crosslinkable group (A) is 10 mgKOH / g from the viewpoint of reduction of residues after development and crack resistance of a cured film. The above is preferable, more preferably 15 mgKOH / g or more, and still more preferably 20 mgKOH / g or more. On the other hand, from the viewpoint of pattern adhesion, the acid value is preferably 200 mgKOH / g or less, more preferably 190 mgKOH / gmol or less, and still more preferably 180 mgKOH / g or less.
Further, when the polysiloxane composition having a radical crosslinkable group contains a polysiloxane having two or more types of (A) radical crosslinkable groups, at least one of them has an acid value within the range described above. It is preferable that it contains the residue of a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride group in such a content that it has.
In the present specification, the acid value means the number of milligrams of potassium hydroxide necessary to neutralize the carboxyl group in 1 g of a sample.
An example of a method for measuring the acid value is as follows:
A 3 g sample is accurately weighed and dissolved in 20 ml of ethanol. Stir the resulting solution at room temperature, add another 5 g of purified water and stir for an additional hour at room temperature. Thereafter, several drops of a phenolphthalein methanol solution are added as an indicator, neutralized with a 1/2 N aqueous potassium hydroxide solution, and the acid value is calculated from the amount of the aqueous potassium hydroxide solution used.
R7R8 a1Si(R9)3-a1
{式中、R7は、光重合性不飽和結合基(例えば、二重結合基)を含む炭素数2~20の1価の有機基を表し、R8は、各々独立に、置換基を有してもよい炭素数1~20の直鎖状若しくは分岐鎖状の有機基、アリール基、又はアルキルアリール基を表し、R9は、各々独立に、水酸基、加水分解可能な脱離基又はハロゲン原子を表し、そしてa1は、0~2の整数である。}で表される少なくとも1種類のシラン化合物を用いる反応によって得られるものであることが、樹脂設計及び作製法の容易性の観点から好ましい。 In this embodiment, (A) the polysiloxane having a radical crosslinkable group is represented by the following general formula (I):
R 7 R 8 a1 Si (R 9 ) 3-a1
{Wherein R 7 represents a monovalent organic group having 2 to 20 carbon atoms including a photopolymerizable unsaturated bond group (for example, a double bond group), and each R 8 independently represents a substituent. Represents a linear or branched organic group having 1 to 20 carbon atoms, an aryl group, or an alkylaryl group which may have, and each R 9 independently represents a hydroxyl group, a hydrolyzable leaving group, or Represents a halogen atom, and a1 is an integer of 0-2. } Is preferable from the viewpoint of resin design and ease of production.
上記一般式(I)において、R7としては、不飽和結合(例えば、二重結合)を有する炭素数2~17の1価の有機基が好ましく、具体的には、例えば、ビニル基、スチリル基、(メタ)アクリル基、3-(メタ)アクリロキシプロピル基、2-(メタ)アクリロキシエチル基、(メタ)アクリロキシメチル基などが挙げられる。このうち、スチリル基、又は3-(メタ)アクリロキシプロピル基が好ましい。また、本明細書では、(メタ)アクリルとは、アクリル基及びメタクリル基を示す。 In the above general formula (I), R 9 is a hydroxyl group, a linear or branched alkoxy group having 1 to 12 carbon atoms, a phenoxy group, an alkylcarbonyloxy group, chlorine (Cl) or bromine (Br). Preferably, at least one monovalent group selected from the group consisting of: a hydroxyl group, a methoxy group, an ethoxy group, an n-propoxy group, or an isopropoxy group, and from the viewpoint of reactivity, a hydroxyl group, a methoxy group, or an ethoxy group. Groups are more preferred.
In the above general formula (I), R 7 is preferably a monovalent organic group having 2 to 17 carbon atoms having an unsaturated bond (for example, a double bond), specifically, for example, a vinyl group, styryl. Group, (meth) acryl group, 3- (meth) acryloxypropyl group, 2- (meth) acryloxyethyl group, (meth) acryloxymethyl group and the like. Of these, a styryl group or a 3- (meth) acryloxypropyl group is preferable. Moreover, in this specification, (meth) acryl shows an acryl group and a methacryl group.
R10R11 a2Si(R9)3-a2
{式中、R9は、上記一般式(I)において定義された通りであり、R10は、アルカリ可溶性基を表し、R11は、各々独立に、置換基を有してもよい炭素数1~20の直鎖状若しくは分岐鎖状の有機基、アリール基、又はアルキルアリール基を表し、そしてa2は、0~2の整数である。}で表される少なくとも1種類のシラン化合物を用いる反応によって得られるものであることが、樹脂設計及び作製法の容易性の観点から好ましい。 In another embodiment, since (A) the polysiloxane having a radical crosslinkable group may contain an alkali-soluble group, at least one silane compound represented by the above general formula (I) and the following general formula Formula (II):
R 10 R 11 a2 Si (R 9 ) 3-a2
{In the formula, R 9 is as defined in the above general formula (I), R 10 represents an alkali-soluble group, and each R 11 independently represents the number of carbon atoms that may have a substituent. 1 to 20 represents a linear or branched organic group, aryl group, or alkylaryl group, and a2 is an integer of 0 to 2. } Is preferable from the viewpoint of resin design and ease of production.
上記一般式(II-1)において、アミド結合を有する基(R10-15)は、アミノ基とジカルボン酸無水物との反応によって得られる、カルボキシル基を含有する基である。また、Rsは、炭素原子数が1~20の直鎖状、分岐鎖状又は環状の2価の有機基である。また、上記一般式(II-1)で表されるジカルボン酸無水物としては、例えば、無水コハク酸、シクロヘキサンジカルボン酸無水物、4-メチル-シクロヘキサンジカルボン酸無水物、5-メチル-シクロヘキサンジカルボン酸無水物、ビシクロヘプタンジカルボン酸無水物、7-オキサビシクロヘプタンジカルボン酸無水物、テトラヒドロフタル酸無水物、トリメリット酸無水物、ピロメリット酸無水物、アジピン酸無水物、無水フタル酸、(3-トリメトキシシリルプロピル)コハク酸無水物、(3-トリエトキシシリルプロピル)コハク酸無水物等の多塩基酸無水物が挙げられる。これらは、それぞれ単独で、又は2種以上を組み合わせて用いてもよい。 In the general formula (II-1), Rx is a linear or branched divalent organic group having 1 to 6 carbon atoms. Among these, from the viewpoint of ease of synthesis, Rx is preferably a hydrocarbon group. Examples of the hydrocarbon group include methylene group, ethylene group, propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, tert-butylene group, n-pentylene group, isopentylene group, neopentylene group, A tert-pentylene group may be mentioned. These groups may contain a double bond and / or a triple bond, and may be used alone or in combination of two or more. Among these, a propylene group is the most preferable.
In formula (II-1), a group having an amide bond (R 10 -15) is obtained by reaction of an amino group with a dicarboxylic acid anhydride, a group containing a carboxyl group. Rs is a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms. Examples of the dicarboxylic acid anhydride represented by the general formula (II-1) include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, and 5-methyl-cyclohexane dicarboxylic acid. Anhydride, bicycloheptane dicarboxylic acid anhydride, 7-oxabicycloheptane dicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, adipic acid anhydride, phthalic acid anhydride, (3- And polybasic acid anhydrides such as (trimethoxysilylpropyl) succinic anhydride and (3-triethoxysilylpropyl) succinic anhydride. These may be used alone or in combination of two or more.
上記一般式(II)において、R10として最も好ましい基は、プロピルコハク酸無水物基(R10-1)、プロピルコハク酸基、又はそのハーフメチルエステル基、又はそのハーフエチルエステル基(R10-8)である。 In the above general formula (II-1), the group having an isocyanuric skeleton (R 10 -16) is a hydroxyl group generated from an isocyanuric skeleton having a glycidyl group via a ring-opening reaction of glycidyl by a reaction with a carboxyl group or a hydroxyl group. It is a group containing a carboxyl group obtained by reacting with a dicarboxylic acid anhydride.
In the general formula (II), the most preferable group as R 10 is a propyl succinic anhydride group (R 10 -1), a propyl succinic acid group, or a half methyl ester group thereof, or a half ethyl ester group thereof (R 10 -8).
R12 a3Si(R9)4-a3
{式中、R9は、上記一般式(I)において定義された通りであり、R12は、各々独立に、置換基を有してもよい炭素数1~20の直鎖状若しくは分岐鎖状の有機基、アリール基、アルキルアリール基を表し、そしてa3は、0~3の整数である。}で表される少なくとも1種のシラン化合物を用いる反応によって得られるものであることが、樹脂設計及び作製法の容易性の観点から好ましい。 In another embodiment, (A) the polysiloxane having a radical crosslinkable group is at least one silane compound represented by the above general formula (I) and at least one kind represented by the above general formula (II). In addition to the silane compound, the following general formula (III):
R 12 a3 Si (R 9 ) 4-a3
{Wherein R 9 is as defined in the above general formula (I), and each R 12 is independently a linear or branched chain having 1 to 20 carbon atoms which may have a substituent. Represents an organic group, an aryl group, or an alkylaryl group, and a3 is an integer of 0 to 3. Are preferably obtained by a reaction using at least one silane compound represented by the following formula from the viewpoint of resin design and ease of production.
加水分解反応は、溶媒中のシラン化合物に酸性触媒及び水を1分~180分に亘って添加することにより行われる。加水分解物を得る過程の温度は、加水分解の反応性の観点から、10℃以上が好ましく、より好ましくは20℃以上であり、一方で、官能基の保護の観点から、150℃以下が好ましく、より好ましくは120℃以下である。加水分怪物を得る過程の反応時間は、加水分解の反応性の観点から0.1時間以上が好ましく、より好ましくは0.5時間以上であり、一方で、官能基の保護の観点から10時間以下が好ましく、より好ましくは5時間以下である。
加水分解反応は、酸性触媒の存在下で行うことが好ましい。酸性触媒としては、塩酸、硝酸、硫酸、蟻酸、酢酸又はリン酸を含む酸性水溶液が好ましい。これらの酸性触媒の好ましい含有量は、加水分解反応時に使用される全シラン化合物に対して、加水分解の反応性の観点から0.01mol%以上が好ましく、官能基の保護の観点から10mol%以下が好ましい。
シラン化合物の加水分解反応によりシラノール化合物を得た後、反応液をそのまま50℃以上、使用される溶媒の沸点以下で、1時間~100時間に亘って加熱し、縮合反応を行うことが好ましい。また、(A)ラジカル架橋性基を有するポリシロキサンの重合度を上げるために、再加熱及び/又は減圧及び/又は塩基性触媒の添加を行なってもよい。 (A) The polysiloxane having a radical crosslinkable group can be synthesized by any method. For example, the silane compound represented by the general formula (I) and the silane compound represented by the general formula (II) And the silane compound represented by the general formula (III) can be obtained by adding water and a catalyst and then condensing the obtained hydrolyzate in the presence or absence of a solvent. .
The hydrolysis reaction is carried out by adding an acidic catalyst and water over 1 minute to 180 minutes to the silane compound in the solvent. The temperature in the process of obtaining a hydrolyzate is preferably 10 ° C. or higher, more preferably 20 ° C. or higher from the viewpoint of hydrolysis reactivity, while 150 ° C. or lower is preferable from the viewpoint of protecting functional groups. More preferably, it is 120 degrees C or less. The reaction time in the process of obtaining the hydrolyzed monster is preferably 0.1 hour or more from the viewpoint of hydrolysis reactivity, more preferably 0.5 hour or more, while 10 hours from the viewpoint of protecting the functional group. The following is preferable, and more preferably 5 hours or less.
The hydrolysis reaction is preferably performed in the presence of an acidic catalyst. As the acidic catalyst, an acidic aqueous solution containing hydrochloric acid, nitric acid, sulfuric acid, formic acid, acetic acid or phosphoric acid is preferable. The preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of hydrolysis reactivity with respect to all silane compounds used during the hydrolysis reaction, and 10 mol% or less from the viewpoint of functional group protection. Is preferred.
After obtaining the silanol compound by the hydrolysis reaction of the silane compound, the reaction solution is preferably heated as it is at 50 ° C. or higher and below the boiling point of the solvent used for 1 hour to 100 hours to carry out the condensation reaction. Moreover, in order to raise the polymerization degree of (A) polysiloxane which has a radical crosslinkable group, you may perform reheating and / or pressure reduction, and / or addition of a basic catalyst.
溶媒の具体例としては、メタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、イソブチルアルコール、t-ブチルアルコール、ペンチルアルコール、イソペンチルアルコール、ジアセトンアルコールなどのアルコール類、エチレングリコール、プロピレングリコールなどのグリコール類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテルなどのエーテル類、メチルエチルケトン、アセチルアセトン、メチルプロピルケトン、メチルブチルケトン、メチルイソブチルケトン、シクロペンタノンなどのケトン類、エチレングリコールモノエチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチルなどのアセテート類、γ-ブチロラクトン、N-メチル-2-ピロリドン、ジメチルスルホキシド、ジメチルアセトアミドなどを挙げることができる。 The solvent used for the hydrolysis reaction of the silane compound and the condensation reaction of the hydrolyzate is not particularly limited, and can be appropriately selected in consideration of the stability, wettability, volatility, etc. of the resin composition. Further, these reactions may be carried out by combining two or more solvents or without solvent.
Specific examples of the solvent include alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, isopentyl alcohol, diacetone alcohol, ethylene glycol, propylene glycol and the like. Glycols, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and other ethers, methyl ethyl ketone, acetylacetone, methyl propyl ketone, methyl butyl ketone, Such as methyl isobutyl ketone and cyclopentanone Tons, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, acetates such as methyl lactate, ethyl lactate, butyl lactate, γ-butyrolactone, N-methyl-2-pyrrolidone, dimethyl sulfoxide, dimethylacetamide, etc. be able to.
加水分解反応に使用する溶媒の量は、全シラン化合物100質量部に対して、80質量部以上、500質量部以下が好ましい。
また、加水分解反応に用いる水は、イオン交換水が好ましい。水の量は、任意に選択されることができるが、加水分解反応に用いられるシラン化合物1モルに対して、1.0モル~4.0モルの範囲であることが好ましい。 When a solvent is produced by the hydrolysis reaction, it can be hydrolyzed without a solvent. It is also preferable to adjust the concentration of the resin composition to an appropriate level by adding a solvent after completion of the hydrolysis reaction. Moreover, according to the use of a resin composition, after hydrolysis, an appropriate amount, such as produced | generated alcohol, may be distilled off under heating and / or pressure reduction, and a suitable solvent may be added after that.
The amount of the solvent used for the hydrolysis reaction is preferably 80 parts by mass or more and 500 parts by mass or less with respect to 100 parts by mass of all silane compounds.
The water used for the hydrolysis reaction is preferably ion exchange water. The amount of water can be arbitrarily selected, but is preferably in the range of 1.0 mol to 4.0 mol with respect to 1 mol of the silane compound used in the hydrolysis reaction.
(A)ラジカル架橋性基を有するポリシロキサン中に存在し、かつ縮合に関与しなかったシラノール(残存シラノール)は、ベーク時の縮合による収縮低減、縮合により発生する水、アルコールの脱ガス低減の観点から、少量であることが好ましく、ほぼなくなることが好ましい。 In this embodiment, (A) the method for producing a polysiloxane having a radical crosslinkable group, in addition to the above reaction, water is generated by dehydration condensation of silanols when handling silanols. And can be reacted without the addition of water and catalyst when handling chlorosilanes.
(A) Silanol (residual silanol) present in the polysiloxane having a radical crosslinkable group and not involved in the condensation is reduced in shrinkage due to condensation during baking, water generated by condensation, and degassing reduction of alcohol. From the viewpoint, a small amount is preferable, and it is preferable that the amount is almost eliminated.
R13 2Si(OH)2
{式中、R13は、炭素原子数が6~20のアリール基、炭素原子数が2~20のアルキルアリール基、炭素原子数が1~20のアルキル基、又は炭素原子数が5~20のシクロアルキル基であり、互いに同一であっても異なっていてもよく、そして共有結合を介して互いに結ばれていてもよい。}で表されるシランジオール化合物を、触媒の存在下で、少なくとも反応させるか、又は好ましくは積極的に水を添加することなく縮合させる方法により得られる。
上記一般式(IV)において、R13としては、例えば、フェニル基、トリル基、キシリル基、トリメチルフェニル基、ナフチル基、メチル基、エチル基、シクロペンチル基、及びシクロヘキシル基を挙げることができる。 (A) The polysiloxane having a radical crosslinkable group preferably has little or no residual silanol. For example, the silane compound represented by the general formula (I) and the general formula (II) ) And the following general formula (IV):
R 13 2 Si (OH) 2
{In the formula, R 13 represents an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 2 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, or 5 to 20 carbon atoms. The cycloalkyl groups may be the same or different from each other, and may be linked to each other via a covalent bond. } Is obtained by a method of reacting at least in the presence of a catalyst, or preferably condensing without actively adding water.
In the general formula (IV), examples of R 13 include a phenyl group, a tolyl group, a xylyl group, a trimethylphenyl group, a naphthyl group, a methyl group, an ethyl group, a cyclopentyl group, and a cyclohexyl group.
積極的に水を添加することなく縮合を行う反応の温度は、縮合の反応性の観点から、40℃以上が好ましく、より好ましくは50℃以上であり、一方で、官能基の保護の観点から、150℃以下が好ましく、より好ましくは130℃以下である。
積極的に水を添加することなく縮合を行う反応の時間は、縮合の反応性の観点から、0.5時間以上が好ましく、1時間以上がより好ましく、一方で、官能基の保護の観点から48時間以下が好ましく、30時間以下がより好ましい。
積極的に水を添加することなく縮合を行う反応では、触媒を用い、水を積極的に添加することは無い。触媒としては、塩基性触媒又は酸性触媒を用いることができる。 Specific examples of the silane diol compound represented by the general formula (IV) include diphenyl silane diol, di-p-toluyl silane diol, dixyl silane diol, ditrimethyl phenyl silane diol, di-p-styryl silane diol, Examples include dinaphthyl silane diol, dicyclopentyl silane diol, cyclohexyl methyl silane diol, and the like, and diphenyl silane diol, dicyclopentyl silane diol, and cyclohexyl methyl silane diol are particularly preferable from the viewpoint of copolymerization and heat resistance.
From the viewpoint of condensation reactivity, the temperature of the reaction for performing condensation without positively adding water is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, while from the viewpoint of protecting functional groups. 150 ° C. or lower is preferable, and 130 ° C. or lower is more preferable.
From the viewpoint of the reactivity of the condensation, the reaction time for performing the condensation without positively adding water is preferably 0.5 hours or more, more preferably 1 hour or more, while from the viewpoint of protecting the functional group. 48 hours or less is preferable, and 30 hours or less is more preferable.
In a reaction in which condensation is performed without positively adding water, a catalyst is used and water is not positively added. As the catalyst, a basic catalyst or an acidic catalyst can be used.
これらの塩基性触媒の好ましい含有量は、全シラン化合物に対して、縮合反応性の観点から0.01mol%以上が好ましく、一方で、官能基の保護の観点から10mol%以下が好ましい。
酸性触媒としては、水を含有しない有機酸性触媒を用いることができる。具体的には、酸性触媒としては、酢酸、トリフルオロ酢酸、アクリル酸、メタクリル酸、クエン酸、リンゴ酸、コハク酸、フタル酸、(3-トリメトキシシリルプロピル)コハク酸、又はそのハーフエステル、及び(3-トリエトキシシリルプロピル)コハク酸、又はそのハーフエステルなどが挙げられる。
これら酸性触媒の好ましい含有量は、全シラン化合物に対して、縮合反応性の観点から0.01mol%以上が好ましく、一方で、官能基の保護の観点から10mol%以下が好ましい。 Alkali metal hydroxides or alkaline earth metal hydroxides such as barium hydroxide, sodium hydroxide, potassium hydroxide, strontium hydroxide, calcium hydroxide, and magnesium hydroxide are used as basic catalysts. May be. NH 4 F (ammonium fluoride) may be used as a basic catalyst. Among these, barium hydroxide, sodium hydroxide, strontium hydroxide, tetra-tert-butoxy titanium, and tetra-iso-propoxy titanium are preferable. In order to achieve a rapid and uniform polymerization reaction, the basic catalyst is preferably liquid in the reaction temperature range.
The preferable content of these basic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
As the acidic catalyst, an organic acidic catalyst containing no water can be used. Specifically, as the acidic catalyst, acetic acid, trifluoroacetic acid, acrylic acid, methacrylic acid, citric acid, malic acid, succinic acid, phthalic acid, (3-trimethoxysilylpropyl) succinic acid, or a half ester thereof, And (3-triethoxysilylpropyl) succinic acid or a half ester thereof.
The preferable content of these acidic catalysts is preferably 0.01 mol% or more from the viewpoint of condensation reactivity with respect to all silane compounds, and is preferably 10 mol% or less from the viewpoint of protection of functional groups.
を有することも、耐熱性の観点から好ましい。(A)ラジカル架橋性基を有するポリシロキサンの珪素原子のうち、上記構造を有する割合が、10mol%~80mol%が好ましく、より好ましくは30mol%~70mol%であり、さらに好ましくは40mol%~60mol%である。 In this embodiment, (A) the polysiloxane having a radical crosslinkable group has the following structure:
It is also preferable from the viewpoint of heat resistance. (A) The ratio of the silicon atom of the polysiloxane having a radical crosslinkable group having the above structure is preferably 10 mol% to 80 mol%, more preferably 30 mol% to 70 mol%, still more preferably 40 mol% to 60 mol%. %.
(B)光ラジカル開始剤は、ポリシロキサン組成物に感光性パターンの形成性を付与するために、ポリシロキサン組成物に添加されることが重要である。
(B)光ラジカル開始剤としては、下記(1)~(10)の光ラジカル開始剤が挙げられる: <(B) Photoradical (polymerization) initiator>
It is important that the (B) photoradical initiator is added to the polysiloxane composition in order to impart a formability of a photosensitive pattern to the polysiloxane composition.
Examples of the (B) photoradical initiator include the following photoradical initiators (1) to (10):
(C)ニトロキシ化合物は、下記一般式(V):
上記一般式(V)において、R1、R2、R3及びR4は、各々独立に、アルキル基又はヘテロ原子で置換されたアルキル基でよい。アルキル基としては、好ましくは、メチル基、エチル基、プロピル基などが挙げられ、そしてヘテロ原子としては、好ましくは、ハロゲン、酸素、硫黄、窒素などが挙げられる。 <(C) Nitroxy Compound>
(C) The nitroxy compound has the following general formula (V):
In the general formula (V), R 1 , R 2 , R 3 and R 4 may each independently be an alkyl group or an alkyl group substituted with a hetero atom. As the alkyl group, a methyl group, an ethyl group, a propyl group and the like are preferable, and as the hetero atom, a halogen, oxygen, sulfur, nitrogen and the like are preferable.
(C)ニトロキシ化合物は、ポリシロキサン組成物に微量でも含有されていればよいが、耐クラック性の観点から、(C)ニトロキシ化合物の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、0.005質量部以上が好ましく、より好ましくは0.009質量部以上であり、一方で、透明性の観点から2質量部以下が好ましく、より好ましくは1質量部以下が好ましい。 More preferable (C) nitroxy compounds include 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-
(C) The nitroxy compound may be contained even in a trace amount in the polysiloxane composition, but from the viewpoint of crack resistance, the content of (C) the nitroxy compound is 100 mass of the total solid content in the polysiloxane composition. Is preferably 0.005 parts by mass or more, more preferably 0.009 parts by mass or more, and preferably 2 parts by mass or less, more preferably 1 part by mass or less from the viewpoint of transparency. .
本実施形態では、ポリシロキサン組成物は、(D)光重合性二重結合を有する化合物をさらに含むことが、耐クラック性の観点から好ましい。(D)光重合性二重結合を有する化合物は、1分子内に少なくとも1個の光重合性二重結合基を含む重合性モノマーである。
(D)光重合性二重結合を有する化合物としては、例えば、ポリエチレングリコールジ(メタ)アクリレート[エチレングリコールユニットの数2~20]、ポリ(1,2-プロピレングリコール)ジ(メタ)アクリレート[1,2-プロピレングリコールユニット数2~20]、ポリテトラメチレングリコールジ(メタ)アクリレート[テトラメチレングリコールユニット数2~10]、トリ-2-ヒドロキシエチルイソシアヌレートトリ(メタ)アクリレート、メチレンビスアクリルアミド、エチレングリコールジグリシジルエーテル-(メタ)アクリル酸付加物、グリセロールジグリシジルエーテル-(メタ)アクリル酸付加物、ビスフェノールAジグリシジルエーテル-(メタ)アクリル酸付加物、N,N’-ビス(2-メタクリロイルオキシエチル)尿素コハク酸変性ペンタエリスリトールトリ(メタ)アクリレート、フタル酸変性ペンタエリスリトールトリ(メタ)アクリレート、イソフタル酸変性ペンタエリスリトールトリ(メタ)アクリレート、テレフタル酸変性ペンタエリスリトールトリ(メタ)アクリレート、ビスフェノールAの両端にそれぞれ平均2モルのプロピレンオキサイドと平均6モルのエチレンオキサイドを付加したポリアルキレングリコールのジメタクリレート、ビスフェノールAの両端にそれぞれ平均5モルのエチレンオキサイドを付加したポリエチレングリコールのジメタクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、3-メチル-1,5-ペンタンジオールジ(メタ)アクリレート、2-ブチル-2-エチル-1,3-プロパンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、トリシクロデカンジメタノール(メタ)アクリレート1,4-シクロヘキサンジオールジ(メタ)アクリレート、2-ジ(p-ヒドロキシフェニル)プロパンジ(メタ)アクリレート、グリセロールトリ(メタ)アクリレート、トリメチロールプロパントリ(メタ)アクリレート、ポリオキシプロピルトリメチロールプロパントリ(メタ)アクリレート、ポリオキシエチルトリメチロールプロパントリアクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、トリメチロールプロパントリグリシジルエーテルトリ(メタ)アクリレート、ビスフェノールAジグリシジルエーテルジ(メタ)アクリレート及び、β-ヒドロキシプロピル-β’-(アクリロイルキシ)プロピルフタレート、フェノキシポリエチレングリコール(メタ)アクリレート、ノニルフェノキシポリエチレングリコール(メタ)アクリレート、ノニルフェニキシポリアルキレングリコール(メタ)アクリレート、ポリプロピレングリコールモノ(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、4-ヒドロキシブチル(メタ)アクリレート、グリセロールモノ(メタ)アクリレート、4-ヒドロキシビニルベンゼン、2-ヒドロキシ-3-フェノキシプロピルアクリレートまたはこれらモノマーのカプロラクトン付加物などが挙げられる。 <(D) Compound having a photopolymerizable double bond>
In the present embodiment, it is preferable from the viewpoint of crack resistance that the polysiloxane composition further includes (D) a compound having a photopolymerizable double bond. (D) The compound having a photopolymerizable double bond is a polymerizable monomer containing at least one photopolymerizable double bond group in one molecule.
Examples of the compound (D) having a photopolymerizable double bond include polyethylene glycol di (meth) acrylate [number of ethylene glycol units 2 to 20], poly (1,2-propylene glycol) di (meth) acrylate [ 1,2-propylene glycol units 2-20], polytetramethylene glycol di (meth) acrylate [tetramethylene glycol units 2-10], tri-2-hydroxyethyl isocyanurate tri (meth) acrylate, methylenebisacrylamide , Ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, bisphenol A diglycidyl ether- (meth) acrylic acid adduct, N, N′-bis (2 -Methacryloy Of (Ruoxyethyl) urea succinic acid modified pentaerythritol tri (meth) acrylate, phthalic acid modified pentaerythritol tri (meth) acrylate, isophthalic acid modified pentaerythritol tri (meth) acrylate, terephthalic acid modified pentaerythritol tri (meth) acrylate, bisphenol A Polyalkylene glycol dimethacrylate with an average of 2 moles of propylene oxide and 6 moles of ethylene oxide added to both ends, polyethylene glycol dimethacrylate with an average of 5 moles of ethylene oxide added to both ends of bisphenol A, 1,6 -Hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) a Relate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decandiol di (meth) acrylate, glycerin di (meth) ) Acrylate, tricyclodecane dimethanol (meth) acrylate 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate, glycerol tri (meth) acrylate, trimethylolpropane tri (Meth) acrylate, polyoxypropyltrimethylolpropane tri (meth) acrylate, polyoxyethyltrimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta ) Acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate, phenoxypolyethylene glycol (meth) acrylate, Nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyalkylene glycol (meth) acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (Meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-pheno Shi propyl acrylate or caprolactone adducts thereof monomers, and the like.
(D)光重合性二重結合を有する化合物の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、各成分を十分に架橋させ基板への密着性を発揮する観点から、5質量部以上が好ましく、より好ましくは10質量部以上であり、一方で、現像後の残渣低減の観点から、45質量部以下が好ましく、より好ましくは40質量部以下である。 Further, (D) the compound having a photopolymerizable double bond may further contain a carboxyl group. Examples of the compound (D) having a photopolymerizable double bond further containing a carboxylic acid include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloxy Examples thereof include ethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, and 2,2,2-triacryloyloxymethyl ethyl succinic acid. These may be used alone or in combination of two or more.
(D) The content of the compound having a photopolymerizable double bond is from the viewpoint of sufficiently cross-linking each component with respect to 100 parts by mass of the total solid content in the polysiloxane composition and exhibiting adhesion to the substrate. 5 mass parts or more is preferable, More preferably, it is 10 mass parts or more, On the other hand, from a viewpoint of the residue reduction after image development, 45 mass parts or less are preferable, More preferably, it is 40 mass parts or less.
本実施形態では、ポリシロキサン組成物の耐光性を向上させ、現像時の残渣を低減するために、(E)紫外線吸収剤をポリシロキサン組成物に含有させることが好ましい。また、(E)紫外線吸収剤を(C)ニトロキシ化合物と組み合わせて使うことで、ポリシロキサン組成物の解像性を大きく向上させることができるために好ましい。(E)紫外線吸収剤としては、例えば、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物などを挙げることができる。具体的には、(E)紫外線吸収剤としては、例えば、2-(2,4-ジヒドロキシフェニル)-4,6-ビス(2,4-ジメチルフェニル)-1,3,5-トリアジンと(2-エチルヘキシル)-グリシド酸エステルの反応生成物(BASF社製 TINUVIN405)、2-(2Hベンゾトリアゾール-2-イル)フェノール、2-(2Hベンゾトリアゾール-2-イル)-4,6-t-ペンチルフェノール、2-(2Hベンゾトリアゾール-2-イル)-4-(1,1,3,3-テトラメチルブチル)フェノール、2-(2Hベンゾトリアゾール-2-イル)-6-ドデシル-4-メチルフェノール、2-(2’-ヒドロキシ-5’-メタクリロキシエチルフェニル)-2H-ベンゾトリアゾール、2-ヒドロキシ―4-メトキシベンゾフェノンなどが挙げられる。
(E)紫外線吸収剤をポリシロキサン組成物に添加する場合の(E)紫外線吸収剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、未露光部分の硬化防止の観点から、0.01質量部以上が好ましく、より好ましくは0.1質量部以上であり、一方で、露光時のラジカル発生によるパターン形成性の観点から、10質量部以下が好ましく、より好ましくは5質量部以下である。 <(E) UV absorber>
In this embodiment, in order to improve the light resistance of the polysiloxane composition and reduce residues during development, it is preferable to include (E) an ultraviolet absorber in the polysiloxane composition. Further, it is preferable to use (E) an ultraviolet absorber in combination with (C) a nitroxy compound because the resolution of the polysiloxane composition can be greatly improved. (E) As an ultraviolet absorber, a benzotriazole type compound, a benzophenone type compound, etc. can be mentioned, for example. Specifically, (E) UV absorbers include, for example, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and ( Reaction product of 2-ethylhexyl) -glycidic acid ester (TINUVIN 405 manufactured by BASF), 2- (2Hbenzotriazol-2-yl) phenol, 2- (2Hbenzotriazol-2-yl) -4,6-t- Pentylphenol, 2- (2Hbenzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2- (2Hbenzotriazol-2-yl) -6-dodecyl-4- Methylphenol, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole, 2-hydroxy-4-methoxybenzof Such as non, and the like.
(E) When the ultraviolet absorber is added to the polysiloxane composition, the content of the (E) ultraviolet absorber is to prevent curing of the unexposed portion with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From a viewpoint, 0.01 mass part or more is preferable, More preferably, it is 0.1 mass part or more, On the other hand, 10 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation | occurrence | production at the time of exposure, More preferably 5 parts by mass or less.
本実施形態では、ポリシロキサン組成物は、(F)アルカリ可溶性樹脂をさらに含むことが好ましい。また、ラジカル架橋性基を有するポリシロキサンが、アルカリ可溶性基を有しており、そしてポリシロキサン組成物のアルカリ現像が可能である場合には、(F)アルカリ可溶性樹脂をポリシロキサン組成物に添加することが好ましい。
また、(F)アルカリ可溶性樹脂とは、アルカリ可溶性基を有し、酸価が10~200mgKOH/gであるアルカリ可溶性樹脂をいう。
(F)アルカリ可溶性樹脂の酸価は、相溶性の観点から(A)ラジカル架橋性基を有するポリシロキサンと近いことが好ましく、現像時の残渣低減の観点から、10mgKOH/g以上が好ましく、より好ましくは20mgKOH/g以上であり、一方で、パターンの密着性の観点から、200mgKOH/g以下が好ましく、より好ましくは190mgKOH/g以下である。
(F)アルカリ可溶性樹脂は、アルカリ可溶性基を有し、かつ酸価が10~200mgKOH/gであれば特に制限されないが、1分子中にカルボキシル基、ジカルボン酸無水物基、又はジカルボン酸無水物基の残基を有していることが好ましい。ポリシロキサン組成物は、(F)アルカリ可溶性樹脂中にカルボキシル基を有していることで、耐熱透明性を維持しながらアルカリ溶解性を発現し、良好な膜物性が得られる。 <(F) Alkali-soluble resin>
In this embodiment, it is preferable that the polysiloxane composition further includes (F) an alkali-soluble resin. In addition, when the polysiloxane having a radical crosslinkable group has an alkali-soluble group and the polysiloxane composition can be alkali-developed, (F) an alkali-soluble resin is added to the polysiloxane composition. It is preferable to do.
The (F) alkali-soluble resin refers to an alkali-soluble resin having an alkali-soluble group and having an acid value of 10 to 200 mgKOH / g.
(F) The acid value of the alkali-soluble resin is preferably close to (A) a polysiloxane having a radical crosslinkable group from the viewpoint of compatibility, and is preferably 10 mgKOH / g or more from the viewpoint of residue reduction during development. Preferably, it is 20 mgKOH / g or more. On the other hand, from the viewpoint of the adhesiveness of the pattern, 200 mgKOH / g or less is preferable, and more preferably 190 mgKOH / g or less.
(F) The alkali-soluble resin is not particularly limited as long as it has an alkali-soluble group and has an acid value of 10 to 200 mgKOH / g. However, a carboxyl group, a dicarboxylic acid anhydride group, or a dicarboxylic acid anhydride is contained in one molecule. It preferably has a group residue. Since the polysiloxane composition has a carboxyl group in the (F) alkali-soluble resin, the polysiloxane composition exhibits alkali solubility while maintaining heat-resistant transparency, and good film properties can be obtained.
(1)重合性二重結合の反応物を主体に構成されるビニル重合体、
(2)エポキシ基と水酸基との付加反応物を主体に構成されるエポキシ重合体、
(3)フェノールとホルムアルデヒドとの反応物を主体に構成される芳香族メチレン重合体、
(4)ジアルコールとジイソシアネートとの反応物を主体に構成されるウレタン重合体、及び
(5)ジカルボン酸とジエポキシドの反応物を主体に構成されるエステル重合体
から成る群より選ばれる少なくとも1種の重合体であることが好ましい。なお、上記重合体(1)~(5)において、主体とは、その成分を分子内に70モル%以上含有することをいう。 (F) The alkali-soluble resin has an alkali-soluble group, and (1) to (5) below:
(1) a vinyl polymer composed mainly of a reactant of a polymerizable double bond,
(2) an epoxy polymer mainly composed of an addition reaction product of an epoxy group and a hydroxyl group,
(3) an aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde,
(4) At least one selected from the group consisting of urethane polymers composed mainly of reactants of dialcohol and diisocyanate, and (5) ester polymers composed mainly of reactants of dicarboxylic acid and diepoxide. The polymer is preferably. In the polymers (1) to (5), the main component means that the component is contained in an amount of 70 mol% or more in the molecule.
(1)重合性二重結合の反応物を主体に構成されるビニル重合体
例えば、下記一般式(4)又は下記一般式(6)で表される、カルボキシル基含有ビニル重合体が挙げられる。
(1) Vinyl polymer mainly composed of a reaction product of a polymerizable double bond For example, a carboxyl group-containing vinyl polymer represented by the following general formula (4) or the following general formula (6) may be mentioned.
(i)α,β-不飽和カルボン酸の中から選ばれる少なくとも1種の化合物(a)と、アルキル(メタ)アクリレート、ヒドロキシアルキル(メタ)アクリレート、(メタ)アクリルアミドとその窒素上の水素をアルキル基又はアルコキシ基に置換した化合物、スチレン及びスチレン誘導体、(メタ)アクリロニトリル、及び(メタ)アクリル酸グリシジルの中から選ばれる少なくとも1種の化合物(b)をビニル共重合する方法。
(ii)前記化合物(a)と前記化合物(b)をビニル共重合した後、ビニル重合物のカルボキシル基と、1分子中にエポキシ基と(メタ)アクリル基を有する化合物の中から選ばれる少なくとも1種の化合物(c)を付加反応させる方法。
(iii)前記化合物(b)と前記化合物(c)をビニル重合した後、ビニル重合物のエポキシ基と前記化合物(a)とを付加反応させ、さらに生成した水酸基にジカルボン酸無水物(d)を付加反応させる方法。 Examples of the method for obtaining the carboxyl group-containing vinyl polymer include the following three methods:
(I) at least one compound (a) selected from α, β-unsaturated carboxylic acids, alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, (meth) acrylamide and hydrogen on the nitrogen thereof. A method of vinyl copolymerizing at least one compound (b) selected from a compound substituted with an alkyl group or an alkoxy group, styrene and a styrene derivative, (meth) acrylonitrile, and glycidyl (meth) acrylate.
(Ii) After vinyl copolymerizing the compound (a) and the compound (b), at least selected from a carboxyl group of the vinyl polymer and a compound having an epoxy group and a (meth) acryl group in one molecule. A method of subjecting one compound (c) to an addition reaction.
(Iii) After vinyl-polymerizing the compound (b) and the compound (c), the epoxy group of the vinyl polymer and the compound (a) are subjected to an addition reaction, and a dicarboxylic acid anhydride (d) is further added to the generated hydroxyl group. Is a method of addition reaction.
カルボキシル基含有ビニル重合体の調製における、カルボキシル基とエポキシ基及び(メタ)アクリル基を有する化合物との付加反応は、重合禁止剤及び触媒を用いて、溶媒中で反応を行うことが好ましく、反応温度は、50℃~120℃で行うことが好ましい。 The vinyl copolymerization in the preparation of the carboxyl group-containing vinyl polymer can be carried out by a conventional method, and known methods such as solution polymerization, suspension polymerization method and emulsion polymerization method are possible. Polymerization is preferred. As the polymerization initiator that can be used in this case, those having a 10-hour half-life temperature in the range of 60 ° C. to 120 ° C. are preferable. Examples of such polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyl). Nitrile), 2,2′-azobis (2-methylpropionate), 2,2′-azobis (N-cyanohexyl-2-methylpropionamide), 2,2′-azobis (N- (2-propenyl) ) -2-methylpropionamide), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-amylperoxy- 2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-amino Peroxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-hexylperoxybenzoate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, etc. Esters, peroxymonocarbonates such as t-hexylperoxyisopropylmonocarbonate, t-butylperoxyisopropylmonocarbonate, t-butylperoxy-2-ethylhexylmonocarbonate, bis-3,5,5-trimethylhexanoyl peroxide, octa Diacyl peroxides such as noyl peroxide, lauroyl peroxide, benzoyl peroxide, p-chlorobenzoyl peroxide, dicumyl peroxide, t- Dialkyl peroxides such as chill cumyl peroxide, and the like. These may be used alone or in combination of two or more.
In the preparation of a carboxyl group-containing vinyl polymer, the addition reaction between a carboxyl group and a compound having an epoxy group and a (meth) acryl group is preferably performed in a solvent using a polymerization inhibitor and a catalyst. The temperature is preferably 50 to 120 ° C.
カルボキシル基含有ビニル重合体の調製における重合禁止剤としては、例えば、ハイドロキノン、メチルハイドロキノン、ハイドロキノンモノメチルエーテル、カテコール、ピロガロール、フェノチアジンなどが挙げられる。これらは、それぞれ単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
さらに、前記反応生成物の水酸基にジカルボン酸無水物を部分的に付加させることができるが、反応温度は、好ましくは50~120℃である。 Examples of the reaction catalyst for the preparation of the carboxyl group-containing vinyl polymer include tertiary amines such as triethylamine, quaternary ammonium salts such as triethylbenzylammonium chloride, imidazole compounds such as 2-ethyl-4-methylimidazole, Examples thereof include phosphorus compounds such as triphenylphosphine, metal salts of organic acids such as lithium, chromium, zirconium, potassium and sodium of naphthenic acid, lauric acid, stearic acid, oleic acid or octoenoic acid. These may be used alone or in combination of two or more.
Examples of the polymerization inhibitor in the preparation of the carboxyl group-containing vinyl polymer include hydroquinone, methyl hydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, and phenothiazine. These may be used alone or in combination of two or more.
Further, although the dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, the reaction temperature is preferably 50 to 120 ° C.
重合体(3)としては、例えば、下記一般式(9)で表される、ノボラック型フェノール重合体が挙げられる。
ノボラック型フェノール重合体の調製に用いられるフェノールの例としては、フェノール、クレゾール、キシレノール、トリメチルフェノール等が挙げられる。これらは、それぞれ単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
ノボラック型フェノール重合体に用いられるエピハロヒドリンの例としては、エピクロルヒドリン、エピブロムヒドリンが挙げられる。これらは、それぞれ単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
ノボラック型フェノール重合体の調製に用いられる、1分子内にカルボキシル基と(メタ)アクリレート基を有する化合物の例としては、(メタ)アクリル酸、(メタ)アクリル酸、カルボキシエチル(メタ)アクリレート、カルボキシペンチル(メタ)アクリレート、2-(メタ)アクリロキシエチルコハク酸、2-(メタ)アクリロキシエチルヘキサヒドロフタル酸、2-(メタ)アクリロキシエチルフタル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、及びマレイン酸ハーフエステル等が挙げられる。これらは、それぞれ単独で用いてもよいし、2種以上を組み合わせて用いてもよい。 The novolak type phenol polymer used in the present embodiment is obtained by reacting an epihalohydrin with a condensation reaction product of phenol and formaldehyde. Furthermore, an epoxy group of the reaction product may be subjected to an addition reaction between a carboxyl group or a (meth) acrylate compound having a hydroxyl group, and the hydroxyl group of the reaction product may be reacted with a dicarboxylic acid anhydride.
Examples of the phenol used for the preparation of the novolak type phenol polymer include phenol, cresol, xylenol, trimethylphenol and the like. These may be used alone or in combination of two or more.
Examples of the epihalohydrin used in the novolac type phenol polymer include epichlorohydrin and epibromohydrin. These may be used alone or in combination of two or more.
Examples of the compound having a carboxyl group and a (meth) acrylate group in one molecule used for the preparation of the novolak type phenol polymer include (meth) acrylic acid, (meth) acrylic acid, carboxyethyl (meth) acrylate, Carboxypentyl (meth) acrylate, 2- (meth) acryloxyethyl succinic acid, 2- (meth) acryloxyethyl hexahydrophthalic acid, 2- (meth) acryloxyethyl phthalic acid, fumaric acid, cinnamic acid, croton Examples include acids, itaconic acid, and maleic acid half esters. These may be used alone or in combination of two or more.
ノボラック型フェノール重合体の調製におけるフェノールとホルムアルデヒドの縮合反応を行う場合、酸触媒を用いるのが好ましく、酸触媒としては、種々のものが使用できるが、塩酸、硫酸、p-トルエンスルホン酸、シュウ酸、三フッ化ホウ素、無水塩化アルミニウム、塩化亜鉛などが好ましく、特に、p-トルエンスルホン酸、硫酸、及び塩酸が好ましい。 Dicarboxylic acid anhydrides used for the preparation of novolak type phenol polymers include succinic anhydride, cyclohexane dicarboxylic acid anhydride, 4-methyl-cyclohexane dicarboxylic acid anhydride, 5-methyl-cyclohexane dicarboxylic acid anhydride, bicycloheptane dicarboxylic acid. Acid anhydride, 7-oxabicycloheptanedicarboxylic acid anhydride, tetrahydrophthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, adipic acid anhydride, phthalic anhydride, (3-trimethoxysilylpropyl) succinate And polybasic acid anhydrides such as acid anhydride and (3-triethoxysilylpropyl) succinic acid anhydride. These may be used alone or in combination of two or more.
When performing the condensation reaction of phenol and formaldehyde in the preparation of the novolak type phenol polymer, it is preferable to use an acid catalyst, and various acid catalysts can be used, such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, Acid, boron trifluoride, anhydrous aluminum chloride, zinc chloride and the like are preferable, and p-toluenesulfonic acid, sulfuric acid and hydrochloric acid are particularly preferable.
反応終了後、反応混合物の水洗浄液のpH値が3~7、好ましくは5~7になるまで水洗処理を行う。水洗処理を行う場合は水酸化ナトリウム、水酸化カリウムなどのアルカリ金属水酸化物、水酸化カルシウム、水酸化マグネシウムなどのアルカリ土類金属水酸化物、アンモニア、リン酸二水素ナトリウムさらにはジエチレントリアミン、トリエチレンテトラミン、アニリン、フェニレンジアミンなどの有機アミンなど様々な塩基性物質等を中和剤として用いて処理してもよい。また、水洗処理の場合は常法に従って行えばよい。例えば、反応混合物中に上記中和剤を溶解した水を加え、分液抽出操作をくり返し、減圧加熱下で溶剤を留去し生成物を得ることができる。 The condensation reaction of phenol and formaldehyde can be performed in the absence of a solvent or in the presence of an organic solvent. Specific examples in the case of using an organic solvent include methyl cellosolve, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone and the like. The amount of the organic solvent used is usually 50 to 300% by mass, preferably 100 to 250% by mass, based on the total mass of the raw materials charged. The reaction temperature is usually 40 ° C. to 180 ° C., and the reaction time is usually 1 hour to 10 hours. These solvents may be used alone or in combination of two or more.
After completion of the reaction, water washing treatment is performed until the pH value of the water washing liquid of the reaction mixture becomes 3 to 7, preferably 5 to 7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate, diethylenetriamine, You may process using various basic substances, such as organic amines, such as ethylenetetramine, aniline, and phenylenediamine, as a neutralizing agent. Moreover, what is necessary is just to perform according to a conventional method in the case of a water-washing process. For example, water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated, and the solvent is distilled off under reduced pressure heating to obtain a product.
反応終了後、生成した塩を濾過、水洗などにより除去し、更に、加熱減圧下トルエン、メチルイソブチルケトンなどの溶剤を留去することにより本発明のエポキシ化合物が得られる。
ノボラック型フェノール重合体の調製におけるエポキシ基と、カルボキシル基又は水酸基及び(メタ)アクリル基を有する化合物との付加反応は、重合禁止剤及び触媒を用いて、溶媒中で反応を行うことが好ましく、反応温度は、50℃~120℃で行うことが好ましい。
ノボラック型フェノール重合体の調製において、反応溶媒、反応触媒及び重合禁止剤としては、それぞれ、上記(1)重合性不飽和二重結合の反応物を主体に構成されるビニル重合体の調製において説明された反応溶媒、反応触媒及び重合禁止剤と同様のものを使用することができる。
さらに、前記反応生成物の水酸基にジカルボン酸無水物を部分的に付加させることができるが、反応温度は、好ましくは50℃~120℃である。 An alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like is added to the dissolved mixture of the phenol-formaldehyde condensate obtained in the above reaction and epihalohydrin such as epichlorohydrin, epibromohydrin or the like. An epoxy resin can be obtained by reacting at ˜120 ° C. for 1 to 10 hours. After the reaction product of these epoxidation reactions is washed with water or without washing, epihalohydrin or other added solvent is removed under reduced pressure by heating at 110 ° C. to 250 ° C. and a pressure of 10 mmHg or less. Further, in order to make an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is dissolved. Further reaction can be performed by adding an aqueous solution to ensure ring closure. The reaction temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.
After completion of the reaction, the produced salt is removed by filtration, washing with water, and the solvent of toluene, methyl isobutyl ketone and the like is distilled off under heating and reduced pressure to obtain the epoxy compound of the present invention.
The addition reaction between the epoxy group and the compound having a carboxyl group or a hydroxyl group and a (meth) acryl group in the preparation of the novolak type phenol polymer is preferably carried out in a solvent using a polymerization inhibitor and a catalyst, The reaction temperature is preferably 50 to 120 ° C.
In the preparation of the novolak-type phenol polymer, the reaction solvent, the reaction catalyst, and the polymerization inhibitor are each described in (1) Preparation of a vinyl polymer mainly composed of a reactant of a polymerizable unsaturated double bond. The same reaction solvent, reaction catalyst and polymerization inhibitor as used can be used.
Further, dicarboxylic anhydride can be partially added to the hydroxyl group of the reaction product, but the reaction temperature is preferably 50 ° C. to 120 ° C.
ラジカル架橋性基を持つポリシロキサンの酸価(A)(mgKOH/g)とアルカリ可溶性樹脂の酸価(F)(mgKOH/g)の比、すなわち、酸価(A)/酸価(F)は、(A)ラジカル架橋性基を持つポリシロキサンと(F)アルカリ可溶性樹脂との極性による相溶性の観点から、0.1以上であることが好ましく、より好ましくは0.2以上であり、さらに好ましくは0.3以上であり、一方で、この比は5.0以下であることが好ましく、より好ましくは4.0以下であり、3.0以下が更に好ましい。 The alkali-soluble resin is mainly composed of a vinyl polymer composed mainly of a polymerizable unsaturated double bond reactant and an addition product of an epoxy group and a hydroxyl group from the viewpoint of heat resistance of the reactant composed mainly of the polymer. At least one selected from the group consisting of an epoxy polymer composed mainly of an aromatic methylene polymer composed mainly of a reaction product of phenol and formaldehyde, and an ester polymer composed mainly of a reaction product of dicarboxylic acid and diepoxide. A seed polymer is preferred.
Ratio of acid value (A) (mgKOH / g) of polysiloxane having radical crosslinkable group and acid value (F) (mgKOH / g) of alkali-soluble resin, that is, acid value (A) / acid value (F) Is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of compatibility by polarity between (A) a polysiloxane having a radical crosslinkable group and (F) an alkali-soluble resin. More preferably, it is 0.3 or more. On the other hand, this ratio is preferably 5.0 or less, more preferably 4.0 or less, and further preferably 3.0 or less.
ポリシロキサン組成物の露光・現像後の硬化膜と基板との密着性を向上させるために、シランカップリング剤をポリシロキサン組成物に添加することができる。例えば、3-(メタ)アクリロキシプロピルトリメトキシシラン、3-(メタ)アクリロキシプロピルトリエトキシシラン、3-(メタ)アクリロキシプロピルメチルジメトキシシラン、3-(メタ)アクリロキシプロピルメチルジエトキシシラン、p-スチリルトリメトキシシラン、p-スチリルトリエトキシシラン、p-(1-プロペニルフェニル)トリメトキシシラン、p-(1-プロペニルフェニル)トリエトキシシラン、p-(2-プロペニルフェニル)トリメトキシシラン、p-(2-プロペニルフェニル)トリエトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)トリメトキシシラン、2-(3,4-エポキシシクロヘキシル)トリエトキシシラン、2-(3,4-エポキシシクロヘキシル)メチルジメトキシシラン、2-(3,4-エポキシシクロヘキシル)メチルジエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-2-(アミノエチル)-3-アミノプロピルメチルジエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、3-アミノプロピルメチルジメトキシシラン、3-アミノプロピルジエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、N-フェニル-3-アミノプロピルトリエトキシシラン、N-(ビニルベンジル)-2-アミノエチル-3-アミノプロピルトリメトキシシランの塩酸塩、3-ウレイドプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-メルカプトプロピルトリエトキシシラン、3-メルカプトプロピルメチルジメトキシシラン、3-メルカプトプロピルメチルジエトキシシラン、ビス(トリメトキシシリルプロピル)テトラスルフィド、ビス(トリエトキシシリルプロピル)テトラスルフィド、3-イソシアネートプロピルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-トリメトキシシリルプロピルコハク酸無水物、3-トリエトキシシリルプロピルコハク酸無水物などを挙げることができる。
シランカップリング剤をポリシロキサン組成物に添加する場合のシランカップリング剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、基板との密着性を発現させる観点から、0.1質量部以上が好ましく、より好ましくは0.5質量部以上であり、一方で、ポリシロキサン組成物の硬化反応性の観点から、20質量部以下が好ましく、より好ましくは15質量部以下である。 <(G) Silane coupling agent>
A silane coupling agent can be added to the polysiloxane composition in order to improve the adhesion between the cured film after exposure and development of the polysiloxane composition and the substrate. For example, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane P-styryltrimethoxysilane, p-styryltriethoxysilane, p- (1-propenylphenyl) trimethoxysilane, p- (1-propenylphenyl) triethoxysilane, p- (2-propenylphenyl) trimethoxysilane , P- (2-propenylphenyl) triethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Diethoxy 2- (3,4-epoxycyclohexyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) triethoxysilane, 2- (3,4-epoxycyclohexyl) methyldimethoxysilane, 2- (3,4 -Epoxycyclohexyl) methyldiethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltri Ethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyl Triethoxysilane, 3-aminopropylmethyldimethyl Xisilane, 3-aminopropyldiethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyl Trimethoxysilane hydrochloride, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercapto Propylmethyldiethoxysilane, bis (trimethoxysilylpropyl) tetrasulfide, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltrimethoxysilane, 3-isocyanate Examples include propyltriethoxysilane, 3-trimethoxysilylpropyl succinic anhydride, and 3-triethoxysilylpropyl succinic anhydride.
The content of the silane coupling agent in the case of adding the silane coupling agent to the polysiloxane composition is such that the adhesiveness with the substrate is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition. 0.1 mass part or more is preferable, More preferably, it is 0.5 mass part or more, On the other hand, from a viewpoint of the curing reactivity of a polysiloxane composition, 20 mass parts or less are preferable, More preferably, 15 mass parts or less It is.
本実施形態では、ポリシロキサン組成物に溶剤を添加して、その粘度を調整することが、塗布膜厚を調整する観点から好ましい。好適な溶剤としては、下記(1)~(6)の溶剤が挙げられる:
(1)脂肪族アルコール:メタノール、エタノール、n-プロパノール、iso-プロパノール、n-ブタノール、iso-ブタノール、sec-ブタノール、tert-ブタノール、1-ペンタノール、イソアミルアルコール、s-アミルアルコール、t-アミルアルコール、2-メチル-1-ブタノール、1-ヘキサノール、2-エチル-1-ブタノール、4-メチル-2-ペンタノール、イソヘキシルアルコール、メチル-1-ペンタノール、s-ヘキサノール、1-ヘプタノール、イソヘプチルアルコール、2,3-ジメチル-1-ペンタノール、1-オクタノール、2-エチルヘキサノール、イソオクチルアルコール、2-オクタノール、3-オクタノール、1-ノナノール、イソノニルアルコール、3,5,5-トリメチルヘキサノール、1-デカノール、イソデシルアルコール、3,7-ジメチル-1-オクタノール、1-ヘンデカノール、1-ドデカノール、イソドデシルアルコール、アリルアルコール、プロパルギルアルコール、ヘキシノール <(I) Solvent>
In the present embodiment, it is preferable from the viewpoint of adjusting the coating film thickness to adjust the viscosity by adding a solvent to the polysiloxane composition. Suitable solvents include the following solvents (1) to (6):
(1) Aliphatic alcohols: methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, tert-butanol, 1-pentanol, isoamyl alcohol, s-amyl alcohol, t- Amyl alcohol, 2-methyl-1-butanol, 1-hexanol, 2-ethyl-1-butanol, 4-methyl-2-pentanol, isohexyl alcohol, methyl-1-pentanol, s-hexanol, 1-heptanol , Isoheptyl alcohol, 2,3-dimethyl-1-pentanol, 1-octanol, 2-ethylhexanol, isooctyl alcohol, 2-octanol, 3-octanol, 1-nonanol, isononyl alcohol, 3, 5, 5 -Trimethyl hex Nord, 1-decanol, isodecyl alcohol, 3,7-dimethyl-1-octanol, 1-Hendekanoru, 1-dodecanol, isododecyl alcohol, allyl alcohol, propargyl alcohol, Hekishinoru
これらは、単独で、又は二種以上の組合せで用いることができる。これらの中でも、プロピレングリコールモノメチルエーテルアセテート、乳酸エチル、ガンマブチロラクトン、ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルなどが塗布膜を加熱して溶媒を蒸発させる観点から好ましい。
これらの溶媒は、塗布膜厚及び粘度に応じて、ポリシロキサン組成物に適宜加えることができるが、ポリシロキサン組成物中の固形分全成分100質量部に対して、50~1,000質量部の範囲で用いることが好ましい。 (6) Others: N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, pyridine, γ-butyrolactone, α-acetyl-γ- Butyrolactone, tetramethylurea, 1,3-dimethyl-2-imidazolinone, N-cyclohexyl-2-pyrrolidone These can be used alone or in combination of two or more. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, gamma butyrolactone, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether and the like are preferable from the viewpoint of heating the coating film and evaporating the solvent.
These solvents can be appropriately added to the polysiloxane composition depending on the coating film thickness and viscosity, but are 50 to 1,000 parts by mass with respect to 100 parts by mass of all solid components in the polysiloxane composition. It is preferable to use in the range.
本実施形態では、ポリシロキサン組成物の塗布適性、及び乾燥後の膜平滑性を確保するために、界面活性剤をポリシロキサン組成物に含有させてもよい。界面活性剤としては、例えば、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンステアリルエーテル、ポリオキシエチレンオレイルエーテルなどのポリオキシエチレンアルキルエーテル類、又はポリオキシエチレンオクチルフェニルエーテル、ポリオキシエチレンノニルフェニルエーテルなどのポリオキシエチレンアリールアルキルエーテル類、又はポリオキシエチレンエチレンジラウレート、ポリオキシエチレンジステアレートなどのポリオキシエチレンジアルキルエステル類、メガファックF171,172,173(大日本インキ製)、フロラードFC430,431(住友スリーエム製)、アサヒガードAG710、サーフロンS-382,SC-101,102,103,104,105(旭硝子製)などのフッ素系界面活性剤、DBE-712,DBE821(ダイセル・サイテック社製)などのシリコーン系界面活性剤などを挙げることができる。
これらの界面活性剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、塗布適性及び残渣低減の観点から、0.01質量部以上が好ましく、より好ましくは0.1質量部以上であり、一方で、現像後のパターン密着性の観点から、10質量部以下が好ましく、より好ましくは5質量部以下である。 <Surfactant>
In the present embodiment, a surfactant may be contained in the polysiloxane composition in order to ensure applicability of the polysiloxane composition and film smoothness after drying. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, or polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Polyoxyethylene arylalkyl ethers, or polyoxyethylene dialkyl esters such as polyoxyethylene ethylene dilaurate and polyoxyethylene distearate, MegaFac F171, 172, 173 (Dainippon Ink), Florard FC430, 431 (Sumitomo) 3M), Asahi Guard AG710, Surflon S-382, SC-101,102,103,104,105 (Asahi Glass) Active agents, such as DBE-712, DBE821 (manufactured by DAICEL-CYTEC Co., Ltd.) silicone surfactants, and the like.
The content of these surfactants is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass, from the viewpoint of coating suitability and residue reduction with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From the viewpoint of pattern adhesion after development, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less.
ポリシロキサン組成物の熱安定性及び保存安定性を向上させるために、ポリシロキサン組成物に、重合禁止剤(例えば、ラジカル重合禁止剤)を含有させてもよい。重合禁止剤としては、例えば、ヒドロキノン、N-ニトロソジフェニルアミン、p-tert-ブチルカテコール、フェノチアジン、N-フェニルナフチルアミン、エチレンジアミン四酢酸、1,2-シクロヘキサンジアミン四酢酸、グリコールエーテルジアミン四酢酸、2,6-ジ-tert-ブチル-p-メチルフェノール、5-ニトロソ-8-ヒドロキシキノリン、1-ニトロソ-2-ナフトール、2-ニトロソ-1-ナフトール、2-ニトロソ-5-(N-エチル-N-スルフォプロピルアミノ)フェノール、N-ニトロソ-N-フェニルヒドロキシアミンアンモニウム塩、N-ニトロソ-N-フェニルヒドロキシルアミンアンモニウム塩、N-ニトロソ-N-(1-ナフチル)ヒドロキシルアミンアンモニウム塩、ビス(4-ヒドロキシ-3,5-ジtert-ブチル)フェニルメタン等を用いることができる。
ポリシロキサン組成物に重合禁止剤を添加する場合の重合禁止剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、光重合性二重結合の重合禁止効果を発現させる観点から、0.001質量部以上が好ましく、より好ましくは0.01質量部以上が好ましく、一方で、露光時のラジカル発生によるパターン形成性の観点から、5質量部以下が好ましく、より好ましくは1質量部以下である。 <Polymerization inhibitor>
In order to improve the thermal stability and storage stability of the polysiloxane composition, the polysiloxane composition may contain a polymerization inhibitor (for example, a radical polymerization inhibitor). Examples of the polymerization inhibitor include hydroquinone, N-nitrosodiphenylamine, p-tert-butylcatechol, phenothiazine, N-phenylnaphthylamine, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid, 2, 6-di-tert-butyl-p-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-N -Sulfopropylamino) phenol, N-nitroso-N-phenylhydroxyamine ammonium salt, N-nitroso-N-phenylhydroxylamine ammonium salt, N-nitroso-N- (1-naphthyl) hydroxylamine ammonium salt, bis ( 4-hide Carboxymethyl-3,5-di-tert- butyl) can be used phenyl methane.
When the polymerization inhibitor is added to the polysiloxane composition, the content of the polymerization inhibitor causes the polymerization inhibiting effect of the photopolymerizable double bond to be expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From a viewpoint, 0.001 mass part or more is preferable, More preferably, 0.01 mass part or more is preferable, On the other hand, 5 mass parts or less are preferable from a viewpoint of pattern formation by the radical generation | occurrence | production at the time of exposure, More preferably 1 part by mass or less.
本実施形態では、酸素存在下でのポリシロキサン組成物の熱安定性を向上させるために、酸化防止剤をポリシロキサン組成物に添加することができる。このような酸化防止剤としては、例えば、ヒンダードフェノール系、リン系、ラクトン系、ビタミンE系、イオウ系のもの等が挙げられる。
具体的には、酸化防止剤としては、限定されるものではないが、トリエチレングリコール-ビス[3-(3-t-ブチル-5--メチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 IRGANOX245)、1,6-ヘキサンジオール-ビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート)(BASF社製 IRGANOX259)、2,4-ビス-(n-オクチルチオ)-6-(4-ヒドロキシ-3,5-ジ-t-ブチルアニリノ)-1,3,5-トリアジン(BASF社製 IRGANOX565)、ペンタエリスリチル・テトラキス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート)(BASF社製 IRGANOX1010)、2,2-チオ-ジエチレンビス[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート](BASF社製 IRGANOX1035)、オクタデシル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート(BASF社製 IRGANOX1076)、N,N’-ヘキサメチレンビス(3,5-ジ-t-ブチル-4-ヒドロキシ-ヒドロシンナマミド)(BASF社製 IRGANOX1098)、3,5-ジ-t-ブチル-4-ヒドロキシベンジルフォスフォネート-ジエチルエステル(BASF社製 IRGAMOD295)、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-t-ブチル--4-ヒドロキシベンジル)ベンゼン(BASF社製 IRGANOX1330)、トリス-(3,5-ジ-t-ブチル-4-ヒドロキシベンジル)-イソシアヌレイト(BASF社製 IRGANOX3114)、オクチル化ジフェニルアミン(BASF社製 IRGANOX5057)、2,4-ビス[(オクチルチオ)メチル)-o-クレゾール(BASF社製 IRGANOX1520L)、イソオクチル-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート(BASF社製 IRGANOX1135)、2,4-ビス(ドデシルチオメチル)-6-メチルフェノール(BASF社製 IRGANOX1726)、2,5,7,8-テトラメチル-2-(4,8,12-トリメチルトリデシル)クロマン-6-オール(BASF社製 IRGANOX E201)、5,7-ジ-t-ブチル-3-(3,4-ジメチルフェニル)ベンゾフラン-2(3H)-オン(IRGANOX HP-136)、トリス(2,4-ジ-t-ブチルフェニル)ホスファイト(BASF社製 IRGAFOS168)、トリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン(BASF社製、IRGAFOS12)、ビス(2,4-ジ-t-ブチル-6-メチルフェニル)エチルホスファイト(BASF社製 IRGAFOS38)、3,3-チオビスプロピオン酸ジドデシルエステル(BASF社製 IRGANOX PS800)、3,3-チオビスプロピオン酸ジオクタデシルエステル(BASF社製 IRGANOX PS802)などが挙げられる。 <(H) Antioxidant>
In the present embodiment, an antioxidant can be added to the polysiloxane composition in order to improve the thermal stability of the polysiloxane composition in the presence of oxygen. Examples of such antioxidants include hindered phenols, phosphoruss, lactones, vitamin Es, and sulfurs.
Specifically, the antioxidant is not limited, but is triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Corporation). IRGANOX 245), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) (IRGANOX 259 manufactured by BASF), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine (IRGANOX565 manufactured by BASF), pentaerythrityl tetrakis [3- (3,5-di-t- Butyl-4-hydroxyphenyl) propionate) (IRGANOX1010 manufactured by BASF), 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (IRGANOX1035 manufactured by BASF), octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ( IRGANOX1076 from BASF), N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (IRGANOX1098 from BASF), 3,5-di-t-butyl -4-Hydroxybenzylphosphonate-diethyl ester (IRGAMOD295 manufactured by BASF), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) Benzene (IRGANOX 1330 manufactured by BASF), Tris- (3,5-di-t-butyl-4- Loxybenzyl) -isocyanurate (IRGANOX3114 manufactured by BASF), octylated diphenylamine (IRGANOX5057 manufactured by BASF), 2,4-bis [(octylthio) methyl) -o-cresol (IRGANOX1520L manufactured by BASF), isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1135 manufactured by BASF), 2,4-bis (dodecylthiomethyl) -6-methylphenol (IRGANOX 1726 manufactured by BASF), 2,5, 7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) chroman-6-ol (IRGANOX E201 manufactured by BASF), 5,7-di-t-butyl-3- (3,4 Dimethylphenyl) benzofuran-2 ( H) -one (IRGANOX HP-136), tris (2,4-di-t-butylphenyl) phosphite (IRGAFOS168 manufactured by BASF), tris [2-[[2,4,8,10-tetrakis (1 , 1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine (BASF, IRGAFOS12), bis (2,4-di-) t-Butyl-6-methylphenyl) ethyl phosphite (IRGAFOS38 manufactured by BASF), 3,3-thiobispropionic acid didodecyl ester (IRGANOX PS800 manufactured by BASF), 3,3-thiobispropionic acid dioctadecyl ester ( And IRGANOX PS802) manufactured by BASF.
これらの酸化防止剤は単独で、又は2種以上の混合物として用いることができる。ポリシロキサン組成物に酸化防止剤を添加する場合の酸化防止剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、酸素存在下での熱安定性効果を発現させる観点から、0.001質量部以上が好ましく、より好ましくは0.01質量部以上、さらに好ましくは0.1質量部以上であり、一方で、露光時のラジカル発生によるパターン形成性の観点から、15質量部以下が好ましく、より好ましくは10質量部以下、さらに好ましくは5質量部以下である。 Specifically, the antioxidant is not limited, but is 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy. ] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (SUMILIZER GA-80, manufactured by Sumitomo Chemical Co., Ltd.), 2,2′-methylenebis (6-t-butyl) -4-methylphenol) (SUMILIZER MDP-S, manufactured by Sumitomo Chemical Co., Ltd.), 4,4′-butylidenebis (6-t-butyl-3-methylphenol) (SUMILIZER BBM-S, manufactured by Sumitomo Chemical Co., Ltd.), 4, 4 ′ -Thiobis (6-tert-butyl-3-methylphenol) (SUMIZER WX-R manufactured by Sumitomo Chemical Co., Ltd.), pentaerythrityl-tetrakis (3-laurylthiopro) ONATE) (SUMILIZER TP-D manufactured by Sumitomo Chemical Co., Ltd.), 2-mercaptobenzimidazole (SUMILIZER MB manufactured by Sumitomo Chemical Co., Ltd.), biphenyl-4,4′-diyl-bis [bis (2,4-di-t-butyl- 5-methylphenoxy) phosphine] (GSY-P101 manufactured by Osaki Kogyo Co., Ltd.), cyclohexane and N-butyl-2,2,6,6, -tetramethyl-4-piperidineamine-2,4,6-trichloro 1 , 3,5-triazine and 2-aminoethanol (TINUVIN152 manufactured by BASF).
These antioxidants can be used alone or as a mixture of two or more. The content of the antioxidant in the case of adding an antioxidant to the polysiloxane composition is such that the heat stability effect in the presence of oxygen is expressed with respect to 100 parts by mass of the total solid content in the polysiloxane composition. From 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and still more preferably 0.1 parts by mass or more. The amount is preferably at most 10 parts by mass, more preferably at most 10 parts by mass, even more preferably at most 5 parts by mass.
さらに、ポリシロキサン組成物には、必要に応じて可塑剤等の添加剤を含有させてもよい。このような添加剤としては、例えばジエチルフタレート等のフタル酸エステル類、o-トルエンスルホン酸アミド、p-トルエンスルホン酸アミド、クエン酸トリブチル、クエン酸トリエチル、アセチルクエン酸トリエチル、アセチルクエン酸トリ-n-プロピル、アセチルクエン酸トリ-n-ブチル、ポリプロピレングリコール、ポリエチレングリコール、ポリエチレングリコールアルキルエーテル、ポリプロピレングリコールアルキルエーテル等が挙げられる。ポリシロキサン組成物に可塑剤を添加する場合の可塑剤の含有量は、ポリシロキサン組成物中の全固形分100質量部に対して、膜の柔軟性を上げる観点から、0.1質量部以上が好ましく、より好ましくは0.5質量部以上であり、さらに好ましくは0.7質量部以上であり、一方でガラス転移温度の観点から、10質量部以下が好ましく、より好ましくは8質量部以下であり、さらに好ましくは5質量部以下である。 <Plasticizer>
Furthermore, the polysiloxane composition may contain additives such as a plasticizer as necessary. Examples of such additives include phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl citrate tri- Examples thereof include n-propyl, tri-n-butyl acetylcitrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. The content of the plasticizer when adding the plasticizer to the polysiloxane composition is 0.1 parts by mass or more from the viewpoint of increasing the flexibility of the film with respect to 100 parts by mass of the total solid content in the polysiloxane composition. Is more preferably 0.5 parts by mass or more, still more preferably 0.7 parts by mass or more. On the other hand, from the viewpoint of the glass transition temperature, 10 parts by mass or less is preferable, and more preferably 8 parts by mass or less. More preferably, it is 5 parts by mass or less.
本実施形態に用いられるポリシロキサン組成物を硬化することにより得られる硬化物において、厚み10μmの該硬化物の大気下、220℃、及び3時間ベーク後の400nmの波長における光の透過率は、70%以上であることが好ましい。また、本発明に用いられるポリシロキサン組成物を硬化することにより、透明絶縁膜を得ることも好ましい。
硬化物中のラジカル含有量は、硬化物1gに対し、0.1×10-6モル以上含まれることが好ましく、さらに好ましくは0.15×10-6モル以上である。一方で、パターン形成の観点から120×10-6モル以下が好ましく、さらに好ましくは60×10-6モル以下である。硬化物中のラジカル含有量の測定方法は、ポリシロキサン組成物について前記したものと同様である。 <Hardened product of photosensitive resin composition>
In the cured product obtained by curing the polysiloxane composition used in the present embodiment, the transmittance of light at a wavelength of 400 nm after baking at 220 ° C. for 3 hours in the atmosphere of the cured product having a thickness of 10 μm, It is preferable that it is 70% or more. It is also preferable to obtain a transparent insulating film by curing the polysiloxane composition used in the present invention.
The radical content in the cured product is preferably contained in an amount of 0.1 × 10 −6 mol or more, more preferably 0.15 × 10 −6 mol or more with respect to 1 g of the cured product. On the other hand, preferably 120 × 10 -6 mol or less from the viewpoint of pattern formation, more preferably 60 × 10 - is 6 mol or less. The method for measuring the radical content in the cured product is the same as that described above for the polysiloxane composition.
硬化レリーフパターンを形成する方法は、基板上にポリシロキサン組成物を塗布する第一の工程、活性光線を照射する第二の工程、現像液で未硬化部分を除去する第三の工程、さらに、加熱硬化させる第4の工程を含む。
まず、上記ポリシロキサン組成物を、シリコンウェハー、セラミック基板、アルミ基板などの所望の各種基材上に塗布する。塗布装置又は塗布方法としては、スピンコーター、ダイコータ-、スプレーコーター、浸漬、印刷、ブレードコーター、ロールコーティング等が利用できる。塗布された基材を80℃~200℃で1分~15分ソフトベークした後、コンタクトアライナー、ミラープロジェクション、ステッパー等の露光投影装置を用いて、所望のフォトマスクを介して活性光線を照射する。
活性光線としては、X線、電子線、紫外線、可視光線などが利用できるが、本発明においては、200nm~500nmの波長のものを用いるのが好ましい。パターンの解像度及び取扱い性の点で、その光源波長は、特にUV-i線(365nm)が好ましく、露光投影装置としてはステッパーが特に好ましい。
この後、光感度の向上などの目的で、必要に応じて、任意の温度、時間の組み合わせ(好ましくは、温度が40℃~200℃であり、そして時間が10秒~360秒である。)による露光後ベーク(PEB)、又は現像前ベークを施してもよい。 Hereinafter, a preferred example of a method for forming a cured relief pattern using the above-described polysiloxane composition will be described.
A method for forming a cured relief pattern includes a first step of applying a polysiloxane composition on a substrate, a second step of irradiating actinic rays, a third step of removing uncured portions with a developer, A fourth step of heat curing is included.
First, the polysiloxane composition is applied on various desired substrates such as a silicon wafer, a ceramic substrate, and an aluminum substrate. As the coating apparatus or coating method, a spin coater, a die coater, a spray coater, dipping, printing, a blade coater, roll coating, or the like can be used. The coated substrate is soft baked at 80 ° C. to 200 ° C. for 1 to 15 minutes, and then irradiated with actinic rays through a desired photomask using an exposure projection apparatus such as a contact aligner, mirror projection, or stepper. .
X-rays, electron beams, ultraviolet rays, visible rays, and the like can be used as the actinic rays. In the present invention, those having a wavelength of 200 nm to 500 nm are preferably used. In light of pattern resolution and handleability, the light source wavelength is particularly preferably UV-i rays (365 nm), and a stepper is particularly preferred as the exposure projection apparatus.
Thereafter, for the purpose of improving the photosensitivity, etc., any combination of temperature and time is used as necessary (preferably, the temperature is 40 ° C. to 200 ° C., and the time is 10 seconds to 360 seconds). Post-exposure baking (PEB) or pre-development baking may be performed.
アルカリ現像液として適した例としては、例えば、アルカリ金属又はアルカリ土塁金属の炭酸塩の水溶液、アルカリ金属の水酸化物の水溶液、水酸化テトラエチルアンモニウム、水酸化テトラプロピルアンモニウム水溶液等の水酸化アンモニウム類、ジエチルアミン、トリエチルアミン、ジエタノールアミン、トリエタノールアミン等のアミン類を挙げることができる。特に、炭酸ナトリウム、炭酸カリウム、炭酸リチウム等の炭酸塩、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム等の水酸化アンモニウム類、ジエチルアミン、ジエタノールアミン等のアミン類を0.05質量%~10質量%含有する弱アルカリ性水溶液を用いて、20℃~35℃の温度で現像するのがよい。 Next, development is carried out, and it can be carried out by selecting from methods such as dipping method, paddle method, shower method and rotary spray method. As the developer, an organic solvent or an alkaline developer is preferable. The good solvent of the composition of the present invention can be used alone, or a good solvent and a poor solvent can be appropriately mixed.
Examples of suitable alkali developers include ammonium hydroxides such as alkali metal or alkaline earth metal carbonate aqueous solutions, alkali metal hydroxide aqueous solutions, tetraethylammonium hydroxide, tetrapropylammonium hydroxide aqueous solutions, and the like. And amines such as diethylamine, triethylamine, diethanolamine, and triethanolamine. In particular, carbonates such as sodium carbonate, potassium carbonate and lithium carbonate, ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and amines such as diethylamine and diethanolamine are contained in an amount of 0.05 to 10% by mass. Development is preferably performed at a temperature of 20 ° C. to 35 ° C. using a weakly alkaline aqueous solution.
現像終了後、リンス液により洗浄を行い、現像液を除去することにより、レリーフパターン付き塗膜が得られる。リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール、プロピレングリコールモノメチルエーテル等を単独で、又は適宜混合して用いるか、又はこれらを段階的に組み合わせて用いることもできる。 Examples of organic solvent developers include glycols such as ethylene glycol and propylene glycol. Examples of glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol. An example is monoethyl ether. Other organic solvent developers include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, gamma butyrolactone, α-acetyl- Examples thereof include gamma butyrolactone, cyclopentanone, and cyclohexanone.
After the development is completed, the film is washed with a rinse solution, and the developer solution is removed to obtain a coating film with a relief pattern. As the rinsing liquid, distilled water, methanol, ethanol, isopropanol, propylene glycol monomethyl ether, and the like can be used alone, or appropriately mixed, or used in a stepwise combination.
上述した硬化レリーフパターンを、例えばシリコンウェハー、ガラス、フィルム、それらに1種類以上の金属をスパッタした基材等の基材上に形成された半導体装置の表面保護膜、層間絶縁膜、α線遮蔽膜、及びマイクロレンズアレイなどのミクロ構造体とそのパッケージ材との間の支持体(隔壁)から成る群から選択されるいずれかとして使用し、他の工程は周知の半導体装置の製造方法を適用することで、タッチパネル、CMOSイメージセンサーなどの光学素子を含む、各種の表示装置、半導体装置を製造することができる。また、上記ポリシロキサン組成物を硬化させた樹脂から成る塗膜を有する電子部品又は半導体装置を得ることができる。 The relief pattern thus obtained is converted into a cured relief pattern at a curing temperature of 150 ° C. to 250 ° C., which is much lower than the conventional polyimide precursor composition. This heat curing can be performed using a hot plate, an inert oven, a temperature rising oven that can set a temperature program, and the like. Air may be used as the atmospheric gas for heat curing, and an inert gas such as nitrogen or argon may be used as necessary.
The above-described cured relief pattern is applied to, for example, a silicon wafer, glass, a film, a surface protection film of a semiconductor device formed on a base material such as a base material on which one or more kinds of metals are sputtered, an interlayer insulating film, an α-ray shielding. It is used as one selected from the group consisting of a film and a support (partition) between a microstructure such as a microlens array and its packaging material, and a known semiconductor device manufacturing method is applied to other processes. As a result, various display devices and semiconductor devices including optical elements such as a touch panel and a CMOS image sensor can be manufactured. Moreover, an electronic component or a semiconductor device having a coating film made of a resin obtained by curing the polysiloxane composition can be obtained.
(ESRの測定方法)
<使用装置・条件>
日本電子社製、ESR(型式:JES-FE2XG)を用いて、大気下、24℃、常圧下、サンプルを400nm以下の波長の光から遮った状態でESRを測定した。標準サンプルマーカーとして、マンガンマーカー(Mn2+)を用いた。
装置の測定条件を下記に示す。
マイクロ波出力:1mW
変調磁場:1G
レスポンス:0.03秒
アンプリチュード:200以上
磁場:3380G
磁場掃引:±250G
磁場掃引時間:4分 Hereinafter, although the method of embodiment is concretely demonstrated according to an Example, this invention is not limited by a following example.
(Measurement method of ESR)
<Devices used and conditions>
Using ESR (model: JES-FE2XG) manufactured by JEOL Ltd., ESR was measured in a state where the sample was shielded from light having a wavelength of 400 nm or less under the atmosphere at 24 ° C. under normal pressure. A manganese marker (Mn 2+ ) was used as a standard sample marker.
The measurement conditions of the apparatus are shown below.
Microwave output: 1 mW
Modulation magnetic field: 1G
Response: 0.03 seconds Amplitude: 200 or more Magnetic field: 3380G
Magnetic field sweep: ± 250G
Magnetic field sweep time: 4 minutes
ESR装置を調整後、ESR試料管(扁平型セル)にアセトンのみを入れて、アンプリチュードを1000に設定し、測定を行い、図1に示すようにMn2+の6本のピークしか見られないことを確認した。
Mn2+の低磁場側から数えて3本目のピークを標準ピークとし、g3=2.034とし、測定したサンプルのg値算出の際に用いる。低磁場側から数えて4本目のピークは、g4=1.981とする。 <Check blank>
After adjusting the ESR apparatus, only acetone is put into the ESR sample tube (flat cell), the amplitude is set to 1000, measurement is performed, and only 6 peaks of Mn 2+ are seen as shown in FIG. It was confirmed.
The third peak counted from the low magnetic field side of Mn 2+ is set as a standard peak, and g3 = 2.034, which is used when calculating the g value of the measured sample. The fourth peak counted from the low magnetic field side is g4 = 1.981.
4-ヒドロキシ-TEMPO(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル)(東京化成工業社製)の1ppmアセトン溶液を調整し、ESR測定を行い、図2に示すように、4-ヒドロキシ-TEMPOのピークが観察されることを確認した。 <Confirmation of sensitivity>
A 1 ppm acetone solution of 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared, and ESR measurement was performed. As shown, it was confirmed that a 4-hydroxy-TEMPO peak was observed.
標準ピークとして、Mn2+の6本あるピークの内、低磁場側から数えて3番目のピークを用いる。標準ピークの吸収磁場をHs、gs値を2.034とし、測定試料の吸収磁場をH0とする。測定試料のg値は、次式で算出した。
g=gs+gs(Hs-H0)/Hs <Calculation method of g value>
Among the six peaks of Mn 2+, the third peak counted from the low magnetic field side is used as the standard peak. The absorption magnetic field of the standard peak is H s , the g s value is 2.034, and the absorption magnetic field of the measurement sample is H 0 . The g value of the measurement sample was calculated by the following formula.
g = g s + g s ( H s -H 0) / H s
20mLサンプル管に、ポリシロキサン1gと9gのアセトンを秤量し、溶解させ、蓋をした。その後、大気下、24℃、常圧下、400nm以下の波長の光を遮光した状態で、24時間静置した後、ESRを測定した。 <Measurement of polysiloxane>
In a 20 mL sample tube, 1 g of polysiloxane and 9 g of acetone were weighed, dissolved, and capped. Thereafter, the sample was allowed to stand for 24 hours in the atmosphere with light of a wavelength of 400 nm or less shielded from light at a temperature of 24 ° C. and normal pressure, and then ESR was measured.
20mLサンプル管に、樹脂組成物を0.3gとアセトン9.7gを秤量し蓋をした。その後、大気下、24℃、常圧下、400nm以下の波長の光を遮光した状態で、24時間静置したのち、ESRを測定した。 <Measurement of resin composition>
In a 20 mL sample tube, 0.3 g of the resin composition and 9.7 g of acetone were weighed and capped. Thereafter, the sample was allowed to stand for 24 hours in the atmosphere with light having a wavelength of 400 nm or less shielded from light at a temperature of 24 ° C. and normal pressure, and then ESR was measured.
4-ヒドロキシTEMPOを分子1モルが1モルのラジカルを持つ標品として用い、検量線を作成し、溶液中のラジカル濃度を分析した。ポリシロキサン組成物、及び感光性樹脂組成物について、TGAを用い、10mgの試料を250℃で30分間保持した熱重量減少を測定し、残った質量を固形分として、固形分含有率を分析した。樹脂組成物の測定により得られたラジカル濃度、及び固形分含有率から、固形分1g当たりに含まれるラジカル量を算出した。 <Analysis of radical concentration>
Using 4-hydroxy TEMPO as a standard having 1 mole of radicals per molecule, a calibration curve was prepared and the radical concentration in the solution was analyzed. About the polysiloxane composition and the photosensitive resin composition, the TGA was used to measure the decrease in thermal weight when a 10 mg sample was held at 250 ° C. for 30 minutes, and the remaining mass was analyzed as the solid content. . From the radical concentration obtained by the measurement of the resin composition and the solid content, the amount of radical contained per gram of the solid content was calculated.
1.解像度の評価
感光性樹脂組成物をベーク後の膜厚が15μmになるように、アルミスパッタしたシリコン基板に塗布し、95℃4分間ホットプレート上でベークした。
上記の塗布膜を有する基板に対し、テストパターン付きレチクルを通して、i線ステッパー(ニコン製 NSR2005 i8A)を用いて露光を行った。露光は、大気中で行い、フォーカスを-15に設定し、60mJ/cm2から1110mJ/cm2まで30mJ/cm2刻みで照射した。 (Evaluation methods)
1. Evaluation of Resolution The photosensitive resin composition was applied to an aluminum-sputtered silicon substrate so that the film thickness after baking was 15 μm, and baked on a hot plate at 95 ° C. for 4 minutes.
The substrate having the above coating film was exposed using an i-line stepper (NSR2005 i8A manufactured by Nikon) through a reticle with a test pattern. Exposure was carried out in the atmosphere, and set the focus to -15 and was then irradiated with 30 mJ / cm 2 increments from 60 mJ / cm 2 to 1110mJ / cm 2.
露光に続いてアルカリ現像液(AZエレクトロニックマテリアルズ社製デベロッパー、2.38%水酸化テトラメチルアンモニウム水溶液)を用い、23℃、30秒×2回の条件下で現像し、純水にてリンスを行い、塗膜の未露光部を除去した。続いて、上記でパターニングした基板を、窒素置換したオーブンで、220℃で30分間ベークし、硬化させた。
(実施例15について)
露光に続いてPGMEA(プロピレングリコールモノメチルエーテルアセテート)を用い、23℃、30秒×2回の条件下で現像し、塗膜の未露光部を除去した。続いて、上記でパターニングした基板を、窒素置換したオーブンで、220℃で30分間ベークし、硬化させた。
実施例1~27、及び比較例1~5で得たパターンの露光量400mJ/cm2の部分で25μm×25μmの正方形に遮光した部分を光学顕微鏡で観察し、下記基準で評価した。
〇:残渣がなく開口していて、パターンに浮き又ははがれが観察されない
△:開口しているが一部残渣があり、パターンに浮き又ははがれが観察されない
×:残渣があり開口していない、又はパターンに浮き又ははがれが生じている (Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)
Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds × 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
(About Example 15)
Following exposure, PGMEA (propylene glycol monomethyl ether acetate) was used and developed under the conditions of 23 ° C. and 30 seconds × 2 times to remove the unexposed portion of the coating film. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
The portions of the patterns obtained in Examples 1 to 27 and Comparative Examples 1 to 5 where the exposure amount was 400 mJ / cm 2 and were shielded from light by a 25 μm × 25 μm square were observed with an optical microscope and evaluated according to the following criteria.
◯: Open with no residue, and no floating or peeling is observed in the pattern. Δ: Open, but there is some residue, no floating or peeling is observed in the pattern. There is floating or peeling in the pattern
上記で得られたパターンを光学顕微鏡で観察し、25μm×25μmの正方形に遮光した部分で、目視による残渣が無く開口していて、かつパターンに浮き又ははがれを生じていない露光量の範囲を解像範囲とし、下記基準で評価した。
◎:解像範囲が420mJ/cm2よりも広い
○:解像範囲が300mJ/cm2よりも広い
△:解像範囲が120mJ/cm2よりも広い
×:解像範囲が120mJ/cm2以下 2. Evaluation of resolution range The pattern obtained above was observed with an optical microscope, and was exposed to a 25 μm × 25 μm square light-shielded area with no visible residue, and the pattern did not float or peel off. The amount range was defined as a resolution range, and evaluation was performed according to the following criteria.
◎: resolution range is wider than 420mJ / cm 2 ○: the resolution range is wider than 300mJ / cm 2 △: wider than the resolution range is 120mJ / cm 2 ×: resolution range is 120mJ / cm 2 or less
ポリシロキサン組成物をベーク後の膜厚が15μmになるように、アルミスパッタしたシリコン基板に塗布し、95℃4分間ホットプレート上でベークした。
上記の塗布膜を有する基板に対し、テストパターン付きレチクルを通して、i線ステッパーを用いて400mJ/cm2露光を行った。露光は、大気中で行い、フォーカスを-15に設定した。 3. Evaluation of crack resistance The polysiloxane composition was applied to an aluminum-sputtered silicon substrate so that the film thickness after baking was 15 μm, and baked on a hot plate at 95 ° C. for 4 minutes.
The substrate having the coating film was exposed to 400 mJ / cm 2 using an i-line stepper through a reticle with a test pattern. Exposure was performed in air and the focus was set to -15.
露光に続いてアルカリ現像液(AZエレクトロニックマテリアルズ社製デベロッパー、2.38%水酸化テトラメチルアンモニウム水溶液)を用い、23℃、30秒×2回の条件下で現像し、純水にてリンスを行い、塗膜の未露光部を除去した。続いて、上記でパターニングした基板を、窒素置換したオーブンで、220℃で30分間ベークし、硬化させた。
(実施例15について)
露光に続いてPGMEAを用い、23℃、30秒×2回の条件下で現像し、塗膜の未露光部を除去した。続いて、上記でパターニングした基板を、窒素置換したオーブンで、220℃で30分間ベークし、硬化させた。
実施例1~27、及び比較例1~5で得たパターニングした基板を、窒素置換したオーブンで、さらに300℃で30分ベークし、続いて、冷熱衝撃試験機を用いて、-40℃15分、120℃15分を1回とするサイクルを100回繰り返した後、目視、光学顕微鏡にて観察し、下記基準で評価した。
◎:5枚の基板内にクラックは確認されない
○:5枚の基板内にクラックが1~5か所発生
△:5枚の基板内にクラックが6~15か所発生
×:5枚の基板内にクラックが16か所以上発生 (Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)
Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds × 2 times, and rinsed with pure water. The unexposed part of the coating film was removed. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
(About Example 15)
Following exposure, PGMEA was used and developed under the conditions of 23 ° C. and 30 seconds × 2 times to remove the unexposed portion of the coating film. Subsequently, the substrate patterned as described above was baked and cured at 220 ° C. for 30 minutes in an oven purged with nitrogen.
The patterned substrates obtained in Examples 1 to 27 and Comparative Examples 1 to 5 were further baked at 300 ° C. for 30 minutes in an oven purged with nitrogen, and subsequently -40 ° C. at 15 ° C. using a thermal shock tester. Minute, 120 ° C. and 15 minutes once were repeated 100 times, then visually and observed with an optical microscope, and evaluated according to the following criteria.
◎: No cracks confirmed in 5 substrates ○: 1-5 cracks occurred in 5 substrates △: 6-15 cracks occurred in 5 substrates ×: 5 substrates There are more than 16 cracks inside
ポリシロキサン組成物を、ガラス基板上に現像後の膜厚が10μmになるように塗布した。続いて、i線ステッパーを用いて、大気中で、全面に400mJ/cm2露光を行った。
(実施例1~14、実施例16~27、比較例1~5について)
露光に続いてアルカリ現像液(AZエレクトロニックマテリアルズ社製デベロッパー、2.38%水酸化テトラメチルアンモニウム水溶液)を用い、23℃、30秒×2回の条件下で現像し、純水にてリンスを行い、塗膜表面を除去した。
(実施例15について)
露光に続いてPGMEAを用い、23℃、30秒×2回の条件下で現像し、塗膜表面を除去した。 4). Evaluation of transmittance The polysiloxane composition was applied on a glass substrate so that the film thickness after development was 10 μm. Subsequently, the entire surface was exposed to 400 mJ / cm 2 in the atmosphere using an i-line stepper.
(Examples 1 to 14, Examples 16 to 27, and Comparative Examples 1 to 5)
Following exposure, an alkali developer (developer made by AZ Electronic Materials Co., Ltd., 2.38% tetramethylammonium hydroxide aqueous solution) was used for development under conditions of 23 ° C. and 30 seconds × 2 times, and rinsed with pure water. And the coating film surface was removed.
(About Example 15)
Following exposure, PGMEA was used for development under conditions of 23 ° C. and 30 seconds × 2 times to remove the coating film surface.
(ポリシロキサンa-1の合成)
1Lのナス型フラスコ中に撹拌子、(3-トリメトキシプロピル)無水コハク酸 0.60モル(173.14g)(商品名 X-12-967C 信越化学工業社製)、Ba(OH)2・H2O粉末 4.00ミリモル(0.83g)(SIGMA-ALDRICH社製)、メタノール 0.58モル(20.30g)を仕込み、マグネチックスターラーを用いて撹拌した。ジムロートを取り付け、オイルバスを用いて、室温から75℃まで昇温し、2.5時間還流させ、無水コハク酸を開環させた。 [Synthesis Example 1]
(Synthesis of polysiloxane a-1)
In a 1 L eggplant-shaped flask, a stirring bar, (3-trimethoxypropyl) succinic anhydride 0.60 mol (173.14 g) (trade name X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.), Ba (OH) 2. 4.00 mmol (0.83 g) of H 2 O powder (manufactured by SIGMA-ALDRICH) and 0.58 mol (20.30 g) of methanol were charged and stirred using a magnetic stirrer. A Dimroth was attached, and the temperature was raised from room temperature to 75 ° C. using an oil bath and refluxed for 2.5 hours to open the ring of succinic anhydride.
(ポリシロキサンa-2の合成)
合成例1におけるDPDをDCPD(ジシクロペンチルシランジオール)とした以外は合成例1と同様にして、ポリシロキサン(a-2、40℃における粘度は25Poise)を得た。このポリシロキサン(a-2)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.54×10-6モル/gであった。 [Synthesis Example 2]
(Synthesis of polysiloxane a-2)
A polysiloxane (a-2, viscosity at 25 ° C. at 25 ° C.) was obtained in the same manner as in Synthesis Example 1 except that DPD in Synthesis Example 1 was changed to DCPD (dicyclopentylsilanediol). When the ESR of this polysiloxane (a-2) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.54 × 10 −6 mol / g.
(ポリシロキサンa-3の合成)
合成例1におけるMEMOを、MEMO(3-メタクリロキシプロピルトリメトキシシラン)1.00モル、フェニルトリメトキシシラン 0.40モルとした以外は合成例1と同様にして、ポリシロキサン(a-3、40℃における粘度は100Poise)を得た。このポリシロキサン(a-3)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.56×10-6モル/gであった。 [Synthesis Example 3]
(Synthesis of polysiloxane a-3)
The polysiloxane (a-3, The viscosity at 40 ° C. was 100 poise). When the ESR of this polysiloxane (a-3) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.56 × 10 −6 mol / g.
(ポリシロキサンa-4の合成)
合成例1におけるMEMOを、MEMO(3-メタクリロキシプロピルトリメトキシシラン)1.00モル、スチリルトリメトキシシラン(信越化学工業社製、KBM1403)0.40モルとした以外は合成例1と同様にして、ポリシロキサン(a-4、40℃における粘度は90Poise)を得た。このポリシロキサン(a-4)のESRを測定すると、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.53×10-6モル/gであった。 [Synthesis Example 4]
(Synthesis of polysiloxane a-4)
In the same manner as in Synthesis Example 1, except that MEMO in Synthesis Example 1 was changed to 1.00 mol of MEMO (3-methacryloxypropyltrimethoxysilane) and 0.40 mol of styryltrimethoxysilane (KBM1403, manufactured by Shin-Etsu Chemical Co., Ltd.). Thus, polysiloxane (a-4, viscosity at 40 ° C. was 90 poise) was obtained. When the ESR of this polysiloxane (a-4) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.53 × 10 −6 mol / g.
(ポリシロキサンa-5の合成)
2Lのセパラブルフラスコ中にDPD(ジフェニルシランジオール)2.00モル(432.52g)(信越化学工業社製)、MEMO(3-メタクリロキシプロピルトリメトキシシラン)2.00モル(496.70g)、4-ヒドロキシ-TEMPO 0.61ミリモル(0.10g)(東京化成工業社製)、Ba(OH)2・H2O粉末 4.00ミリモル(0.83g)(SIGMA-ALDRICH社製)を仕込み、撹拌羽とスリーワンモーターを用いて撹拌させた。ジムロートを取り付け、オイルバスを用い、室温から95℃まで昇温した。1時間後、加熱を継続した状態でジムロートを取り外し、三方コック、コールドトラップ、バキュームコントローラー、真空ポンプに接続し、メタノールを除去した。真空引きしながら加熱を10時間継続した後、常圧に戻し、室温まで冷却することで、透明なポリシロキサン(a-5、40℃における粘度は75Poise)を得た。このポリシロキサン(a-5)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.51×10-6モル/gであった。 [Synthesis Example 5]
(Synthesis of polysiloxane a-5)
In a 2 L separable flask, DPD (diphenylsilanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxysilane) 2.00 mol (496.70 g) 4-hydroxy-TEMPO 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), Ba (OH) 2 .H 2 O powder 4.00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH) The mixture was stirred and stirred using a stirring blade and a three-one motor. A Dimroth was attached and the temperature was raised from room temperature to 95 ° C. using an oil bath. After 1 hour, while the heating was continued, the Dimroth was removed, connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump, and methanol was removed. Heating was continued for 10 hours while evacuating, and then the pressure was returned to normal pressure, followed by cooling to room temperature, whereby transparent polysiloxane (a-5, viscosity at 40 ° C. was 75 poise) was obtained. When the ESR of this polysiloxane (a-5) was measured, a peak with a g value = 2.007 was observed. The radical concentration in the solid content was calculated to be 0.51 × 10 −6 mol / g.
(ポリシロキサンa-6の合成)
合成例1における4-ヒドロキシ-TEMPOを添加しなかった以外は合成例1と同様にして、ポリシロキサン(a-6、40℃における粘度は83Poise)を得た。このポリシロキサン(a-6)のESRを測定したところ、g値2.034~1.984の範囲にピークが観察されなかった。 [Synthesis Example 6]
(Synthesis of polysiloxane a-6)
A polysiloxane (a-6, viscosity at 83 ° C. at 83 ° C.) was obtained in the same manner as in Synthesis Example 1 except that 4-hydroxy-TEMPO in Synthesis Example 1 was not added. When the ESR of this polysiloxane (a-6) was measured, no peak was observed in the g value range of 2.034 to 1.984.
(ポリシロキサンa-7の合成)
1Lのナス型フラスコ中に撹拌子、(3-トリメトキシプロピル)無水コハク酸 0.30モル(86.57g)(商品名 X-12-967C 信越化学工業社製)、Ba(OH)2・H2O粉末 2.00ミリモル(0.41g)(SIGMA-ALDRICH社製)、メタノール 0.29モル(10.15g)を仕込み、マグネチックスターラーを用いて撹拌した。ジムロートを取り付け、オイルバスを用いて、室温から75℃まで昇温し、2.5時間還流させ、無水コハク酸を開環させた。
2Lのセパラブルフラスコ中にフェニルトリメトキシシラン 1.00モル(198.29g)(東京化成工業社製)、MEMO(3-メタクリロキシプロピルトリメトキシシラン)0.70モル(173.84g)、4-ヒドロキシ-TEMPO(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル)0.30ミリモル(0.05g)(東京化成工業社製)、上記で調製した(3-トリメトキシプロピル)無水コハク酸開環物の全量、PGMEA(プロピレングリコールモノメチルエーテルアセテート)400gを仕込み、撹拌羽とスリーワンモーターを用いて撹拌させた。
続いて、蒸留水 36.00gと、5mol/Lの塩酸 4.67gを混合したものを滴下し、30分間撹拌を行った。
ジムロートを取り付け、オイルバスを用い、室温から95℃まで昇温した。2時間後、加熱を継続した状態でジムロートを取り外し、三方コック、コールドトラップ、バキュームコントローラー、真空ポンプに接続し、メタノール、水、PGMEAを除去した。真空引きしながら加熱を4時間継続した後、常圧に戻し、室温まで冷却することで、透明なポリシロキサン(a-7、40℃における粘度は50Poise)を得た。このポリシロキサン(a-7)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.60×10-6モル/gであった。 [Synthesis Example 7]
(Synthesis of polysiloxane a-7)
In a 1 L eggplant-shaped flask, a stirring bar, (3-trimethoxypropyl) succinic anhydride 0.30 mol (86.57 g) (trade name X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.), Ba (OH) 2. 2.00 mmol (0.41 g) of H 2 O powder (manufactured by SIGMA-ALDRICH) and 0.29 mol (10.15 g) of methanol were charged and stirred using a magnetic stirrer. A Dimroth was attached, and the temperature was raised from room temperature to 75 ° C. using an oil bath and refluxed for 2.5 hours to open the ring of succinic anhydride.
In a 2 L separable flask, 1.00 mol (198.29 g) of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.70 mol (173.84 g) of MEMO (3-methacryloxypropyltrimethoxysilane), 4 -Hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) 0.30 mmol (0.05 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), prepared above (3- The total amount of trimethoxypropyl) succinic anhydride ring-opened product and 400 g of PGMEA (propylene glycol monomethyl ether acetate) were charged and stirred using a stirring blade and a three-one motor.
Subsequently, a mixture of 36.00 g of distilled water and 4.67 g of 5 mol / L hydrochloric acid was dropped and stirred for 30 minutes.
A Dimroth was attached and the temperature was raised from room temperature to 95 ° C. using an oil bath. After 2 hours, the Dimroth was removed while heating was continued, and connected to a three-way cock, cold trap, vacuum controller, and vacuum pump, and methanol, water, and PGMEA were removed. Heating was continued for 4 hours while evacuating, and then the pressure was returned to normal pressure, followed by cooling to room temperature. Thus, a transparent polysiloxane (a-7, viscosity at 40 ° C. was 50 poise) was obtained. When the ESR of this polysiloxane (a-7) was measured, a peak with a g value of 2.007 was observed. The radical concentration in the solid content was calculated to be 0.60 × 10 −6 mol / g.
(ポリシロキサンa-8の合成)
1Lのナスフラスコに、撹拌子、無水ハイミック酸(東京化成工業社製)、トリメトキシシラン(東京化成工業社製)、キシレン を仕込み、白金(0)-1,3-ジビニル-1,1,3,3-テトラメチルジシロキサン錯体 溶液(シグマアルドリッチ社製)を撹拌下で滴下した。ジムロートを取り付け、80℃で4時間加熱後、さらに100℃で4時間加熱を行った。冷却後、蒸留にて精製し、無水ハイミック酸にヒドロシリル化された化合物Aを得た。
1Lのナス型フラスコ中に撹拌子、化合物A 0.60モル(171.81g)、Ba(OH)2・H2O粉末 4.00ミリモル(0.83g)(SIGMA-ALDRICH社製)、メタノール 0.58モル(20.30g)を仕込み、マグネチックスターラーを用いて撹拌した。ジムロートを取り付け、オイルバスを用いて、室温から75℃まで昇温し、2.5時間還流させ、無水コハク酸を開環させた。
2Lのセパラブルフラスコ中にDPD(ジフェニルシランジオール)2.00モル(432.52g)(信越化学工業社製)、MEMO(3-メタクリロキシプロピルトリメトキシシラン)1.40モル(347.69g)、4-ヒドロキシ-TEMPO(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル)0.61ミリモル(0.10g)(東京化成工業社製)、上記で調製した(3-トリメトキシプロピル)無水コハク酸開環物の0.6モルを仕込み、撹拌羽とスリーワンモーターを用いて撹拌させた。ジムロートを取り付け、オイルバスを用い、室温から95℃まで昇温した。1時間後、加熱を継続した状態でジムロートを取り外し、三方コック、コールドトラップ、バキュームコントローラー、真空ポンプに接続し、メタノールを除去した。真空引きしながら加熱を10時間継続した後、常圧に戻し、室温まで冷却することで、透明なポリシロキサン(a-8、40℃における粘度は75Poise)を得た。このポリシロキサン(a-8)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.58×10-6モル/gであった。 [Synthesis Example 8]
(Synthesis of polysiloxane a-8)
A 1 L eggplant flask was charged with a stir bar, hymic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.), trimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and xylene, and platinum (0) -1,3-divinyl-1,1, A 3,3-tetramethyldisiloxane complex solution (manufactured by Sigma-Aldrich) was added dropwise with stirring. A Dimroth was attached, heated at 80 ° C. for 4 hours, and further heated at 100 ° C. for 4 hours. After cooling, it was purified by distillation to obtain Compound A hydrosilylated to hymic anhydride.
In a 1 L eggplant-shaped flask, 0.60 mol (171.81 g) of compound A, 4.00 mmol (0.83 g) of Ba (OH) 2 .H 2 O powder (manufactured by SIGMA-ALDRICH), methanol 0.58 mol (20.30 g) was charged and stirred using a magnetic stirrer. A Dimroth was attached, and the temperature was raised from room temperature to 75 ° C. using an oil bath and refluxed for 2.5 hours to open the ring of succinic anhydride.
In a 2 L separable flask, DPD (diphenylsilanediol) 2.00 mol (432.52 g) (manufactured by Shin-Etsu Chemical Co., Ltd.), MEMO (3-methacryloxypropyltrimethoxysilane) 1.40 mol (347.69 g) 4-hydroxy-TEMPO (4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), prepared above ( 0.6 mol of 3-trimethoxypropyl) succinic anhydride ring-opened product was charged and stirred using a stirring blade and a three-one motor. A Dimroth was attached and the temperature was raised from room temperature to 95 ° C. using an oil bath. After 1 hour, while the heating was continued, the Dimroth was removed, connected to a three-way cock, a cold trap, a vacuum controller, and a vacuum pump, and methanol was removed. Heating was continued for 10 hours while evacuating, and then the pressure was returned to normal pressure and cooled to room temperature to obtain transparent polysiloxane (a-8, viscosity at 40 ° C. was 75 poise). When ESR of this polysiloxane (a-8) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.58 × 10 −6 mol / g.
(ポリシロキサンa-9の合成)
無水ハイミック酸を、cis-4-シクロヘキセン-1,2-ジカルボン酸無水物(東京化成工業社製)に変えた以外は、ポリシロキサンa-8と同様にして、ポリシロキサン(a-9、40℃における粘度は80Poise)を得た。このポリシロキサン(a-9)のESRを測定したところ、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.51×10-6モル/gであった。 [Synthesis Example 9]
(Synthesis of polysiloxane a-9)
Polysiloxane (a-9, 40) was prepared in the same manner as polysiloxane a-8, except that the hymic anhydride was changed to cis-4-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). The viscosity at 80 ° C. was 80 poise). When the ESR of this polysiloxane (a-9) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.51 × 10 −6 mol / g.
(ポリシロキサンa-10の合成)
無水ハイミック酸を、無水イタコン酸(東京化成工業社製)に変えた以外は、ポリシロキサンa-8と同様にして、ポリシロキサン(a-10、40℃における粘度は70Poise)を得た。このポリシロキサン(a-10)のESRを測定すると、g値=2.007のピークが観察された。また、固形分中のラジカル濃度を算出すると、0.52×10-6モル/gであった。
[合成例11]
(ポリシロキサンa-11の合成)
1Lのナス型フラスコ中に撹拌子、(3-トリメトキシプロピル)無水コハク酸 0.60モル(173.14g)(商品名 X-12-967C 信越化学工業社製)、4-ヒドロキシ-TEMPO(4-ヒドロキシ-2,2,6,6-テトラメチルピペリジン1-オキシル フリーラジカル)0.61ミリモル(0.10g)(東京化成工業社製)、Ba(OH)2・H2O粉末 4.00ミリモル(0.83g)(SIGMA-ALDRICH社製)、メタノール 0.58モル(20.30g)を仕込み、マグネチックスターラーを用いて撹拌した。ジムロートを取り付け、オイルバスを用いて、室温から75℃まで昇温し、2.5時間還流させ、無水コハク酸を開環させた。 [Synthesis Example 10]
(Synthesis of polysiloxane a-10)
A polysiloxane (a-10, viscosity at 40 ° C. was 70 poise) was obtained in the same manner as polysiloxane a-8, except that the hymic anhydride was changed to itaconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.). When the ESR of this polysiloxane (a-10) was measured, a peak with a g value = 2.07 was observed. The radical concentration in the solid content was calculated to be 0.52 × 10 −6 mol / g.
[Synthesis Example 11]
(Synthesis of polysiloxane a-11)
In a 1 L eggplant-shaped flask, a stirring bar, (3-trimethoxypropyl) succinic anhydride 0.60 mol (173.14 g) (trade name X-12-967C manufactured by Shin-Etsu Chemical Co., Ltd.), 4-hydroxy-TEMPO ( 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical) 0.61 mmol (0.10 g) (manufactured by Tokyo Chemical Industry Co., Ltd.), Ba (OH) 2 .H 2 O powder 00 mmol (0.83 g) (manufactured by SIGMA-ALDRICH) and 0.58 mol (20.30 g) of methanol were charged and stirred using a magnetic stirrer. A Dimroth was attached, and the temperature was raised from room temperature to 75 ° C. using an oil bath and refluxed for 2.5 hours to open the ring of succinic anhydride.
[実施例1]
広口のサンプル容器に、合成例1で得られたポリシロキサン(a-1)46.57g、IRGACURE819(BASF社製)0.79g、4-ヒドロキシ-TEMPO(東京化成工業社製)(0.01g)、EA-1020(新中村化学工業社製、EA-1020)37.26g、TINUVIN 405(BASF社製)1.16g、EA-6340(新中村化学工業社製)9.31g(希釈溶媒を除く)、KBM5103(3-アクリロキシプロピルトリメトキシシラン)4.66g、TINUVIN 152(BASF社製)0.23g、PGMEA(プロピレングリコールモノメチルエーテルアセテート)28.87gを仕込み、ウェブローターにて撹拌し、混合した。これを孔径2.5ミクロンのPP製フィルターで加圧ろ過し、ポリシロキサン組成物を得た。 (Preparation of polysiloxane composition)
[Example 1]
In a wide-mouthed sample container, 46.57 g of polysiloxane (a-1) obtained in Synthesis Example 1, IRGACURE 819 (manufactured by BASF) 0.79 g, 4-hydroxy-TEMPO (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.01 g) ), EA-1020 (manufactured by Shin-Nakamura Chemical Co., Ltd., EA-1020), 37.26 g, TINUVIN 405 (manufactured by BASF) 1.16 g, EA-6340 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 9.31 g (diluting solvent) Except), 4.66 g of KBM5103 (3-acryloxypropyltrimethoxysilane), 0.23 g of TINUVIN 152 (manufactured by BASF), 28.87 g of PGMEA (propylene glycol monomethyl ether acetate), and agitation with a web rotor, Mixed. This was pressure filtered through a PP filter with a pore size of 2.5 microns to obtain a polysiloxane composition.
実施例2~27及び比較例1~5については、以下の表1、表2、及び表3に記載した成分を同表に記載した比率で用いたこと以外は、実施例1と同様にポリシロキサン組成物又は樹脂組成物を得た。 [Examples 2 to 27 and Comparative Examples 1 to 5]
For Examples 2 to 27 and Comparative Examples 1 to 5, the same as in Example 1 except that the components described in Table 1, Table 2, and Table 3 below were used in the ratios described in the same table. A siloxane composition or a resin composition was obtained.
実施例1~8、12~27のポリシロキサン組成物、及び比較例5の樹脂組成物では、図4に示すg値2.007のピークが観察された。 For the polysiloxane compositions of Examples 1 to 27 and the resin compositions of Comparative Examples 1 to 5, the amplitude was set to 200 and ESR was measured.
In the polysiloxane compositions of Examples 1 to 8, 12 to 27, and the resin composition of Comparative Example 5, a peak with a g value of 2.007 shown in FIG. 4 was observed.
比較例4の樹脂組成物では、図10に示すように、g値2.007のピークが観察された。 In the resin compositions of Comparative Examples 1 to 3, as shown in FIG. 9, a peak was observed in the g value range of 2.034 to 1.984, but the radical concentration was outside the range specified in the claims.
In the resin composition of Comparative Example 4, a peak with a g value of 2.007 was observed as shown in FIG.
Irgacure819:BASF社製 <(B) component>
Irgacure 819: manufactured by BASF
c-1:下記式:
c-2:下記式:
c-3:下記式:
c-4:下記式:
c-1: The following formula:
c-2: The following formula:
c-3: The following formula:
c-4: The following formula:
EA-1020:新中村化学工業社製
A600:新中村化学工業社製 <(D) component>
EA-1020: Shin-Nakamura Chemical Co., Ltd. A600: Shin-Nakamura Chemical Co., Ltd.
TINUVIN405:BASF社製 <(E) component>
TINUVIN405: manufactured by BASF
EA-6340:新中村化学工業社製 酸価:85mgKOH/g
SPC1001:昭和電工社製 酸価:86mgKOH/g <(F) component>
EA-6340: Shin-Nakamura Chemical Co., Ltd. Acid value: 85 mgKOH / g
SPC1001: Showa Denko KK Acid value: 86 mgKOH / g
KBM5103:信越化学工業株式会社製 <(G) component>
KBM5103: Shin-Etsu Chemical Co., Ltd.
TINUVIN152:BASF社製 <(H) component>
TINUVIN152: manufactured by BASF
PEGMEA:東京化成工業社製 <(I) component>
PEGMEA: manufactured by Tokyo Chemical Industry Co., Ltd.
比較例5は、露光し現像を行ったところ、膜が残らなかったため、評価することができなかった。 The crack resistance of Examples 1 to 27 was evaluated using a Mo-sputtered silicon wafer. As a result, in Examples 1 to 20 and Examples 24 to 27, the pattern was not peeled off and no cracks were generated. However, in Examples 21 to 23, the pattern peeled off.
Comparative Example 5 could not be evaluated because exposure and development did not leave a film.
Claims (13)
- 大気下、24℃、常圧、及び400nm以下の波長の光を遮光した条件下、24時間静置した後、電子スピン共鳴(ESR)装置を用いて測定されるとき、g値2.034~1.984のピークを持ち、かつ組成物中の固形分1gに対し、0.1×10-6~120×10-6モルのラジカルを含む、ラジカル架橋性基を有するポリシロキサン組成物。 When measured using an electron spin resonance (ESR) apparatus after standing for 24 hours under the condition of shielding light of a wavelength of 400 nm or less in the atmosphere at 24 ° C., normal pressure, and a g value of 2.034 to 1.984. A polysiloxane composition having a radical crosslinkable group having a peak and containing 0.1 × 10 −6 to 120 × 10 −6 mol of radicals with respect to 1 g of a solid content in the composition.
- 下記構造:
- アルカリ可溶性基をさらに有する、請求項1又は2に記載のラジカル架橋性基を有するポリシロキサン組成物。 The polysiloxane composition having a radically crosslinkable group according to claim 1 or 2, further comprising an alkali-soluble group.
- (B)光ラジカル開始剤
をさらに含む、ポリシロキサン組成物。 (B) A polysiloxane composition further comprising a photoradical initiator. - 前記ポリシロキサン組成物中の全固形分100質量部に対して、1質量部~99質量部の(A)ラジカル架橋性基を有するポリシロキサン、0.01質量部~15質量部の(B)光ラジカル開始剤;及び0.005質量部~2質量部の(C)ニトロキシ化合物を含む、請求項4に記載のポリシロキサン組成物。 1 part by mass to 99 parts by mass of (A) a polysiloxane having a radical crosslinkable group, 0.01 part by mass to 15 parts by mass of (B) with respect to 100 parts by mass of the total solid content in the polysiloxane composition. The polysiloxane composition according to claim 4, comprising a photo radical initiator; and 0.005 to 2 parts by mass of (C) a nitroxy compound.
- 前記(C)ニトロキシ化合物は、下記一般式:
- 前記(A)ラジカル架橋性基を有するポリシロキサンは、(メタ)アクリロイル基及び/又はスチリル基を有するポリシロキサンである、請求項1~6のいずれか1項に記載のポリシロキサン組成物。 The polysiloxane composition according to any one of claims 1 to 6, wherein the polysiloxane (A) having a radical crosslinkable group is a polysiloxane having a (meth) acryloyl group and / or a styryl group.
- 前記ポリシロキサン組成物中の全固形分100質量部に対して、5質量部~45質量部の(D)光重合性二重結合を有する化合物をさらに含む、請求項1~7のいずれか1項に記載のポリシロキサン組成物。 The composition according to any one of claims 1 to 7, further comprising (D) a compound having a photopolymerizable double bond in an amount of 5 to 45 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition. The polysiloxane composition according to Item.
- 前記ポリシロキサン組成物中の全固形分100質量部に対して、0.01質量部~10質量部の(E)紫外線吸収剤をさらに含む、請求項1~8のいずれか1項に記載のポリシロキサン組成物。 The composition according to any one of claims 1 to 8, further comprising 0.01 to 10 parts by mass of (E) an ultraviolet absorber with respect to 100 parts by mass of the total solid content in the polysiloxane composition. Polysiloxane composition.
- 前記ポリシロキサン組成物中の全固形分100質量部に対して、1質量部~50質量部の(F)酸価が10~200mgKOH/gであるアルカリ可溶性樹脂をさらに含む、請求項1~9のいずれか1項に記載のポリシロキサン組成物。 10. The composition further comprises an alkali-soluble resin having an acid value of 10 to 200 mg KOH / g of (F) 1 to 50 parts by mass with respect to 100 parts by mass of the total solid content in the polysiloxane composition. The polysiloxane composition according to any one of the above.
- 前記(A)ラジカル架橋性基を有するポリシロキサンは、下記一般式:
- 請求項1~11のいずれか1項に記載のポリシロキサン組成物を硬化して得られる硬化物。 A cured product obtained by curing the polysiloxane composition according to any one of claims 1 to 11.
- 請求項1~11のいずれか1項に記載のポリシロキサン組成物を硬化して得られる透明絶縁膜。 A transparent insulating film obtained by curing the polysiloxane composition according to any one of claims 1 to 11.
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WO2015118992A1 (en) * | 2014-02-07 | 2015-08-13 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Addition-cured silicone composition |
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WO2017188047A1 (en) * | 2016-04-25 | 2017-11-02 | 東レ株式会社 | Resin composition, cured film of same and method for manufacturing same, and solid-state imaging element |
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Also Published As
Publication number | Publication date |
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TW201402700A (en) | 2014-01-16 |
KR101566138B1 (en) | 2015-11-04 |
CN104245846A (en) | 2014-12-24 |
JPWO2013157643A1 (en) | 2015-12-21 |
JP5886420B2 (en) | 2016-03-16 |
KR20140128404A (en) | 2014-11-05 |
TWI491675B (en) | 2015-07-11 |
CN104245846B (en) | 2016-08-24 |
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