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CN102375340A - Radioactive Ray Sensitive Resin Composite, Solidification Film, Preparing Method Of Solidification Film, Color Filter And Preparing Method Of Color Filter - Google Patents

Radioactive Ray Sensitive Resin Composite, Solidification Film, Preparing Method Of Solidification Film, Color Filter And Preparing Method Of Color Filter Download PDF

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Publication number
CN102375340A
CN102375340A CN2011102355584A CN201110235558A CN102375340A CN 102375340 A CN102375340 A CN 102375340A CN 2011102355584 A CN2011102355584 A CN 2011102355584A CN 201110235558 A CN201110235558 A CN 201110235558A CN 102375340 A CN102375340 A CN 102375340A
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compound
acid
sensitive resin
methyl
radiation
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米田英司
西信弘
儿玉诚一郎
猪俣克巳
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JSR Corp
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JSR Corp
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Abstract

The invention relates to radioactive ray sensitive resin composite, solidification film, preparing method of solidification film, color filter and preparing method of color filter. The invention aims to provide the radioactive ray sensitive resin composite that can be stored stably and short term low temperature roasting, and has enough sensitivity and develop capability. The invention aims to provide the solidification film having good compressing characteristic, good heat resisting performance, good relative dielectric constant, good solvent resistance, good rigidity and good voltage retention rate. The invention aims to provide the preparing method of solidification film. The invention aims to provide the color filter having good heat resistance, good solvent resistance and good voltage retention rate. The radioactive ray sensitive resin composite contains alkali soluble resin (A), photopolymerization compound having ethylene unsaturated bond (B), polymerization initiator (C), compound (D) indicated by the following formula (1) and compound as organic acid or inorganic acid. The viscosity of the radioactive ray sensitive resin composite in 25 DEG C is 1.0 Mpa.S - 50mPa.S.

Description

The formation method of formation method, color filter and the color filter of radiation sensitive resin composition, cured film, cured film
Technical field
The present invention relates to the formation method of formation method, color filter and the color filter of a kind of radiation sensitive resin composition, cured film, cured film.
Background technology
In recent years, the liquid crystal display cells that in LCD TV, mobile phone etc., is widely used requires liquid crystal display cells can realize bigger pictureization, high brightnessization, slimming etc.Therefore, from shortening the viewpoint of activity time and cutting down cost, require radiation sensitive resin composition ability high sensitiveization and high resolving powerization as the material of cured film such as the interlayer dielectric that in display element, uses, diaphragm, pad.In addition, require the gained cured film can have (TOHKEMY 2009-36858 communiques) such as higher flatness, adhesiveness, high permeabilityizatioies.
On the other hand, flexible display such as e-book is popularized.As the substrate of this flexible display, studying flexible substrates such as polyethylene terephthalate.This substrate is the meeting stretch/shrink when heating, produces the not good situation of the function that harms display, therefore must low temperatureization in the calcining process of cured film.
In view of the above fact, even developed gate insulating film that the flexible display that comprises polyimide precursor that low-temperature bake also can solidify uses technology (referring to TOHKEMY 2009-4394 communique) with coating fluid.Yet this coating fluid does not form the ability of pattern through exposure imaging, therefore can't form fine pattern.In addition, maybe since the carrying out of curing reaction insufficient, the compression property of gained cured film, thermotolerance, relative dielectric constant, solvent resistance, hardness, voltage retention etc. can't arrive satisfied degree.
Therefore; Through also having considered through adding amines as the hardening agent of epoxies material; Even thereby also can carry out the method for cross-linking reaction at low temperatures; Through adding common amines, can carry out time dependent reaction with the epoxy radicals that in composition, exists, storage stability can reduce (referring to WO2008/099732A1).
Because this situation; The expectation exploitation can have the low-temperature bake property of storage stability and short time concurrently, and has radiation sensitive resin composition and compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and the voltage retention excellent in curing film of enough susceptibilitys and development property.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-36858 communique
Patent documentation 2: TOHKEMY 2009-4394 communique
Patent documentation 3:WO2008/099732A1
Summary of the invention
The present invention makes in view of above situation; Its objective is provides a kind of low-temperature bake property that has storage stability and short time concurrently, and has the excellent color filters such as formation method and thermotolerance, solvent resistance, voltage retention of radiation sensitive resin composition, compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention excellent in curing film, this cured film of enough susceptibilitys and development property.
The invention that can solve above-mentioned problem is a kind of radiation sensitive resin composition, and it contains,
[A] alkali soluble resin (below; Be also referred to as [A] alkali soluble resin); Its through at least a kind of compound in the group that (A1) is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and constitutes (below; Be also referred to as " (A1) compound ") obtain with the unsaturated compound that (A2) contains epoxy radicals (below, be also referred to as " (A2) compound ") copolymerization,
[B] has the polymerizable compound (below, be also referred to as " [B] polymerizable compound ") of ethene property unsaturated link;
[C] radiation-sensitive polymerization initiator;
The compound of [D] following formula (1) expression (below, be also referred to as " [D] compound "); With
[E] as the compound of organic acid or mineral acid (below, be also referred to as " [E] compound "), its viscosity under 25 ℃ is 1.0mPas～50mPas,
In formula (1), m is 2～6 integer, and wherein, the partly or entirely optional of the hydrogen atom that the alkylidene in the formula (1) has replaced by organic group.
This radiation sensitive resin composition contains [A] alkali soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound, [E] compound.As exposure, the development of this radiation sensitive resin composition through utilizing radiation-sensitive of radiation-sensitive material, thereby can easily form fine and exquisite pattern, in addition, also have enough susceptibilitys and development property.In addition, this radiation sensitive resin composition is through containing [C] radiation-sensitive polymerization initiator, thereby even under the situation of low exposure, also can further improve the characteristic that requires as cured film such as thermotolerance.In addition, this radiation sensitive resin composition is through containing [D] compound and [E] compound, thereby can play the effect of effective curing catalysts, can be with the viscosity Control of this radiation sensitive resin composition under 25 ℃ at 1.0mPas～50mPas.As a result, this radiation sensitive resin composition can have the curing facilitation of the cured film under storage stability and the low-temperature bake simultaneously high-levelly.In addition, above-mentioned so-called alkylidene is meant alkylidene and the (CH in above-mentioned (1) in the tetrahydrochysene pyrazine ring 2) alkylidene represented of m both.
[C] radiation-sensitive polymerization initiator is preferably O-acyl group oxime compound.As [C] radiation-sensitive polymerization initiator, through using above-mentioned specific compound, thereby even under the situation of low exposure, also can further improve thermotolerance etc.
This radiation sensitive resin composition preferably mixes the amidine salt that is formed by [D] compound and [E] compound and prepares in [A] alkali soluble resin, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator.Through above-mentioned operation, can prepare this radiation sensitive resin composition that contains amidine salt effectively.
Amidine salt is preferably sulphonate.Through making amidine salt is sulphonate, thereby can further improve the effect as curing catalysts.
In addition; In the present invention; The manufacturing approach that also comprises a kind of radiation sensitive resin composition; The mixed amidine salt that is formed by [D] compound and [E] compound and preparing in [A] alkali soluble resin, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator wherein, the viscosity under 25 ℃ is 1.0mPas～50mPas.
The cured film that this radiation sensitive resin composition is preferably as interlayer dielectric, diaphragm or pad forms usefulness, in addition, in the present invention, preferably includes the cured film as interlayer dielectric, diaphragm or pad.The cured film as interlayer dielectric, diaphragm or pad that is formed by this radiation sensitive resin composition is excellent on compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention.
Color filter of the present invention has this cured film; The alignment films that forms in this cured film laminated, through aligning agent for liquid crystal.Color filter of the present invention is excellent at aspects such as thermotolerance, solvent resistance, voltage retention.
Above-mentioned aligning agent for liquid crystal is preferably the aligning agent for liquid crystal that comprises the radiation-sensitive polymkeric substance with light orientation group, or comprises the aligning agent for liquid crystal of the polyimide that does not have light orientation group.
The formation method of cured film of the present invention has:
(1) this radiation sensitive resin composition of coating on substrate, the operation that formation is filmed,
(2) on above-mentioned at least a portion of filming the irradiation radioactive ray operation,
(3) with the above-mentioned operation that is coated with film development of having shone radioactive ray and
(4) filming of above-mentioned development carried out the operation of roasting.
Through formation method of the present invention, can form compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention excellent in curing film.
As the sintering temperature of above-mentioned operation (4), be preferably below 200 ℃.Therefore this radiation sensitive resin composition can realize low-temperature bake owing to containing like above-mentioned [D] compound and [E] compound as curing accelerator, preferably the formation material of the middle cured film of using such as flexible display of conduct expectation low-temperature bake.
The formation method of color filter of the present invention has operation (1)～(4) and (5) the coating of liquid crystalline alignment agent on the filming of roasting of the formation method of above-mentioned cured film, through in the heating below 200 ℃, forms the operation of alignment films.
Through the formation method of this color filter, can form color filter with alignment films that liquid crystal aligning uses.
In addition, so-called in this instructions " roasting " is meant to be heated to obtain the skin hardness that in cured film such as interlayer dielectric, diaphragm and pad, requires.In addition, " radioactive ray " of " radiation sensitive resin composition " are the notions that comprises luminous ray, ultraviolet ray, far ultraviolet, X ray, charged particle line etc.In addition, above-mentioned viscosity is used E type viscosity meter (eastern machine industry is made, VISCONIC ELD.R), measures the value of 25 ℃ of following said composition viscosity (mPas).
That kind as described above, radiation sensitive resin composition of the present invention have the low-temperature bake of storage stability and short time concurrently for can easily form fine and exquisite pattern, and have enough susceptibilitys and development property.In addition, the cured film that is formed by this radiation sensitive resin composition is excellent on compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention.Therefore, this radiation-ray sensitive composition is preferably used as the formation material of the cured film such as interlayer dielectric, diaphragm, pad of use in the flexible display etc. of expectation low-temperature bake.In addition, it is excellent at aspects such as thermotolerance, solvent resistance, voltage retention to have a color filter of this cured film that forms alignment films.
Embodiment
< radiation sensitive resin composition >
Radiation sensitive resin composition of the present invention contains [A] alkali soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound, [E] compound, and the viscosity under 25 ℃ is more than the 1.0mPas, below the 50mPas.In addition, this radiation sensitive resin composition only otherwise damage effect of the present invention just can also contain optional member.Below, each composition is described in detail.
< [A] alkali soluble resin >
[A] alkali soluble resin can be in solvent, in the presence of polymerization initiator, (A1) compound is synthesized with (A2) compound copolymerization.In addition, in [A] alkali soluble resin synthetic, can also (A1) compound with (A2) compound with as above-mentioned (A1) compound of (A3) compound and (A2) compound unsaturated compound in addition carry out free-radical polymerized.Below, each composition is described in detail.Again, each compound can two or more and usefulness.
(A1) compound
(A1) compound is at least a kind of compound that is selected from the group that unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides constitute.As (A1) compound, can enumerate the list of unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid acid anhydride, polybasic carboxylic acid [(methyl) acryloxyalkyl] ester for example, two ends have the polymkeric substance of carboxyl and hydroxyl list (methyl) acrylic ester, have the unsaturated polycyclic compound and the acid anhydrides thereof of carboxyl.
As unsaturated monocarboxylic acid, can enumerate for example acrylic acid, methacrylic acid, crotonic acid etc.As unsaturated dicarboxylic acid, can enumerate for example maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid etc.As the unsaturated dicarboxylic acid acid anhydride, for example can enumerate acid anhydrides as the illustrative compound of above-mentioned dicarboxylic acids.As list [(methyl) acryloxyalkyl] ester of polybasic carboxylic acid, can enumerate for example mono succinate [2-(methyl) acryloxy ethyl ester], phthalic acid list [(methyl) acryloxy ethyl ester] etc.As list (methyl) acrylic ester that has the polymkeric substance of carboxyl and hydroxyl at two ends, can enumerate for example ω-carboxyl polycaprolactone list (methyl) acrylic ester etc.As unsaturated polycyclic compound and acid anhydrides thereof with carboxyl; Can enumerate for example 5-carboxyl dicyclo [2.2.1] hept-2-ene", 5; 6-dicarboxyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-5-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-carboxyl-6-methyl bicycle [2.2.1] hept-2-ene", 5-carboxyl-6-ethyl dicyclo [2.2.1] hept-2-ene", 5, the acid anhydrides of 6-dicarboxyl dicyclo [2.2.1] hept-2-ene" etc.
Wherein, the acid anhydrides of preferred monocarboxylic acid, dicarboxylic acids is from copolyreaction property, to the dissolubility of aqueous alkali and the easy property of acquisition, more preferably (methyl) acrylic acid, maleic anhydride.
As proportional in [A] alkali soluble resin, with respect to the entire infrastructure unit, be preferably 5mol%～35mol%, more preferably 10mol%～30mol% from containing of the structural unit of (A1) compound.Through making from proportionally being 5mol%～35mol% containing of the structural unit of (A1) compound; Thereby can make [A] alkali soluble resin that the dissolubility of aqueous alkali is reached optimization, and can obtain linear susceptibility of radiation and the excellent radiation sensitive resin composition of development property.
[(A2) compound]
(A2) compound is the unsaturated compound that contains epoxy radicals.As epoxy radicals, can enumerate oxa-cyclopropyl (1, the 2-epoxy construction), oxa-cyclobutyl (1, the 3-epoxy construction).
As unsaturated compound with oxa-cyclopropyl; Can enumerate for example acrylic acid glycidyl esters, methyl propenoic acid glycidyl base ester, acrylic acid 2-methyl glycidyl esters, acrylic acid 2-methyl glycidyl esters α-Yi Jibingxisuan glycidyl esters, α-n-pro-pyl acrylic acid glycidyl esters, α-normal-butyl acrylic acid glycidyl esters, acrylic acid-3; 4-epoxy butyl ester, methacrylic acid-3; 4-epoxy butyl ester, acrylic acid-6; 7-epoxy heptyl ester, methacrylic acid-6; 7-epoxy heptyl ester, α-Yi Jibingxisuan-6,7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate etc.
As unsaturated compound with oxa-cyclobutyl, for example can enumerate,
3-(acryloyl-oxy ylmethyl) oxetanes, 3-(acryloyl-oxy ylmethyl)-2-methyl oxetanes, 3-(acryloyl-oxy ylmethyl)-3-ethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-trifluoromethyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-five fluoropropyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2-phenyl oxetanes, 3-(acryloyl-oxy ylmethyl)-2; 2-difluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2; 2; 4-trifluoro oxetanes, 3-(acryloyl-oxy ylmethyl)-2; 2; 4; 4-tetrafluoro oxetanes, 3-(2-acryloxy ethyl) oxetanes, 3-(2-acryloxy ethyl)-2-ethyl oxetanes, 3-(2-acryloxy ethyl)-3-ethyl oxetanes, 3-(2-acryloxy ethyl)-2-trifluoromethyl oxetanes, 3-(2-acryloxy ethyl)-2-five fluoropropyl oxetanes, 3-(2-acryloxy ethyl)-2-phenyl oxetanes, 3-(2-acryloxy ethyl)-2,2-difluoro oxetanes, 3-(2-acryloxy ethyl)-2,2; 4-trifluoro oxetanes, 3-(2-acryloxy ethyl)-2; 2,4, acrylic ester such as 4-tetrafluoro oxetanes;
3-(methacryloxy methyl) oxetanes, 3-(methacryloxy methyl)-2-methyl oxetanes, 3-(methacryloxy methyl)-3-ethyl oxetanes, 3-(methacryloxy methyl)-2-trifluoromethyl oxetanes, 3-(methacryloxy methyl)-2-five fluoropropyl oxetanes, 3-(methacryloxy methyl)-2-phenyl oxetanes, 3-(methacryloxy methyl)-2; 2-difluoro oxetanes, 3-(methacryloxy methyl)-2; 2; 4-trifluoro oxetanes, 3-(methacryloxy methyl)-2; 2; 4; 4-tetrafluoro oxetanes, 3-(2-methacryloxyethyl) oxetanes, 3-(2-methacryloxyethyl)-2-ethyl oxetanes, 3-(2-methacryloxyethyl)-3-ethyl oxetanes, 3-(2-methacryloxyethyl)-2-trifluoromethyl oxetanes, 3-(2-methacryloxyethyl)-2-five fluoropropyl oxetanes, 3-(2-methacryloxyethyl)-2-phenyl oxetanes, 3-(2-methacryloxyethyl)-2,2-difluoro oxetanes, 3-(2-methacryloxyethyl)-2,2; 4-trifluoro oxetanes, 3-(2-methacryloxyethyl)-2; 2,4, methacrylates such as 4-tetrafluoro oxetanes etc.
Wherein, From copolyreaction property and the viewpoint that improves the resin combination curable; Preferable methyl acrylic acid glycidyl esters, methacrylic acid-6; 7-epoxy heptyl ester, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate.
As proportional in [A] alkali soluble resin, with respect to the entire infrastructure unit, be preferably 5mol%～70mol%, more preferably 10mol%～60mol% from containing of the structural unit of (A2) compound.Through making from proportionally being 5mol%～70mol% containing of the structural unit of (A2) compound, thereby can form cured film with excellent in resistance solvent borne.
[(A3) compound]
(A3) compound is (A1) compound and (A2) compound beyond the compound, so long as have free-radical polymerised unsaturated compound, just has no particular limits.As (A3) compound, can enumerate for example methacrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, the methacrylate with hydroxyl, acrylic acid cyclic alkyl ester, aryl methacrylate, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, dicyclo unsaturated compound, maleimide compound, unsaturated aromatics, conjugated diolefine, have the tetrahydrofuran skeleton, the unsaturated compound of the skeleton of furans skeleton, oxinane skeleton, pyrans skeleton, following formula (2) expression, the unsaturated compound with phenol property hydroxyl and other unsaturated compounds of following formula (3) expression.
Figure BSA00000558049100101
In following formula (2), R 1Be hydrogen atom or methyl.S is the integer more than 1.
Figure BSA00000558049100102
In following formula (3), R 2It for hydrogen atom or carbon number 1～4 alkyl.R 3～R 7Represent that independently of one another hydrogen atom, hydroxyl or carbon number are 1～4 alkyl.Y be singly-bound ,-COO-or-CONH-.P is 0～3 integer.Wherein, R 3～R 7In at least 1 be hydroxyl.
As above-mentioned methacrylic acid chain-like alkyl ester, can enumerate for example methyl methacrylate, Jia Jibingxisuanyizhi, n-BMA, the secondary butyl ester of methacrylic acid, metering system tert-butyl acrylate, methacrylic acid 2-Octyl Nitrite, isodecyl methacrylate, methacrylic acid dodecyl ester, methacrylic acid tridecyl ester, methacrylic acid n-octadecane base ester etc.
As above-mentioned methacrylic acid cyclic alkyl ester, can enumerate for example cyclohexyl methacrylate, methacrylic acid 2-ethyl cyclohexyl, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, methacrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base oxygen ethyl, isobornyl methacrylate etc.
As methacrylate with above-mentioned hydroxyl; Can enumerate for example methacrylic acid hydroxyl methyl esters, 2-hydroxyethyl methacrylate, methacrylic acid 3-hydroxy propyl ester, methacrylic acid 4-hydroxyl butyl ester, methacrylic acid binaryglycol ester, methacrylic acid 2,3-dihydroxy propyl ester, 2-methacryloxyethyl glucoside, methacrylic acid 4-hydroxylphenyl ester etc.
As aforesaid propylene acid cyclic alkyl ester, can enumerate for example cyclohexyl acrylate, acrylic acid 2-methyl cyclohexane ester, acrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base ester, acrylic acid three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-base oxygen base ethyl ester, isobornyl acrylate etc.
As above-mentioned aryl methacrylate, can enumerate for example phenyl methacrylate, benzyl methacrylate etc.
As aforesaid propylene acid aryl ester, can enumerate for example phenyl acrylate, benzyl acrylate etc.
As above-mentioned unsaturated dicarboxylic acid diester, can enumerate for example diethyl maleate, DEF, diethyl itaconate etc.
As above-mentioned dicyclo unsaturated compound; Can enumerate for example dicyclo [2.2.1] hept-2-ene", 5-methyl bicycle [2.2.1] hept-2-ene", 5-ethyl dicyclo [2.2.1] hept-2-ene", 5-methoxyl dicyclo [2.2.1] hept-2-ene", 5-ethoxy dicyclo [2.2.1] hept-2-ene", 5; 6-dimethoxy dicyclo [2.2.1] hept-2-ene", 5; 6-diethoxy dicyclo [2.2.1] hept-2-ene", 5-tert-butoxycarbonyl dicyclo [2.2.1] hept-2-ene", 5-cyclohexyl oxygen base carbonyl dicyclo [2.2.1] hept-2-ene", 5-phenyloxycarbonyl dicyclo [2.2.1] hept-2-ene", 5; 6-two (tert-butoxycarbonyl) dicyclo [2.2.1] hept-2-ene", 5; 6-two (cyclohexyl-carbonyl) dicyclo [2.2.1] hept-2-ene", 5-(2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5; 6-dihydroxy dicyclo [2.2.1] hept-2-ene", 5; 6-two (hydroxymethyl) dicyclo [2.2.1] hept-2-ene", 5,6-two (2 '-hydroxyethyl) dicyclo [2.2.1] hept-2-ene", 5-hydroxy-5-methyl base dicyclo [2.2.1] hept-2-ene", 5-hydroxyl-5-ethyl dicyclo [2.2.1] hept-2-ene", 5-hydroxymethyl-5-methyl bicycle [2.2.1] hept-2-ene" etc.
As above-mentioned maleimide compound, can enumerate for example N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-(4-hydroxy phenyl) maleimide, N-(4-hydroxybenzyl) maleimide, N-succinimide-3-maleimide benzoic ether, N-succinimide-4-maleimide butyric ester, N-succinimide-6-maleimide capronate, N-succinimide-3-maleimide propionic ester, N-(9-acridinyl) maleimide etc.
As above-mentioned unsaturated aromatics, for example can enumerate styrene, AMS, a methyl styrene, p-methylstyrene, vinyltoluene, to methoxy styrene etc.
As above-mentioned conjugated diolefine, can enumerate for example 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene etc.
As the above-mentioned unsaturated compound that contains the tetrahydrofuran skeleton, for example can enumerate (methyl) acrylic acid tetrahydrofuran ester, 2-methacryloxy-propionic acid tetrahydrofuran ester, 3-(methyl) acryloyl group tetrahydrofuran-2-ketone etc.
As the above-mentioned unsaturated compound that contains the furans skeleton, for example can enumerate that 2-methyl-5-(3-furyl)-1-defends-3-ketone, (methyl) acrylic acid furans ester, 1-furans-2-butyl-3-alkene-2-ketone, 1-furans-2-butyl-3-methoxyl-3-alkene-2-ketone, 6-(2-furyl)-2-methyl isophthalic acid-hexene-3-one, 6-furans-2-base-oneself-1-alkene-3-ketone, acrylic acid-2-furans-2-base-1-methyl-ethyl ester, 6-(2-furyl)-6-methyl isophthalic acid-heptan-3-alkene etc.
As the above-mentioned unsaturated compound that contains the oxinane skeleton; Can enumerate for example methacrylic acid (oxinane-2-yl) methyl esters, 2,6-dimethyl-8-(oxinane-2-base oxygen base)-Xin-1-alkene-3-ketone, 2-methacrylic acid oxinane-2-ester, 1-(oxinane-2-oxygen base)-butyl-3-alkene-2-ketone etc.
As the above-mentioned unsaturated compound that contains the pyrans skeleton, can enumerate for example 4-(1,4-dioxa-5-oxo-6-heptenyl)-6-methyl-2-pyrans, 4-(1,5-dioxa-6-oxo-octenyl)-6-methyl-2-pyrans etc.
As unsaturated compound, can enumerate for example single (methyl) acrylic ester of polyglycol (n=2～10), single (methyl) acrylic ester of polypropylene glycol (n=2～10) etc. with following formula (2) expression skeleton.
As the unsaturated compound that contains phenol property hydroxyl of following formula (3) expression, can enumerate the compound of following formula (4)～(8) expression etc.
In following formula (4), q is 1～3 integer.R 2～R 7Identical with following formula (3) definition.
Figure BSA00000558049100132
In following formula (5), R 2～R 7Identical with following formula (3) definition.
Figure BSA00000558049100141
In following formula (6), r is 1～3 integer.R 2～R 7Identical with following formula (3) definition.
Figure BSA00000558049100142
In following formula (7), R 2～R 7Identical with following formula (3) definition.
Figure BSA00000558049100143
In following formula (8), R 2～R 7Identical with following formula (3) definition.
As other unsaturated compounds, can enumerate for example vinyl cyanide, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic amide, Methacrylamide, vinyl acetate etc.
In these (A3) compounds; Preferable methyl acrylic acid chain-like alkyl ester, methacrylic acid cyclic alkyl ester, maleimide compound, have the unsaturated compound of the skeleton of tetrahydrofuran skeleton, furans skeleton, oxinane skeleton, pyrans skeleton, following formula (2) expression, the unsaturated compound with phenol property hydroxyl, unsaturated aromatics, the acrylic acid cyclic alkyl ester of following formula (3) expression; From copolyreaction property with to the deliquescent viewpoint of aqueous alkali, more preferably styrene, methacrylic acid tertiary butyl ester, methacrylic acid dodecyl ester, three ring [5.2.1.0 2.6] last of the ten Heavenly stems-8-ylmethyl acrylic ester, to single (methyl) acrylic ester of methoxy styrene, 2-methylcyclohexyl acrylic ester, N-phenylmaleimide, N-cyclohexyl maleimide, tetrahydrofuran (methyl) acrylic ester, polyglycol (n=2～10), 3-(methyl) acryloxy tetrahydrofuran-2-copper, 4-hydroxybenzyl (methyl) acrylic ester, 4-hydroxy phenyl (methyl) acrylic ester, a hydroxy styrenes, para hydroxybenzene ethene, Alpha-Methyl-para hydroxybenzene ethene.
As proportional in [A] alkali soluble resin,, be preferably 10mol%～80mol% with respect to the entire infrastructure unit from containing of (A3) compound structure unit.Proportional for 10mol%～80mol% through making from containing of (A3) compound structure unit, thus the radiation sensitive resin composition of solvent resistance excellence of the solidfied material of development property and formation can be obtained.
As the weight-average molecular weight (Mw) of [A] alkali soluble resin, more preferably 2 * 10 3～1 * 10 5, more preferably 5 * 10 3～5 * 10 4Through the Mw that makes [A] alkali soluble resin is 2 * 10 3～1 * 10 5Thereby, can improve the susceptibility and the development property of this radiation sensitive resin composition.In addition, Mw in this instructions and number-average molecular weight (Mn) are to measure through the gel permeation chromatography (GPC) according to following condition.
Device: GPC-101 (clear and electrician society)
Post: combine GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804
Mobile phase: tetrahydrofuran
Column temperature: 40 ℃
Flow velocity: 1.0mL/ branch
Sample solution concentration: 1.0 quality %
Sample injection rate IR: 100 μ L
Detecting device: differential refractometer
Standard substance: monodisperse polystyrene
As the solvent that uses in the polyreaction that is used for making [A] alkali soluble resin, can enumerate for example alcohol, glycol ethers, monoethylene glycol alkyl ether acetic acid esters, diethylene glycol monoalky lether, diethylene glycol dialkyl ether, DPG dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, propylene-glycol monoalky lether propionic ester, ketone, ester etc.
As alcohol, can enumerate for example benzylalcohol etc.;
As glycol ethers, can enumerate for example glycol monoethyl ether, ethylene glycol monoethyl ether etc.;
As monoethylene glycol alkyl ether acetic acid esters, can enumerate for example ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetic acid esters etc.;
As the diethylene glycol monoalky lether, can enumerate for example diethylene glycol monomethyl ether, diethylene glycol monoethyl ether etc.;
As diethylene glycol dialkyl ether, can enumerate for example diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether etc.
As the DPG dialkyl ether, can enumerate for example DPG dimethyl ether, DPG diethyl ether, DPG ethyl-methyl ether etc.;
As propylene-glycol monoalky lether, can enumerate for example propylene glycol monomethyl ether, propylene-glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether etc.;
As propylene glycol alkyl ether acetic acid ester, can enumerate for example propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters etc.;
As the propylene-glycol monoalky lether propionic ester, can enumerate for example propylene glycol monomethyl ether acetate, propylene-glycol ethyl ether propionic ester, propylene glycol propyl ether propionic ester etc.;
As ketone, can enumerate for example MEK, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, methyl isoamyl ketone etc.;
As ester, can enumerate for example ethyl acetate, butyl acetate, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate, glycolic acid butyl ester, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 2-ethoxyl ethyl propionate, 2-ethoxy-c propyl propionate, 2-ethoxy-c acid butyl ester, 2-butoxy methyl propionate, 2-butoxy ethyl propionate, 2-butoxy propyl propionate, 2-butoxy butyl propionate, 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-ethoxy-c propyl propionate, 3-ethoxy-c acid butyl ester, 3-propoxyl group methyl propionate etc.
In these solvents; Preferred monoethylene glycol alkyl ether acetic acid esters, diethylene glycol monoalky lether, diethylene glycol dialkyl ether, propylene-glycol monoalky lether, propylene glycol alkyl ether acetic acid ester, more preferably diethylene glycol dimethyl ether, diethylene glycol ethyl-methyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate.
Polymerization initiator as using in the polyreaction that is used for making [A] alkali soluble resin can use usually as the radical polymerization initiator known substances.As radical polymerization initiator, for example can enumerate 2,2 '-azoisobutyronitrile, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo-compounds such as (4-methoxyl-2,4-methyl pentane nitriles); Benzoyl peroxide, lauroyl peroxide, tert-butyl hydroperoxide valerate, 1, organic peroxide and hydrogen peroxide such as 1 '-two-(tert-butyl hydroperoxide) cyclohexanes.Using under the situation of superoxide as radical polymerization initiator, superoxide also uses as reductive agent, forms the oxidation-reduction type initiating agent.
In the polyreaction that is used for making [A] alkali soluble resin,, can use molecular weight adjustment agent in order to adjust molecular weight.As molecular weight adjustment agent, can enumerate for example halogenated hydrocarbon such as chloroform, carbon tetrabromide; Thio-alcohols such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, uncle's lauryl mercaptan, sulfo-two alkyd; Xanthan classes such as dimethyl xanthan thioether, diisopropyl xanthan disulfide; Terpinolene, α-Jia Jibenyixierjuwu etc.
< [B] polymerizable compound >
As [B] polymerizable compound contained in this radiation sensitive resin composition; So long as have the polymerizable compound of ethene property unsaturated link; Just there is not special qualification; Can enumerate for example ω-carboxyl polycaprolactam list (methyl) acrylic ester, monoethylene glycol (methyl) acrylic ester, 1; 6-hexanediol two (methyl) acrylic ester, 1; 9-nonanediol two (methyl) acrylic ester, TEG two (methyl) acrylic ester, polyglycol two (methyl) acrylic ester, polypropylene glycol two (methyl) acrylic ester, two phenoxetol fluorenes two (methyl) acrylic ester, dihydroxymethyl tristane two (methyl) acrylic ester, 2-hydroxyl-3-(methyl) acryloxy propyl methyl acid esters, 2-(2 '-ethyleneoxy ethoxy) ethyl (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, three (2-(methyl) acryloxy ethyl) phosphate, oxirane modification pentaerythrite six acrylic ester, succinic acid modification pentaerythritol triacrylate etc.; In addition; Can also enumerate and have straight-chain alkyl-sub-and ester ring type structure; And compound with 2 above NCOs; With the hydroxyl that in molecule, has more than 1, and has polyurethane (methyl) acrylate compounds that the compound reaction of 3～5 (methyl) acryloxies obtains etc.
As the commercially available article of [B] polymerizable compound, for example can enumerate,
ア ロ ニ Star Network ス M-400; ア ロ ニ Star Network ス M-402; ア ロ ニ Star Network ス M-405; ア ロ ニ Star Network ス M-450; ア ロ ニ Star Network ス M-1310; ア ロ ニ Star Network ス M-1600; ア ロ ニ Star Network ス M-1960; ア ロ ニ Star Network ス M-7100; ア ロ ニ Star Network ス M-8030; ア ロ ニ Star Network ス M-8060; ア ロ ニ Star Network ス M-8100; ア ロ ニ Star Network ス M-8530; ア ロ ニ Star Network ス M-8560; ア ロ ニ Star Network ス M-9050; ア ロ ニ Star Network ス TO-1450; ア ロ ニ Star Network ス TO-1382 (above is that society is synthesized in East Asia);
KAYARAD DPHA, KAYARADDPCA-20, KAYARADDPCA-30, KAYARADDPCA-60, KAYARADDPCA-120, KAYARADMAX-3510 (above be Japanese chemical drug society);
PVC ス コ one ト 295, PVC ス コ one ト 300, PVC ス コ one ト 360, PVC ス コ one ト GPT, PVC ス コ one ト 3PA, PVC ス コ one ト 400 (above is Osaka organic chemistry industry society);
As ウ レ タ Application ア Network リ レ one ト based compound, can enumerate ニ ユ one Off ロ Application テ イ ア R-1150 (first industrial pharmacy society);
KAYARAD DPHA-40H, UX-5000 (above be Japanese chemical drug society);
UN-9000H (industrial society on the root);
ア ロ ニ Star Network ス M-5300, ア ロ ニ Star Network ス M-5600, ア ロ ニ Star Network ス M-5700, M-210, ア ロ ニ Star Network ス M-220, ア ロ ニ Star Network ス M-240, ア ロ ニ Star Network ス M-270, ア ロ ニ Star Network ス M-6200, ア ロ ニ Star Network ス M-305, ア ロ ニ Star Network ス M-309, ア ロ ニ Star Network ス M-310, ア ロ ニ Star Network ス M-315 (above is that society is synthesized in East Asia);
KAYARAD HDDA, KAYARAD HX-220, KAYARADHX-620, KAYARADR-526, KAYARADR-167, KAYARADR-604, KAYARADR-684, KAYARADR-551, KAYARADR-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above be Japanese chemical drug society);
ア one ト レ ジ Application UN-9000PEP, ア one ト レ ジ Application UN-9200A, ア one ト レ ジ Application UN-7600, ア one ト レ ジ Application UN-333, ア one ト レ ジ Application UN-1003, ア one ト レ ジ Application UN-1255, ア one ト レ ジ Application UN-6060PTM, ア one ト レ ジ Application UN-6060P (above is industrial society on the root);
SH-500B PVC ス コ one ト 260, PVC ス コ one ト 312, PVC ス コ one ト 335HP (above is Osaka organic chemistry industry society) etc.
[B] polymerizable compound can use separately, or two or more mixing are used.As the content of [B] polymerizable compound in this radiation sensitive resin composition,, be preferably 20 mass parts～200 mass parts, more preferably 40 mass parts～160 mass parts with respect to 100 quality branch [A] alkali soluble resins.Through making containing of [B] polymerizable compound proportional in above-mentioned particular range, thereby the adhesiveness that can obtain this radiation sensitive resin composition and substrate is excellent, under low exposure, also has the cured film of enough hardness.
< [C] radiation-sensitive polymerization initiator >
[C] radiation-sensitive polymerization initiator contained in this radiation sensitive resin composition is to respond to radioactive ray, produces the composition of the spike of the polymerization that causes [B] polymerizable compound.As this [C] radiation-sensitive polymerization initiator, can enumerate O-acyl group oxime compound, acetophenone compound, double imidazole compound etc.In addition, [C] radiation-sensitive polymerization initiator can be with two or more couplings.
As O-acyl group oxime compound; Can enumerate ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), 1-[9-ethyl-6-benzoyl-9H-carbazole-3-yl]-octane-1-ketoxime-O-acetic acid esters, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-ethane-1-ketoxime-O-acetic acid esters, 1-[9-normal-butyl-6-(2-ethylamino benzonitrile acyl group)-9H-carbazole-3-yl]-ethane-1-ketoxime-O-benzoic ether, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-THP trtrahydropyranyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9H-carbazole-3-yl]-1-(O-acetyl oxime) etc.Wherein, Preferred ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuran base benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) or ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2; 2-dimethyl-1, the 3-dioxolanyl) the methoxybenzoyl base }-9H-carbazole-3-yl]-1-(O-acetyl oxime).
As acetophenone compound, can enumerate for example alpha-amido ketonic compound, alpha-hydroxyacetone compounds.
As the alpha-amido ketonic compound, can enumerate 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholine third-1-ketone etc.
As alpha-hydroxyacetone compounds, can enumerate 1-phenyl-2-hydroxy-2-methyl third-1-ketone, 1-(4-isopropyl phenyl)-2-hydroxy-2-methyl third-1-ketone, 4-(2-hydroxyl-oxethyl) phenyl-(2-hydroxyl-2-propyl group) ketone, 1-hydroxycyclohexylphenylketone etc.
In these acetophenone compounds, preferred alpha-amido ketonic compound, more preferably 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone, 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholine-4-base-phenyl)-Ding-1-ketone.
As double imidazole compound, can enumerate for example 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-four (4-ethoxy carbonyl phenyl)-1,2 '-two imidazoles, 2; 2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, 2,2 '-two (2; 4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, 2,2 '-two (2; 4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles etc.Wherein, preferred 2,2 '-two (2-chlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, 2; 2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, 2,2 '-two (2; 4,6-trichlorobenzene base)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles, more preferably 2; 2 '-two (2,4-dichloro-phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-two imidazoles.
As the commercially available article of [C] radiation-sensitive polymerization initiator, can enumerate for example 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholine third-1-ketone (イ Le ガ キ ユ ア 907), 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morpholinyl phenyl)-Ding-1-ketone (イ Le ガ キ ユ ア 379), ethane-1-[9-ethyl-6-(2-toluyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (イ Le ガ キ ユ ア OXE02) (above is チ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ society) etc.
Content as [C] radiation-sensitive polymerization initiator in this radiation sensitive resin composition with respect to 100 mass parts [A] alkali soluble resin, is preferably 1 mass parts～40 mass parts, more preferably 5 mass parts～30 mass parts.Through making containing of [C] radiation-sensitive polymerization initiator proportional is 1 mass parts～40 mass parts, thereby has high rigidity and adhering cured film even this radiation sensitive resin composition under the situation of low exposure, still can form.
< [D] compound >
[D] compound is the compound of following formula (1) expression, as [D] compound, so long as the compound of following formula (1) expression does not just have special qualification, is preferably the compound that can form amidine salt with [E] compound.This radiation sensitive resin composition is through containing [D] compound and [E] compound, thereby the storage stability of this radiation-ray sensitive composition and the curing promotion of the cured film under the low-temperature bake are maintained on the high level.
[D] compound is the compound of following formula (1) expression.In following formula (1), m is 2～6 integer.The part of the hydrogen atom that wherein, alkylidene has in the formula (1) or whole choosing wantonly are replaced by organic group.
As the compound of following formula (1) expression, for example can enumerate 1,5-diazabicyclo [4,3,0]-nonene-5 (DBN), 1; 5-diazabicyclo [4,4,0]-nonene-5,1,8-diazabicyclo [5; 4,0]-and hendecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5,4; 0]-and hendecene-7,5-dibutylamino-1,8-diazabicyclo [5,4,0]-hendecene-7 etc.Wherein, preferred DBN, DBU.
As above-mentioned organic group, can for example enumerate
Carbon numbers such as methyl, ethyl, isopropyl, normal-butyl, the tert-butyl group, n-hexyl are 1～6 alkyl;
Carbon numbers such as hydroxymethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxyl isopropyl, the 3-hydroxyl tert-butyl group, 6-hydroxyl hexyl are 1～6 hydroxy alkyl;
Carbon numbers such as dimethylamino, Methylethyl amino, diethylamino, diisopropylaminoethyl, dibutylamino, tert-butyl group methylamino, di-n-hexyl amino are 2～12 dialkyl amido etc.
< [E] compound >
[E] compound is the compound as organic acid or mineral acid.As [E] compound,, preferably can form the compound of amidine salt with [D] compound so long as organic acid or mineral acid just do not have special qualification.
As organic acid, can enumerate carboxylic acid, monoalkyl carbonic acid, aromatic hydroxy compound, sulfonic acid etc.
As carboxylic acid, can for example enumerate
Saturated fatty acids such as formic acid, acetate, 2 ethyl hexanoic acid, isovaleric acid;
Unsaturated carboxylic acids such as acrylic acid, crotonic acid, methacrylic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), fumaric acid, maleic acid, palmitoleic acid, oleic acid, linoleic acid, leukotrienes, octadecadienoic acid, parinaric acid, eicosatetraenoic acid, cinnamic acid, naphthoic acid, benzoic acid, toluic acid;
α substituted acetic acids such as chloracetic acid, aminoacetic acid, dichloro-acetate, three chloro acetate, trimethylace tonitric, fluoro acetate, monobromo-acetic acid, methoxyacetic acid, TGA, iodo acetate, vinyl acetic acid, oxo acetate, phenylacetic acid, phenoxyacetic acid;
Dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, azelaic acid, suberic acid, decanedioic acid;
Hydroxycarboxylic acids such as two alkyd, lactic acid, citric acid, d-tartrate, mesotartaric acid, ascorbic acid, mandelic acid;
Keto carboxylic acid such as pyruvic acid, laevulic acid;
Halogenated carboxylic acids such as 2-chloropropionic acid, 3-chloropropionic acid.
As monoalkyl carbonic acid, can enumerate for example methyl carbonic acid, ethyl carbonate etc.
As aromatic hydroxy compound, can enumerate for example phenol, cresols, naphthols etc.
As sulfonic acid, can enumerate for example octyl group benzene sulfonic acid, butyl benzene sulfonic acid, toluenesulfonic acid, benzene sulfonic acid, Loprazolam etc.
As mineral acid, can enumerate for example halogenated acids such as hydrochloric acid, hydrofluorite, hydrobromic acid; High hydracids such as carbonic acid, perchloric acid, hyperbromic acid etc.
As [E] compound; Preferred organic acid, more preferably carboxylic acid, aromatic hydroxy compound, sulfonic acid further are preferably saturated fatty acid, aromatic hydroxy compound, sulfonic acid; Preferred especially sulfonic acid, most preferably toluenesulfonic acid, Loprazolam, octyl group benzene sulfonic acid as strong acid.
< amidine salt >
In this radiation sensitive resin composition, part [D] compound forms amidine salt with [E] compound at least.If common amines and epoxy compound coexistence then in the preservation of composition solution, because amine can produce curing reaction to the nucleophillic attack of epoxy radicals, probably can damage the quality of product.Yet, in the present invention, through containing the amidine salt of ring-type ammonium salt, thereby in built-up section, even with the epoxy compound coexistence, storage stability is also good, is formed by composition and films, and when heating, can also fully play the effect of catalyzer.
Amidine salt is preferably sulphonate, is sulphonate through making amidine salt, thereby can further improve as the effect of curing catalysts point.As amidine salt, the salt of the salt of salt, DBN and the toluenesulfonic acid of the salt of DBU and toluenesulfonic acid, DBU and octyl group benzene sulfonic acid, DBN and octyl group benzene sulfonic acid more preferably.
Amidine salt can use separately, or uses two or more.Be pre-formed amidine salt; Be included under the situation in this radiation sensitive resin composition; Content as amidine salt in this radiation sensitive resin composition; With respect to 100 mass parts [A] alkali soluble resin, be preferably 0.01 mass parts～3 mass parts, more preferably 0.01 mass parts～1 mass parts.Content through making amidine salt in above-mentioned particular range, thereby can have the storage stability of this radiation sensitive resin composition and the curing facilitation of cured film simultaneously in simultaneously high-level.
< optional member >
This radiation-sensitive resin combination is except above-mentioned [A] alkali soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound and [E] the compound; In the scope of not damaging desired effects; As required, can also contain optional members such as bonding agent, surfactant, preserving stabilizer and heat-resisting improving agent.These optional members can use separately, also can two or more mixing be used.Below each optional member is described in detail.
[bonding agent]
Bonding agent can be used for further improving the cohesive of gained cured film and substrate.As this bonding agent; The functional silanes coupling agent that preferably has carboxyl, methacryl, vinyl, NCO, Oxyranyle isoreactivity functional group; Can enumerate for example trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-NCO propyl-triethoxysilicane, γ-glycidyl propyl trimethoxy silicane, β-(3,4-epoxy radicals cyclohexyl) ethyl trimethoxy silane etc.
As the use amount of bonding agent, with respect to 100 mass parts [A] alkali soluble resin, be preferably below 20 mass parts, more preferably below 15 mass parts.If the use amount of bonding agent surpasses 20 mass parts, then exist to be easy to generate the residual tendency of developing.
[surfactant]
Surfactant can be used for further improving the formation property of filming of radiation-ray sensitive composition.As surfactant, can enumerate for example fluorine class surfactant, polysiloxane-based surfactant and other surfactants.As above-mentioned fluorine class surfactant, preferred endways, arbitrary at least position of main chain and side chain has the compound of fluoro-alkyl and/or fluoro alkylidene, for example can enumerate 1,1,2,2-tetrafluoro-n-octyl (1; 1,2,2-tetrafluoro-n-pro-pyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, six ethylene glycol bisthioglycolates (1; 1,2,2,3,3-hexafluoro-n-pentyl) ether, eight ethylene glycol bisthioglycolates (1; 1,2,2-tetrafluoro-normal-butyl) ether, six propylene glycol two (1,1,2; 2,3,3-hexafluoro-n-pentyl) ether, eight propylene glycol two (1,1,2; 2-tetrafluoro-normal-butyl) ether, perfluor dodecyl sodium sulfonate, 1,1,2,2,3; 3-hexafluoro-n-decane, 1,1,2,2,8; 8,9,9,10,10-ten fluoro-n-dodecanes, fluoro-alkyl benzene sulfonic acid sodium salt, fluoro-alkyl sodium phosphate, fluoro-alkyl carboxylic acid sodium, two glycerine four (fluoro-alkyl polyoxyethylene ether), fluoro-alkyl ammonium iodide, fluoro-alkyl betaine, other fluoro-alkyl polyoxyethylene ethers, perfluoroalkyl poly oxyethanol, perfluoroalkyl alcoholates, carboxylic acid fluoroalkyl etc.
As the commercially available article of fluorine class surfactant, for example can enumerate BM-1000, BM-1100 (above be BM CHEMIE company), メ ガ Off ア Star Network F142D, メ ガ Off ア Star Network F172, メ ガ Off ア Star Network F173, メ ガ Off ア Star Network F183, メ ガ Off ア Star Network F178, メ ガ Off ア Star Network F191, メ ガ Off ア Star Network F471, メ side Off ア Star Network F476 (above for big Japanese ink chemical industrial company), Off ロ ラ one De FC-170C, Off ロ ラ one De FC-171, Off ロ ラ one De FC-430, Off ロ ラ one De FC-431 (above be Sumitomo ス リ one エ system company), サ one Off ロ Application S-112, サ one Off ロ Application S-113, サ one Off ロ Application S-131, サ one Off ロ Application S-141, サ one Off ロ Application S-145, サ one Off ロ Application S-382, サ one Off ロ Application SC-101, サ one Off ロ Application SC-102, サ one Off ロ Application SC-103, サ one Off ロ Application SC-104, サ one Off ロ Application SC-105, サ one Off ロ Application SC-106 (above be Asahi Glass company), エ Off ト Star プ EF301, エ Off ト Star プ EF303, エ Off ト Star プ EF352 (above change into company), Off タ one ジ エ Application ト FT-100, Off タ one ジ エ Application ト FT-110, Off タ one ジ エ Application ト FT-140A, Off タ one ジ エ Application ト FT-150, Off タ one ジ エ Application ト FT-250, Off タ one ジ エ Application ト FT-251, Off タ one ジ エ Application ト FT-300, Off タ one ジ エ Application ト FT-310, Off タ one ジ エ Application ト FT-400S, Off タ one ジ エ Application ト FTX-218, Off タ one ジ エ Application ト FTX-251 (above Wei ネ オ ス company) etc. for new autumn fields.
As the commercially available article of polysiloxane-based surfactant, for example can enumerate ト one レ シ リ コ one Application DC3PA, ト one レ シ リ コ one Application DC7PA, ト one レ シ リ コ one Application SH11PA, ト one レ シ リ コ one Application SH21PA, ト one レ シ リ コ one Application SH28PA, ト one レ シ リ コ one Application SH29PA, ト one レ シ リ コ one Application SH30PA, ト one レ シ リ コ one Application SH-190, ト one レ シ リ コ one Application SH-193, ト one レ シ リ コ one Application SZ-6032, ト one レ シ リ コ one Application SF-8428, ト one レ シ リ コ one Application DC-57, ト one レ シ リ コ one Application DC-190 (above for eastern レ ダ ウ コ one ニ Application グ シ リ コ one Application company), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (above be シ リ コ one Application company of GE Toshiba), organic siloxane polymer KP341 (chemical industrial company of SHIN-ETSU HANTOTAI) etc.
As other surfactant, can enumerate for example polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl acyl group ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ether such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether; Nonionic class surfactants such as polyoxyethylene dialkyls such as polyoxyethylene dilauryl ester, polyoxyethylene distearyl acyl group ester, (methyl) acrylic acid series copolymer Port リ Block ロ one No.57, Port リ Block ロ one No.95 (above is chemical company of common prosperity society) etc.
As the use amount of surfactant, with respect to 100 mass parts [A] alkali soluble resin, be preferably below 1.0 mass parts, more preferably below 0.8 mass parts.If the use amount of surfactant surpasses 1.0 mass parts, it is irregular then to be easy to generate film.
[preserving stabilizer]
As preserving stabilizer, can enumerate for example sulphur, quinones, hydroquinones, polyoxy compounds, amine, nitro nitroso compound etc., more particularly, can enumerate 4-metoxyphenol, N-nitroso--N-phenyl hydramine aluminium etc.
As the use amount of preserving stabilizer, with respect to 100 mass parts [A] alkali soluble resin, be preferably below 3.0 mass parts, more preferably below 1.0 mass parts.If the use amount of preserving stabilizer surpasses 3.0 mass parts, then the susceptibility of this radiation sensitive resin composition reduces, and pattern form is variation sometimes.
[thermotolerance improving agent]
As the thermotolerance improving agent, can enumerate for example N-(alkoxy methyl) glycol ureas compound, N-(alkoxy methyl) melamine compound etc.
As N-(alkoxy methyl) glycol ureas compound, can enumerate for example N, N ', N ", N " '-four (methoxy) glycol ureas, N; N ', N ", N " '-four (ethoxyl methyl) glycol ureas, N, N ', N "; N " '-four (n-propoxymethyl) glycol ureas, N, N ', N ", N " '-four (isopropoxy methyl) glycol ureas, N, N '; N ", N " and '-four (n-butoxy methyl) glycol ureas, N, N ', N ", N " '-four (tert-butoxy methyl) glycol ureas etc.Wherein, preferred N, N ', N ", N " and '-four (methoxy) glycol ureas.
As N-(alkoxy methyl) melamine compound, can enumerate for example N, N, N ', N ', N ", N "-six (methoxy) melamine, N, N; N ', N ', N ", N "-six (ethoxyl methyl) melamine, N, N, N ', N ', N "; N "-six (n-propoxymethyl) melamine, N, N, N ', N ', N ", N "-six (isopropoxy methyl) melamine, N, N, N '; N ', N ", N "-six (n-butoxy methyl) melamine, N, N, N ', N ', N ", N "-six (tert-butoxy methyl) melamine etc.Wherein, preferred N, N, N ', N ', N ", N "-six (methoxy) melamine, as commercially available article, for example can enumerate ニ カ ラ Star Network N-2702, ニ カ ラ Star Network MW-30M (more than be three with ケ ミ カ Le ズ company) etc.
As the use amount of thermotolerance improving agent, with respect to 100 mass parts [A] alkali soluble resin, be preferably below 50 mass parts, more preferably below 30 mass parts.If the use amount of thermotolerance improving agent surpasses 50 mass parts, then the susceptibility of this radiation sensitive resin composition reduces, and pattern form is variation sometimes.
< preparation method of radiation sensitive resin composition >
Radiation sensitive resin composition of the present invention is except mixing [A] alkali soluble resin, [B] polymerizable compound, [C] radiation-sensitive polymerization initiator, [D] compound and [E] the compound; Can also be as required; With the mixed of optional member, thereby prepare with regulation.This radiation sensitive resin composition can be mixed in the amidine salt that is formed by [D] compound and [E] compound in [A] alkali soluble resin, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator and prepares.Through above-mentioned operation, can make this radiation sensitive resin composition that contains amidine salt efficiently.
As the solvent that in the preparation of this radiation sensitive resin composition, uses, can use can be with each composition uniform dissolution or dispersion, but not can with the material of each composition reaction.As this solvent, can enumerate with the solvent that can be used for synthetic above-mentioned [A] alkali soluble resin the same material of illustrative material.Solvent can use separately, also can two or more mixing be used.
From the dissolubility of each composition, with non-reacted, the viewpoints such as easy property of filming and forming of each composition, can especially preferably use for example diethylene glycol monoethyl ether acetic acid esters, diethylene glycol diethyl ether, diethylene glycol ethyl-methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic acid esters, 3-methoxyl butylacetic acid ester, adnoral acetate, benzylalcohol, 3-methoxybutanol.
In addition, in order to improve the surface uniformity of above-mentioned solvent and thickness, can the coupling high boiling solvent.As high boiling solvent; Can enumerate for example N-Methyl pyrrolidone, DMAC N,N, benzylisoeugenol, hexyl ether, acetonyl acetone, 1-octanol, 1 nonyl alcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, dipropyl carbonate etc.Wherein, preferred N-Methyl pyrrolidone, gamma-butyrolacton or DMAC N,N.
As the solvent of this radiation sensitive resin composition, under the situation of coupling high boiling solvent,, be preferably below the 50 quality % with respect to whole quantity of solvent as its use amount, more preferably below the 40 quality %, be preferably especially below the 30 quality %.In the use amount of high boiling solvent is 50 quality % when following, and the film thickness uniformity of filming, susceptibility and residual film ratio are good.
Under situation with this radiation sensitive resin composition of prepare of solvent state; Solid component concentration (in composition solution shared solvent beyond composition) can be according to the value of application target or expectation thickness etc., sets concentration (for example 5～50 quality %) arbitrarily for.As preferred solid component concentration, different according to the formation method of filming on substrate, it is described in the back.The composition solution of preparation uses after using millipore filter about the 0.5 μ m of aperture etc. to filter thus.
< the formation method of cured film >
This radiation sensitive resin composition is preferred for forming the cured film as interlayer dielectric, diaphragm or pad, preferably contains in the present invention as the cured film of interlayer dielectric, diaphragm or pad.As the cured film of the interlayer dielectric that forms by this radiation sensitive resin composition, diaphragm or pad, excellent on compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention.
The formation method of cured film of the present invention has:
(1) this radiation sensitive resin composition of coating on substrate, the operation that formation is filmed,
The operation of at least a portion irradiation radioactive ray of (2) filming to above-mentioned,
(3) will shine above-mentioned radioactive ray the operation that is coated with film development and
(4) filming after the above-mentioned development carried out the operation of roasting.
Through formation method of the present invention, can form compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention excellent in curing film.Below, each operation is described in detail.
[operation (1)]
In this operation, on the one side of transparency carrier, form nesa coating, on this nesa coating, form filming of radiation sensitive resin composition.As transparency carrier, can enumerate glass substrates such as soda-lime glass, alkali-free glass; Resin substrate that constitutes by plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide etc.
As the nesa coating that on a face of transparency carrier, is provided with, can enumerate by tin oxide (SnO 2) constitute NESA film (registered trademark of U.S. PPG society), by indium oxide-tin oxide (In 2O 3-SnO 2) the ITO film that constitutes etc.
Forming through rubbing method under the situation of filming, behind the solution of this radiation sensitive resin composition of coating on the above-mentioned nesa coating, preferably coated face is being heated (prebake), filming thereby form.As the solid component concentration of the composition solution that in rubbing method, uses, be preferably 5 quality %～50 quality %, more preferably 10 quality %～40 quality % are preferably 15 quality %～35 quality % especially.As the coating process of this radiation sensitive resin composition, for example can adopting, spraying process, rolling method, method of spin coating (spin-coating method), slot coated method (slit die rubbing method), rod are coated with appropriate method such as method, ink-jet application method.In these coating processes, preferred especially spin-coating method or slot coated method.
As the condition of above-mentioned prebake, different according to the kind of each composition, blending ratio etc., be preferably under 70～120 ℃ and carry out about 1～15 minute.As the thickness of filming after the prebake, be preferably 0.5～10 μ m, more preferably about 1.0～7.0 μ m.
[operation (2)]
In this operation, at least a portion that formation is filmed is shone radioactive ray.At this moment, when only the part of coating being shone, can adopt the method for for example shining through mask with predetermined pattern.
As the radioactive ray that in irradiation, use, can enumerate luminous ray, ultraviolet ray, far ultraviolet etc.Wherein, the radioactive ray of optimal wavelength in 250～550nm scope more preferably comprise the ultraviolet radioactive ray of 365nm.
Radiation exposure amount (exposure) is preferably 100J/m with the value meter of the illumination among the wavelength 365nm that measures the radioactive ray that shine through illuminometer (OAI model 356, Optical Associates Inc. makes) 2～5000J/m 2, 200J/m more preferably 2～3000J/m 2
This radiation sensitive resin composition and known composition relatively susceptibility are high, though in above-mentioned radiation exposure amount at 850J/m 2Following situation also can access desirable thickness, good shape, the closely connected property of excellence and the cured film of high rigidity.
[operation (3)]
In this operation, through filming behind the radiation exposure developed, thereby remove unwanted part, form the pattern of regulation.As the developer solution that in development, uses, can use the for example WS of alkali compounds such as quaternary ammonium salt such as inorganic bases such as NaOH, potassium hydroxide, sodium carbonate, tetramethyl-ammonium oxyhydroxide, tetraethyl ammonium oxyhydroxide.In the WS of above-mentioned alkali compounds, can suitably add water-miscible organic solvent and/or surfactants such as methyl alcohol, ethanol.
As developing method, can be any of Sheng liquid method (revolve and cover immersion method), infusion process, shower method etc., development time preferably is about 10～180 seconds at normal temperatures.After development treatment, for example, air-dry with pressurized air or compressed nitrogen then with flowing water washing 30 seconds～90 seconds, thus the pattern of acquisition expectation.
[operation (4)]
In this operation, through suitable heating arrangements such as hot plate, baking ovens, filming of gained patterning carried out roasting (afterwards curing), thereby obtain cured film.As sintering temperature, be preferably below 200 ℃ more preferably 150 ℃～180 ℃.As roasting time, for example can enumerate and on hot plate, preferably carry out 5～30 minutes, in baking oven, preferably carried out 30～180 minutes.This radiation sensitive resin composition contains [D] compound and [E] compound as curing accelerator because as stated, therefore can realize low-temperature bake, is preferably used as the formation material of the middle cured film of using such as flexible display of expectation low-temperature bake.
< the formation method of color filter >
Color filter of the present invention has
This cured film with
In this cured film laminated, through the alignment films of aligning agent for liquid crystal formation.
Color filter of the present invention is excellent on thermotolerance, solvent resistance, voltage retention etc.
[operation (5)]
The formation method of color filter of the present invention has operation (1)～(4) and (5) the coating of liquid crystalline alignment agent on the filming of roasting of the formation method of above-mentioned this cured film, is heating below 200 ℃, thereby is forming the operation of alignment films.According to the formation method of this color filter, can form color filter with alignment films that liquid crystal aligning uses.
Above-mentioned aligning agent for liquid crystal is preferably the aligning agent for liquid crystal that comprises radiation-sensitive polymkeric substance with light orientation group (below, be also referred to as " [F] radiation-sensitive polymkeric substance "), or
The aligning agent for liquid crystal that comprises the polyimide that do not have light orientation group (below, be also referred to as " [G] polyimide ").
As the coating process of above-mentioned aligning agent for liquid crystal, preferred spraying process, rolling method, method of spin coating (spin-coating method), slot coated method (slit die rubbing method), rod are coated with appropriate method such as method, ink-jet application method.Wherein, preferred spin-coating method or slot coated are sent out.In addition, behind the coating of liquid crystalline alignment agent,, thereby can form alignment films through the heating coated face.Above-mentioned aligning agent for liquid crystal all can form alignment films under the heating-up temperature of low temperature (for example below 200 ℃).In addition, above-mentioned aligning agent for liquid crystal only otherwise damage effect of the present invention as optional member, can also contain for example hardening agent, curing catalysts, epoxy compound, functional silanes compound, surfactant, photosensitizing agent etc.Below, [F] radiation-sensitive polymkeric substance and [G] polyimide are described in detail.
< [F] radiation-sensitive polymkeric substance >
The light orientation group that [F] radiation-sensitive polymkeric substance has is can give anisotropic functional group to film through rayed, through photoisomerization reaction or light dimerization reaction, thereby gives anisotropy to film.As light orientation group, can enumerate the group that has from the structure of at least a kind of compound in the group that is selected from azobenzene, talan, alpha-imino-'beta '-ketoester, spiro-pyrans 、 Luo oxazine, cinnamic acid, chalcone, stibazole, benzylidene phthalimide, cumarin, tolane (ジ Off エ ニ Le ア セ リ レ Application) and anthracene formation.As light orientation group, preferably has structure from cinnamic acid.
As [F] radiation-sensitive polymkeric substance, preferred light orientation group directly or the polymkeric substance through the linking group bonding.As this [F] radiation-sensitive polymkeric substance, can enumerate for example polymkeric substance of bonding light orientation group etc. in polymkeric substance such as polyamic acid, polyimide.In addition, as [F] radiation-sensitive polymkeric substance, can enumerate have polyamic acid, polyimide and other polymkeric substance, these other polymkeric substance are the material with light orientation group.As the basic framework of other polymkeric substance, can for example enumerate and gather (methyl) acrylic ester, gather (methyl) acrylic amide, polyvinylether, gather fluorenes, polysiloxane etc.
As [F] radiation-sensitive polymkeric substance, be the polymkeric substance of basic framework preferably with polyamic acid, polyimide, polysiloxane.More preferably polysiloxane.[F] radiation-sensitive polymkeric substance can be synthetic through the method for for example WO2009/025386A1 record.
< [G] polyimide >
Do not have [G] polyimide of light orientation group can be, carry out imidizate and synthesize through will there not being the polyamic acid dehydration closed-loop of light orientation group.Above-mentioned polyamic acid can be according to the method for the record of TOHKEMY 2010-97188 communique for example, makes tetracarboxylic dianhydride and diamine reactant and synthesizes.
[G] polyimide can be the complete imidizate thing of whole amic acid structure dehydration closed-loops that the polyamic acid as precursor is had; Also can be only with part amic acid structure dehydration closed-loop, the part imidizate thing that makes amic acid structure and imide ring structure and deposit.Imidizate rate as [G] polyimide is preferably more than 30%, and more preferably 50%～99%, be preferably 65%～99% especially.The imidizate rate accounts for the quantity of imide ring structure the ratio of summation of quantity of quantity and imide ring structure of the amic acid structure of polyimide, representes with number percent.
Color filter with the cured film that has formed the alignment films that liquid crystal aligning uses also preferably is contained among the present invention.This color filter is excellent on thermotolerance, solvent resistance, voltage retention etc.As forming the aligning agent for liquid crystal of this color filter, preferably contain [F] radiation-sensitive polymkeric substance with alignment films.
Embodiment
Below, describe the present invention based on embodiment, but in this embodiment, the present invention is not made determinate explanation.
< synthesizing of [A] alkali soluble resin >
[synthetic example 1]
In flask, add 7 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 200 mass parts diethylene glycol ethyl-methyl ethers with condenser pipe and stirrer.Then add 16 mass parts and encircle [5.2.1.0 as the GMA and 16 mass parts of (A2) compound as three of (A3) compound as methacrylic acid, 20 mass parts of (A1) compound 2.6] last of the ten Heavenly stems-8-ylmethyl acrylic ester, 38 mass parts methyl methacrylates and 10 mass parts styrene; Behind nitrogen replacement, slowly stir, and solution is warming up to 70 ℃; Keep this temperature to carry out polymerization in 4 hours; Thereby obtain to contain multipolymer (A-1) solution (solid component concentration=34.4 quality %, Mw=8000, Mw/Mn=2.3).In addition, solid component concentration is meant that copolymer quality accounts for the ratio of copolymer solution all-mass.
[synthetic example 2]
In flask, add 8 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 220 mass parts diethylene glycol ethyl-methyl ethers with condenser pipe and stirrer.Then add 20 mass parts as the methacrylic acid of (A1) compound, the GMA of 20 mass parts conduct (A2) compound, the positive Lauryl Ester of methacrylic acid and the 30 mass parts styrene of 30 mass parts conduct (A3) compound; Behind nitrogen replacement, slowly stir, and solution is warming up to 70 ℃; Keep this temperature to carry out polymerization in 5 hours; Thereby obtain to contain multipolymer (A-2) solution (solid component concentration=31.9 quality %, Mw=8000, Mw/Mn=2.3).
[synthetic example 3]
In flask, add 8 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 220 mass parts diethylene glycol ethyl-methyl ethers with condenser pipe and stirrer.Then add 20 mass parts and encircle [5.2.1.0 as GMA, 25 mass parts of (A2) compound as three of (A3) compound as methacrylic acid, 50 mass parts of (A1) compound 2.6] last of the ten Heavenly stems-8-ylmethyl acrylic ester and 5 mass parts styrene, behind nitrogen replacement, slowly stir; And solution is warming up to 70 ℃, keep this temperature to carry out polymerization in 5 hours, thereby obtain to contain the solution (solid component concentration=32.3 quality % of multipolymer (A-3); Mw=8000, Mw/Mn=2.3).
[synthetic example 4]
In flask, add 8 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile) and 220 mass parts diethylene glycol ethyl-methyl ethers with condenser pipe and stirrer.Then add 20 mass parts and encircle [5.2.1.0 as methacrylic acid 2-methyl ethylene oxidic ester, 25 mass parts of (A2) compound as three of (A3) compound as methacrylic acid, 50 mass parts of (A1) compound 2.6] last of the ten Heavenly stems-8-ylmethyl acrylic ester and 5 mass parts styrene, behind nitrogen replacement, slowly stir; And solution is warming up to 70 ℃, keep this temperature to carry out polymerization in 5 hours, thereby obtain to contain the solution (solid component concentration=32.3 quality % of multipolymer (A-4); Mw=8500, Mw/Mn=2.2).
< preparation of radiation sensitive resin composition >
The detailed composition of each that in the preparation of each radiation sensitive resin composition, use illustrates following.
< [B] polymerizable compound >
B-1:KAYARAD DPHA (Japanese chemical drug company)
B-2:KAYARAD DPHA-40H (Japanese chemical drug company)
B-3:KAYARAD DPEA-12 (Japanese chemical drug company)
< [C] radiation-sensitive polymerization initiator >
C-1:2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-Ding-1-ketone (イ Le ガ キ ユ ア 369, ヂ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company)
C-2:2-methyl isophthalic acid-(4-methyl sulfenyl phenyl)-2-morpholine third-1-ketone (イ Le ガ キ ユ ア 907, ヂ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company)
C-3: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-yl]-1-(O-acetyl oxime) (ヂ バ ス ペ シ ヤ Le テ イ one ケ ミ カ Le ズ company, イ Le ガ キ ユ ア OX02)
[D] compound
D-1:1,5-diazabicyclo [4.3.0]-nonene-5
D-2:1,8-diazabicyclo [5.4.0]-hendecene-7
< [E] compound >
E-1: toluenesulfonic acid
E-2: carboxylic acid
< amidine salt >
As the H-1～H-3 of amidine salt shown in following, be respectively the salt that forms by above-mentioned [D] compound and [E] compound.
The toluene sulfonate of H-1:D-1
The toluene sulfonate of H-2:D-2
The carboxylate of H-3:D-2
H-1: triethylamine
[embodiment 1～14 and synthetic example 5～7]
Each composition of kind shown in the table 1, content is mixed, in propylene glycol methyl ether acetate, dissolve, making solid component concentration is 30 quality %, through the micro-pore-film filtration with aperture 0.5 μ m, prepares each radiation sensitive resin composition.Again, this composition is not used in the expression of "-" in the table 1.The mensuration result of the viscosity (mPas) of each radiation sensitive resin composition under 25 ℃ also is shown in addition, in the lump.
Table 1
Figure BSA00000558049100381
< evaluation >
Use each radiation sensitive resin composition of preparation,, carry out following evaluation like following formation cured film.The result is shown in the table 2.
< formation of cured film >
Use each radiation sensitive resin composition of record in the table 2, form cured film respectively, as the cured film of embodiment 1～14 and comparative example 1～9 according to sintering temperature and the roasting time put down in writing in the table 2.Below, the formation of cured film is described in detail.
On alkali-free glass substrate, be coated with each radiation sensitive resin composition solution of table 2 record respectively through spinner, then under 85 ℃, with hot plate prebake 2 minutes, thus the filming of formation thickness 3.50 μ m.Then, in gained is filmed on, through having the photomask that diameter is the round shape residual pattern of 13 μ m, 250 μ m make public with exposing clearance.Then,, develop down, used pure water drip washing afterwards 1 minute at 25 ℃ with the potassium hydroxide aqueous solution of 0.05 quality % (1.5wt%CD150CR).In baking oven, carry out roasting again, thereby form pad through the sintering temperature and the roasting time of table 2 record.Do not make public, operate equally with forming pad afterwards,, form other cured film through development, roasting through mask.This cured film can be used as diaphragm, interlayer dielectric is estimated.
[susceptibility (J/m 2)]
The residual film ratio that is expressed from the next is estimated susceptibility (J/m 2).
Residual film ratio (%)=(thickness after the thickness/exposure after the roasting) * 100
With this residual film ratio is that exposure more than 90% is as susceptibility.In exposure is 850J/m 2Under the following situation, judge that susceptibility is good.
[development property (second)]
After development, being determined at unexposed portion does not have residue (residual development), forms the shortest development time (second) of pattern, as development property.Judge that development time is short more, development property is just good more.
[compression property]
Carrying out and the same operation of above-mentioned susceptibility evaluation, is that exposure more than 90% forms the residual pattern of ball shape on substrate with residual film ratio.In Off イ Star シ ヤ one ス コ one プ H100C (Off イ Star シ ヤ one イ Application ス ト Le メ Application Star company), use the plane of 50 μ m square shapes to press son, the load through 50mN carries out compression test, measures compress variation.As compression property, be under the situation below the 0.5 μ m in the value of compress variation, can be referred to as the pattern-like film is high rigidity, thinks that therefore compression property is " A " (being judged as good).Value at compress variation surpasses under the situation of 0.5 μ m, thinks that compression property is " B " (being judged as not good).
< formation of cured film >
On the polysiloxane substrate, use spinner, be coated with radiation sensitive resin composition (S-1)～(S-14) and (CS-1)～(CS-3) respectively, afterwards, 90 ℃ down with hot plate prebake 2 minutes, thereby the filming of formation thickness 3.0 μ m.(Canon Inc. MPA-600FA), is 9000J/m with the accumulative total exposure to use exposure machine 2Make public, this substrate in the cleaning baking oven, is carried out roasting through the sintering temperature and the roasting time of table 2 record, thereby form cured film.
[thermotolerance (%)]
Cured film again in baking oven, 180 ℃ of heating 30 minutes down, is measured the Thickness Variation before and after the heating.The rate of change of representing with following formula (%) is as thermotolerance.
Rate of change (%)=(append the thickness/roasting of heating back after thickness) * 100
At rate of change is under the situation more than 96%, judges that thermotolerance is good.
[relative dielectric constant (%)]
On the SUS substrate, to carry out forming same operation with above-mentioned cured film, formation is filmed, and then through vapour deposition method, on this cured film, forms the Pt/Pd electrode pattern, processes specific inductive capacity mensuration and uses sample.Have on the substrate of electrode pattern at this, use HP16451B electrode and HP4284A プ レ シ ジ ヨ Application LCR meter (above be Yokogawa ヒ ユ one レ Star ト パ Star カ one De company), under frequency number 10kHz, measure relative dielectric constant (%) through the CV method.
[solvent resistance (%)]
In the formation of above-mentioned cured film,, be 3000J/m with the accumulative total exposure except through mercury vapor lamp 2Beyond irradiation ultraviolet radiation makes public, operate equally, obtain cured film.Measure the thickness (T1) of gained cured film.Then, the siloxane substrate that forms this cured film was controlled to be in 70 ℃ the dimethyl sulfoxide (DMSO) dipping 20 minutes in temperature, measures the thickness (t1) of this cured film then, go out the Thickness Variation rate (%) that dipping causes by computes, as solvent resistance.In the Thickness Variation rate is under the situation below 5%, judges that solvent resistance is good.
Thickness Variation rate (%)=(t1-T1)/T1} * 100
[hardness]
For the substrate that in above-mentioned solvent resistance evaluation, forms,, measure the hardness of cured film through the 8.4.1 pencil test of JIS K-5400-1990 with cured film.Under the situation more than the 3H, judge that hardness is good.
[voltage retention (%)]
Form the SiO that can prevent the sodion stripping from the teeth outwards 2Film, again on the soda glass substrate with regulation shape vapor deposition ITO (indium oxide-tin oxide alloy) electrode, the spin coating radiation sensitive resin composition, prebake 2 minutes in 90 ℃ cleaning baking oven forms filming of thickness 2.0 μ m then.Then, do not use photomask, adopt the radioactive ray of each wavelength that contains 365nm, 405nm and 436nm to filming, with 3000J/m 2Accumulative total exposure exposure make public.Then, adopt the tetramethylammonium hydroxide aqueous solution of 2.38 quality %,, develop according to infusion process 25 ℃, 80 seconds time.Cure according to described sintering temperature of table 2 and roasting time again, form cured film.Then, have on the substrate of this cured film, scatter the beaded glass pad of 5.5 μ m diameters after; With from the teeth outwards only according to the rules the soda-lime glass substrate of shape vapor deposition ITO electrode vacate liquid crystal injecting port with relative status, adopt the sealant of the beaded glass mixed 0.8mm to fit on four limits; Inject メ Le Network system liquid crystal (MLC6608); Then, the sealing liquid crystal injecting port prepares liquid crystal cell thus.Then in 60 ℃ thermostat layer, put into liquid crystal cell, measure the voltage retention (%) that system (VHR-1A type, Dongyang テ Network ニ カ company) measures liquid crystal cell through the liquid crystal voltage conservation rate.This moment apply the square ripple that voltage is 5.5V, the mensuration frequency number is 60Hz.Wherein so-called voltage retention is the value that following formula is calculated.The value of the voltage retention of liquid crystal cell is low more, and the possibility that liquid crystal panel when forming the not good situation that what is called " burns screen " is high more.On the one hand, the value of voltage retention is low more, and liquid crystal cell can't mean liquid crystal fully is orientated with applying the level that voltage remains on regulation in the time of 16.7 microseconds, causes the dangerous higher of image retention etc. " burning screen ".
Voltage retention (%)=(during through the liquid crystal cell potential difference (PD) after 16.7 milliseconds)/(applying the voltage after 0 millisecond) * 100 by benchmark
[storage stability (%)]
Carry out and the same operation of above-mentioned solvent resistance evaluation, form the cured film of the radiation sensitive resin composition solution after preparing, measure thickness (in following formula, being called " thickness after the preparation ").In addition, under 25 ℃, the solution of radiation sensitive resin composition was preserved 5 days, after 5 days, measured the thickness (in following formula, being called " thickness after 5 days ") of the same cured film that forms.Go out thickness increment rate (%) by computes.
Thickness increment rate (%)=(thickness after the thickness-preparation after 5 days)/(thickness after the preparation) * 100
In the thickness increment rate is under the situation below 2%, and the judgement storage stability is A (well).In the thickness increment rate is under the situation more than 3%, and the judgement storage stability is B (not good).
Table 2
Figure BSA00000558049100421
Figure BSA00000558049100431
Result by table 2 finds that this radiation sensitive resin composition has good susceptibility, development property and storage stability.In addition, the cured film that is formed by this radiation sensitive resin composition can not only form through the low-temperature bake below 200 ℃, and compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and voltage retention are also excellent.
Radiation sensitive resin composition of the present invention can easily form fine and exquisite pattern, has the low-temperature bake of storage stability and short time concurrently, and has enough susceptibilitys and development property.In addition, the cured film that is formed by this radiation sensitive resin composition is excellent aspect compression property, thermotolerance, relative dielectric constant, solvent resistance, hardness and the voltage retention.Therefore this radiation sensitive resin composition is preferably as middle formation materials that uses cured film such as interlayer dielectric, diaphragm, pad such as the flexible displays of expecting low-temperature bake.In addition, it is excellent at aspects such as thermotolerance, solvent resistance, voltage retention to have a color filter of this cured film that forms alignment films.

Claims (12)

1. radiation sensitive resin composition, it contains,
[A] alkali soluble resin, its through at least a kind of compound in the group that (A1) is selected from unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides and constitutes obtain with the unsaturated compound copolymerization that (A2) contains epoxy radicals,
[B] have ethene property unsaturated link polymerizable compound,
[C] radiation-sensitive polymerization initiator,
The compound of [D] following formula (1) expression and
[E] as the compound of organic acid or mineral acid,
Its viscosity under 25 ℃ is 1.0mPas～50mPas,
In formula (1), m is 2～6 integer, and wherein, the part or all of hydrogen atom that alkylidene had in the formula (1) is optional to be replaced by organic group.
2. radiation sensitive resin composition as claimed in claim 1, wherein, [C] radiation-sensitive polymerization initiator is an O-acyl group oxime compound.
3. radiation sensitive resin composition as claimed in claim 1, wherein, the mixed amidine salt that is formed by [D] compound and [E] compound prepares in [A] alkali soluble resin, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator.
4. radiation sensitive resin composition as claimed in claim 3, wherein, above-mentioned amidine salt is sulphonate.
5. like any described radiation sensitive resin composition of claim 1～4, it is used to form the cured film as interlayer dielectric, diaphragm or pad.
6. the manufacturing approach of a radiation sensitive resin composition; Wherein, The mixed amidine salt that is formed by [D] compound and [E] compound prepares in [A] alkali soluble resin, [B] polymerizable compound and [C] radiation-sensitive polymerization initiator, and the viscosity of said composition under 25 ℃ is 1.0mPas～50mPas.
7. cured film that forms by the described radiation sensitive resin composition of claim 5 as interlayer dielectric, diaphragm or pad.
8. color filter, the alignment films that it has the described cured film of claim 7 and forms in this cured film laminated, through aligning agent for liquid crystal.
9. color filter as claimed in claim 8, wherein, above-mentioned aligning agent for liquid crystal is the aligning agent for liquid crystal that comprises the radiation-sensitive polymkeric substance with light orientation group, or for comprising the aligning agent for liquid crystal of the polyimide that does not have light orientation group.
10. the formation method of a cured film, it has,
(1) the said radiation sensitive resin composition of coating claim 5 on substrate forms the operation of filming;
(2) operation of irradiation radioactive ray on above-mentioned at least a portion of filming;
(3) with the above-mentioned operation that is coated with film development of having shone radioactive ray; With
(4) filming of above-mentioned development carried out the operation of roasting.
11. the formation method of cured film as claimed in claim 10, wherein, the sintering temperature of above-mentioned operation (4) is below 200 ℃.
12. the formation method of a color filter, it has the described operation of claim 10 (1)～(4) and (5) coating of liquid crystalline alignment agent on filming after the roasting, through the operation that adds the thermosetting alignment films below 200 ℃.
CN2011102355584A 2010-08-10 2011-08-10 Radioactive Ray Sensitive Resin Composite, Solidification Film, Preparing Method Of Solidification Film, Color Filter And Preparing Method Of Color Filter Pending CN102375340A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
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CN105934478A (en) * 2014-01-29 2016-09-07 日立化成株式会社 Resin composition, method for manufacturing semiconductor device using resin composition, and solid-state imaging element
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CN117590695B (en) * 2023-11-29 2024-07-30 深圳市道尔顿电子材料股份有限公司 Low-temperature-curable negative photosensitive resin composition, hardening film and preparation method thereof

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