JP2002348357A - Photopolymerizable resin composition, cured product thereof and manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photopolymerizable resin composition highly sensitive to ultraviolet rays, a cured product excellent in heat resistance, exhibiting low shrinking properties and low water-absorbing properties, excellent in transparency to the visible light, having a high refractive index and excellent in water repellence, and its manufacturing method. SOLUTION: The photopolymerizable resin composition is comprised of (A) a fluorene derivative represented by formula (1), a polysilane represented by formula (2): (R<7> R<8> Si)x (R<9> Si)y (Si)z and (B) a photo acid-generating agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable resin composition used for a photocured coating film, a photoresist, a printing plate material, an optical thin film, etc., a cured product thereof, and a production method.

[0002]

2. Description of the Related Art Conventionally, a screen printing method has been employed as an image forming method for patterning a printed wiring board or the like. In the screen printing method, a pattern is directly printed on a substrate or the like with a resist ink, and it is difficult to form a fine pattern. Therefore, at present, the photographic method is mainly employed in order to meet the demand for miniaturization and higher precision of images.

In the photographic method, a photosensitive resin composition such as a photoresist is coated on a substrate or the like, and the photosensitive resin composition is exposed through a photomask using a low-pressure mercury lamp or the like as a light source. By developing with an appropriate developer,
This is a method of forming a desired pattern on a substrate or the like.
The photosensitive resin composition used in this photographic method has properties such as high photosensitivity and good developability in order to realize high resolution of an image, and the cured product has heat resistance, It is required to have properties such as low shrinkage, low water absorption, and chemical resistance.

In the development step of the photographic method, development with an alkaline aqueous solution is mainly employed without using an organic solvent for reasons such as environmental pollution. Need to have

[0005] As such a photosensitive resin composition developable with an aqueous alkali solution, an epoxy anhydride (meth) acrylate obtained by reacting an epoxy resin with (meth) acrylic acid is reacted with an acid anhydride to form a carboxyl group. Introduced carboxyl group-containing epoxy (meth) acrylates (JP-A-61-243869 and JP-A-63-25)
No. 8975), a photosensitive resin composition containing an epoxy resin, an alkali-soluble polymer having a phenolic hydroxyl group and a photoacid generator (JP-A-10-97068), a phenol resin, an epoxy resin and a photoacid generator. A photosensitive resin composition containing a carboxyl group in a phenol resin or an epoxy resin (Japanese Patent Application Laid-Open No.
No. 0-136230). However, these photosensitive resin compositions and any cured products are not sufficient in terms of the characteristics described above.

In recent years, materials for use in optical thin films such as a high refractive index layer of an antireflection film used for a liquid crystal display and a reflector have been developed. These materials are desired to have excellent transparency of visible light and to have a high refractive index. Also, when using the high refractive index layer of the anti-reflection film as the outermost layer, in order to have a surface antifouling function,
It is desirable that the material has good water repellency. However, among photosensitive resin compositions having good productivity, a material having excellent transparency in visible light, a sufficient refractive index, and good water repellency has not yet been developed.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a photopolymerizable resin composition having high sensitivity to ultraviolet light. Another object of the present invention is to provide a cured product of the photopolymerizable resin composition, which has excellent heat resistance, low dimensional stability due to low shrinkage, and low humidity due to low water absorption. An object of the present invention is to provide a cured product which is hardly affected by change, has excellent transparency to visible light, has a high refractive index, and has good water repellency, and a method for producing the same.

[0008]

The present invention provides (A) a fluorene derivative represented by the following formula (1), (B) a photoacid generator, and (C) a compound represented by the following formula (2). A photopolymerizable resin composition comprising:

[0009]

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In the formula (1), R ^{1 to} R ⁴ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^{1 to} R ⁴ may be all the same or two or more may be different. R
⁵ and R ⁶ represent a hydrogen atom or a methyl group. R ⁵ and R ⁶ may be the same or different. n
Represents an integer of 0 to 10.

(R ⁷ R ⁸ Si) _x (R ⁹ Si) _y (Si) _z (2) In the formula (2), R ^{7 to} R ⁹ are a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl Group, aryl group,
Represents an alkoxyl group or a silyl group. R ^{7 to} R ⁹ may be all the same or two or more may be different. x, y and z each represent an integer of 0 or more;
The sum of x, y and z is 5-400.

Preferably, (A) 0.5 to 500 parts by weight of the fluorene derivative and (B) 0.1 to 0.5 parts by weight of the photoacid generator.
1 to 20 parts by weight, and (C) 100 parts by weight of the polysilane.

More preferably, (A) 1 to 100 parts by weight of the fluorene derivative and (B) 0.1 to 100 parts by weight of the photoacid generator.
5 to 10 parts by weight, (C) 100 parts by weight of the polysilane.

According to the present invention, the photopolymerizable resin composition comprises (A) a fluorene derivative represented by the general formula (1), (B) a photoacid generator, and (C) a photoacid generator. ), It can be developed with an aqueous alkali solution. Further, the cured product has excellent heat resistance, low water absorption and shrinkage, transparency in visible light, high refractive index, and good water repellency based on the fluorene skeleton and the polysilane structure.

Further, the present invention is a cured product of the photopolymerizable resin composition obtained by subjecting the photopolymerizable resin composition to a crosslinking reaction.

According to the present invention, the photopolymerizable resin composition undergoes a crosslinking reaction by irradiating or heating with ultraviolet light, and is cured to have excellent heat resistance and low water absorption. It is hardly affected, and has a small shrinkage, so that a cured product having excellent dimensional stability, transparency to visible light, high refractive index, and good water repellency can be provided. Such physical properties of the cured product, as a photo-crosslinking agent,
This is caused by using (A) a fluorene derivative having two epoxy groups represented by the general formula (1) and (C) polysilane represented by the general formula (2).

The present invention also provides (A) a fluorene derivative represented by the general formula (1), (B) a photoacid generator,
(C) a photopolymerizable resin composition preparing step of preparing a photopolymerizable resin composition containing the polysilane represented by the general formula (2), and irradiating the photopolymerizable resin composition with ultraviolet light. And a step of irradiating an ultraviolet light for a cross-linking reaction with the photopolymerizable resin composition.

Preferably, after the ultraviolet light irradiation step, a heating step of heating the photopolymerizable resin composition which has been subjected to a crosslinking reaction by irradiating ultraviolet light is further included.

According to the present invention, by irradiating the photopolymerizable resin composition with ultraviolet light, (B) cations are generated from the photoacid generator, and the cations are used as a catalyst to form (A)
A crosslinking reaction proceeds between the fluorene derivative and (C) the polysilane, whereby the photopolymerizable resin composition is cured. Further, by heating after irradiation with ultraviolet light, the crosslinking reaction of the photopolymerizable resin composition can be promoted.

The present invention also provides a coating step of applying the photopolymerizable resin composition on a substrate to form a coating film, and irradiating the coating film with ultraviolet light through a photomask. An ultraviolet light irradiation step of cross-linking the polymerizable resin composition, a development step of removing an ultraviolet light unexposed portion of the coating film, which is an ultraviolet light non-irradiation area where no ultraviolet light is irradiated by a photomask, and irradiation of ultraviolet light And a heating step of heating an ultraviolet light-exposed portion of the coating film, which is a region irradiated with ultraviolet light, in this order, to provide a cured method of the photopolymerizable resin composition. The developing step may be performed after the heating step. Further, the ultraviolet irradiation step and the heating step may be performed in parallel.

According to the present invention, particularly, a fine image of a printed wiring board or the like can be formed with high precision.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION A photopolymerizable resin composition according to one embodiment of the present invention comprises (A) a fluorene derivative represented by the following general formula (1) and (C) a fluorene derivative represented by the following general formula (2). And (B) a photoacid generator.

[0023]

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(R ⁷ R ⁸ Si) _x (R ⁹ Si) _y (Si) _z (2) The fluorene derivative (A) will be described below. In the general formula (1), R ^{1 to} R ⁴ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ^{1 to} R ⁴ may be all the same or two or more may be different. R ⁵ and R ⁶ represent a hydrogen atom or a methyl group.
R ⁵ and R ⁶ may be the same or different. n represents an integer of 0 to 10.

Examples of the alkyl group having 1 to 6 carbon atoms for R ^{1 to} R ⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group,
Examples include a pentyl group and a hexyl group.

Examples of the fluorene derivative (A) include bisphenol fluorenediic glycidyl ether represented by the following structural formula (3) (wherein R ^{1 to} R ⁴ are all hydrogen atoms and n is 0); And bisphenoxyethanol full orange glycidyl ether (R ^{1 to} R ⁶ are all hydrogen atoms and n is 1) represented by (4).

[0027]

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[0028]

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The fluorene derivative (A) can be synthesized by a known method (for example, JP-A-2-73823 and JP-A-10-36485). For example, the following general formula (5) [wherein, R ^{1 to} R ⁶ and n represent the same meaning as in the general formula (1). ]
By reacting a compound represented by the formula with epihalohydrin such as epichlorohydrin in the presence of an alkali metal hydroxide.

[0030]

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Hereinafter, the polysilane (C) will be described. In the general formula (2), R ^{7 to} R ⁹ represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl group, an alkoxyl group or a silyl group. R ^{7 to} R ⁹ may be all the same or two or more may be different. x, y and z are each 0
Represents the above integer, and the sum of x, y and z is 5 to 400.

The structure of the polysilane represented by the general formula (2) is composed of at least one of the structures represented by the following formulas (6) to (8). The combination of Expressions (6) to (8) may be any combination that satisfies the above-described conditions of x, y, and z. The arrangement of the structures represented by the formulas (6) to (8) is not particularly limited, and examples thereof include block shapes, random shapes, alternating shapes, graft shapes, and mixtures thereof.

[0033]

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[0034]

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[0035]

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The alkyl group of R ^{7 to} R ^9, the alkyl moiety of the arylalkyl group and the alkyl moiety of the alkoxyl group may be linear, cyclic or branched and have 1 to 1 carbon atoms.
4, preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

The alkenyl group represented by R ^{7 to} R ⁹ is a monovalent linear, cyclic or branched C 1-14 having at least one carbon-carbon double bond, preferably having 1 to 14 carbon atoms. 10, and more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms.

The aryl group of R ^{7 to} R ^{9 and} the aryl moiety of the arylalkyl group include an aromatic hydrocarbon group, preferably a phenyl group and a naphthyl group. Further, the aromatic hydrocarbon group may have one or more substituents. Such a substituent is not particularly limited, but is preferably selected from the group consisting of an alkyl group, an alkoxyl group, an amino group and a silyl group.

As the polysilane (C), polymethylphenylsilane represented by the following structural formula (9) (one of R ⁷ and R ⁸ is a methyl group, the other is a phenyl group, and y and z are Both are 0), polyphenylsilin represented by the following structural formula (10) (R ⁹ is a phenyl group, and x and z are both 0), and a copolymer of the above-mentioned polymethylphenylsilane and polyphenylcillin. A poly (methylphenylsilane) 0.5 (phenylsilin) 0.5 copolymer represented by the following structural formula (11), and a polydiphenylsilane (R ⁷ and R ⁸ are phenyl groups) represented by the following structural formula (12) , Y and z are both 0).

[0040]

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[0041]

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[0042]

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[0043]

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As the polysilane (C), those having one or more phenyl groups in R ^{7 to} R ⁹ are preferably used because the refractive index of the cured product of the photopolymerizable resin composition of the present invention is improved.

The polysilane (C) used in the present invention is preferably a polysilane in which at least one hydroxyl group is directly bonded to a terminal silicon atom of the polysilane, that is, a polysilane having at least one silanol group at a terminal. The hydroxyl group directly bonded to the silicon atom shows good reactivity with the epoxy group of the fluorene derivative, and a high-level crosslinked structure is formed between the fluorene derivative and the polysilane by irradiation with ultraviolet light or heating. Further, polysilane in which a phenol group is bonded to a terminal silicon atom may be used.

The content ratio of such a hydroxyl group is, on average, about 0.005 to 2.5, preferably about 0.01 to 2.3, more preferably about 0,0 per silicon atom. It is about .02 to about two.

The polysilane (C) can be manufactured by using a known method. For example, a polysilane can be produced by polymerizing a monomer having each structural unit as a raw material by the following method. That is, a method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal ("Kipping method" J. Am. Chem. Soc., 1
10, 124 (1988), Macromolecules, 23, 3423 (1990)), a method of dehalogenating polycondensation of halosilanes by electrode reduction (J. Chem. Soc., Chem. Commun., 1161 (1990), J. Chem. So
c., Chem. Commun., 897 (1992)), a method of dehalogenating polycondensation of halosilanes using magnesium as a reducing agent (International Publication No. WO 98/29476), a dehydrocondensation polymerization of hydrosilanes in the presence of a metal catalyst. Method (Japanese Unexamined Patent Application Publication No.
-334551), a method by anionic polymerization of disilene crosslinked with biphenyl or the like (Macromolecules, 2
3,4494 (1990)), and a method based on ring-opening polymerization of cyclic silanes.

The polysilane (C) having a hydroxyl group can also be produced by a known method. For example, in the above-described method of dehalogenating polycondensation of halosilanes in the presence of an alkali metal (Kipping method), the compound can be easily produced by adding water at the end of the polycondensation reaction.

The photoacid generator (B) will be described below. A conventionally known compound can be used for the photoacid generator (B). For example, onium salts, metallocene complexes and the like can be mentioned.

As the onium salt, diazonium salt, sulfur
Ruphonium salt, iodonium salt, phosphonium salt, selenium
And the like, and as these counter ions,
CF _ThreeSO_Three ^- , BF_Four ^- , PF₆ ^- , AsF₆ ^- , S
bF₆ ^- And the like.

Examples of the photoacid generator (B) include triphenylsulfonium triflate, 4-chlorobenzenediazonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, (4-
(Phenylthiophenyl) diphenylsulfonium hexafluoroantimonate, (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoroantimonate, bis [4- (diphenyl Sulfonio) phenyl] sulfide-bis-hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium hexafluoroantimonate, (4-methoxyphenyl) phenyliodonium hexafluoroantimonate, bis (4-t-
Butylphenyl) iodonium hexafluorophosphate, benzyltriphenylphosphonium hexafluoroantimonate, triphenyl selenium hexafluorophosphate, (eta ⁵ - isopropylbenzene)
(Η ⁵ -cyclopentadienyl) iron (II) hexafluorophosphate. These photoacid generators may be used alone or in combination of two or more.

The photopolymerizable resin composition may further contain an appropriate amount of a polymer having a functional group capable of reacting with an epoxy group as the fourth component (D). As such a polymer, any polymer having a functional group capable of reacting with an epoxy group, such as polyphenol and polyalkyl (meth) acrylate, can be used without particular limitation. Here, “functional groups that can react with epoxy groups” include not only functional groups that directly react with epoxy groups, but also those that react directly with epoxy groups by irradiation of acid generated from the photoacid generator (B) or ultraviolet light. And a functional group capable of forming a functional group.

The polyphenols include novolak type phenol resins, bisphenol resins, resole resins, homo- and copolymers of alkenyl phenols,
Examples include homopolymers and copolymers of N-hydroxyphenyl-maleimide.

Examples of the polyalkyl (meth) acrylate include poly (meth) acrylic acid and its alkyl ester. Examples of the alkyl group constituting the alkyl ester include a hydrocarbon group having 1 to 12 carbon atoms,
Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclohexyl, tricyclo [5.2.1.0
^2,6 ] decyl group, adamantyl group, norbornyl group, isobornyl group and the like.

The photopolymerizable resin composition contains not only the above components (A) to (C) and the fourth component (D) but also, if necessary, a pigment, a thickener, an antioxidant, and the like. Agent,
Known additives such as an antifoaming agent and a leveling agent may be added.

The photopolymerizable resin composition according to one embodiment of the present invention contains the components (A), (B) and (C), and if necessary, the components (D) and (C). Additive,
It is obtained by adding a solvent, a dispersant, and the like, and uniformly mixing them by dissolution, dispersion, mixing, kneading, and the like.

The components (A), (B) and (C) are mixed in a proportion of 0.5 to 500 parts by weight, based on 100 parts by weight of component (C). It is preferably 1 to 100 parts by weight, and the component (B) is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

The photopolymerizable resin composition having such a compounding ratio has high photosensitivity. In addition, the cured product obtained by irradiation with ultraviolet light or heating as described below has excellent heat resistance, is less susceptible to environmental changes such as humidity due to low water absorption, and has small dimensional stability due to a small shrinkage. Excellent,
It has visible light transparency, high refractive index and good water repellency.

On the other hand, when component (C) is 100 parts by weight and component (A) is less than 0.5 part by weight, sufficient crosslinking is not formed, and the heat resistance of the cured product is reduced. When the amount of the component (A) is more than 500 parts by weight, the refractive index of the cured product decreases, and it becomes impossible to obtain good water repellency.

When the component (C) is 100 parts by weight and the component (B) is less than 0.1 part by weight, the acid generated from the photoacid generator as the component (B) is small.
The curability of the photopolymerizable resin composition deteriorates. When the amount of the component (B) is more than 20 parts by weight, the developability of the photopolymerizable resin composition deteriorates.

Such a photopolymerizable resin composition is used, for example, for producing a thin film on a substrate. When applying a photopolymerizable resin composition to a substrate to form a coating film, the photopolymerizable resin composition may be applied to the substrate as it is, or the photopolymerizable resin composition may be dissolved or dispersed in a solvent and applied to the substrate. Is also good.

Examples of the solvent include 2-butanone, cyclohexanone, diglyme, diethylene glycol methyl ethyl ether, propylene glycol methyl acetate, propylene glycol monomethyl ether, tetrahydrofuran, dimethoxyethane and the like. These solvents may be used alone or in combination of two or more, and are used in an appropriate amount so as to obtain a coating solution viscosity suitable for coating.

The coating method includes flow coating, spin coating, spray coating,
Examples include a screen printing method, a casting method, a bar coating method, a curtain coating method, a roll coating method, a dip method, and a slit method.

The thickness of the coating varies depending on the use of the photopolymerizable resin composition according to one embodiment of the present invention.
The thickness is about 0.05 μm to 10 μm, about 10 μm to 5 mm when used for manufacturing a printed wiring board, and about 0.1 μm to 100 μm when used for manufacturing an optical thin film.

A cured product of the photopolymerizable resin composition according to another embodiment of the present invention is applied to the coating film prepared as described above.
It is obtained by irradiating ultraviolet light and further heating the coating film.

More specifically, when a coating film composed of a photopolymerizable resin composition containing a fluorene derivative (A), a polysilane (C) and a photoacid generator (B) is irradiated with ultraviolet light, photoacid generation occurs. The agent (B) is decomposed to generate an acid such as a Lewis acid or a Bronsted acid. This acid acts as a catalyst to cause a ring-opening addition reaction of the epoxy group of the fluorene derivative (A), and a cross-linking reaction with the epoxy group of another fluorene derivative (A) or the silanol group of the polysilane (C). It happens in three dimensions. Furthermore, by heating this coating film, a crosslinking reaction is promoted, and the coating film is cured,
A cured product of the photopolymerizable resin composition is obtained.

Further, by irradiating the polysilane (C) with ultraviolet light of a specific wavelength or heating at a high temperature of about 200 ° C. or more, a part of the Si—Si bond of the polysilane (C) is cut, and the cut end is cut. A cross-linking reaction occurs with the epoxy group of the fluorene derivative (A), and the curing of the coating film made of the photopolymerizable resin composition is accelerated.

Taking a specific example of polymethylphenylsilane, irradiation of ultraviolet light with a specific wavelength of about 335 nm or heating at a high temperature of about 200 ° C. or more causes Si—Si
A part of the bond is cleaved, and the cleaved end becomes a silicon radical. The silicon radical or a silanol group formed by the reaction of the silicon radical with moisture in the atmosphere causes a cross-linking reaction with the epoxy group of the fluorene derivative (A) to form a coating film composed of the photopolymerizable resin composition. Acceleration is accelerated.

By irradiating the coating film with ultraviolet light and heating as described above, a cured product of the photopolymerizable resin composition is obtained. This cured product is excellent in heat resistance, low in water absorption, is not easily affected by environmental changes such as humidity, and has small shrinkage, excellent dimensional stability, visible light transparency, high refractive index Yes, good water repellency.

The irradiation of the coating film with ultraviolet light includes a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a deuterium lamp, a halogen lamp, a helium-cadmium laser,
A light source such as an excimer laser can be used. The irradiation amount of the ultraviolet light varies depending on the thickness of the coating film, but is preferably ^{2 to} 2000 mJ / cm ² , more preferably 5 to 2000 mJ / cm ² .
５００500 mJ / cm ² .

The heating temperature is preferably 60
C. to 250C, more preferably 100C to 200C. The heating time is preferably 5 seconds to 2 hours, more preferably 20 seconds to 30 minutes. In some cases, such heating need not be performed.

The photopolymerizable resin composition according to one embodiment of the present invention is used for manufacturing a printed wiring board.
In this case, a photopolymerizable resin composition is applied on a substrate to form a coating film, and the coating film is irradiated with ultraviolet light through a photomask. Next, an unexposed portion of the coating film, which is not irradiated with ultraviolet light by the photomask, which is not irradiated with ultraviolet light, is removed by dissolving with an aqueous alkali solution or the like. Then, the ultraviolet light exposed portion of the coating film, which is an ultraviolet light irradiated region remaining on the base material and irradiated with ultraviolet light, is heated, a high degree of crosslinking reaction is performed, and the printed wiring board is manufactured by curing. I do. Further, after irradiating the coating film with ultraviolet light and then heating, the unexposed portion of the coating film may be developed, or the coating film may be irradiated with ultraviolet light and heated, and then the ultraviolet light of the coating film may be developed. The unexposed portion may be developed.

When a printed wiring board is manufactured by such a method using the photopolymerizable resin composition according to one embodiment of the present invention, a fine and highly accurate pattern is formed on the base material. be able to.

Further, the photopolymerizable resin composition according to one embodiment of the present invention is used for producing an optical thin film such as a high refractive index layer of an antireflection film and a reflector. In this case, a photopolymerizable resin composition is applied on a substrate, a lower layer thin film, or the like to form a coating film. Then, the coating film is irradiated with ultraviolet light, and further heated to perform a high degree of crosslinking reaction on the coating film, and cured to produce an optical thin film such as a high refractive index layer of an antireflection film and a reflection plate. I do.

When an optical thin film such as a high-refractive-index layer of an antireflection film or a reflector is manufactured by using the photopolymerizable resin composition according to an embodiment of the present invention in this manner, visible light can be reduced. An optical thin film such as a high-refractive-index layer of an antireflection film and a reflector having excellent transparency, high refractive index, and good water repellency can be formed.

[0076]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to these examples.

Example 1 Bisphenoxyethanol full orange glycidyl ether (epoxy equivalent 293)
1 part by weight of polymethylphenylsilane (molecular weight 1120
(0, Mw / Mn = 1.5) 4 parts by weight and 0.25 parts by weight of triphenylsulfonium triflate were dissolved in cyclohexanone to prepare a solution of a photopolymerizable resin composition. The solution was applied on a silicon wafer by a spin coater, and heated at 60 ° C. for 2 minutes to remove the solvent, thereby forming a coating film having a thickness of about 0.11 μm. Next, using a low-pressure mercury lamp, the coating film was irradiated with ultraviolet light of 254 nm for 1 hour.
After irradiation with 00 mJ / cm ² , the mixture was cured by heating at 120 ° C. for 5 minutes. Thereafter, the coating film was developed by immersing it in tetrahydrofuran (hereinafter, referred to as a THF solvent) as a developing solution for 10 minutes. As a result, the coating film was insoluble.

In this example, when no ultraviolet light was irradiated, no insolubilization of the coating film occurred.

Example 2 1 part by weight of bisphenol full orange glycidyl ether (epoxy equivalent: 243)
Polymethylphenylsilane (molecular weight 11200, Mw /
(Mn = 1.5) 4 parts by weight and 0.25 parts by weight of triphenylsulfonium triflate were dissolved in cyclohexanone to prepare a solution of the photopolymerizable resin composition. The solution was applied on a silicon wafer by a spin coater,
To remove the solvent by heating for 2 minutes at a thickness of about 0.1.
An 11 μm coating was formed. Then, using a low-pressure mercury lamp, the coating film was irradiated with ultraviolet light of 254 nm at 200 mJ /.
After irradiation with cm ² , the mixture was heated at 120 ° C. for 5 minutes to be cured. Then, when the said coating film was developed by immersing in a THF solvent for 10 minutes, the coating film was insolubilized.

In this example, when no ultraviolet light was irradiated, no insolubilization of the coating film occurred.

Example 3 Bisphenoxyethanol full orange glycidyl ether (epoxy equivalent: 293)
1 part by weight, polyphenylsilin (molecular weight 2200, Mw
/Mn=1.3) 4 parts by weight and 0.25 parts by weight of triphenylsulfonium triflate were dissolved in cyclohexanone to prepare a solution of the photopolymerizable resin composition. The solution is applied on a silicon wafer with a spin coater,
The mixture was heated at 2 ° C. for 2 minutes to remove the solvent, thereby forming a coating having a thickness of about 0.11 μm. Then, using a low-pressure mercury lamp, the coating film was irradiated with ultraviolet light of 254 nm for 200 m.
After irradiation with J / cm ² , the mixture was heated at 140 ° C. for 5 minutes to be cured. Then, when the said coating film was developed by immersing in a THF solvent for 10 minutes, the coating film was insolubilized.

In this example, when no ultraviolet light was irradiated, no insolubilization of the coating film occurred.

Example 4 2 parts by weight of bisphenol full orange glycidyl ether (epoxy equivalent: 243)
Poly (methylphenylsilane) 0.5 (phenylsilin)
0.5 copolymer (molecular weight 7000, Mw / Mn = 1.
4) 3 parts by weight and 0.25 parts by weight of triphenylsulfonium triflate were dissolved in cyclohexanone to prepare a solution of the photopolymerizable resin composition. The solution was applied on a silicon wafer by a spin coater, and heated at 60 ° C. for 2 minutes to remove the solvent, thereby forming a coating film having a thickness of about 0.11 μm. Next, the coating film was irradiated with ultraviolet light of 254 nm at 200 mJ / cm ² using a low-pressure mercury lamp, and then heated at 140 ° C. for 5 minutes to be cured. Then, when the said coating film was developed by immersing in a THF solvent for 10 minutes, the coating film was insolubilized.

In this example, when no ultraviolet light was irradiated, no insolubilization of the coating film occurred.

[0085]

As described above, the photopolymerizable resin composition of the present invention has high sensitivity to ultraviolet light, and therefore cures with a small amount of exposure. The cured product has excellent heat resistance, solvent resistance, low shrinkage, and low water absorption, has visible light transparency, has a high refractive index, and has good water repellency. Therefore, the photopolymerizable resin composition of the present invention and the cured product thereof,
Paint, insulating material for electrical equipment, wire covering material, sealing material for electronic equipment and printed wiring board, protective film, photoresist,
It can be suitably used for printing plate materials, inks, adhesives, adhesives, high refractive index layers of antireflection films such as liquid crystal displays, and reflectors.

Continued on the front page (72) Inventor Haruyuki Okamura 1-1-1, Gakuen-cho, Sakai City, Osaka Prefecture, Osaka Prefecture University (72) Inventor Tomoka Harada 1-1-1, Gakuen-cho, Sakai City, Osaka Prefecture, Osaka (72) Invention Go Tsuyoshi Fujiki 4-1-2 Hirano-cho, Chuo-ku, Osaka-shi, Osaka Inside Osaka Gas Co., Ltd. (72) Inventor Shinichi Kawasaki 4-1-2, Hirano-cho, Chuo-ku, Osaka-shi, Osaka F-term in Osaka Gas Co., Ltd. (Reference) 2H025 AA10 AA13 AB03 AC01 AD01 BD03 CA48 CC17 CC20 FA17 4J036 AB01 AB07 AB10 AD04 AD11 AE07 FB16 GA01 GA03 GA04 GA07 HA02 JA01 JA09 KA01 KA03

Claims (9)

[Claims] 1. A composition comprising (A) a fluorene derivative represented by the following general formula (1), (B) a photoacid generator, and (C) a polysilane represented by the following general formula (2). Characteristic photopolymerizable resin composition. Embedded image In the formula (1), R ^{1 to} R ⁴ represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
Represents an alkyl group. R ^{1 to} R ⁴ may be all the same or two or more may be different. R ⁵ and R
⁶ represents a hydrogen atom or a methyl group. R ⁵ and R
⁶ may be the same or different. n is 0
Represents an integer of 10. (R ⁷ R ⁸ Si) _x (R ⁹ Si) _y (Si) _z (2) In the formula (2), R ^{7 to} R ⁹ are a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl Group,
Represents an alkoxyl group or a silyl group. R ^{7 to} R ⁹ may be all the same or two or more may be different. x, y and z each represent an integer of 0 or more;
The sum of x, y and z is 5-400. 2. The method of claim 1, wherein (A) said fluorene derivative is 0.5 to
The photopolymerizable resin composition according to claim 1, comprising 500 parts by weight, (B) 0.1 to 20 parts by weight of the photoacid generator, and (C) 100 parts by weight of the polysilane. 3. The method according to claim 1, wherein (A) the fluorene derivative is 1 to 10
2. The photopolymerizable resin composition according to claim 1, comprising: 0 parts by weight, (B) 0.5 to 10 parts by weight of the photoacid generator, and (C) 100 parts by weight of the polysilane. 3. 4. A cured product of the photopolymerizable resin composition obtained by subjecting the photopolymerizable resin composition according to claim 1 to a crosslinking reaction. 5. Photopolymerization comprising (A) a fluorene derivative represented by the following general formula (1), (B) a photoacid generator, and (C) a polysilane represented by the following general formula (2). A photopolymerizable resin composition preparing step of preparing a reactive resin composition, and a photopolymerizable resin step, comprising: irradiating the photopolymerizable resin composition with ultraviolet light to perform a crosslinking reaction. A method for producing a cured product of a resin composition. Embedded image In the formula (1), R ^{1 to} R ⁴ represent a hydrogen atom or a carbon atom having 1 to 6 carbon atoms.
Represents an alkyl group. R ^{1 to} R ⁴ may be all the same or two or more may be different. R ⁵ and R
⁶ represents a hydrogen atom or a methyl group. R ⁵ and R
⁶ may be the same or different. n is 0
Represents an integer of 10. (R ⁷ R ⁸ Si) _x (R ⁹ Si) _y (Si) _z (2) In the formula (2), R ^{7 to} R ⁹ are a hydrogen atom, a hydroxyl group, an alkyl group, an alkenyl group, an arylalkyl group, an aryl Group,
Represents an alkoxyl group or a silyl group. R ^{7 to} R ⁹ may be all the same or two or more may be different. x, y and z each represent an integer of 0 or more;
The sum of x, y and z is 5-400. 6. The photopolymerization according to claim 5, further comprising, after the ultraviolet light irradiation step, a heating step of heating the photopolymerizable resin composition which has been cross-linked by irradiating ultraviolet light. A method for producing a cured product of a conductive resin composition. 7. A coating step of coating the photopolymerizable resin composition according to claim 1 on a substrate to form a coating, and applying ultraviolet light to the coating via a photomask. By irradiating,
An ultraviolet light irradiating step of cross-linking the photopolymerizable resin composition, a developing step of removing an unexposed portion of the coating film, which is an unexposed area of the ultraviolet light not irradiated by the photomask, and an ultraviolet light. And a heating step of heating an ultraviolet-light-exposed portion of the coating film, which is an ultraviolet-irradiated area irradiated with the ultraviolet ray, in this order. 8. A coating step of applying the photopolymerizable resin composition according to claim 1 on a substrate to form a coating film, and applying ultraviolet light to the coating film via a photomask. By irradiating,
An ultraviolet light irradiating step of cross-linking the photopolymerizable resin composition, a heating step of heating the coating film, and an ultraviolet light non-irradiated area which is not irradiated with ultraviolet light by a photomask; And a developing step for removing the polymer in this order. 9. A coating step of applying the photopolymerizable resin composition according to claim 1 on a substrate to form a coating, and applying ultraviolet light to the coating via a photomask. Irradiating and heating to cause a crosslinking reaction of the photopolymerizable resin composition, and an ultraviolet light irradiation and heating step; and an ultraviolet light non-irradiated area which is not irradiated with ultraviolet light by a photomask. And a developing step for removing a part in this order. A method for producing a cured product of a photopolymerizable resin composition, comprising: