JP2010026352A - Radiation-sensitive resin composition, microlens and method for forming the same, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which is superior in various properties, including film thickness, resolution, pattern shape, transparency, heat resistance and solvent resistance, in particular, in the heat resistance, and which is able to form a microlens that is superior in balance of the various properties. <P>SOLUTION: The radiation-sensitive resin composition comprises: a polymerizable unsaturated compound having an acidic functional group; an alkali-soluble copolymer obtained by polymerizing a polymerizable unsaturated compound having an alicyclic hydrocarbon group and another polymerizable unsaturated compound; a polymerizable unsaturated compound; a photopolymerization initiator; and a compound represented by a specific chemical formula and having monovalent groups, each of which independently has a hydrogen atom or a (meth)acryloyl group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, a microlens, a method for forming the same, and a liquid crystal display element.

Liquid crystal display elements are the most widely used flat panel displays in recent years because of their excellent features such as high-definition display performance, low power consumption, high reliability, flexibility for all sizes, and thin and light weight. Demands for display performance and low power consumption are becoming stricter.
In order to meet these requirements, Patent Documents 1 to 4 provide a method of improving the brightness and contrast of a liquid crystal display element by providing a microlens array and condensing external light or backlight light in an opening. Proposed. In many cases, these methods have a very short focal length from the light-collecting layer where the microlens is present to the liquid crystal pixel opening, so that the refractive index difference between the material forming the microlens and the planarization film is increased, In addition, it is necessary to precisely control the radius of curvature of the lens.
As a method for forming such a microlens for a liquid crystal display element, conventionally, a glass substrate is dry etched to form a dent, and this is filled with a high refractive index ultraviolet curable resin, and a lens pattern is formed. After that, the pattern is melt-flowed by heat treatment, and this is used as it is as a lens. A pattern is formed from the radiation-sensitive resin composition and then melt-flowed to produce a mask having a predetermined shape. For example, a method of transferring a predetermined lens shape to a base by performing dry etching through the substrate has been employed. However, in any of these methods, the microlens formation process is complicated and expensive, and is not industrially advantageous.
For this reason, the formation of microlenses in recent years can satisfy various characteristics required for microlenses, such as film thickness uniformity, resolution, pattern shape, transparency, heat resistance, solvent resistance, and storage stability. A radiation-sensitive resin composition that is good and can form microlenses by a simple method is widely used (Patent Document 5).

In recent years, with the spread of OA devices such as portable personal computers and word processors, mobile phones, and the like, liquid crystal display elements have been increasingly used in an environment that has not been assumed in the past. In particular, even if the equipment is not specially designed and developed for in-vehicle use, it should be a natural requirement that it is left in the car for a long time and left in a high temperature environment for a long time without any problem in display performance. It has become. Therefore, development of a method for forming a microlens having higher heat resistance than before has been strongly demanded for the microlens.
Furthermore, many of the radiation sensitive resin compositions used for forming microlenses for liquid crystal display elements contain an organic solvent. In order to form a film on a substrate using such a composition, a coating method such as a spin coating method, a dipping method, or a spray method is usually used. Such a technique requires time required for obtaining conditions for obtaining a predetermined film thickness, and has problems in terms of environment such as solvent volatilization. Therefore, the formation of microlenses by a dry film method, which is simple, short-time and low-cost, has been studied (Patent Documents 6 and 7).
However, a radiation-sensitive resin composition capable of forming a microlens having various properties required for the microlens as described above, in particular, excellent heat resistance and well-balanced performance has not been known. A method for forming such microlenses by a film method is not known.
JP 2001-154181 A JP 2001-117114 A JP-A-11-109417 Japanese Patent Laid-Open No. 10-268305 JP-A-6-347601 JP 2006-11371 A JP 2006-48020 A J. et al. Org. Chem., Vol. 28, p. 229 (1963)

The present invention has been made on the basis of the above circumstances, and its purpose is excellent in various performances such as film thickness, resolution, pattern shape, transparency, heat resistance, solvent resistance, and particularly in heat resistance. Another object of the present invention is to provide a radiation-sensitive resin composition capable of forming a microlens excellent in balance of various performances and having good storage stability.
Another object of the present invention is to provide a microlens exhibiting high heat resistance and a method for forming the microlens, and particularly to form a microlens that can form the microlens as described above by a simple process using a radiation-sensitive dry film. It is to provide a method.
Still another object of the present invention is to provide a liquid crystal display device that has excellent display quality, low power consumption, and excellent heat resistance.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
(A) (a) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having no acidic functional group 20 to 60 And an alkali-soluble copolymer obtained by polymerizing 5% by weight and (c) 5-40% by weight of other polymerizable unsaturated compounds (where (a) + (b) + (c) = 100% by weight) , "(A) copolymer"), (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) a radiation sensitive compound containing a compound represented by the following general formula (I). This is achieved by the conductive resin composition.

(In the formula (I), R is independently of each other a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or — (CH ₂ ) _n1 —R ^I (where R ^I is a (meth) acryloyl group or carbon A monovalent group having an alkoxyl group of 1 to 6 or a cycloalkyl group having 3 to 8 carbon atoms, a carboxyl group, an oxiranyl group, an oxetanyl group or a vinyl group, and the oxetanyl group and the oxiranyl group each have may be substituted with 1-6 alkyl groups, n1 is an integer of 0 to 3, it is when n1 is 0 R ^I is a monovalent group having an alkoxyl group having 1 to 6 carbon atoms However, not all of the 24 Rs in total are hydrogen atoms,
X is independently of each other a methylene group or an alkylene group having 2 to 10 carbon atoms,
Y is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a phenoxy group. ,
q is 0 or 1 independently of each other. )
The above objects and advantages of the present invention are, secondly,
This is achieved by a method for forming a microlens including at least the following steps (1) to (4) in the order described below.
(1) forming a film of the radiation sensitive resin composition on a substrate;
(2) A step of irradiating at least a part of the coating with radiation,
(3) a step of developing the film after irradiation, and (4) a step of heating the film after development.
In this case, the step of forming a coating of the radiation sensitive resin composition on the substrate in the step (1) in the above method is provided with a radiation sensitive layer obtained from the radiation sensitive resin composition on the base film. When it is made using a radiation sensitive dry film, the advantages of the present invention will be maximized.
Furthermore, the above objects and advantages of the present invention are thirdly achieved by a microlens formed from the above radiation sensitive resin composition, and fourthly,
This is achieved by a liquid crystal display device comprising the microlens.

The radiation-sensitive resin composition of the present invention can form high-definition microlenses and microlens arrays having high resolution, excellent storage stability, applicability, and the like and an excellent property balance.
In addition, the microlens of the present invention has an excellent balance of properties such as film thickness, resolution, pattern shape, transparency, heat resistance, heat discoloration resistance, and solvent resistance, and in particular, various OA devices, liquid crystal television sets, mobile phones, and the like. It can be used very suitably for liquid crystal display elements such as telephones and projectors.
Moreover, according to the preferable aspect of the formation method of the micro lens of this invention, the high-definition micro lens and micro lens array which have the outstanding characteristic can be formed by the simple process using a radiation sensitive dry film.

Radiation-sensitive resin composition The radiation-sensitive resin composition of the present invention comprises (A) a copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) the above general formula (I). The compound represented by these is contained.
Hereinafter, each component contained in the radiation sensitive resin composition of this invention is demonstrated in detail.
-(A) Copolymer-
The copolymer (A) in the present invention comprises (a) a polymerizable unsaturated compound having an acidic functional group (hereinafter also referred to as “(a) polymerizable unsaturated compound”), 10 to 50% by weight, (b) 20 to 60% by weight of a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having no acidic functional group (hereinafter also referred to as “(b) polymerizable unsaturated compound”) and (c) other It is an alkali-soluble copolymer obtained by polymerizing 5 to 40% by weight of a polymerizable unsaturated compound (however, (a) + (b) + (c) = 100% by weight).
(A) As an acidic functional group in a polymerizable unsaturated compound, a carboxyl group, an acid anhydride group, a sulfonic acid group etc. can be mentioned, for example, Especially preferably, they are a carboxyl group or an acid anhydride group.

Examples of the polymerizable unsaturated compound having a carboxyl group or an acid anhydride group include, for example, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and acid anhydride thereof, half ester of unsaturated dicarboxylic acid, unsaturated dicarboxylic acid A half amide, a carboxyl group-containing (meth) acrylic acid ester and the like can be mentioned.
Examples of the unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, and compounds in which the α-position of acrylic acid or crotonic acid is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. ;
Examples of unsaturated dicarboxylic acids and acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
As the half ester of unsaturated dicarboxylic acid, for example, the hydrogen atom of one carboxyl group in the unsaturated dicarboxylic acid is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl. A half ester substituted with a group, t-butyl group, phenyl group, o-tolyl group, m-tolyl group or p-tolyl group;
Examples of the half amide of unsaturated dicarboxylic acid include a half amide in which one carboxyl group in the unsaturated dicarboxylic acid is amidated;
Examples of carboxyl group-containing (meth) acrylic acid esters include monoesterified products of 2-hydroxyethyl (meth) acrylate and succinic acid, monoesterified products of 2-hydroxyethyl (meth) acrylate and maleic acid, 2-hydroxy Examples thereof include monoesterified products of ethyl (meth) acrylate and hexahydrophthalic acid (hereinafter referred to as “2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate”) and the like.
In the present invention, the polymerizable unsaturated compound (a) includes at least one selected from the group consisting of (meth) acrylic acid and 2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate among the above. It is preferable to use it.
In the present invention, the polymerizable unsaturated compound (a) can be used alone or in admixture of two or more, and in particular, (meth) acrylic acid and 2-mono (hexahydrophthaloyloxy) ethyl ( It is preferable to use in combination with (meth) acrylate.
(A) The copolymerization ratio of the (a) polymerizable unsaturated compound in the copolymer is 10 to 50% by weight, preferably 20 to 40% by weight. In this case, if the copolymerization ratio of the polymerizable unsaturated compound (a) is less than 10% by weight, the resulting copolymer is difficult to dissolve in an alkaline developer, resulting in film residue after development, and sufficient resolution. On the other hand, if this value exceeds 50% by weight, the solubility of the resulting copolymer in an alkaline developer becomes too high, resulting in a large reduction in film thickness at the radiation irradiated part.

Examples of the polymerizable unsaturated compound (b) include cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 2 -(Tricyclodecanyloxy) ethyl (meth) acrylate etc. can be mentioned.
Of these (b) polymerizable unsaturated compounds, tricyclodecanyl (meth) acrylate is preferable, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate is particularly preferable.
In the present invention, the polymerizable unsaturated compound (b) can be used alone or in admixture of two or more.
The copolymerization ratio of the polymerizable unsaturated compound (b) in the copolymer (A) is 20 to 60% by weight, preferably 30 to 50% by weight. In this case, when the content of the polymerizable unsaturated compound (b) is less than 20% by weight, the molecular weight of the obtained copolymer is not sufficiently increased, and it becomes difficult to form a coating film having a thickness of 10 μm or more. On the other hand, when it exceeds 60% by weight, the solubility of the resulting copolymer in a solvent or an organic solvent is lowered.

(C) Other polymerizable unsaturated compounds are mainly used for the purpose of controlling the mechanical properties of the (A) copolymer.
(C) Other polymerizable unsaturated compounds include, for example, (meth) acrylic acid esters, diesters of unsaturated dicarboxylic acids exemplified for the polymerizable unsaturated compounds (a), aromatic vinyl compounds, conjugated diolefins, Examples thereof include unsaturated compounds having a nitrile group, chlorine-containing unsaturated compounds, unsaturated compounds having an amide bond, and fatty acid vinyl esters.
(C) As other polymerizable unsaturated compounds, more specifically, as a (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (Meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, neopentyl (meth) acrylate, 4-i-pentylhexyl ( (Meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraquinonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meta) Acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, glycidyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 2,2,2-trifluoroethyl ( (Meth) acrylate, pentafluoroethyl (meth) acrylate, heptafluoro-n-propyl (meth) acrylate, heptafluoro-i-propyl (meth) acrylate, 2- (N, N-dimethylamino) ethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, α- (meth) acryloyloxy-γ-butyrolac Down, beta-a (meth) acryloyloxy -γ- butyrolactone;

As unsaturated dicarboxylic acid diesters, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate, diethyl itaconate and the like;
Examples of aromatic vinyl compounds include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, and the like;
1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc. as conjugated diolefins;
Examples of nitrile group-containing unsaturated compounds include (meth) acrylonitrile, vinylidene cyanide, etc .;
Examples of chlorine-containing unsaturated compounds include vinyl chloride and vinylidene chloride;
As amide bond-containing unsaturated compounds, (meth) acrylamide, maleic acid diamide, fumaric acid diamide and the like;
Examples of the fatty acid vinyl ester include vinyl acetate and vinyl propionate.
(C) As other polymerizable unsaturated compounds, it is preferable to use one or more selected from the group consisting of tetrahydrofurfuryl (meth) acrylate, styrene, 1,3-butadiene and isoprene among the above.
In the present invention, (c) other polymerizable unsaturated compounds can be used alone or in admixture of two or more, but in particular, combined use of styrene and tetrahydrofurfuryl (meth) acrylate, or styrene And 1,3-butadiene and / or isoprene are preferred.
(A) The copolymerization ratio of the other polymerizable unsaturated compound (c) in the copolymer is 5 to 40% by weight, preferably 10 to 35% by weight.

(A) The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer measured by gel permeation chromatography is preferably 2,000 to 100,000, more preferably 5,000. ~ 50,000. In this case, if the Mw of the copolymer (A) is less than 2,000, the alkali developability, the remaining film ratio, etc. may be decreased, and the pattern shape, heat resistance, etc. may be inferior, whereas 100,000 If it exceeds 1, the sensitivity may be lowered or the pattern shape may be inferior.
Further, for the copolymer (A), the ratio of the polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography to the above Mw (hereinafter referred to as “Mw / Mn”). , Preferably it is 1.0-5.0, More preferably, it is 1.0-3.0.
The copolymer (A) is composed of (a) a polymerizable unsaturated compound, (b) a polymerizable unsaturated compound, and (c) another polymerizable unsaturated compound, preferably in a suitable solvent, and initiating a suitable radical polymerization. It can manufacture by copolymerizing in presence of an agent.
As a solvent that can be preferably used for the polymerization, for example,
Alcohols such as methanol, ethanol, diacetone alcohol;
Ethers such as tetrahydrofuran, tetrahydropyran, dioxane;
Ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol ethyl monoether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;

Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, n-lactic acid Butyl, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, Ethoxyacetic acid n- Chill, n-propoxyacetate methyl, n-propoxyacetate ethyl, n-propoxyacetate n-propyl, n-propoxyacetate n-butyl, n-butoxyacetate methyl, n-butoxyacetate, n-butoxyacetate n-propyl, n-Butoxyacetate n-butyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methoxypropionate n-propyl, 2-methoxypropionate n-butyl, 2-ethoxypropionate methyl, 2-ethoxy Ethyl propionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate N-butyl 2-n-propoxypropionate, -Methyl n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, 3-methoxypropionate Ethyl acetate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-ethoxypropionate n -Butyl, methyl 3-n-propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, 3-n-butoxypropionic acid Methyl, ethyl 3-n-butoxypropionate, 3- Other esters such as n-propyl n-butoxypropionate and n-butyl 3-n-butoxypropionate can be mentioned.
These solvents can be used alone or in admixture of two or more.
Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), and 2,2′-azobis (4-methoxy-2). Azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t-butylperoxy) cyclohexane, hydrogen peroxide, Etc. When a peroxide is used as the radical polymerization initiator, a redox initiator may be used in combination with a reducing agent.
In the present invention, the copolymer (A) can be used alone or in admixture of two or more.

-(B) polymerizable unsaturated compound-
The (B) polymerizable unsaturated compound in the present invention is a compound that can be polymerized by irradiation with radiation in the presence of (C) a photopolymerization initiator.
(B) Examples of the polymerizable unsaturated compound include a compound having one ethylenically unsaturated bond in the molecule, a compound having two ethylenically unsaturated bonds in the molecule, and three or more ethylenes in the molecule. And compounds having an ionic unsaturated bond.
Examples of the compound having one ethylenically unsaturated bond in the molecule include (A) a polymerizable unsaturated compound or (c) another unsaturated compound used for synthesizing a copolymer. The unsaturated compound mentioned above, the compound represented by following formula (1), the compound which has one ethylenically unsaturated bond in another molecule | numerator, etc. can be mentioned.

(In formula (1), k is an integer of 0 to 8, and R ¹ is a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms.)
The compound represented by the above formula (1) may be used as a single type of compound may be used as a mixture of the value or more compounds of different types of R ¹ of k.
As a commercial item of the compound represented by the above formula (1), for example, as a mixture of compounds having different k values, for example, Aronix M-101 (k: about 2, R ¹ : H), M-102 ( k: about 4, R ¹ : H), M-111 [k: about 1, R ¹ : nC ₉ H ₁₉ (represents an n-nonyl group; the same shall apply hereinafter)], M-113 (k : About 4, R ¹ : n-C ₉ H ₁₉ ), M-114 (k: about 8, R ¹ : n-C ₉ H ₁₉ ), M-117 (k: about 2.5, R ¹ : N-C ₉ H ₁₉ ) [manufactured by Toagosei Co., Ltd.], KAYARAD R-564 (k: about 2.3, R ¹ : H) [manufactured by Nippon Kayaku Co., Ltd.] it can. The above k values are all average values.
Other commercially available compounds having one ethylenically unsaturated bond in the molecule include, for example, KAYARAD TC-110S, TC-120S, R-526 [above, manufactured by Nippon Kayaku Co., Ltd.], V -158, 2311 [above, manufactured by Osaka Organic Chemical Industry Co., Ltd.].
Examples of the compound having two ethylenically unsaturated bonds in the molecule include compounds represented by the following formula (2), (3), (4), (5-1) or (5-2) and A compound having two ethylenically unsaturated bonds in the other molecule can be exemplified.

(In the formula (2), m and n are, independently of one another, an integer from 0 to 8, each R ^2, independently of one another, a hydrogen atom or a methyl group.)

(In Formula (3), R ³ is a linear or branched alkylene group having 2 to 12 carbon atoms, p is an integer of 1 to 15, provided that the alkylene group of R ³ is interrupted by an oxygen atom. And a part of the hydrogen atom of the alkylene group may be substituted with a hydroxyl group.)

(In the formula (4), each R ⁴ is independently a hydrogen atom or a methyl group, M is a dihydric alcohol residue, N is a dibasic acid residue, and q is 0. It is an integer of ~ 15.)

(In Formula (5-1), r and s are each independently an integer of 0 to 2 and r + s = 2, and in Formula (5-2), t and u are independently of each other. , An integer from 0 to 4 and t + u = 4.)
The compound represented by the above formula (2) may be used as a single kind of compound, or may be used as a mixture of plural kinds of compounds having different values of m or n or R ² . Specific examples of the compound represented by the above formula (2) include, as a mixture of compounds having different values of m or n, trade names such as Aronics M-210 (m: about 2, n: about 2, R ² : CH ₃ ) (manufactured by Toagosei Co., Ltd.), KAYARAD R-551 (m + n: about 4, R ² : CH ₃ ), R-712 (m + n: about 4, R ² : H) [above, Nippon Kayaku Co., Ltd.]. The values of m and n are both average values.
The compound represented by the above formula (3) may be used as a single type of compound, or may be used as a mixture of a plurality of types of compounds having different values of p or different types of R ³ . Specific examples of the compound represented by the above formula (3) are trade names such as Aronix M-220 [R ³ : — (CH ₂ ) ₃ —, p: about 3], M-225 [R ³ _{:-( CH 2) 3 -, p} : about 7], the M-270 _{^{[R 3 :-( CH 2) 3 -}} , p: about 12], the M-240 ^[R 3: _{-CH 2} CH 2 -, p: about 4], the M-245 _{^{[R 3: -CH 2 CH 2 -}} , p: about 9] [manufactured by Toagosei Co.], KAYARAD HDDA ^[R 3 :-( CH _{2) 6} -, p: 1], the NPGDA _{^{[R 3: -CH 2 C (CH}} 3) 2 CH 2 -, p: 1 ], the TPGDA _{^{[R 3: -CH 2 CH (CH}} 3) -, p: 1], the PEG400DA _{^{[R 3: -CH 2 CH 2 -}} , p: about 8], the MANDA _{^{[R 3: -CH 2 C (CH}} 3) 2 C ₂ -, p: 1], the R-167 _{^{[R 3: -CH 2 CH (OH}} ) CH 2 O (CH 2) 6 OCH 2 CH (OH) CH 2 -, p: 1 ] [more, Japan of manufactured medicine (Ltd.), light acrylate 1.9-NDA _{^{[R 3 :-( CH 2) 8 -}} , p: 1 ] and the like. In the above, what is added with “about” to the value of p is a mixture of compounds having different values of p, and the value of p in this case is an average value.

Examples of the residue of the M dihydric alcohol in the formula (4) include an alkylene group having 2 to 10 carbon atoms (however, a part of hydrogen atoms of the alkylene group may be substituted with a hydroxyl group) and the like. be able to. Examples of the residue of N dibasic acid in formula (4) include an oxygen atom, a methylene group, and an alkylene group having 2 to 6 carbon atoms.
The compound represented by the above formula (4) may be used as a single type of compound, or may be used as a mixture of a plurality of types of compounds having different q values or different types of R ⁴ , M or N. Specific examples of the compound represented by the above formula (4) include trade names such as Aronix M-6100, M-6200, M-6250, M-6300, M-6400, M-6500. [Above, manufactured by Toagosei Co., Ltd.], light ester EG (q: 0, M: —CH ₂ CH ₂ —, R ⁴ : CH ₃ , 2EG (q: 1, M: — (CH ₂ CH ₂ )) ^{-, N: -O-, R 4} : CH 3), the _{1.4BG (q: 0, M :-(} CH 2) 4 -, R 4: CH 3), the 1.6HX (q: 0, ^{_{M :-( CH 2) 6 -,}} R 4: CH 3), the _{1.9ND (q: 0, M :-(} CH 2) 9 -, R 4: CH 3), the G-101P (q: 0, M: —CH ₂ CH (OH) CH ₂ —, R ⁴ : CH ₃ ), light acrylate 3EG-A (q: 2, M: — (CH ₂ CH ₂ ) —, N: —O—, R ⁴ : H), 4EG-A (q: about 3, M :—( CH ₂ CH ₂ ) —, N: —O—, R ⁴ : H) 9EG-A (q: about 8, M: — (CH ₂ CH ₂ ) —, N: —O—, R ⁴ : H), 14EG-A (q: about 13, M: — (CH _{2 CH 2) -, N: -O-} , R 4: H), the _{1.6HX-A (q: 0,} M :-( CH 2) 6 -, R 4: H), the 1.9ND-A (Q: 0, M: — (CH ₂ ) ₉ —, R ⁴ : H) [above, manufactured by Kyoeisha Chemical Co., Ltd.] etc. In the above, “about” is added to the value of q. Is a mixture of compounds having different values of q, in which case the value of q is an average value.

The compound represented by the above formula (5-1) or (5-2) may be used as a single kind of compound, or as a mixture of plural kinds of compounds having different values of r or s or t or u. Also good. Specific examples of the compound represented by the formula (5-1) include KAYARAD HX-220 (manufactured by Nippon Kayaku Co., Ltd.) under the trade name; and the compound represented by the formula (5-2). Specific examples include KAYARAD HX-620 (manufactured by Nippon Kayaku Co., Ltd.) and the like under the trade name.
Examples of the compound having two ethylenically unsaturated bonds in the other molecule include R-604 (manufactured by Nippon Kayaku Co., Ltd.), V-260, V-312, V-335HP [above, Osaka Organic Chemical Industry Co., Ltd.].

  Examples of the compound having 3 or more ethylenically unsaturated bonds in the molecule include poly (meth) acrylates of trivalent or higher alcohols, preferably the following formulas (6), (7), (8) or (9 ) And the like.

(In the formula (6), v is an integer of 0 to 8, ^{R 5} is a hydrogen atom, a hydroxyl group, a methyl group, group _CH 2 = CHCOO- or a group _{(CH 2 = CHCOOCH 2) 2} (R a CH 2 O ) CCH ₂ O— (R ^a is a hydrogen atom or a group CH ₂ ═CHCO—).

(In formula (7), R ⁶ is an oxygen atom or a methylene group.)

(In formula (8), each R ⁷ is independently a hydrogen atom or a methyl group, X ¹ and X ² are each a residue of a trivalent alcohol, and Y is the residue of a dibasic acid. And w is an integer of 0 to 15.)

(In the formula (9), six A's are independently of each other a group CH ₂ ═CHCO— or a group CH ₂ ═CHCO— (OC ₅ H ₁₀ CO) _x —, wherein x is 1 or 2. is there.)
The compound represented by the above formula (6) may be used as a single kind of compound, or may be used as a mixture of plural kinds of compounds having different values of v or R ⁵ . Specific examples of the compound represented by the above formula (6) are trade names such as Aronix M-305 (v: 0, R ⁵ : OH), M-309 (v: 0, R ⁵ : CH _3). ), M-310 (v: about 1, R ⁵ : CH ₃ ), M-320 (v: about 2, R ⁵ : CH ₃ ), M-450 (v: 0, R ⁵ : CH _2). = CHCOO), the _{^{M-402 (v: 0,}} R 5: (CH 2 = CHCOOCH 2) 2 (RCH 2 O) CCH 2 -O-, provided that ^{R a} is _CH 2 = CHCO- hydrogen atom or a group [Above, manufactured by Toagosei Co., Ltd.], KAYARAD TMPTA (v: 0, R ⁵ : CH ₃ ) [manufactured by Nippon Kayaku Co., Ltd.], V-295 (v: 0, R ⁵ : CH ₃ ) ^{, V-300 (v: 0} , R 5: OH) [more, Osaka Organic Chemical Industry Co., Ltd.] and the like, etc. Kill. In the above, what is added with “about” to the value of v is a mixture of compounds having different values of v, and the value of v in this case is an average value.

Specific examples of the compound represented by the above formula (7) include, for example, Aronix M-400 (manufactured by Toagosei Co., Ltd.) under the trade name.
Examples of the residue of the trivalent alcohol represented by X ¹ and X ² in formula (8) include a trivalent group obtained by removing three hydrogen atoms from an alkane having 1 to 6 carbon atoms. Specifically, for example, a trivalent group C (CH ₂ CH ₃ ) in which the leftmost carbon atom has three bonds can be exemplified. Examples of the residue of the dibasic acid represented by Y in the formula (8) include an oxygen atom and an alkylene group having 2 to 6 carbon atoms (provided that the alkylene group is an oxygen atom, an ester bond, and a divalent divalent having 6 to 12 carbon atoms). may be interrupted by at least one selected from alicyclic group, the total number of carbon radicals Y in this case is 18 or less.) can be exemplified, and specifically groups -CH ₂ OCH ₂ —, the following formula (Y-1)

The bivalent group etc. which are represented by these can be mentioned. Specific examples of the compound represented by the formula (8) are trade names such as Aronix M-7100, M-8030, M-8060, M-8100 (X ¹ , X ² : C (CH ₂ CH ₃ ), Y: a divalent group represented by the above formula (Y-1)), M-9050 [above, manufactured by Toagosei Co., Ltd.], KAYARAD T-1420 (T) (X ¹ , X _{^{2: C (CH 2 CH 3}} ), Y: -CH 2 OCH 2 -), can be exemplified by Nippon Kayaku Co., Ltd.] and the like.
The compound of the formula (9) may be used as a single type of compound, and the number of groups CH ₂ ═CHCO— and groups CH ₂ ═CHCO— (OC ₅ H ₁₀ CO) _x — out of six A or A _May contain a group CH ₂ ═CHCO— (OC ₅ H ₁₀ CO) _x — as a mixture of a plurality of compounds having different values of x. Specific examples of the compound represented by the above formula (9) are trade names such as KAYARAD DPCA-20 (x: about 1, a: about 2, b: about 4), DPCA-30 (x: about 1, a: about 3, b: about 3), DPCA-60 (x: about 1, a: about 6, b: about 0), DPCA-120 (x: about 2, a: about 6, b : About 0) [above, manufactured by Nippon Kayaku Co., Ltd.], V-360, V-GPT, V-3PA, V-400 [above, manufactured by Osaka Organic Chemical Industry Co., Ltd.]. However, in the above, each product is a mixture of plural types of compounds, x is an average value, a is an average value of the number of groups CH ₂ ═CHCO— (OC ₅ H ₁₀ CO) _x —, b Is the average number of groups CH ₂ ═CHCO—.
In this invention, (B) polymeric unsaturated compound can be used individually or in mixture of 2 or more types.
Of these (B) polymerizable unsaturated compounds, compounds having two ethylenically unsaturated bonds in the molecule or compounds having three or more ethylenically unsaturated bonds in the molecule are preferred, and more preferably It is a compound represented by Formula (4) or (8).
In this invention, the usage-amount of (B) polymerizable unsaturated compound becomes like this. Preferably it is 10-150 weight part with respect to 100 weight part of (A) copolymers, More preferably, it is 30-100 weight part. (B) When the amount of the polymerizable unsaturated compound used is less than 10 parts by weight, the sensitivity to radiation may be insufficient. On the other hand, when it exceeds 150 parts by weight, the compatibility with the copolymer (A) is poor. There is a risk of film roughness on the coating surface.

-(C) Photopolymerization initiator-
The (C) photopolymerization initiator in the present invention is a photopolymerization initiator that generates active species (for example, radicals and the like) capable of initiating polymerization of the polymerizable unsaturated compound (B) upon irradiation with radiation.
Examples of such (C) photopolymerization initiator include α-diketones such as benzyl and diacetyl;
Acyloins such as benzoin;
Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;
Thioxanthone such as thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid;
Benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone;
Acetophenones such as acetophenone, p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone;
Quinones such as anthraquinone and 1,4-naphthoquinone;
Halogen compounds such as phenacyl chloride, tribromomethyl phenyl sulfone, tris (trichloromethyl) -s-triazine;
Peroxides such as di-t-butyl peroxide;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide;

1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -nonane-1,2-nonane-2-oxime-O-benzoate, 1- (9-ethyl-6-benzoyl) -9.H.-carbazol-3-yl) -nonane-1,2-nonane-2-oxime-O-acetate, 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl ) -Pentane-1,2-pentane-2-oxime-O-acetate, 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -octane-1-one oxime-O-acetate 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione -1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2 -Octadion-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- [O- (4-methylbenzoyl) O-acyl oximes such as oxime)] and the like.

Commercially available products of such (C) photopolymerization initiators are trade names such as Irgacure 184, 500, 651, 907, 369, 379, CG24-61 (and above, Ciba Specialty). Chemicals), Lucirin LR8728, Lucirin TPO (above, manufactured by BASF), Darocur 1116, 1173 (above, manufactured by Merck), Ubekril p36 (produced by UCB), and the like.
In the present invention, the photopolymerization initiator (C) can be used alone or in admixture of two or more. Moreover, 1 or more types of radiosensitizers can also be used together.
Of these (C) photopolymerization initiators, acetophenone, halogen compounds or acylphosphine oxides are preferred, and in particular, 2-methyl [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, phenacyl chloride, tribromomethylphenyl sulfone or 2,4,6-trimethylbenzoyldiphenylphosphine oxide or two of these The above combination is preferable.
The amount of the (C) photopolymerization initiator used in the present invention is preferably 0.01 to 100 parts by weight, more preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the (B) polymerizable unsaturated compound. More preferably, it is 0.5 to 40 parts by weight. When the amount of (C) the photopolymerization initiator used is less than 0.01 parts by weight, the sensitivity tends to decrease. On the other hand, when it exceeds 100 parts by weight, (A) a copolymer or (B) polymerizable There exists a tendency for compatibility with a saturated compound to worsen or the storage stability of the resin composition obtained to fall.

-(D) Compound represented by the above general formula (I)-
Examples of the monovalent group having a (meth) acryloyl group R ^I in formula (I), for example the following formula (R-1)

（式（Ｒ−１’）中、Ｒ^ＩＩ、ｎ２およびｎ３は、それぞれ上記式（Ｒ−１）におけるのと同義である。）
で表される基が好ましい。
上記Ｒ^Ｉの炭素数１〜６のアルコキシル基を有する基としては、例えば下記式（Ｒ−２） (In Formula (R-1), ^RII is a hydrogen atom or a methyl group, n2 is an integer of 1 to 5, and n3 and n4 are independently 0 or 1.)
The group represented by these can be mentioned. Of the groups represented by the formula (R-1), a group in which n4 is 1 in the formula (R-1), that is, the following formula (R-1 ′)

(In formula (R-1 ′), R ^II , n2 and n3 have the same meanings as in formula (R-1)).
The group represented by these is preferable.
Examples of the group having an alkoxyl group having 1 to 6 carbon atoms of R ^I include, for example, the following formula (R-2)

(In Formula (R-2), R ^III is an alkyl group having 1 to 6 carbon atoms, n4 is 2 or 3, and n5 is an integer of 1 to 10.)
The group represented by these can be mentioned.
Examples of the substituent for the oxiranyl group of the R ^I, 1-methyl group is preferred.
The oxetanyl group of R ^I is preferably a 2-oxetanyl group. Examples of the substituent for the oxetanyl group of R and R ^I, respectively, 1-methyl or 1-ethyl group is preferred.
Preferred R in the above formula (1) is, for example, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, and the following formulas (R-3) to (R-16).

(In the formula, n1, respectively, the above equation _- has the same meaning as in ^{_{(CH 2) n1 -R I,}} n5 are each the same as in the formula ^(R-2), R ^A They are each an alkyl group having 2 or 3 carbon atoms, R ^B is a hydrogen atom or a methyl group.)
And groups represented by each of the above.
The 24 Rs in the above formula (I) may all be of the same type or may contain two or more types of R, but all 24 Rs are hydrogen atoms. Absent.
Examples of the compound represented by the formula (I) include the following formula (I-1)

(In formula (I-1), R has the same meaning as in formula (I) above.)
Is preferable because it can be produced with good yield.
The compound represented by the above formula (I) may be used as a single type of compound, and when it contains two or more types of R, the proportion thereof, the types of X and Y, and one of q You may use as a mixture of the multiple types of compound from which a kind or more differs.
The compound represented by the above formula (I), a part of R is a hydrogen atom, the other R is an alkyl group having 1 to 12 carbon atoms and the _- of _{(CH 2)} n1 -R ^I It is preferable that it is 1 or more types, It is more preferable that the ratio of what is not a hydrogen atom among R is 10-90 mol% with respect to the whole of R, and this ratio is 20-80 mol%. Further preferred. When this ratio is less than 10 mol%, the solubility in the resulting radiation-sensitive composition solution may be insufficient. On the other hand, when it exceeds 90 mol%, the storage stability in the resulting radiation-sensitive composition solution may be insufficient. In the case where the compound represented by the formula (I) is used as a mixture of a plurality of types of compounds, the ratio is understood to be an average value for all the compounds represented by the formula (I). Should.
The proportion of R that is not a hydrogen atom can be calculated from the result of ¹ H-NMR analysis.

  The compound represented by the above formula (I) is, for example, a meta-dihydroxybenzene having q Y (wherein q and Y are as defined in the above formula (I)) and the compound CHO—. By the condensation reaction with X—CHO (where X is as defined in the above formula (I)), the following general formula (Ia)

(In the formula (Ia), X, Y and q have the same meanings as in the above formula (I).)
And then reacting it directly or indirectly with a compound having a desired functional group.
In the condensation reaction of the above-mentioned q Y-meta-dihydroxybenzene and the above compound CHO-X-CHO, both are preferably reacted in the presence of an appropriate acid catalyst, preferably at 60 to 90 ° C. for 12 to 50 hours. Can be done.
Although there is no restriction | limiting in particular in the usage-amount with the said compound CHO-X-CHO, From a viewpoint that the yield of the precursor compound obtained becomes high, it is q piece with respect to 1 mol of compound CHO-X-CHO. The meta-dihydroxybenzene having Y is preferably 1 to 8 mol, more preferably 2 to 6 mol, and particularly preferably 3 to 5 mol.
The condensation reaction can be performed in a suitable solvent. In this case, the proportion of the total of q-meta-dihydroxybenzene having Y and compound CHO-X-CHO in the reaction solution is 2 mol / L from the viewpoint that the yield of the obtained precursor compound is increased. Preferably, it is preferably 4 mol / L or more, more preferably 4 to 10 mol / L.

When R is a group having 1 to 12 carbon atoms, a group represented by the above formula (R-3) to (R-9), (R-11) or (R-12), a precursor compound The compound represented by the above formula (I) is obtained by directly reacting the hydroxyl group of the compound with the compound R—X (where R is a desired functional group and X is a halogen atom). Can do. Compound R-X may be a mixture of a plurality of compounds.
Specific examples of the compound R-X include 1-bromopropane, 1-bromo-n-hexane, bromocyclohexane, 2-bromoethyl ethyl ether, epichlorohydrin, β-methylepichlorohydrin, Examples include 3-chloro-3-oxetanylpropane, allyl chloride, acryloyl chloride, methacryloyl chloride, and the like.
When R is a group represented by the above formula (R-10), for example, first, the hydroxyl group of the precursor compound is reacted with bromoacetyl-t-butyl ester, and then the t-butyl group with an acid or alkali. The compound represented by the above formula (I) can be obtained by removing.
When R is a group represented by the above formula (R-13) or (R-14), for example, first, the hydroxyl group of the precursor compound is reacted with epichlorohydrin, and then (meta) ) A compound represented by the above formula (I) can be obtained by reacting acrylic acid.
When R is a group represented by the above formula (R-15) or (R-16), for example, first, the hydroxyl group of the precursor compound and epichlorohydrin are reacted, and then ω- Carboxy-polycaprolactone monoacrylate (commercially available from Toagosei Co., Ltd. as product name “M-5300”) or acrylic acid dimer (commercially available from Toagosei Co., Ltd. as product name “M-5600”) .) Is preferably reacted in the presence of an amine to obtain a compound represented by the above formula (I).

The ratio of the amount of the precursor compound used and the amount of the above compound RX (the total amount when RX is used as a mixture) is not particularly limited, but the product obtained From the viewpoint that the yield of the compound is high, the compound RX is preferably 1 mol or more, more preferably 5 to 40 mol, and more preferably 5 to 20 mol with respect to 1 mol of the precursor compound. Further preferred.
The reaction between the precursor compound and compound RX is preferably performed in a suitable solvent in the presence of an acid or a base at −20 to 100 ° C. for 1 to 20 hours.
The amount of the compound represented by (D) the general formula (I) in the present invention is preferably 0.5 to 50 parts by weight, more preferably 100 parts by weight of the copolymer (A). 5 to 40 parts by weight, more preferably 5 to 30 parts by weight.

-Other ingredients-
The radiation-sensitive resin composition of the present invention is represented by the above (A) copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) the above general formula (I). Although a compound is contained as an essential component, other components can be contained as necessary. Examples of such other components include (E) a thermopolymerizable compound, a thermal polymerization inhibitor, a surfactant, an adhesion aid, a dissolution accelerator, a dissolution controller, a solubility modifier, a filler, a colorant, and a viscosity modifier. An agent etc. can be mentioned.
The (E) thermopolymerizable compound is a compound that polymerizes by heating but does not polymerize by irradiation of radiation, and it is desirable to cause thermal polymerization at 80 to 250 ° C., preferably 150 to 220 ° C.
(E) Although the molecular weight of the thermopolymerizable compound is not particularly limited, it preferably has a molecular weight of about a monomer or an oligomer.
(E) As a thermopolymerizable compound, the compound which has 1 or more types or 1 or more types of thermopolymerizable functional groups, for example, an oxiranyl group, an episulfide group, an oxetanyl group etc. in a molecule | numerator can be mentioned. However, the (E) thermopolymerizable compound having an oxiranyl group does not include a functional silane coupling agent having an oxiranyl group among the adhesion assistants described later.

(E) Among the thermally polymerizable compounds, examples of the compound having one oxiranyl group include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, sec-butyl. Alkyl glycidyl ethers such as glycidyl ether and t-butyl glycidyl ether;
Alkylene glycol monoglycidyl ethers such as ethylene glycol monoglycidyl ether, propylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, 1,6-hexanediol monoglycidyl ether;
Polyalkylene glycol monoglycidyl ethers such as polyethylene glycol monoglycidyl ether and polypropylene monoglycidyl ether;
Glycidyl ethers such as phenyl glycidyl ether, o-tolyl glycidyl ether, m-tolyl glycidyl ether, p-tolyl glycidyl ether, o-ethylphenyl glycidyl ether, m-ethyl glycidyl ether, p-ethylphenyl glycidyl ether Or

[(3,4-epoxycyclohexyl) methyl] methyl ether, [(3,4-epoxycyclohexyl) methyl] ethyl ether, [(3,4-epoxycyclohexyl) methyl] n-propyl ether, [(3,4- [Epoxycyclohexyl) methyl] i-propyl ether, [(3,4-epoxycyclohexyl) methyl] n-butyl ether, [(3,4-epoxycyclohexyl) methyl] sec-butyl ether, [(3,4-epoxycyclohexyl) methyl ] [(3,4-epoxycyclohexyl) methyl] alkyl ethers such as t-butyl ether;
Ethylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether, propylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether, 1,4-butanediol mono [(3,4-epoxycyclohexyl) methyl] Ethers, alkylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether such as 1,6-hexanediol mono [(3,4-epoxycyclohexyl) methyl] ether;
Polyalkylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether such as polyethylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether and polypropylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether;
[(3,4-epoxycyclohexyl) methyl] phenyl ether, [(3,4-epoxycyclohexyl) methyl] o-tolyl ether, [(3,4-epoxycyclohexyl) methyl] m-tolyl ether, [(3 4-epoxycyclohexyl) methyl] p-tolyl ether, [(3,4-epoxycyclohexyl) methyl] o-ethylphenyl ether, [(3,4-epoxycyclohexyl) methyl] m-ethylphenyl ether, [(3 And compounds having a 3,4-epoxycyclohexyl group such as [(3,4-epoxycyclohexyl) methyl] aryl ether such as 4-epoxycyclohexyl) methyl] p-ethylphenyl ether.

Examples of the compound having two or more oxiranyl groups include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and hydrogenated bisphenol AD. Diglycidyl ethers of bisphenol compounds such as diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether Glycidyl ether;
Polyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Bisphenol A type epoxy resin; Bisphenol F type epoxy resin; Phenol novolac type epoxy resin; Cresol novolac type epoxy resin; Polyphenol type epoxy resin; Other alicyclic epoxy resins, other aliphatic polyglycidyl ethers, higher polyvalent fatty acids Polyglycidyl ester; epoxidized soybean oil, epoxidized linseed oil,

Hereinafter, as a bisphenol A type epoxy resin under the trade name, for example, Epicoat 825, 828, 834, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 8000, 8034 As above, manufactured by Japan Epoxy Resin Co., Ltd.]
Examples of the bisphenol F type epoxy resin include Epicoat 807 [manufactured by Japan Epoxy Resin Co., Ltd.] and the like;
Examples of the phenol novolac type epoxy resin include Epicoat 152, 154, and 157S65 [above, manufactured by Japan Epoxy Resin Co., Ltd.], EPPN 201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.) and the like;
Examples of the cresol novolac type epoxy resin include EOCN102, 103S, 104S, 1020, 1025, 1025 [above, manufactured by Nippon Kayaku Co., Ltd.], Epicoat 180S75 (manufactured by Japan Epoxy Resin Co., Ltd.), etc .;
As polyphenol type epoxy resin, for example, Epicoat 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.), etc.
As other alicyclic epoxy resins, for example, CY-175, 177, 179, Araldite CY-182, 192, 184 [above, manufactured by Ciba Specialty Chemicals], ERL-4206, -4221, 4234, -4299 (above, manufactured by UC Corporation), Shodyne 509 (manufactured by Showa Denko KK), Epicron 200, 400 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Epicote 871 872 [above, manufactured by Japan Epoxy Resin Co., Ltd.], ED-5661, -5662 [above, manufactured by Celanese Coating Co., Ltd.], etc.
Other aliphatic polyglycidyl ethers include, for example, Epolite 100MF (manufactured by Kyoeisha Chemical Co., Ltd.), Epiol TMP (manufactured by Nippon Oil & Fats Co., Ltd.), etc.

As a compound having two or more 3,4-epoxycyclohexyl groups, [(3,4-epoxycyclohexyl) methyl] ester of 3,4-epoxycyclohexanecarboxylic acid, 2- (3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexane metadioxane, bis [(3,4-epoxycyclohexyl) methyl] adipate, bis [(3,4-epoxy-6-methylcyclohexyl) methyl] adipate, 3,4- (3,4-epoxy-6-methylcyclohexyl) ester of epoxy-6-methylcyclohexanecarboxylic acid, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, bis [(3,4-epoxy (Cyclohexyl) methyl] ether, Bis Ji glycol (3,4-epoxycyclohexane carboxylate) ester, 3,4-epoxycyclohexane carboxylic acid [(3,4-epoxycyclohexyl) methyl] reaction products of esters and polycaprolactone and the like;
Examples of the compound having an epoxy group and a 3,4-epoxycyclohexyl group include 1,2: 8,9-diepoxy limonene and the like.

As the compound having an episulfide group, the oxiranyl group in the compound having one or more oxiranyl groups is exemplified by Non-Patent Document 1 (J. Org. Chem., Vol. 28, p. 229 (1963)). In accordance with the method shown in the above, compounds converted into episulfide groups can be exemplified.
Examples of the compound having one oxetanyl group include 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-methoxymethyloxetane, 3-methyl-3-ethoxymethyloxetane, and 3-ethyl-3-ethoxymethyl. Oxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-phenoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-methyl-3-benzyloxy Methyl oxetane, 3-ethyl-3-benzyloxymethyl oxetane, 3-methyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-methyl-3- (Nn-butylamidomethoxy) oxy Tan, 3-ethyl -3- (N-n- butyl amide methoxy) can be mentioned oxetane like.

Examples of the compound having two or more oxetane ring skeletons include 3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 ′-[1,3- (2-methylenyl) propanediylbis (oxymethylene). ] Bis (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, bis [(3-ethyl-3-oxetanyl) methyl] terephthalate, 1,2-bis [ (3-Ethyl-3-oxetanyl) methoxymethyl] ethane, 1,3-bis [(3-ethyl-3-oxetanyl) methoxymethyl] propane, ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether , Diethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [( 3-ethyl-3-oxetanyl) methyl] ether, tetraethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclo Decanediyldimethylenebis [(3-ethyl-3-oxetanyl) methyl] ether, trimethylolpropane tris [(3-ethyl-3-oxetanyl) methyl] ether, 1,4-bis [(3-ethyl-3- Oxetanyl) methoxy] butane, 1,6-bis [(3-ethyl-3-oxetanyl) methoxy] hexane, pentaerythritol tris [(3-ethyl-3-oxetanyl) methyl] ether, pentaerythritol tetrakis [(3-ethyl -3-Oxetanyl) methyl] ether, polyester Lenglycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) ) Methyl] ether, dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether,

Reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone, reaction product of dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether and caprolactone , Ditrimethylolpropanetetrakis [(3-ethyl-3-oxetanyl) methyl] ether, reaction product of bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide, bisphenol A bis [( Reaction product of 3-ethyl-3-oxetanyl) methyl] ether and propylene oxide, reaction product of hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide, hydrogenated bisphenol A bis [( - ethyl-3-oxetanyl) methyl] reaction products of ether and propylene oxide, may be mentioned reaction products of bisphenol F bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene oxide.
Among these (E) thermopolymerizable compounds, bisphenol A type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl) methyl] ester or bis [(3 -Ethyl-3-oxetanyl) methyl] terephthalate is preferred.
In the present invention, (E) the thermally polymerizable compound can be used alone or in admixture of two or more.
The use ratio of the (E) thermopolymerizable compound in the present invention is preferably 100 parts by weight or less, more preferably 1 to 50 parts by weight, and more preferably 5 parts per 100 parts by weight of the copolymer (A). It is preferable that it is -30 weight part. In this case, if the use ratio of the (E) thermopolymerizable compound exceeds 100 parts by weight, the developability of the resulting resin composition may be impaired.

When the radiation sensitive resin composition of the present invention contains the (E) thermopolymerizable compound, the thermal polymerization inhibitor can be used to suppress a decrease in developability due to hot fog during pre-baking. .
Examples of such thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, t-butylcatechol, methylhydroquinone, n-amylquinone, n-amyloyloxyhydroquinone, n-butylphenol, phenol, hydroquinone mono-n-propyl. Ether, 4,4 ′-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] diphenol, 1,1,3-tris (2,5-dimethyl-4 -Hydroxyphenyl) -3-phenylpropane and the like.
These thermal polymerization inhibitors can be used alone or in admixture of two or more.
The use ratio of the thermal polymerization inhibitor is preferably 5 parts by weight or less with respect to 100 parts by weight of the (E) thermopolymerizable compound.

The said surfactant can be used in order to improve the applicability | paintability, defoaming property, leveling property, etc. of the radiation sensitive resin composition of this invention.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and the like.
Examples of the fluorosurfactant include BM-1000, -1100 (above, manufactured by BM CHIMIE), MegaFuck F142D, F172, F173, F183 [above, DIC Corporation]. Manufactured], FLORARD FC-135, FC-170C, FC-430, FC-431 [above, manufactured by Sumitomo 3M Limited], Surflon S-112, S-113, S-131, S -141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 [above, manufactured by Asahi Glass Co., Ltd. And the like.
Examples of the silicone-based surfactants include trade names such as SH-28PA, -190, -193, SZ-6032, SF-8428, DC-57, -190 [above, Toray Dow Corning Silicone. KP341 [manufactured by Shin-Etsu Chemical Co., Ltd.], F-top EF301, EF303, EF352 [manufactured by Shin-Akita Kasei Co., Ltd.], and the like.
Examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl. Examples include polyoxyethylene aryl ethers such as phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.
Furthermore, as other surfactants, for example, Polyflow No. 57, no. 90 [above, manufactured by Kyoeisha Chemical Co., Ltd.].
These surfactants can be used alone or in admixture of two or more.
The addition amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the copolymer (A). In this case, if the addition amount of the surfactant exceeds 5 parts by weight, the coating film may be easily roughened during coating.

The said adhesion adjuvant can be used in order to improve the adhesiveness with respect to the board | substrate of the microlens formed from the radiation sensitive resin composition of this invention.
As such an adhesion assistant, for example, a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an oxiranyl group is preferable. Specifically, for example, trimethoxysilylbenzoic acid is used. , Γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Examples thereof include ethyltrimethoxysilane.
These adhesion assistants can be used alone or in admixture of two or more.
The addition amount of the adhesion assistant is preferably 20 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

To the radiation-sensitive resin composition of the present invention, a dissolution accelerator, a dissolution controller, or a solubility modifier can be added in order to adjust the solubility of the (A) copolymer in an alkaline developer. That is, when the solubility of the copolymer (A) in the alkaline developer is too low, the solubility is increased and the dissolution having an action of appropriately increasing the dissolution rate of the copolymer (A) during alkali development. An accelerator can be blended. On the other hand, when the solubility of the copolymer in the alkaline developer is too high, the solubility control agent controls the solubility and moderately reduces the dissolution rate of the copolymer (A) during alkali development. Can be blended. Furthermore, a solubility modifier can be added for fine adjustment of solubility.
The type of the dissolution accelerator and the dissolution control agent is not particularly limited, but a compound that does not change chemically in the steps such as heating, exposure and development of the radiation sensitive film is preferable. Examples of the dissolution accelerator include low molecular weight phenolic compounds having about 2 to 6 benzene rings. Specifically, bisphenol and its derivatives, tris (hydroxyphenyl) methane, etc. Can be mentioned. Specific examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned.
There is no limitation in particular about the usage-amount of the said dissolution promoter and a dissolution control agent, It can be set as a various ratio according to the kind of (A) copolymer to be used. The blending amount of the dissolution accelerator is preferably 50 parts by mass or less, more preferably 30 parts by mass or less per 100 parts by mass of the copolymer (A). It is preferable that the usage-amount of the said dissolution control agent is 50 mass parts or less per 100 mass parts of (A) copolymers, More preferably, it is 30 mass parts or less.

The solubility modifier is preferably a compound having a carboxyl group or a carboxylic anhydride group or both. Examples of the solubility regulator include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3- Hydroxymono, such as hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid carboxylic acid;
Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, Trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid Carboxylic acids; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, phthalic anhydride, anhydrous Pyromellitic acid, trimellitic anhydride, 1,2,3,4-butanetetracarbo Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, ethylene glycol bis (trimellitate) dianhydride, Examples include acid anhydrides such as glycerin tris (trimellitate) dianhydride.
These solubility regulators can be used alone or in admixture of two or more.
The use ratio of the solubility modifier is preferably 10 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

The filler, colorant, and viscosity modifier are within a range that does not impair the original characteristics of the radiation-sensitive resin composition of the present invention, preferably the total use ratio of these is the total of the resulting radiation-sensitive resin composition. It can be used within a range of 50% by weight or less.
Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, and powdered glass. These fillers can be used alone or in admixture of two or more.
Examples of the colorant include extender pigments such as alumina white, clay, barium carbonate, and barium sulfate;
Inorganic pigments such as zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, carbon black;
Organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green;
Basic dyes such as magenta and rhodamine;
Direct dyes such as direct scarlet and direct orange;
Examples include acid dyes such as roserine and methanyl yellow. These colorants can be used alone or in admixture of two or more.
Examples of the viscosity modifier include bentonite, silica gel, and aluminum powder. These viscosity modifiers can be used alone or in admixture of two or more.

-Radiosensitive resin composition-
The radiation-sensitive resin composition of the present invention is represented by (A) a copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) the above formula (I). For the purpose of uniformly mixing the compound and other components used as necessary, and further facilitating the coating operation on the substrate, it is preferable to dilute it with an organic solvent to obtain a liquid composition.
As said organic solvent, what can dissolve or disperse | distribute each component which comprises a radiation sensitive resin composition uniformly, does not react with each component, and has moderate volatility is preferable.
Examples of such an organic solvent include those similar to those described above as the organic solvent that can be used in the polymerization for producing the copolymer (A), N-methylformamide, N, N-dimethylformamide, N- Methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol And high-boiling solvents such as benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.
Of these organic solvents, polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether because of solubility, reactivity with each component, and ease of coating formation;
Alkyl ether acetates of polyhydric alcohols such as ethylene glycol monoethyl ether acetate;
Esters such as ethyl lactate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate;
Ketones such as diacetone alcohol are preferred.

These organic solvents can be used alone or in admixture of two or more.
The use ratio of the organic solvent can be appropriately selected according to the specific use of the radiation-sensitive resin composition, the coating method, etc., but the solid content concentration of the radiation-sensitive resin composition (other than the solvent in the composition) The ratio of the total weight of the components to the total weight of the composition) is preferably 20 to 60% by weight.
The preparation of the radiation-sensitive resin composition of the present invention can be carried out by stirring and mixing in the usual manner when no filler or pigment is added. When a filler or pigment is added, a dissolver or homogenizer is used. It can be carried out by dispersing and mixing using an appropriate dispersing machine such as a three-roll mill.
The radiation-sensitive resin composition mixed and prepared as described above may be subjected to use after further filtration with an appropriate mesh, membrane filter or the like, if necessary.
The radiation sensitive resin composition of the present invention as described above can be suitably used for forming a microlens.

Microlens The microlens of the present invention is formed from the radiation sensitive resin composition as described above.
The microlens according to the present invention includes an imaging optical system for on-chip color filters such as various OA devices, liquid crystal televisions, mobile phones, projectors, facsimiles, electronic copying machines, solid-state image sensors, and the like. It can be used very suitably for fiber connectors and the like.
Microlens Formation Method The microlens formation method of the present invention includes at least the following steps (1) to (4) in the order described below.
(1) A step of forming a film of the radiation sensitive resin composition of the present invention on the substrate as described above,
(2) A step of irradiating at least a part of the coating with radiation,
(3) a step of developing the film after irradiation, and (4) a step of heating the film after development.

Hereinafter, these steps will be described.
-Step (1)-
In the step (1), the radiation-sensitive resin composition for forming a microlens is used in a liquid state. The radiation-sensitive resin composition is applied on a flexible base film in advance, and the solvent is removed to perform the sensitization. A method of forming a radiation film (radiation sensitive layer) and transferring it to a substrate (dry film method) or the like can be employed.
When used in a liquid state, the radiation-sensitive resin composition is applied onto a substrate by a coating method, and pre-baked to remove the solvent, thereby forming a film (coating film).
Examples of the substrate that can be used here include a glass substrate, a resin substrate, a silicon wafer, and a substrate on which various metal layers are formed.
The method for applying the liquid composition is not particularly limited, and an appropriate method such as a spray method, a roll coating method, a spin coating method, a bar coating method, or the like can be employed.
As prebaking conditions, although it changes also with the kind of each component contained in the radiation sensitive resin composition of this invention, a usage rate, etc., Preferably it is about 30 seconds-15 minutes at 60-130 degreeC.
The film thickness of the formed coating film is preferably about 10 to 30 μm as the value after removal of the solvent.

On the other hand, when adopting the dry film method, a radiation-sensitive resin composition is applied on a flexible base film in advance, and then the solvent is removed to form a radiation-sensitive coating film (radiation-sensitive layer). Then, this is affixed to the substrate, and the radiation-sensitive layer is transferred onto the substrate by an appropriate method such as thermocompression bonding to form a film. The radiation sensitive layer formed on the base film can be stored by laminating a cover film on the radiation sensitive layer when not in use.
As the base film for the dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET) film, polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm.
For forming the coating film, an appropriate method such as an applicator, a bar coater, a roll coater, or a curtain flow coater can be employed.
The cover film for the dry film is for stably protecting the radiation-sensitive layer when not in use, and is removed during use. Therefore, it is necessary to have an appropriate releasability so that it does not peel off when not in use and can be easily peeled off when in use. As the cover film satisfying such conditions, a PET film, a polypropylene film, a polyethylene film, etc., each coated or baked with silicone, can be used. The cover film may be about 15 μm thick.
In the case of the dry film method, the cover film is removed so that the base film is on top. While applying pressure, the dry film is transferred onto the substrate. The kind of board | substrate which can be used here is the same as that of the case where a radiation sensitive resin composition is used with a liquid state.
As for the film thickness of the coating film formed, about 10-30 micrometers is preferable.

-Step (2)-
In the step (2), at least a part of the formed film is irradiated with radiation. In order to irradiate a part of the film with radiation, for example, a method of irradiating radiation through a mask having a predetermined pattern can be used.
Although it does not specifically limit as a radiation used here, For example, according to the kind etc. of (C) photoinitiator to be used, g line (wavelength 436nm), i line (wavelength 365nm), etc. UV rays, far ultraviolet rays such as KrF excimer laser, X-rays such as synchrotron radiation, charged particle beams such as electron beams, and the like are appropriately selected.
Of these radiations, ultraviolet rays are preferable, and radiation containing g-line or i-line or both is particularly preferable.
The dose of radiation as the (exposure), about 50~10,000J / m ² is preferred.
When the dry film method is used in step (1), the base film on the radiation-sensitive layer may be peeled off before the exposure step, or peeled off after the exposure step and before the development step. Also good.

-Step (3)-
In step (3), the film irradiated with radiation is developed with a developer, preferably an alkali developer, to remove unexposed portions, thereby forming a pattern with a predetermined shape.
Examples of the alkali developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, and triethylamine. , Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [ 4.3.0] -5-nonene and other basic compound aqueous solutions. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the aqueous solution of the basic compound.
After developing with an alkaline developer, it is preferable to wash with running water, for example.
In the case of a radiation-sensitive resin composition that does not contain insoluble components such as pigments and fillers, various organic solvents that dissolve each component constituting the composition may be used as a developer.
As a developing method, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, a shower method, or the like can be employed.
The development time varies depending on the composition of the radiation sensitive resin composition, but is preferably about 30 to 300 seconds at room temperature.
In the conventional radiation-sensitive resin composition used for forming the microlens, if the development time exceeds about 20 to 25 seconds from the optimum condition, the formed pattern is peeled off. Therefore, it is necessary to strictly control the development time. However, in the case of the radiation sensitive resin composition of the present invention, even when the excess time from the optimum development time is 30 seconds or more, a good pattern can be formed, which is advantageous in terms of product yield.

-Step (4)-
In the step (4), the film after development is heated (baked) with an appropriate heating device such as a hot plate or an oven to cure the film.
The baking conditions vary depending on the type and ratio of each component constituting the radiation-sensitive resin composition, the desired pattern shape, the heating device, and the like, but in the case of a hot plate, for example, 10-30 at 150 to 240 ° C. In the case of an oven, it is about 150 to 240 ° C. for about 30 to 90 minutes. Further, when baking, a step baking method in which heat treatment is performed twice or more may be employed.
Liquid crystal display element The liquid crystal display element of the present invention comprises a microlens formed from the radiation-sensitive resin composition of the present invention as described above. The remaining configuration of the liquid crystal display element of the present invention may be a known one.
The liquid crystal display element of the present invention can be very suitably applied to various OA devices, liquid crystal televisions, mobile phones, projectors and the like.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples.
-(A) Synthesis example of copolymer-
Synthesis example 1
After the flask equipped with a dry ice / methanol system reflux was purged with nitrogen, 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 100.0 g of diethylene glycol dimethyl ether and 50 g of diethylene glycol monomethyl ether as solvents. 0 g was charged and stirred until the radical polymerization initiator was dissolved. Thereafter, 15.0 g of methacrylic acid, 15.0 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 40.0 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 15. 0 g and 15.0 g of tetrahydrofurfuryl methacrylate were charged and stirring was started gently. Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours.
After polymerization, the reaction solution is dropped into a large amount of methanol to solidify the reaction product, and the resulting solidified product is washed with water, then redissolved in tetrahydrofuran of the same weight as the solidified product, and again into a large amount of methanol. It dropped and solidified. After performing this re-dissolution-coagulation operation 3 times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A-1) which is a copolymer (A).
Synthesis example 2
The flask equipped with a dry ice / methanol system reflux was purged with nitrogen, and then charged with 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150.0 g of diacetone alcohol as a solvent, and radical polymerization was performed. Stir until the initiator is dissolved. Then, 20.0 g of methacrylic acid, 15.0 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 40.0 g of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and styrene 15. 0 g and 5.0 g of isoprene were charged and stirring was started gently. Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours.
After polymerization, the reaction solution is dropped into a large amount of methanol to solidify the reaction product, and the resulting solidified product is washed with water, then redissolved in tetrahydrofuran of the same weight as the solidified product, and again into a large amount of methanol. It was dripped and solidified. After performing this re-dissolution-coagulation operation three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A-2) as a copolymer (A).

-Synthesis example of the compound represented by the general formula (1)-
Synthesis example 3
To a solution of 22.0 g (200 mmol) of resorcinol in 45 mL of ethanol, 15 mL of hydrochloric acid was added. While cooling this solution to 5 ° C. while stirring, 10.0 g (50 mmol) of a 50 wt% aqueous solution of glutaraldehyde was slowly added dropwise. Thereafter, the mixture was heated at 80 ° C. for 48 hours to obtain a cloudy yellow suspension.
This suspension was poured into methanol and the resulting precipitate was collected by filtration. This precipitate was washed with methanol three times. The washed precipitate was dried under reduced pressure at room temperature for 24 hours to obtain a powdery pale yellow solid (n) (yield: 11.2 g (yield: 79%)).
The structure of the obtained pale yellow solid (n) was confirmed by MALDI-TOF-MS (model number SHIMAZU / KRATOS matrix-assisted laser ionization time-of-flight mass spectrometer KOMPACT MALDI IV tDE, manufactured by Shimadzu Corporation), IR (model number) FT-IR 420 type, manufactured by JASCO Corporation) and ¹ H-NMR (model number JNM-ECA-500 type, manufactured by JEOL Ltd.). These results are shown below.
MALDI-TOF-MS: It was shown that only a compound with a molecular weight of 1,705 was obtained.
IR (film method): 3,406 cm ⁻¹ (ν _OH ); 2,931 cm ⁻¹ (ν _C—H ); 1,621 cm ⁻¹ , 1,505 cm ⁻¹ , 1,436 cm ⁻¹ (ν _{C = C (Aromatic)} )
¹ H-NMR (500 MHz, solvent: DMSO-d ₆ , internal standard: TMS): δ (ppm) = 0.86 to 2.35 (b, 12.0 H), 3.98 to 4.22 (m, 4.0H), 6.09-7.42 (m, 8.0H), 8.65-9.56 (m, 8.0H)

After adding 3.5 g (2.05 mmol, OH equivalent 49.2 mmol) of the pale yellow solid (n) obtained above to 40 g of 1-methyl-2-pyrrolidone, 0.8 g of tetrabutylammonium bromide was further added, It stirred at 70 degreeC for 4 hours, and melt | dissolved. To this solution, 3.3 g of potassium carbonate was added and stirred at 70 ° C. for 1 hour. Next, 2.73 g (29.5 mmol) of epichlorohydrin was added, and the reaction was further continued at 80 ° C. for 48 hours. After completion of the reaction, the reaction mixture was diluted with ethyl acetate, washed 3 times with distilled water, and the organic layer was dried over anhydrous magnesium sulfate. The desiccant was filtered off and concentrated, and compound (N-1) was obtained by reprecipitation using chloroform as a good solvent and n-hexane as a poor solvent.
The structure of the compound (N-1) obtained above was confirmed by IR, ¹ H-NMR and MALDI-TOF-MS. As a result, the compound (N-1) represented by the general formula (I-1) , 40 mol% of all R was a glycidyl group, and the remaining R was a hydrogen atom.

Synthesis example 4
2.0 g of the compound (N-1) obtained in Synthesis Example 3 was taken and dissolved in methylene chloride. After adding 0.8 g of tetrabutylammonium bromide, 2.18 g (29.5 mmol) of acrylic acid was added. ) Was gradually added and stirred at 50 ° C. for 4 hours to cause a reaction.
After completion of the reaction, the reaction mixture was washed successively with dilute hydrochloric acid, aqueous sodium hydrogen carbonate solution and distilled water, and the organic layer was dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was removed to obtain compound (N-2).
When the structure of the obtained compound (N-2) was confirmed by IR and ¹ H-NMR, all glycidyl groups of the compound (N-1) reacted to give n1 in the above formula (R-13). Was converted to a group of 1.

Example 1
Preparation of Radiation Sensitive Resin Composition 10.0 g of the copolymer (A-1) obtained in Synthesis Example 1 above was dissolved in 10.0 g of methyl 3-methoxypropanoate, and (B) polymerizable unsaturated. 2.0 g of Aronix M8100 as a compound and 1.0 g of KAYARAD R-526 and (C) 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name “Lucirin TPO”, manufactured by BASF) as a photopolymerization initiator 2.0 g and 1.0 g of Irgacure 651 were added, and 2.0 g of compound (N-1) obtained in Synthesis Example 3 as component (D) and 1.0 g of Epicoat 152 as (E) thermopolymerizable compound were added. In addition, after adding methyl 3-methoxypropionate to make a solution with a solid concentration of 50% by weight, filter with a membrane filter with a pore size of 5 μm. By radiation-sensitive resin composition (S-1) was prepared.
Formation of Patterned Thin Film After applying the liquid composition (S-1) on a glass substrate using a spinner, it was pre-baked on a hot plate at 100 ° C. for 5 minutes to form a coating film.
Next, the obtained coating film was irradiated with ultraviolet rays having an intensity of 200 W / m ^{2 at} a wavelength of 365 nm for 5 seconds through a mask having a predetermined pattern. Thereafter, shower development was performed with a 0.5 wt% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 2 minutes, followed by washing with pure water for 1 minute to form a pattern. Thereafter, this pattern was baked in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film (microlens) having a thickness of 19.4 μm.
Subsequently, evaluation was performed in the following manner. The evaluation results are shown in Table 1.

-Evaluation of resolution-
Regarding the patterned thin film formed above, the resolution is “excellent” when the pattern of line / space = 10 μm / 10 μm is resolved, and the pattern of line / space = 10 μm / 10 μm is not resolved, but the line / space = 20 μm / 20 μm pattern was evaluated as resolution “good”, and when both patterns were not resolved, resolution “bad”.
-Evaluation of pattern shape-
Among the patterned thin films formed above, the cross-sectional shape of the pattern of line / space = 30 μm / 30 μm was observed with a transmission electron microscope to evaluate which shape corresponds to FIG. It can be said that the pattern shape is good when it is a semi-convex lens shape as in (a).
-Evaluation of transparency-
The transmittance (%) at a wavelength of 400 nm of the patterned thin film formed above was measured and evaluated with a spectrophotometer 150-20 type double beam (manufactured by Hitachi, Ltd.). When this transmittance exceeds 95%, it can be said that the transparency is good.
-Evaluation of heat resistance-
The patterned thin film formed above was heated in an oven at 220 ° C. for 60 minutes, and evaluated by the reduction rate (%) of the film thickness before and after heating. When the film thickness reduction rate is within 5%, it can be said that the heat resistance is good.
-Evaluation of heat discoloration-
The patterned thin film formed above is heated in an oven at 220 ° C. for 60 minutes, and the transmittance of the patterned thin film before and after heating at a wavelength of 400 nm is measured using a spectrophotometer 150-20 type double beam (manufactured by Hitachi, Ltd.). ) And evaluated by the rate of decrease in transmittance (%). When the rate of decrease in transmittance is within 5%, it can be said that the heat discoloration is good.
Comparative Example 1
In Example 1, except that the compound (N-1) was not added, a radiation-sensitive resin composition (s-1) was prepared in the same manner as in Example 1, and a patterned thin film was formed and evaluated. The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 2
Preparation of Radiation Sensitive Resin Composition 10.0 g of the copolymer (A-2) obtained in Synthesis Example 2 was dissolved in 10.0 g of methyl 3-methoxypropanoate, and (B) polymerizable unsaturated. 2.0 g of Aronix M8100 and 1.0 g of KAYARAD R-526 as the compound, and 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and Irgacure 651 as the photopolymerization initiator 1.0 g of the compound (N-2) obtained in Synthesis Example 4 was added as component (D), and methyl 3-methoxypropionate was further added to obtain a solid content of 50% by weight. Then, a radiation sensitive resin composition (S-2) was prepared by filtering with a membrane filter having a pore size of 5 μm.
Formation and Evaluation of Patterned Thin Film In Example 1, the radiation-sensitive resin composition (S-2) prepared above was used instead of the radiation-sensitive resin composition (S-1), and the dry film was used instead of the spinner. A patterned thin film was formed and evaluated in the same manner as in Example 1 except that the film method was used. The base film was peeled and removed before the exposure process. The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film. Table 1 also shows the evaluation results of the following transferability.
Dry film preparation and transfer were performed as follows.
A radiation-sensitive resin composition (S-2) is applied onto a polyethylene terephthalate film having a thickness of 38 μm using an applicator, the coating film is heated at 100 ° C. for 5 minutes, and a radiation-sensitive dry film having a thickness of 25 μm ( J-1) was produced. Next, the radiation-sensitive transfer dry film is superposed on the surface of the glass substrate so that the surface of the radiation-sensitive transfer layer is in contact, and the radiation-sensitive dry film (J-1) is laminated on the glass substrate by thermocompression bonding. Transcribed to.
-Evaluation of transferability of dry film to glass substrate-
When the radiation-sensitive layer is transferred onto the glass substrate using the radiation-sensitive dry film (J-1) by the thermocompression bonding method, the transfer property is “good” when the dry film can be uniformly transferred onto the glass substrate. When the dry film could not be uniformly transferred onto the glass substrate, such as when the dry film partially remained on the base film or the dry film did not adhere to the glass substrate, the transferability was evaluated as “bad”. .
Comparative Example 2
In Example 2 above, a radiation-sensitive resin composition (s-2) was prepared in the same manner as in Example 2 except that the compound (N-2) was not added, and a radiation-sensitive dry film ( J-2) was prepared and a patterned thin film was formed and evaluated. The evaluation results are shown in Table 1 together with the evaluation results of the film thickness and transferability of the patterned thin film.

The schematic diagram showing the cross-sectional shape of a micro lens.

Claims (11)

(A) (a) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having no acidic functional group 20 to 60 An alkali-soluble copolymer obtained by polymerizing 5% by weight and (c) 5 to 40% by weight of other polymerizable unsaturated compounds (where (a) + (b) + (c) = 100% by weight); A radiation-sensitive resin composition comprising B) a polymerizable unsaturated compound, (C) a photopolymerization initiator, and (D) a compound represented by the following general formula (I).

(In the formula (I), R is independently of each other a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or — (CH ₂ ) _n1 —R ^I (where R ^I is a (meth) acryloyl group or carbon A monovalent group having an alkoxyl group of 1 to 6 or a cycloalkyl group having 3 to 8 carbon atoms, a carboxyl group, an oxiranyl group, an oxetanyl group or a vinyl group, and the oxetanyl group and the oxiranyl group each have may be substituted with 1-6 alkyl groups, n1 is an integer of 0 to 3, it is when n1 is 0 R ^I is a monovalent group having an alkoxyl group having 1 to 6 carbon atoms However, not all of the 24 Rs in total are hydrogen atoms,
X is independently of each other a methylene group or an alkylene group having 2 to 10 carbon atoms,
Y is independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group or alkynyl group having 2 to 20 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or a phenoxy group. ,
q is 0 or 1 independently of each other. )   The radiation sensitive resin composition according to claim 1, wherein X in the formula (I) is a trimethylene group. The R ^I is a cycloalkyl group having 3 to 8 carbon atoms, a carboxyl group, an oxiranyl group, an oxetanyl group, a vinyl group, or the following formula (R-1 ′)

(In Formula (R-1 ′), R ^II is a hydrogen atom or a methyl group, n2 is an integer of 1 to 5, and n3 is 0 or 1.)
A group represented by
The radiation sensitive resin composition of Claim 1 or 2 whose ratio of what is not a hydrogen atom among said R is 10-90 mol% with respect to the whole of R.   (E) The radiation sensitive resin composition of Claim 1 or 2 which further contains a thermopolymerizable compound.   The radiation sensitive resin composition according to any one of claims 1 to 4, which is used for forming a microlens.   The microlens formed from the radiation sensitive resin composition as described in any one of Claims 1-4. A method for forming a microlens, comprising at least the following steps (1) to (4) in the order described below.
(1) The process of forming the film of the radiation sensitive resin composition as described in any one of Claims 1-4 on a board | substrate,
(2) A step of irradiating at least a part of the coating with radiation,
(3) a step of developing the film after irradiation, and (4) a step of heating the film after development.   A radiation-sensitive dry film, wherein a radiation-sensitive layer obtained from the radiation-sensitive resin composition according to any one of claims 1 to 4 is provided on a base film.   The radiation-sensitive dry film according to claim 8, which is used for forming a microlens.   8. The micro of claim 7, wherein the step of forming a film of the radiation sensitive resin composition on the substrate in the step (1) is performed using the radiation sensitive dry film of claim 8. Lens forming method.   A liquid crystal display element comprising the microphone black lens according to claim 6.

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