JP2006343709A - Radiation sensitive resin composition, microlens and process for forming the same, and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition capable of forming microlenses excellent in thickness, resolution, pattern shape, heat resistance, transparency, heat discoloration resistance, solvent resistance, and also capable of having good storage stability. <P>SOLUTION: The radiation sensitive resin composition comprises: (A) an alkali-soluble copolymer obtained by polymerizing 100 wt.%, in total, of 10-50 wt.% of a polymerizable unsaturated compound (a) having an acidic functional group, 20-60 wt.% of a polymerizable unsaturated compound (b) having an alicyclic hydrocarbon group but not having an acidic functional group and 5-40 wt.% of another polymerizable unsaturated compound (c); (B) a polymerizable unsaturated compound including a polymerizable unsaturated compound having an alicyclic hydrocarbon group but not having an acidic functional group as an essential component; and (C) a photopolymerization initiator. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

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

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. With the spread of office automation equipment such as personal computers and word processors, LCD TVs, mobile phones, projectors, and the like, 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, a glass substrate is dry-etched to form a dent, and then filled with a high refractive index ultraviolet curable resin, and a lens pattern is formed and then heated. By processing, the pattern is melt-flowed and used as a lens as it is, a pattern is formed from the radiation-sensitive resin composition and melt-flowed to create a mask with a predetermined shape, and dry etching is performed through this mask. For example, a method of transferring a predetermined lens shape to the base may be used. However, in any of these methods, the microlens formation process is complicated and expensive, and it is not industrially sufficient.
Therefore, various characteristics required for microlenses, such as film thickness, resolution, pattern shape, transparency, heat resistance, solvent resistance, etc., can be satisfied, storage stability is good and Development of a radiation sensitive resin composition capable of forming a lens is strongly demanded.

Further, with the recent spread of liquid crystal display elements, there is an increasing demand for weight reduction and manufacturing cost reduction.
Therefore, instead of the conventionally used glass, as disclosed in Patent Document 5, attempts have been made to use a resin substrate. Accordingly, in order to avoid deformation and yellowing of the resin substrate, a low heating temperature is used. Development of a radiation-sensitive resin composition and method capable of forming a microlens is strongly demanded.

In addition, a method for forming a microlens for a liquid crystal display element using a radiation-sensitive resin composition is often performed by using a resin composition containing an organic solvent by a method such as a spin coating method, a dipping method, or a spray method. It has undergone a process of forming a coating film thereon. In such a method, time required for obtaining the conditions for obtaining a predetermined film thickness is required, and environmental problems such as volatilization of organic solvents have been pointed out.
Therefore, it is desired to develop a microlens forming method that is free from environmental problems and can be made in a shorter time and at a lower cost than a conventional microlens forming method.

JP 2001-154181 A JP 2001-117114 A JP-A-11-109417 Japanese Patent Laid-Open No. 10-268305 Japanese Patent Laid-Open No. 2000-10087

The present invention has been made based on the circumstances as described above, and the problem is that even when the temperature of the heat treatment is low, the film thickness, resolution, pattern shape, heat resistance, transparency, and heat discoloration. An object of the present invention is to provide a radiation-sensitive resin composition that can form a microlens excellent in properties, solvent resistance, and the like, and also has good storage stability.
Another object of the present invention is to form a microlens having the above-mentioned excellent characteristics by a simple process including the case of using a radiation-sensitive dry film, and can be formed even when the temperature of the heat treatment is low. Another object is to provide a method for forming a microlens.
Still another object of the present invention is to provide a liquid crystal display device including the microlens.

The present invention, first,
(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 compound (where (a) + (b) + (c) = 100% by weight); B) a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having a polymerizable unsaturated compound having no acidic functional group as essential components, and (C) a photopolymerization initiator. A radiation sensitive resin composition,
Consists of.
The “radiation” as used in the present invention means a substance containing ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beams, and the like.

The present invention secondly,
The radiation-sensitive resin composition for forming microlenses (hereinafter also referred to as “radiation-sensitive resin composition for forming microlenses”),
Consists of.

Third, the present invention
A microlens formed from a radiation-sensitive resin composition for forming a microlens,
Consists of.

The present invention fourthly,
A radiation-sensitive dry film obtained by laminating a radiation-sensitive layer comprising the radiation-sensitive resin composition on a base film;
Consists of.

The present invention fifthly,
A method for forming a microlens, comprising at least the following steps (a) to (d) in the order of description described below:
(A) a step of forming a coating of a radiation-sensitive resin composition for forming a microlens on a substrate;
(B) irradiating at least a part of the coating with radiation;
(C) developing the film after irradiation;
(D) a step of heat-treating the developed film;
Consists of.
In the method for forming the microlens, the temperature of the heat treatment in step (d) can be set to 160 ° C. or less.

Sixth, the present invention
A liquid crystal display device comprising the microlens,
Consists of.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive resin composition- (A) copolymer-
The component (A) in the present invention comprises (a) a polymerizable unsaturated compound having an acidic functional group (hereinafter referred to as “(a) polymerizable unsaturated compound”), 10 to 50% by weight, and (b) alicyclic. 20 to 60% by weight of a polymerizable unsaturated compound having a hydrocarbon group and having no acidic functional group (hereinafter referred to as “(b) polymerizable unsaturated compound”) and (c) other polymerizable unsaturated compounds It consists of an alkali-soluble copolymer (hereinafter referred to as “(A) copolymer”) composed of 5 to 40% by weight of the compound (however, (a) + (b) + (c) = 100% by weight).

(A) In the polymerizable unsaturated compound, examples of the acidic functional group include a carboxyl group and a sulfonic acid group, and a carboxyl group is particularly preferable.
Examples of the (a) polymerizable unsaturated compound having a carboxyl group (hereinafter referred to as “(a1) polymerizable unsaturated compound”) include (meth) acrylic acid, crotonic acid, and α of acrylic acid or crotonic acid. Unsaturated monocarboxylic acids such as compounds substituted at the -position with a substituent such as a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group or a cyano group; maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid, Unsaturated dicarboxylic acids such as itaconic acid or acid anhydrides thereof; the hydrogen atom of one carboxyl group in the unsaturated dicarboxylic acid is a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group , Sec-butyl groups, t-butyl groups, phenyl groups, o-tolyl groups, m-tolyl groups, p-tolyl groups and the like substituted half esters Half amides in which one carboxyl group in the unsaturated dicarboxylic acid is converted to an amide group; monoesterified product of 2-hydroxyethyl (meth) acrylate and succinic acid, 2-hydroxyethyl (meth) acrylate and maleic acid Monoesterified product of 2-hydroxyethyl (meth) acrylate and hexahydrophthalic acid (hereinafter referred to as “2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate”), etc. And carboxyl group-containing (meth) acrylic acid esters.
Of these (a1) polymerizable unsaturated compounds, (meth) acrylic acid, 2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate, and the like are preferable.
In the present invention, (a) the polymerizable unsaturated compound 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 (meth) acrylate in combination.

  (A) The content of the polymerizable unsaturated compound (a) in the copolymer is 10 to 50% by weight, preferably 20 to 40% by weight. In this case, if the content 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 is obtained. On the other hand, if the amount exceeds 50% by weight, the solubility of the resulting copolymer in an alkaline developer tends to be too high, and the film thickness of the radiation irradiated portion tends to increase.

(B) Examples of the polymerizable unsaturated compound include cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-methylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and 1-methylcyclohexyl (meth). Examples include acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and the like. .
Of these (b) polymerizable unsaturated compounds, tricyclodecanyl (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.

  (A) The content rate of the (b) polymerizable unsaturated compound which occupies in a copolymer is 20 to 60 weight%, Preferably it is 30 to 50 weight%. In this case, if the content of the polymerizable unsaturated compound (b) is less than 20% by weight, the resulting copolymer may not have a sufficiently high molecular weight, which may make it difficult to form a sufficiently thick film. On the other hand, if it exceeds 60% by weight, the solubility of the resulting copolymer in a solvent or an organic solvent tends to decrease.

(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, unsaturated dicarboxylic acid diesters exemplified for the above-mentioned (a1) polymerizable unsaturated compound, aromatic vinyl compounds, and conjugated diesters. Examples include olefins, nitrile group-containing unsaturated compounds, chlorine-containing unsaturated compounds, amide bond-containing unsaturated compounds, and fatty acid vinyl esters.

  Examples of the (meth) acrylic acid esters include 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 (meth) acrylate, benzyl (meth) acrylate Rate, phenethyl (meth) acrylate, cresyl (meth) acrylate, glycidyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, pentafluoro Ethyl (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-butyrolactone, β- (meth) acryloyloxy-γ -Butyrolactone etc. can be mentioned.

Examples of the unsaturated dicarboxylic acid diesters include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconate, and diethyl itaconate.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and the like.
Examples of the conjugated diolefins include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Examples of the nitrile group-containing unsaturated compound include (meth) acrylonitrile, vinylidene cyanide, and the like.
Examples of the chlorine-containing unsaturated compound include vinyl chloride and vinylidene chloride.
Examples of the amide bond-containing unsaturated compound include (meth) acrylamide, maleic acid diamide, and fumaric acid diamide.
Examples of the fatty acid vinyl esters include vinyl acetate and vinyl propionate.

Of these (c) other polymerizable unsaturated compounds, tetrahydrofurfuryl (meth) acrylate, styrene, 1,3-butadiene, isoprene and the like are preferable.
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.
The content of (c) other polymerizable unsaturated compound in the copolymer (A) is 5 to 40% by weight, preferably 10 to 35% by weight.

(A) The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer is preferably 2,000 to 100,000, and more preferably 5,000 to 50,000. In this case, when the Mw of the copolymer (A) is less than 2,000, alkali developability, residual film ratio, pattern shape, heat resistance and the like tend to decrease, whereas when it exceeds 100,000, the sensitivity And the pattern shape tends to decrease.
The ratio (Mw / Mn) of Mw of the copolymer (A) to polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) is usually 1.0 to 5.0, preferably 1.0. ~ 3.0.

(A) The copolymer comprises (a) a polymerizable unsaturated compound, (b) a polymerizable unsaturated compound, and (c) another polymerizable unsaturated compound, for example, in a suitable solvent in a radical polymerization initiator. It can be produced by polymerizing in the presence.
As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol and diacetone alcohol; ethers such as tetrahydrofuran, tetrahydropyran and dioxane; ethylene glycol alkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate and ethylene glycol mono Ethylene glycol monoalkyl ether acetates such as ethyl 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, and 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 monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene Propylene glycol monoalkyl ether acetates such as glycol mono-n-propyl ether acetate and propylene glycol mono-n-butyl ether acetate; propylene glycol monomethyl ether propionate, propylene glycol ethyl monoether propionate, propylene glycol mono-n- Propyl ether propionate, propionate Propylene glycol monoalkyl ether propionates such as ethylene glycol mono-n-butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, 4-hydroxy-4 -Ketones such as 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-butyl peroxypivalate, 1,1′-bis (t-butylperoxy) cyclohexane, hydrogen peroxide, etc. Can be mentioned. 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 (A) copolymer can be used alone or in admixture of two or more.

-(B) polymerizable unsaturated compound-
The component (B) in the present invention is an essential component of a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having no acidic functional group (hereinafter referred to as “(B1) polymerizable unsaturated compound”). And (C) a polymerizable unsaturated compound that is polymerized by irradiation with radiation in the presence of a photopolymerization initiator.
Examples of the polymerizable unsaturated compound (B1) include cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-methylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and 1-methylcyclohexyl (meth). Examples include acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 2-dicyclopentanyloxyethyl (meth) acrylate, and the like. .
Of these (B1) polymerizable unsaturated compounds, tricyclodecanyl (meth) acrylate is particularly preferable.
In the present invention, the polymerizable unsaturated compound (B1) can be used alone or in admixture of two or more.

  In the present invention, the content of the (B1) polymerizable unsaturated compound in the (B) polymerizable unsaturated compound component is preferably 5 to 80% by weight, more preferably 10 to 70% by weight. In this case, if the content of the polymerizable unsaturated compound (B1) is less than 5% by weight, there is a risk that the film thickness of the radiation irradiated portion will increase. On the other hand, if it exceeds 80% by weight, the desired lens shape is obtained. It may be difficult to obtain.

Examples of the (B) polymerizable unsaturated compound other than the (B1) polymerizable unsaturated compound include, for example, a compound having one ethylenically unsaturated bond (hereinafter, “other monofunctional polymerizable unsaturated compound”). A compound having two ethylenically unsaturated bonds (hereinafter referred to as “another bifunctional polymerizable unsaturated compound”), a compound having three or more ethylenically unsaturated bonds (hereinafter “others”) And a polyfunctional polymerizable unsaturated compound.).
Examples of other monofunctional polymerizable unsaturated compounds include mono (meth) acrylates of monohydric alcohols, preferably compounds represented by the following formula (1).

〔式（１）中、ｎは０〜８の整数であり、Ｒ¹ は水素原子または炭素数１〜９の直鎖状、分岐状もしくは環状のアルキル基を示す。〕

Wherein (1), n is an integer of 0 to 8, R ¹ is a straight, branched or cyclic alkyl group having 1 to 9 carbon hydrogen atom or a carbon. ]

Specific examples of the compound represented by the formula (1) include, under the trade names, Aronix M-101 (n = about 2, R ¹ = H), M-102 (n = about 4, R ¹ = H), M-111 [n = about 1, R ¹ = n—C ₉ H ₁₉ (n-nonyl group, the same shall apply hereinafter)], M-113 (n = about 4, R ¹ = n-nonyl group), M-114 (n = about 8, R ¹ = n-nonyl group), M-117 (n = 2.5, R ¹ = n-nonyl group) [above, manufactured by Toa Gosei Chemical Co., Ltd.] , KAYARAD R-564 (n = about 2.3, R ¹ = H) [manufactured by Nippon Kayaku Co., Ltd.].

  In addition, as monofunctional polymerizable unsaturated compounds other than the compound represented by the formula (1), for example, KAYARAD TC-110S and TC-120S [manufactured by Nippon Kayaku Co., Ltd.] under trade names V-158, V-2311 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), unsaturated carboxylic acid diesters such as dimethyl maleate and diethyl maleate, and the like (a) Polymerizability in the copolymer (A) Examples thereof include the same compounds as those exemplified for the unsaturated compound, (b) the polymerizable unsaturated compound, or (c) the other polymerizable unsaturated compound.

  Next, as another bifunctional polymerizable unsaturated compound, for example, di (meth) acrylates of dihydric alcohol, preferably a compound represented by the following formula (2), a compound represented by the following formula (3) And compounds represented by the following formula (4).

〔式（２）中、ｎおよびｍはそれぞれ０〜８の整数であり、各Ｒ² は相互に独立に水素原子またはメチル基を示す。〕

Wherein (2), n and m are each an integer of 0 to 8, each R ² represents a hydrogen atom or a methyl group independently of each other. ]

〔式（３）中、Ｅは炭素数２〜８の直鎖状もしくは分岐状のアルキレン基を示し、ｉは１〜１０の整数である。〕

[In Formula (3), E shows a C2-C8 linear or branched alkylene group, and i is an integer of 1-10. ]

〔式（４）中、各Ｒ² は相互に独立に水素原子またはメチル基を示し、各Ｍは相互に独立に２価アルコールの残基を示し、Ｎは２塩基酸の残基を示し、ｊは０または１である。〕

[In the formula (4), each R ² independently represents a hydrogen atom or a methyl group, each M independently represents a dihydric alcohol residue, N represents a dibasic acid residue, j is 0 or 1. ]

Specific examples of the compound represented by the formula (2) include, under the trade name, Aronix M-210 (n = about 2, m = about 2, R ² = methyl group) [manufactured by Toa Gosei Chemical Co., Ltd.], KAYARAD R-551 (n + m = about 4, R ² = methyl group), R-712 (n + m = about 4, R ² = H) [manufactured by Nippon Kayaku Co., Ltd.].

Further, specific examples of the compound represented by the formula (3) include, under the trade name, Aronix M-240 [E = —CH ₂ CH ₂ —, i = about 4], M-245 [E = —CH _2]. CH ₂ −, i = about 9] [above, manufactured by Toa Gosei Chemical Co., Ltd.]
KAYARAD HDDA [E = − (CH ₂ ) ₆ −, i = 1],
NPGDA [E = —CH ₂ C (CH ₃ ) ₂ CH ₂ —, i = 1],
The TPGDA _{[E = -CH 2 CH (CH 3} ) -, i = 1 ],
PEG400DA [E = —CH ₂ CH ₂ —, i = about 8] [Nippon Kayaku Co., Ltd.], light acrylate 1.9-NDA [E = — (CH ₂ ) ₈ —, i = 1 And the like.

  Moreover, as a specific example of the compound represented by Formula (4), it is a brand name, Aronix M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 [ As mentioned above, Toa Gosei Chemical Co., Ltd.] and the like can be mentioned.

  Furthermore, as other bifunctional polymerizable unsaturated compounds other than those described above, a compound represented by the following formula (5-1) [trade name KAYARAD HX-220, manufactured by Nippon Kayaku Co., Ltd.], the following formula (5 -2) [trade name KAYARAD HX-620, manufactured by Nippon Kayaku Co., Ltd.] and trade names KAYARAD R-526, R-604, MANDA [manufactured by Nippon Kayaku Co., Ltd.] ], V-260, V-312, V-335HP [above, manufactured by Osaka Organic Chemical Industry Co., Ltd.].

〔式（５−１）中、ｐおよびｑはそれぞれ０〜２の整数で、ｐ＋ｑ＝２である。〕
〔式（５−２）中、ｒおよびｓはそれぞれ０〜４の整数で、ｒ＋ｓ＝４である。〕

[In Formula (5-1), p and q are each an integer of 0 to 2, and p + q = 2. ]
[In the formula (5-2), r and s are each an integer of 0 to 4, and r + s = 4. ]

  Next, as other polyfunctional polymerizable unsaturated compounds, for example, poly (meth) acrylates of trivalent or higher alcohols, preferably compounds represented by the following formula (6), represented by the following formula (7): A compound represented by the following formula (8), a compound represented by the following formula (9), and the like.

〔式（６）中、ｎは０〜８の整数であり、Ｒ³ は水素原子、水酸基またはメチル基を示す。〕

Wherein (6), n is an integer of 0 to 8, R ³ represents a hydrogen atom, a hydroxyl group or a methyl group. ]

〔式（７）中、Ｇは酸素原子またはメチレン基を示す。〕

[In Formula (7), G represents an oxygen atom or a methylene group. ]

〔式（８）中、各Ｒ² は相互に独立に水素原子またはメチル基を示し、各Ｘは相互に独立に３価アルコールの残基を示し、Ｙは２塩基酸の残基を示し、ｔは０〜１５の整数である。〕

[In the formula (8), each R ² independently represents a hydrogen atom or a methyl group, each X independently represents a residue of a trihydric alcohol, Y represents a residue of a dibasic acid, t is an integer of 0-15. ]

〔式（９）中、ＡはＣＨ₂ ＝ＣＨＣＯ−を示し、ｕは１または２であり、ａは２〜６の整数、ｂは０〜４の整数で、ａ＋ｂ＝６である。〕

Wherein (9), A represents a CH ₂ = CHCO-, u is 1 or 2, a is an integer of from 2 to 6, b is an integer of 0 to 4, which is a + b = 6. ]

  Specific examples of the compound represented by formula (6) include, under the trade names, Aronix M-309 (n = 0, R = methyl group), M-310 (n = about 1, R = methyl group) , Manufactured by Toa Gosei Chemical Industry Co., Ltd.], KAYARAD TMPTA (n = 0, R = methyl group) [manufactured by Nippon Kayaku Co., Ltd.], V-295 (n = 0, R = methyl group), V-300 (N = 0, R = hydroxyl group) [above, manufactured by Osaka Organic Chemical Industry Co., Ltd.].

  Moreover, as a specific example of the compound represented by Formula (7), Aronix M-400 [made by Toa Gosei Chemical Co., Ltd.] etc. can be mentioned by a brand name.

  Further, specific examples of the compound represented by the formula (8) include, under trade names, Aronix M-7100, M-8030, M-8060, M-8100, M-9050 [above, Toa Gosei Chemical Co., Ltd. Manufactured by Kogyo Co., Ltd.].

  Further, specific examples of the compound represented by the formula (9) include KAYARAD DPCA-20 (u = about 1, a = about 2, b = about 4), and DPCA-30 (u = about 1) as trade names. , A = about 3, b = about 3), DPCA-60 (u = about 1, a = about 6, b = about 0), DPCA-120 (u = about 2, a = about 6, b = About 0) [Nippon Kayaku Co., Ltd.], V-360, V-GPT, V-3PA, V-400 [Osaka Organic Chemical Co., Ltd.], and the like.

Of these (B) polymerizable unsaturated compounds other than these (B1) polymerizable unsaturated compounds, other bifunctional polymerizable unsaturated compounds and other polyfunctional polymerizable unsaturated compounds are preferred, and more preferably A compound represented by (4), a compound represented by formula (8), and the like.
In this invention, (B) polymerizable unsaturated compounds other than (B1) polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

  The amount of the (B) polymerizable unsaturated compound used in the present invention is preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the (A) copolymer. In this case, if the amount of the (B) polymerizable unsaturated compound used is less than 5 parts by weight, the sensitivity at the time of irradiation with radiation tends to be low, and a desired lens shape may be difficult to obtain. If it exceeds the parts by weight, the compatibility with the copolymer (A) is deteriorated, and there is a risk of film roughness on the coating film surface.

-(C) Photopolymerization initiator-
(C) component in this invention consists of a photoinitiator which produces the active species (for example, radical etc.) which can start superposition | polymerization of (B) polymerizable unsaturated compound by irradiation of a 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 and benzoin isopropyl ether; thioxanthone Thioxanthones such as 2,4-diethylthioxanthone and thioxanthone-4-sulfonic acid; benzophenones such as benzophenone, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; acetophenone, Acetophenones such as p-dimethylaminoacetophenone, α, α′-dimethoxyacetoxybenzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone; anthraquinone, 1,4-na Quinones such as phthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone, tris (trichloromethyl) -s-triazine; peroxides such as di-t-butyl peroxide; 2,4,6-trimethylbenzoyl Acylphosphine oxides such as diphenylphosphine oxide; 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -nonane-1,2-nonane-2-oxime-O-benzo Art, 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- ( - ethyl-6-benzoyl -9.H.- carbazol-3-yl) - octan-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.

  Moreover, (C) As a commercial item of a photoinitiator, Irgacure 184, 500, 651, 907, 369, 379, CG24-61 (above, manufactured by Ciba Geigy Co., Ltd.), Lucillin LR8728, Lucillin TPO (above, manufactured by BASF), Darocur 1116, 1173 (above, made by Merck), Ubekrill p36 (made by UCB), and the like can be mentioned.

Of these (C) photopolymerization initiators, 2-methyl [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 Acetophenones such as -morpholinophenyl) butan-1-one, phenacyl chloride, tribromomethylphenylsulfone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.
In the present invention, the photopolymerization initiator (C) can be used alone or in admixture of two or more, and can also be used in combination with one or more radiosensitizers.

  The amount of the (C) photopolymerization initiator used in the present invention is usually 0.01 to 100 parts by weight, preferably 0.01 to 50 parts by weight, based on 100 parts by weight of the (B) polymerizable unsaturated compound. More preferably, it is 0.5-40 weight part. In this case, if the amount of the (C) photopolymerization initiator used is less than 0.01 parts by weight, the sensitivity tends to decrease. On the other hand, if it exceeds 100 parts by weight, the copolymer (A) or (B) There exists a tendency for compatibility with a polymerizable unsaturated compound to worsen and for the storage stability of the resin composition obtained to fall.

-Additives-
The radiation-sensitive resin composition of the present invention can be added with a thermopolymerizable compound that is polymerized by heating but not polymerized by irradiation with radiation.
As such a heat-polymerizable compound, those which are thermally polymerized preferably at 80 to 250 ° C., more preferably 80 to 160 ° C., particularly preferably 100 to 150 ° C. are desirable.
In the radiation-sensitive resin composition for forming a microlens, it is preferable to add a thermopolymerizable compound, particularly when forming a microlens at a heat treatment temperature of 160 ° C. or lower.
The thermopolymerizable compound is generally a monomer, but its molecular weight is not particularly limited, and may have a molecular weight of about an oligomer.
Examples of the thermopolymerizable compound include compounds having one or more or one or more types of thermopolymerizable functional groups in the molecule, such as an epoxy group, an episulfide group, and an oxetanyl group. However, among the adhesion assistants described later, a functional silane coupling agent having an epoxy group is also included in the thermally polymerizable compound having an epoxy group.

  Among the thermally polymerizable compounds, examples of the compound having one epoxy group include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, i-propyl glycidyl ether, n-butyl glycidyl ether, sec-butyl glycidyl ether. Alkyl glycidyl ethers such as t-butyl glycidyl ether; alkylene glycol monoglycidyl such as ethylene glycol monoglycidyl ether, propylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, 1,6-hexanediol monoglycidyl ether Ethers: Polyalkylene glycol monoglycidyl ethers such as polyethylene glycol monoglycidyl ether and polypropylene monoglycidyl ether Aryl 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 A compound having a glycidyl group such as

[(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] ether, 1,6-hexanediol mono [(3,4-epoxycyclohexyl) methyl] ether and other alkylene glycol mono [(3,4- Epoxycyclohexyl) methyl] ethers; Polyalkylene glycol mono [(3,4) such as polyethylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether and polypropylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether -(Epoxycyclohexyl) methyl] ethers; [(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-ethyl Examples include compounds having a 3,4-epoxycyclohexyl group such as [(3,4-epoxycyclohexyl) methyl] aryl ethers such as phenyl ether and [(3,4-epoxycyclohexyl) methyl] p-ethylphenyl ether. be able to.

Examples of the compound having two or more epoxy groups include:
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and 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 ethers;
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 (for example, ethylene oxide, propylene oxide, etc.) 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 esters; epoxidized soybean oil, epoxidized linseed oil,

In the following trade names, as bisphenol A type epoxy resin, Epicoat 825, 828, 834, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 8000, 8034 Japan Epoxy Resin Co., Ltd.]; Bisphenol F type epoxy resin, Epicoat 807 [Japan Epoxy Resin Co., Ltd.], etc .; Phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 [above, Japan Epoxy Resin Co., Ltd.], EPPN 201, 202 (above, Nippon Kayaku Co., Ltd.) and the like; Cresol novolac type epoxy resin, EOCN102, 103S, 104S, 1020, 1025, 1027 [above, Nippon Kayaku Co., Ltd.], Epicote 80S75 [manufactured by Japan Epoxy Resin Co., Ltd.], etc .; as polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, manufactured by Japan Epoxy Resin Co., Ltd.), etc .; As other alicyclic epoxy resins, CY-175 177, 179, Araldite CY-182, 192, 184 [above, manufactured by Ciba Specialty Chemicals Co., Ltd.], ERL-4206, -4221, -4234, -4299 (above, U.S. Pat. C.C), Shodyne 509 [manufactured by Showa Denko KK], Epicron 200, 400 [above, Dainippon Ink Co., Ltd.], Epicoat 871, 872 [above, Japan Epoxy Resin Co., Ltd.] Manufactured], ED-5661, -5562 [above, manufactured by Celanese Coating Co., Ltd.], etc .; other aliphatic poly As glycidyl ether EPOLIGHT 100MF [manufactured by Kyoeisha Chemical Co.], Epiol TMP [manufactured by NOF Corporation] Other such,

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, methylene bis (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.

  In addition, as a compound having an episulfide group, for example, an epoxy group in a compound having one or more epoxy groups is converted into an episulfide group in accordance with, for example, the method disclosed in Non-Patent Document 1. A compound etc. can be mentioned.

J. et al. Org. Chem., Vol. 28, p. 229 (1963)

  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- Ethoxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-phenoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, 3-methyl-3- Benzyloxymethyloxetane, 3-ethyl-3-benzyloxymethyloxetane, 3-methyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-ethyl-3-[(2-ethylhexyloxy) methyl] oxetane, 3-methyl-3- (Nn-butyramide Butoxy) oxetane, 3-ethyl -3- (N-n- butyl amide methoxy) can be mentioned oxetane.

Examples of the compound having two or more oxetanyl groups 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, tetra Ethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, tricyclodecanediyldimethylene bis [(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, polyethylene glycol bis [ (3-ethyl-3-oxetanyl) Til] 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 thermopolymerizable compounds, bisphenol A type epoxy resin, phenol novolac type epoxy resin, 3,4-epoxycyclohexanecarboxylic acid [(3,4-epoxycyclohexyl) methyl] ester, bis [(3-ethyl- 3-Oxetanyl) methyl] terephthalate and the like are preferred.

The said thermopolymerizable compound can be used individually or in mixture of 2 or more types.
The amount of the thermopolymerizable compound added is preferably 100 parts by weight or less, more preferably 50 parts by weight or less with respect to 100 parts by weight of the copolymer (A). In this case, when the addition amount of the thermally polymerizable compound exceeds 100 parts by weight, the developability of the resulting resin composition may be impaired.

A thermal polymerization inhibitor can be added to the radiation-sensitive resin composition of the present invention in order to suppress deterioration in developability due to heat fogging 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 addition amount of the thermal polymerization inhibitor is preferably 5 parts by weight or less, more preferably 3 parts by weight or less, with respect to 100 parts by weight of the thermopolymerizable compound.

A surfactant can be added to the radiation-sensitive resin composition of the present invention in order to improve coating properties, antifoaming properties, leveling properties, and the like.
Examples of such surfactants include fluorine surfactants, silicone surfactants, nonionic surfactants, and the like.
Examples of the fluorine-based surfactant include BM-1000, -1100 (above, manufactured by BM CHIMIE), MegaFuck F142D, F172, F173, F183 [above, Dainippon Ink & Chemicals, Inc.]. Industrial Co., Ltd.], Fluorad 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, Asahi Glass Manufactured by Co., Ltd.].

Moreover, as said silicone type surfactant, it is a brand name, for example, SH-28PA, the same -190, the same -193, SZ-6032, SF-8428, DC-57, the same -190 [more, Toray Dow Corning Silicone Co., Ltd.], KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), F-top EF301, EF303, EF352 [above, 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, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxy And polyoxyethylene aryl ethers such as ethylene n-nonylphenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate.
Furthermore, as a surfactant other than the above, 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 tends to be rough during coating.

An adhesion aid can be added to the radiation sensitive resin composition of the present invention in order to improve the adhesion to the substrate.
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 epoxy group is preferable, and more specifically, trimethoxysilyl benzoate. Acid, 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, more preferably 10 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

  In the radiation sensitive resin composition of the present invention, a dissolution accelerator or a dissolution control agent can be added in order to adjust the solubility of the copolymer (A) 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. Conversely, when the solubility of the copolymer (A) in the alkali developer is too high, the solubility is controlled, and the dissolution rate of the copolymer (A) during alkali development is appropriately reduced. A dissolution control agent can be blended.

The dissolution accelerator and the dissolution controller are not particularly limited, but compounds that do not chemically change in steps such as pre-baking, exposing, and developing the radiation-sensitive resin composition are preferable.
Examples of the dissolution accelerator include low molecular weight phenolic compounds having about 2 to 6 benzene rings, and more specifically, bisphenols, tris (hydroxyphenyl) methanes, and the like. Can do.
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. And the like.
These dissolution promoters and dissolution control agents can be used alone or in admixture of two or more.

  The addition amount of the dissolution accelerator and the dissolution control agent can be appropriately adjusted according to the type of (A) copolymer to be used, but is preferably relative to 100 parts by mass of (A) copolymer respectively. 50 parts by mass or less, more preferably 30 parts by mass or less.

In the radiation-sensitive resin composition of the present invention, a compound having a carboxyl group and / or a carboxylic acid anhydride group (hereinafter referred to as “carboxylic acid-based additive”) is used to finely adjust the solubility in an alkali developer. ) Can be added.
Examples of carboxylic acid-based additives 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, Such as 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-hydroxycinnamic acid, m-hydroxycinnamic acid, p-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc. Hydroxy monocarboxylic acids; 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 Polyvalent carboxylic acids such as 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, Tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, 1,2,3,4-butanetetracarboxylic acid Dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic dianhydride, ethylene glycol bis (trimellitate) dianhydride, glycerin And acid anhydrides such as tris (trimellitate) dianhydride.
These carboxylic acid-based additives can be used alone or in admixture of two or more.
The addition amount of the carboxylic acid-based additive is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the copolymer (A).

Furthermore, the radiation-sensitive resin composition of the present invention is provided with a filler, a colorant, a viscosity modifier and the like in a range that does not impair the original characteristics of the radiation-sensitive resin composition, preferably a total addition amount. It can also be added within a range of 50% by weight or less of the total composition.
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, barium sulfate; zinc white, lead white, yellow lead, red lead, ultramarine, bitumen, titanium oxide, zinc chromate, bengara, Inorganic pigments such as carbon black; organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, and phthalocyanine green; basic dyes such as magenta and rhodamine; direct dyes such as direct scarlet and direct orange And acid dyes such as roserine and metanyl 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.

The radiation-sensitive resin composition of the present invention is obtained by uniformly mixing (A) a copolymer, (B) a polymerizable unsaturated compound, (C) a photopolymerization initiator and an additive used as necessary, In order to facilitate the coating operation on the substrate, it is preferable to dilute with an organic solvent to obtain a liquid composition.
As said organic solvent, each component which comprises a radiation sensitive resin composition can be melt | dissolved thru | or disperse | distributed uniformly, and what does not react with this each component and has moderate volatility is preferable.
Examples of such an organic solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, in addition to the same organic solvents as those exemplified for the polymerization for producing the copolymer (A). N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol And high-boiling solvents such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

Of these organic solvents, alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether; solubility, reactivity with each component, and ease of film formation; ethylene glycol monoethyl ether acetate Preferred are alkyl ether acetates of polyhydric alcohols such as; other esters such as ethyl lactate, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate; ketones such as diacetone alcohol.
The said organic solvent can be used individually or in mixture of 2 or more types.
The usage-amount of an organic solvent can be suitably selected according to the specific use of a radiation sensitive resin composition, a coating method, etc.

  When preparing the radiation-sensitive resin composition of the present invention, when no filler or pigment is added, it is only necessary to stir and mix by a usual method. When a filler or pigment is added, a dissolver or homogenizer is used. What is necessary is just to disperse and mix using dispersers, such as a 3 roll mill. Moreover, you may use the radiation sensitive resin composition of this invention for a use after filtration with a mesh, a membrane filter, etc. after preparation as needed.

  The radiation-sensitive resin composition of the present invention is preferably used as a liquid composition or a radiation-sensitive dry film, particularly preferably for forming microlenses for liquid crystal display elements.

Microlens The microlens of the present invention is formed from the radiation-sensitive resin composition for forming a microlens of the present invention.
The microlens of the present invention is an imaging optical system for on-chip color filters such as various OA devices, liquid crystal televisions, mobile phones, projectors, facsimiles, electronic copiers, solid-state image sensors, etc. It can be used very suitably for fiber connectors and the like.

Radiation-sensitive dry film The radiation-sensitive dry film of the present invention is obtained by laminating a radiation-sensitive layer comprising the radiation-sensitive resin composition of the present invention on a base film, preferably a flexible base film. is there.
The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying a radiation-sensitive resin composition on a base film, preferably as a liquid composition, and then drying.

As the base film of the radiation-sensitive 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. Moreover, in order to give moderate release property to the surface of these synthetic resin films, for example, a silicone-type release agent can be applied or baked.
The thickness of the base film is suitably in the range of 15 to 125 μm.
The coating method when laminating the radiation sensitive layer on the base film is not particularly limited, but for example, an appropriate method such as applicator coating method, bar coating method, roll coating method, curtain flow coating method is adopted. can do.
As for the film thickness of the obtained radiation sensitive layer, about 10-30 micrometers is preferable.

Further, when the radiation-sensitive dry film is not used, a cover film can be further laminated and stored on the radiation-sensitive layer.
This cover film is for stably protecting the radiation-sensitive layer when not in use, and is removed during use. Therefore, the cover film needs 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 a cover film satisfying such conditions, for example, a film obtained by applying or baking a silicone release agent on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, or polyvinyl chloride can be used. .
A thickness of about 25 μm is usually sufficient for the cover film.

Microlens Forming Method The microlens forming method of the present invention includes at least the following steps (a) to (d) in the order described below.
(A) forming a coating of the radiation-sensitive resin composition for forming a microlens of the present invention on a substrate;
(B) irradiating at least a part of the coating with radiation (hereinafter referred to as “exposure”);
(C) a step of developing the film after exposure;
(D) A step of heat-treating (hereinafter referred to as “baking”) the film after development.

Hereinafter, these steps will be described.
-(I) Process-
In this step, either a method of using the radiation-sensitive resin composition as a liquid composition or a method of using it as a radiation-sensitive dry film (hereinafter referred to as “dry film method”) can be used.

When the radiation-sensitive resin composition is used as a liquid composition, the liquid composition is applied on a substrate and prebaked to form a film.
Examples of the substrate that can be used 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 for example, an appropriate method such as a spray coating method, a roll coating method, a rotation coating method, or a bar coating method can be employed.
The pre-baking conditions vary depending on the types of components used in the radiation-sensitive resin composition, the usage ratio, and the like, but are usually about 60 to 130 ° C. for about 30 seconds to 15 minutes.
The film thickness obtained is preferably about 10 to 30 μm as the value after pre-baking.

  In the case of the dry film method, if the cover film is laminated, after peeling it off, the radiation-sensitive dry film is subjected to a normal pressure hot roll pressure bonding method so that the radiation-sensitive layer is on the substrate side, Using an appropriate pressure bonding method such as vacuum hot roll pressure bonding or vacuum heat press pressure bonding, the radiation sensitive layer is transferred onto the substrate surface by applying pressure and heat to the substrate while applying appropriate heat and pressure. A film of the radiation-sensitive resin composition is formed.

-(B) Process-
In this step, at least a part of the formed film of the radiation sensitive resin composition is exposed. When a part of the film is exposed, it is usually exposed through a photomask having a predetermined pattern.
The radiation used for the exposure is not particularly limited, and, for example, g-line (wavelength 436 nm), i-line (wavelength 365 nm), etc., depending on the type of (C) photopolymerization initiator used. Ultraviolet 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 can be appropriately selected. Among these radiations, ultraviolet rays are preferable, particularly g-line and Radiation containing i / rays is preferred.
The exposure amount is about 50~10,000J / m ² is preferred.
When the dry film method is used in the step (a), the base film used for the radiation-sensitive dry film may be peeled off before exposure, or may be peeled off after exposure and before development.

-(C) Process-
In this step, the exposed film is developed with a developer, preferably an alkali developer, and the unexposed areas are removed to form 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] An aqueous solution of a basic compound such as -5-nonene can be mentioned.
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.
In addition, after developing with an alkali developing solution, it is usually washed, for example, with running water.
Moreover, in the case of the radiation sensitive resin composition which does not contain insoluble components, such as a pigment and a filler, the various organic solvent which melt | dissolves each component which comprises the said composition can also be used as a developing solution.

The developing method is not particularly limited, and an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, or a shower method can be employed.
The development time varies depending on the composition of the radiation sensitive resin composition, but is usually 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 for forming a microlens 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. is there.

-(D) Process-
In this step, a microlens is formed by baking the developed film, for example, with a heating device such as a hot plate or an oven, so that the film is cured and melt-flowed into a predetermined lens shape. Can do.
The baking conditions vary depending on the types and use ratios of the components of the radiation-sensitive resin composition, the desired pattern shape, the heating device, and the like. In the case of an oven, it is about 150 to 240 ° C. for about 3 to 90 minutes. When a low heat-resistant substrate such as a resin substrate is used, the baking temperature is preferably 160 ° C. or lower, and preferably 100 to 150 ° C. Moreover, in baking, the step baking method etc. which heat-process twice or more can also be employ | adopted.

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 televisions, mobile phones, etc. It can be used very suitably for liquid crystal display elements such as telephones and projectors.
Moreover, according to the method for forming a microlens of the present invention, a high-definition microlens and a microlens array having excellent characteristics can be formed by a simple process. Furthermore, in the method for forming a microlens of the present invention by the dry film method, the time required for obtaining conditions for obtaining a predetermined film thickness is insoluble, and there are no environmental problems such as volatilization of organic solvents.

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.
Synthesis example 1
After substituting the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator, 100.0 g of diethylene glycol dimethyl ether and 50 of diethylene glycol monomethyl ether as a solvent. 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 tricyclodecanyl methacrylate, 15.0 g of styrene, and 15.0 g of tetrahydrofurfuryl methacrylate were charged gently. Stirring was started. Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-1).

Synthesis example 2
After substituting the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobis-2,4-dimethylvaleronitrile as a radical polymerization initiator, 100.0 g of diethylene glycol diethyl ether as a solvent and lactic acid 150.0 g of ethyl was charged and stirred until the radical polymerization initiator was dissolved. Thereafter, 10.0 g of methacrylic acid, 15.0 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 40.0 g of tricyclodecanyl methacrylate, 15.0 g of styrene, and 20.0 g of tetrahydrofurfuryl methacrylate were charged gently. Stirring was started. Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-2).

Synthesis example 3
After replacing the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150.0 g of diacetone alcohol as a solvent were charged, and radical polymerization was performed. Stir until the initiator is dissolved. Thereafter, 20.0 g of methacrylic acid, 15.0 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 40.0 g of tricyclodecanyl methacrylate, 15.0 g of styrene and 5.0 g of isoprene were charged and gently stirred. I started. Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-3).

Synthesis example 4
After substituting the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 150 ethyl ethyl 3-ethoxypropionate as a solvent 0.0 g was charged and stirred until the radical polymerization initiator was dissolved. Thereafter, 15 g of methacrylic acid, 15.0 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 45.0 g of tricyclodecanyl methacrylate, 15.0 g of styrene and 10.0 g of isoprene were charged, and gentle stirring was started. . Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-4).

Synthesis example 5
After substituting the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150 g of methyl 3-methoxypropionate as a solvent were added to form a radical. Stir until the polymerization initiator is dissolved. Thereafter, 20 g of methacrylic acid, 15 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 45 g of tricyclodecanyl methacrylate, 15.0 g of styrene and 5.0 g of 1,3-butadiene were charged, and gentle stirring was started. . Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-5).

Synthesis Example 6
After substituting the flask equipped with a dry ice / methanol system reflux with nitrogen, 4.0 g of 2,2′-azobisisobutyronitrile as a radical polymerization initiator and 150 g of methyl 3-methoxypropionate as a solvent were added to form a radical. Stir until the polymerization initiator is dissolved. Thereafter, 15 g of methacrylic acid, 15 g of 2-mono (hexahydrophthaloyloxy) ethyl methacrylate, 45 g of tricyclodecanyl methacrylate, 15.0 g of styrene and 10.0 g of 1,3-butadiene were started and gently stirred. . Thereafter, the temperature of the reaction solution was raised to 80 ° C., and polymerization was carried out at this temperature for 4 hours. After the polymerization, the reaction solution is dropped into a large amount of methanol to coagulate the reaction product, and the obtained coagulated product is washed with water, then redissolved in tetrahydrofuran of the same weight as the coagulated product, and again into a large amount of methanol. It was dripped and solidified. After this re-dissolution-coagulation operation was performed three times in total, the reaction product was vacuum-dried at 40 ° C. for 48 hours to obtain a copolymer (A).
This (A) copolymer is referred to as copolymer (A-6).

Example 1
Preparation of liquid composition As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B) 2.0 g of tricyclodecanyl methacrylate. 2.0 g of Aronix M8100 and 1.0 g of KAYARAD R-526, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) as component (C) and 1.0 g of Irgacure 651 In addition, methyl 3-methoxypropionate was further added to obtain a solution having a solid content concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to obtain a liquid composition (S-1 ) Was prepared.
-Evaluation of storage stability-
The liquid composition (S-1) was stored in an oven at 40 ° C. for 1 week, and evaluated by the rate of increase in viscosity (%) before and after storage. When the rate of increase in viscosity is within 5%, it can be said that the storage stability is good. The evaluation results are shown in Table 1.

Formation of Patterned Thin Film A liquid composition (S-1) was applied on a glass substrate using a spinner, and then prebaked on a hot plate at 100 ° C. for 5 minutes to form a film.
Next, the obtained film was exposed to ultraviolet rays having an intensity of 200 W / m ^{2 at} a wavelength of 365 nm for 5 seconds through a photomask 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, the film was baked and cured in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film 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-
The pattern thin film can be resolved when the pattern of line / space = 10 μm / 10 μm is resolved, and when the pattern of line / space = 20 μm / 20 μm is resolved, both patterns can be resolved. The case where it was not evaluated as x was evaluated.
-Evaluation of pattern shape-
With respect to the patterned thin film, a pattern of line / space = 50 μm / 50 μm or 30 μm / 30 μm was observed with a transmission electron microscope to evaluate which shape corresponds to FIG. When it is a semi-convex lens shape as in (a), the pattern shape is good.

-Evaluation of heat resistance-
The patterned thin film 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 transparency-
The transmittance (%) at a wavelength of 450 nm of the patterned thin film was measured and evaluated with a spectrophotometer 150-20 type double beam [manufactured by Hitachi, Ltd.]. When this transmittance is 89% or more, it can be said that the transparency is good.

-Evaluation of heat discoloration-
The patterned thin film was heated in an oven at 220 ° C. for 60 minutes, and the transmittance of the patterned thin film at a wavelength of 450 nm before and after heating was measured with a spectrophotometer 150-20 type double beam (manufactured by Hitachi, Ltd.). Evaluation was made based on the reduction rate (%) of the transmittance. When the transmittance decrease rate is within 5%, it can be said that the heat discoloration is good.
-Evaluation of solvent resistance-
The glass substrate on which the patterned thin film was formed was immersed in N-methylpyrrolidone at 50 ° C. for 15 minutes, and the change rate (%) of the film thickness of the patterned thin film before and after the immersion [= (film thickness after immersion−immersion The film thickness was evaluated according to the previous film thickness) × 100 / film thickness before immersion. When the rate of change in film thickness is within ± 5%, it can be said that the solvent resistance is good.

Example 2
As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and 2.0 g of KAYARAD HDDA And 1.0 g of KAYARAD R-526, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucyrin TPO) and 1.0 g of Irgacure 651 as component (C), and 3-methoxypropion Methyl acid was added to obtain a solution having a solid content concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to prepare a liquid composition (S-2) of a radiation sensitive resin composition.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-2) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 3
As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and 2 Aronix M309 are added. 1.0 g and 1.0 g of KAYARAD R-526, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) as component (C) and 1.0 g of Irgacure 651, Epicoat as additive After adding 2.0 g of 828 and further adding methyl 3-methoxypropionate to obtain a solution having a solid concentration of 50% by weight, the solution was filtered with a membrane filter having a pore size of 5 μm to obtain a liquid composition of the radiation-sensitive resin composition. A product (S-3) was prepared.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-3) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 4
As component (A), 10.0 g of copolymer (A-2) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and light acrylate 1. 2.0 g of 9-NDA and 1.0 g of KAYARAD R-526, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as component (C), Further, methyl 3-methoxypropionate was added to obtain a solution having a solid concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to obtain a liquid composition (S-4) of the radiation sensitive resin composition. Prepared.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-4) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 5
As component (A), 10.0 g of copolymer (A-3) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and 2 Aronix M8100 are added. 1.0 g and 1.0 g of KAYARAD MANDA, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 as component (C) were added, and methyl 3-methoxypropionate was added. Was added to obtain a solution having a solid content concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to prepare a liquid composition (S-5) of a radiation sensitive resin composition.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-5) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 6
As component (A), 10.0 g of copolymer (A-4) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and 2 KAYARAD NPGDA are added. 1.0 g and 1.0 g of KAYARAD HX-220, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added as component (C). Methyl methoxypropionate was added to obtain a solution having a solid concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to prepare a liquid composition (S-6) of a radiation sensitive resin composition.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-6) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 7
As component (A), 10.0 g of copolymer (A-5) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate, KAYARAD DPCA-20 And 1.0 g of KAYARAD HX-620, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) as component (C) and 1.0 g of Irgacure 651, additive After adding 2.0 g of [(3,4-epoxycyclohexyl) methyl] ester of 3,4-epoxycyclohexanecarboxylic acid, and further adding methyl 3-methoxypropionate to obtain a solution having a solid concentration of 50% by weight. The liquid composition of the radiation sensitive resin composition is filtered through a membrane filter having a pore size of 5 μm. (S-7) was prepared.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-7) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 8
As component (A), 10.0 g of copolymer (A-6) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 2.0 g of tricyclodecanyl methacrylate and 2 Aronix M9050 are added. 1.0 g and 1.0 g of KAYARAD R-604, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) as component (C) and 1.0 g of Irgacure 651, bis as an additive After adding 2.0 g of [(3-ethyl-3-oxetanyl) methyl] terephthalate and further adding methyl 3-methoxypropionate to obtain a solution having a solid concentration of 50% by weight, the solution was filtered through a membrane filter having a pore size of 5 μm. Thus, a liquid composition (S-8) of the radiation sensitive resin composition was prepared.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-8) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 9
The liquid composition (S-1) of the radiation sensitive resin composition is applied onto a PET film having a thickness of 38 μm using an applicator, the coating film is prebaked at 100 ° C. for 5 minutes, and the film thickness of the radiation sensitive layer. A 25 μm-radiation sensitive dry film was produced. Thereafter, the radiation-sensitive dry film was transferred to the glass substrate by superimposing the radiation-sensitive dry film on the surface of the glass substrate so that the radiation-sensitive layer was in contact with the glass substrate.
Next, after removing the base film from the radiation-sensitive dry film on the substrate, a patterned thin film was formed and evaluated in the same manner as in Example 1.
In addition, transferability was evaluated in the following manner.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

-Evaluation of transferability-
When the radiation-sensitive dry film is transferred to the glass substrate and the base film is peeled and removed, “○” indicates that the radiation-sensitive layer can be uniformly transferred onto the glass substrate, and the radiation-sensitive layer is partially on the base film. The case where the radiation-sensitive layer could not be uniformly transferred to the glass substrate, such as remaining on the glass substrate, or the radiation-sensitive layer did not adhere to the glass substrate surface, was evaluated as “x”.

Example 10
In Example 9, it replaced with the liquid composition (S-1) of a radiation sensitive resin composition, and it replaced with the liquid composition (S-2) of the radiation sensitive resin composition, and was carried out similarly to Example 9. Thus, a radiation-sensitive dry film was produced.
Next, after peeling off and removing the base film from the radiation-sensitive dry film on the substrate, a patterned thin film was formed and evaluated in the same manner as in Example 1, and the transferability was evaluated in the same manner as in Example 9. Went.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 11
In Example 1, instead of the liquid composition (S-1) of the radiation sensitive resin composition, the liquid composition (S-7) of the radiation sensitive resin composition was used, and the patterned thin film was heated at 150 ° C. Except for baking for 5 minutes and curing, the storage stability was evaluated 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 12
In Example 1, except that 0.1 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one was used as the component (C), A liquid composition (S-9) of a radiation sensitive resin composition was prepared.
Next, the liquid composition (S-9) of the radiation sensitive resin composition was applied on a PET film having a thickness of 38 μm using an applicator, and the coating film was pre-baked at 100 ° C. for 5 minutes to form a radiation sensitive layer. A radiation-sensitive dry film having a thickness of 25 μm was produced. Thereafter, the radiation-sensitive dry film was transferred to the glass substrate by superimposing the radiation-sensitive dry film on the surface of the glass substrate so that the radiation-sensitive layer was in contact with the glass substrate.
Next, after peeling off and removing the base film from the radiation-sensitive dry film on the substrate, a patterned thin film was formed and evaluated in the same manner as in Example 1, and the transferability was evaluated in the same manner as in Example 9. Went.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 13
In Example 7, except that 0.1 g of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one was used as the component (C), A liquid composition (S-10) of a radiation sensitive resin composition was prepared.
Next, the liquid composition (S-10) of the radiation sensitive resin composition was applied onto a PET film having a thickness of 38 μm using an applicator, and the coating film was prebaked at 100 ° C. for 5 minutes to form a radiation sensitive layer. A radiation-sensitive dry film having a thickness of 25 μm was produced. Thereafter, the radiation-sensitive dry film was transferred to the glass substrate by superimposing the radiation-sensitive dry film on the surface of the glass substrate so that the radiation-sensitive layer was in contact with the glass substrate.
Next, after peeling off and removing the base film from the radiation-sensitive dry film on the substrate, a patterned thin film was formed and evaluated in the same manner as in Example 1, and the transferability was evaluated in the same manner as in Example 9. Went.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 14
As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate. As component (B), 4.4 g of tricyclodecanyl methacrylate and Aronix M8100 are 0. .4 g and 0.2 g of KAYARAD R-526, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added as component (C), and 3-g Methyl methoxypropionate was added to make a solution with a solid concentration of 50% by weight, followed by filtration with a membrane filter having a pore size of 5 μm to prepare a liquid composition (S-11) of a radiation sensitive resin composition.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-11) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 15
As component (A), 10.0 g of copolymer (A-6) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and as component (B), 4.4 g of tricyclodecanyl methacrylate and Aronix M9050 are 0. .4 g and KAYARAD R-604 0.2 g, (C) component 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucyrin TPO) 2.0 g and Irgacure 651 1.0 g, bis After adding 2.0 g of [(3-ethyl-3-oxetanyl) methyl] terephthalate and further adding methyl 3-methoxypropionate to obtain a solution having a solid concentration of 50% by weight, the solution was filtered through a membrane filter having a pore size of 5 μm. Then, a liquid composition (S-12) of the radiation sensitive resin composition was prepared.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (S-12) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Comparative Example 1
As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and 2.0 g of Aronics M8100 and KAYARAD R-526 are used as the polymerizable unsaturated compound. 1.0 g, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added as component (C), and methyl 3-methoxypropionate was further added. After preparing a solution having a solid content concentration of 50% by weight, the solution was filtered through a membrane filter having a pore size of 5 μm to prepare a liquid composition (s-1) of a radiation sensitive resin composition.
Subsequently, it preserve | saved like Example 1 except having replaced with the liquid composition (S-1) of the radiation sensitive resin composition, and having used the liquid composition (s-1) of the radiation sensitive resin composition. The stability was evaluated and a patterned thin film was formed for evaluation.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Comparative Example 2
As component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropanoate, and 2.0 g of KAYARAD HDDA and KAYARAD R-526 are used as the polymerizable unsaturated compound. 0 g, 2.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added as component (C), and methyl 3-methoxypropionate was added to form a solid. After preparing a solution with a partial concentration of 50% by weight, the solution was filtered through a membrane filter having a pore size of 5 μm to prepare a liquid composition (s-2) of a radiation sensitive resin composition.
Next, in the same manner as in Example 9, except that the liquid composition (s-2) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition, A radiation dry film was prepared and transferred to a glass substrate.
Next, after peeling off and removing the base film from the radiation-sensitive dry film on the substrate, a patterned thin film was formed and evaluated in the same manner as in Example 1, and the transferability was evaluated in the same manner as in Example 9. Went.
The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

It is a schematic diagram which shows the cross-sectional shape of a micro lens.

Claims (9)

  (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 compound (where (a) + (b) + (c) = 100% by weight); B) a polymerizable unsaturated compound having an alicyclic hydrocarbon group and having a polymerizable unsaturated compound having no acidic functional group as essential components, and (C) a photopolymerization initiator. A radiation-sensitive resin composition.   The radiation-sensitive resin composition according to claim 1, further comprising (D) a thermopolymerizable compound.   The radiation-sensitive resin composition according to claim 1 or 2, which is used for forming a microlens.   A microlens formed from the radiation-sensitive resin composition of claim 3.   A radiation-sensitive dry film obtained by laminating a radiation-sensitive layer comprising the radiation-sensitive resin composition according to claim 1 or 2 on a base film. A method for forming a microlens, comprising at least the following steps (a) to (d) in the order described below.
(A) forming a film of the radiation-sensitive resin composition according to claim 3 on a substrate;
(B) irradiating at least a part of the coating with radiation;
(C) developing the film after irradiation;
(D) A step of heat-treating the developed film.   The method for forming a microlens according to claim 6, wherein the temperature of the heat treatment in the step (d) is 160 ° C. or less.   In the step (a), the radiation-sensitive layer of the radiation-sensitive dry film according to claim 5 is transferred to the substrate surface to form a coating of the radiation-sensitive resin composition on the substrate. A method for forming a microlens according to claim 6 or 7.   A liquid crystal display device comprising the microlens according to claim 4.

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