KR20060052059A - Radiation sensitive resin composition, mircrolens and process for forming the same, and a liquid crystal display device - Google Patents

Abstract

This invention provides the radiation sensitive resin composition etc. which can form the micro lens excellent in film thickness, the resolution, pattern shape, heat resistance, transparency, heat discoloration resistance, solvent resistance, etc., and are excellent also in storage stability.

The radiation-sensitive resin composition of the present invention comprises (A) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) 20 to 60% by weight of a polymerizable unsaturated compound having an alicyclic hydrocarbon group and no acidic functional group. %, And (c) Alkali-soluble copolymer obtained by superposing | polymerizing 5-40 weight% of other polymerizable unsaturated compounds ((a) + (b) + (c) = 100 weight%), (B) alicyclic type It is characterized by containing the polymerizable unsaturated compound which has a hydrocarbon group and which does not have an acidic functional group as an essential component, and (C) photoinitiator.

Radiation-sensitive resin composition, microlens, polymerizable unsaturated compound, acidic functional group, alicyclic hydrocarbon group, photoinitiator

Description

Radiation Sensitive Resin Composition, Mircrolens and Process for Forming the Same, and a Liquid Crystal Display Device

1 is a schematic diagram showing a cross-sectional shape of a microlens.

[Document 1] Japanese Unexamined Patent Publication No. 2001-154181

[Document 2] Japanese Unexamined Patent Publication No. 2001-117114

[Document 3] Japanese Unexamined Patent Publication No. 11-109417

[Document 4] Japanese Unexamined Patent Publication No. 10-268305

[Document 5] Japanese Unexamined Patent Publication No. 2000-10087

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

Liquid crystal display devices are the most widely used among flat panel displays because of their excellent features such as high precision and colorful display performance, low power consumption, high reliability, flexibility to cope with all sizes, thin and lightweight, and OA such as personal computers or word processors. As devices, liquid crystal televisions, mobile phones, projectors, and the like become popular, demands for display performance and low power consumption are increasing.

In response to these demands, Japanese Patent Laid-Open No. 2001-154181, Japanese Patent Laid-Open No. 2001-117114, Japanese Patent Laid-Open No. 11-109417 and Japanese Patent Laid-Open No. 10-268305 A method of improving the brightness or contrast of a liquid crystal display device by providing a microlens array in the light and condensing external light or backlight light in an opening portion has been proposed. In these methods, in most cases, the focal length from the light collecting layer where the microlens is present to the liquid crystal pixel opening is very short, thereby increasing the refractive index difference between the material forming the microlens and the planarization film and precisely controlling the radius of curvature of the lens. Needs to be.

As a method of forming such a microlens for a liquid crystal display element, the glass substrate is dry-etched to form a recess, and the pattern is melt-flowed by heat treatment after forming a lens pattern and a method of embedding it with a high refractive index ultraviolet curable resin. A method of producing a mask having a predetermined shape by forming a pattern from the radiation-sensitive resin composition and melt-flowing the same, and performing dry etching through the mask to transfer the predetermined lens shape to the background. have. However, in any of these methods, the microlens formation process is complicated and expensive, and it cannot be said that it is industrially sufficient.

Therefore, various characteristics required for the microlenses, for example, film thickness, resolution, pattern shape, transparency, heat resistance, solvent resistance, etc. can be satisfied, storage stability is also good, and the microlens can be formed by a simple method. The development of a radiation sensitive resin composition is strongly demanded.

In addition, with the recent spread of the liquid crystal display device, there is an increasing demand for reduction in weight or manufacturing cost.

Therefore, an attempt has been made to use a resin substrate, as disclosed in Japanese Patent Laid-Open No. 2000-10087, instead of the glass that has been used in the past, and thus, a low heating temperature in order to avoid deformation or yellowing of the resin substrate. There is a strong demand for the development of a radiation sensitive resin composition capable of forming microlenses and a method thereof.

Moreover, in the method of forming the microlens for liquid crystal display elements using a radiation sensitive resin composition, the coating film is formed on a board | substrate by the methods, such as a rotary coating method, an immersion method, or the spraying method, in the resin composition containing the organic solvent most of them. Going through the process. In such a method, environmental problems such as volatilization of an organic solvent or the like are required for creating a condition for obtaining a predetermined film thickness.

Therefore, there is no environmental problem, and it is also required to develop a microlens formation method at a low cost in a short time compared with the conventional microlens formation method.

This invention is made | formed in view of the above situation, The subject is the microlens excellent in the film thickness, the resolution, pattern shape, heat resistance, transparency, heat discoloration resistance, solvent resistance, etc., even if the temperature of heat processing is made low. It is possible to form, and to provide a radiation sensitive resin composition having good storage stability.

Another object of the present invention is to form a microlens having such excellent characteristics by a simple process including the case of using a radiation-sensitive dry film, and to form a microlens even at a low temperature of the heat treatment. It is to provide a method of forming a lens.

Another object of the present invention is to provide a liquid crystal display device having the microlens.

First, the present invention

(A) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) 20 to 60% by weight of a polymerizable unsaturated compound having an alicyclic hydrocarbon group and no acidic functional group, and (c) another polymerizable property. Alkali-soluble copolymer obtained by superposing | polymerizing 5-40 weight% of unsaturated compounds (it is (a) + (b) + (c) = 100 weight%),

(B) a polymerizable unsaturated compound having as an essential component a polymerizable unsaturated compound having an alicyclic hydrocarbon group and not having an acidic functional group, and

(C) photoinitiator

It contains a radiation sensitive resin composition characterized by containing.

"Radiation" as used in the present invention means ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular rays, gamma rays, synchrotron radiation, proton beams, and the like.

Secondly, the present invention includes the radiation-sensitive resin composition (hereinafter, also referred to as "radiation-sensitive resin composition for microlens formation") for microlens formation.

Third, the present invention includes a microlens formed of a radiation sensitive resin composition for forming a microlens.

Fourth, the present invention includes a radiation-sensitive dry film formed by laminating a radiation-sensitive layer made of the radiation-sensitive resin composition on a base film.

Fifth, the present invention includes a method for forming a microlens, comprising at least the following steps (a) to (d) in the following order.

(A) process of forming the film of the radiation sensitive resin composition for microlens formation on a board | substrate,

(B) irradiating at least a portion of the coating with radiation,

(C) developing the film after irradiation;

(D) Process of heat-processing the film after image development.

In the method of forming the microlens, the heat treatment temperature of step (d) may be 160 ° C or less.

Sixthly, the present invention includes a liquid crystal display device comprising the microlens.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Radiation  Resin composition

-(A) copolymer-

Component (A) in the present invention is (a) a polymerizable unsaturated compound having an acidic functional group (hereinafter referred to as "(a) polymerizable unsaturated compound") 10 to 50% by weight, (b) having an alicyclic hydrocarbon group and acidic 20 to 60% by weight of a polymerizable unsaturated compound having no functional group (hereinafter referred to as "(b) polymerizable unsaturated compound"), and (c) 5 to 40% by weight of another polymerizable unsaturated compound ((a) + An alkali-soluble copolymer (Hereinafter, it is called "(A) copolymer") containing (b) + (c) = 100 weight%.

(a) In a polymerizable unsaturated compound, an example of an acidic functional group is a carboxyl group, a sulfonic acid group, etc., A carboxyl group is especially preferable.

Examples of the (a) polymerizable unsaturated compound (hereinafter, referred to as "(a1) polymerizable unsaturated compound") having a carboxyl group include (meth) acrylic acid, crotonic acid or acrylic acid or crotonic acid at the α-position of a haloalkyl group and an alkoxyl group. Unsaturated monocarboxylic acids such as compounds substituted with substituents such as halogen atoms, nitro groups, and cyano groups; Unsaturated dicarboxylic acids or acid anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; The hydrogen atom of one carboxyl group in the said unsaturated dicarboxylic acid is methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, phenyl group, o-tolyl group, m Half esters substituted with substituents such as a tolyl group and a p-tolyl group; Half amides in which one carboxyl group in the unsaturated dicarboxylic acid is converted to an amide group; Monoesters of 2-hydroxyethyl (meth) acrylate and succinic acid, Monoesters of 2-hydroxyethyl (meth) acrylate and maleic acid, 2-hydroxyethyl (meth) acrylate and hexahydrophthalic acid Carboxyl group-containing (meth) acrylic acid esters, such as the mono-esterified substance (it calls "2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate" hereafter)), etc. are mentioned.

Among these (a1) polymerizable unsaturated compounds, (meth) acrylic acid, 2-mono (hexahydrophthaloyloxy) ethyl (meth) acrylate, etc. are preferable.

In the present invention, (a) the polymerizable unsaturated compound may be used alone or in combination of two or more thereof, but in particular (meth) acrylic acid and 2-mono (hexahydrophthaloyloxy) ethyl (meth) It is preferable to use an acrylate together.

The content rate of the (a) polymerizable unsaturated compound in (A) copolymer is 10 to 50 weight%, Preferably it is 20 to 40 weight%. In the case where the content of the polymerizable unsaturated compound (a) is less than 10% by weight, the resulting copolymer becomes difficult to dissolve in the alkaline developer, resulting in film residue after development, which may make it difficult to obtain sufficient resolution, while 50% by weight When exceeding%, the solubility with respect to the alkaline developing solution of the copolymer obtained will become large too much, and there exists a tendency for the film reduction of a radiation irradiation part to become large.

(b) Examples of the polymerizable unsaturated compound include cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-methylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1- Methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 2 -Dicyclopentanyloxyethyl (meth) acrylate, etc. are mentioned.

Especially among these (b) polymerizable unsaturated compounds, tricyclo decanyl (meth) acrylate is preferable.

In the present invention, the polymerizable unsaturated compound (b) may be used alone or in combination of two or more thereof.

The content rate of the (b) polymerizable unsaturated compound in (A) copolymer is 20 to 60 weight%, Preferably it is 30 to 50 weight%. In the case where the content of the polymerizable unsaturated compound (b) is less than 20% by weight, the molecular weight of the copolymer obtained may not be sufficiently increased, so that a film having a sufficient film thickness may be difficult to be formed. There exists a tendency for the solubility to the solvent or organic solvent of the copolymer obtained to fall.

(c) The other polymerizable unsaturated compound is mainly used for the purpose of controlling the mechanical properties of the (A) copolymer.

Examples of (c) other polymerizable unsaturated compounds include (meth) acrylic acid esters, diesters of unsaturated dicarboxylic acids exemplified for the (a1) polymerizable unsaturated compounds, aromatic vinyl compounds, conjugated diolefins, nitriles And 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) acryl Late, 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, salicylic (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, glycidyl (meth) acrylate, triphenylmethyl ( Meth) acrylate, cumyl (meth) acrylate, 2,2,2-trifluoro Ethyl (meth) acrylate, pentafluoroethyl (meth) acrylate, heptafluoro-n-propyl (meth) acrylate, heptafluoro-i-propyl (meth) acrylate, 2- (N, N- Dimethylamino) ethyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylic The rate, (alpha)-(meth) acryloyloxy- (gamma) -butyrolactone, (beta)-(meth) acryloyloxy- (gamma) -butyrolactone, etc. are mentioned.

Examples of the diesters of the unsaturated dicarboxylic acid include dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dimethyl itaconic acid and diethyl itaconic acid.

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.

(Meth) acrylonitrile, vinylidene cyanide, etc. are mentioned as an example of the said nitrile-group containing unsaturated compound.

Examples of the chlorine-containing unsaturated compound include vinyl chloride, vinylidene chloride and the like.

Examples of the amide bond-containing unsaturated compound include (meth) acrylamide, maleic acid diamide, fumaric acid diamide, and the like.

Examples of the fatty acid vinyl esters include vinyl acetate, vinyl propionate and the like.

Among these (c) other polymerizable unsaturated compounds, tetrahydrofurfuryl (meth) acrylate, styrene, 1,3-butadiene, isoprene, etc. are preferable.

In the present invention, (c) another polymerizable unsaturated compound may be used alone or in combination of two or more thereof, in particular, in combination of styrene and tetrahydrofurfuryl (meth) acrylate, or styrene and 1, Combination of 3-butadiene and / or isoprene is preferred.

The content rate of (c) another polymerizable unsaturated compound in (A) copolymer is 5 to 40 weight%, Preferably it is 10 to 35 weight%.

The polystyrene reduced weight average molecular weight (hereinafter, referred to as "Mw") of the copolymer (A) is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. Here, when Mw of (A) copolymer is less than 2,000, alkali developability, residual film rate, pattern shape, heat resistance, etc. tend to fall, and when it exceeds 100,000, sensitivity or pattern shape tends to fall. .

In addition, the ratio (Mw / Mn) of Mw of a (A) copolymer and polystyrene conversion number average molecular weight (henceforth "Mn") is 1.0-5.0 normally, Preferably it is 1.0-3.0.

The copolymer (A) can be produced by polymerizing (a) a polymerizable unsaturated compound, (b) a polymerizable unsaturated compound and (c) another polymerizable unsaturated compound in the presence of a radical polymerization initiator, for example in a suitable solvent.

Examples of the solvent used for the polymerization include

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 monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and propylene glycol mono-n-butyl ether; Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, and propylene glycol mono-n-butyl ether acetate; Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol ethyl monoether propionate, propylene glycol mono-n-propyl ether propionate, and propylene glycol mono-n-butyl ether propionate Nates; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, methyl lactate, ethyl lactate, n-propyl lactate , N-butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionic acid, n-butyl 3-hydroxypropionic acid, methyl 2-hydroxy-2-methylpropionate, 2 Ethyl hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetic acid, ethyl methoxyacetic acid, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, methyl ethoxyacetic acid Ethyl ethoxyacetate, ethoxyacetic acid n-propyl, ethoxyacetic acid n-butyl, n-propoxyacetic acid methyl, n-propoxyacetic acid ethyl, n-propoxyacetic acid n-propyl, n-propoxyacetic acid n- part , n-butoxyacetic acid methyl, n-butoxyacetic acid ethyl, n-butoxyacetic acid n-propyl, n-butoxyacetic acid n-butyl, 2-methoxypropionate methyl, 2-methoxypropionate ethyl, 2-methol N-propyl oxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, n-propyl 2-ethoxypropionate, n-butyl 2-ethoxypropionate, 2-n Methyl propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-propoxypropionate, n-butyl 2-npropoxypropionate, methyl 2-n-butoxypropionate, 2-n- Ethyl butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, 3-methoxypropionic acid n-butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid ethyl, 3-ethoxypropionic acid n-propyl, 3-ethoxypropionic acid n-butyl, 3-n-propoxypropionic acid methyl, 3-n-propoxypropionic acid ethyl, 3-n-propoxypropionic acid n-propyl, 3-n-propoxypropionic acid n Other esters such as -butyl, 3-n-butoxypropionate methyl, 3-n-butoxypropionate ethyl, 3-n-butoxypropionic acid n-propyl, and 3-n-butoxypropionic acid n-butyl Can be.

These solvents may be used alone or in combination of two or more thereof.

Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy- Azo compounds such as 2,4-dimethylvaleronitrile); Organic peroxides, such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxy pivalate, 1,1'-bis (t-butyl peroxy) cyclohexane, hydrogen peroxide, etc. are mentioned. When using a peroxide as a radical polymerization initiator, it can also be set as a redox initiator by using a reducing agent together.

In the present invention, the (A) copolymer may be used alone or in combination of two or more thereof.

-(B) polymerizable unsaturated compound-

Component (B) in the present invention is a polymerizable unsaturated compound (hereinafter referred to as "(B1) polymerizable unsaturated compound") having an alicyclic hydrocarbon group and no acidic functional group as an essential component, and (C) a photopolymerization initiator. And a polymerizable unsaturated compound which is polymerized by irradiation in the presence of.

Examples of the (B1) polymerizable unsaturated compound include cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 2-methylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 1- Methylcyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) acrylate, 2- Dicyclopentanyloxyethyl (meth) acrylate etc. are mentioned.

Especially among these (B1) polymerizable unsaturated compounds, tricyclo decanyl (meth) acrylate is preferable.

In the present invention, the polymerizable unsaturated compound (B1) may be used alone or in combination of two or more thereof.

In this invention, the content rate of the (B1) polymerizable unsaturated compound in a (B) polymerizable unsaturated compound component becomes like this. Preferably it is 5-80 weight%, More preferably, it is 10-70 weight%. Here, when the content rate of the (B1) polymerizable unsaturated compound is less than 5% by weight, there is a fear that the film reduction of the radiation irradiation part is increased, while when it exceeds 80% by weight, it is difficult to obtain a desired lens shape.

Examples of the (B) polymerizable unsaturated compound other than the (B1) polymerizable unsaturated compound include compounds having one ethylenically unsaturated bond (hereinafter referred to as “other monofunctional polymerizable unsaturated compounds”) and two ethylenic compounds. The compound which has an unsaturated bond (henceforth "other bifunctional polymerizable unsaturated compound"), and the compound which has three or more ethylenically unsaturated bonds (henceforth "other polyfunctional polymerizable unsaturated compound") are mentioned. .

Examples of other monofunctional polymerizable unsaturated compounds include mono (meth) acrylates of monohydric alcohols, preferably compounds represented by the following general formula (1).

Wherein n is an integer of 0 to 8, and R ¹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 9 carbon atoms.

Specific examples of the compound represented by the formula (1) include trade names Alonics M-101 (n = about 2, R ¹ = H), M-102 (n = about 4, R ¹ = H), M-111 (n = About 1, R ¹ = nC ₉ H ₁₉ (n-nonyl group, the same below)), 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 Toagosei Kagaku Kogyo Co., Ltd.], KAYARAD R-564 (n = about 2.3, R ¹ = H) [Nippon Kayaku Co., Ltd.] etc. are mentioned.

Examples of monofunctional polymerizable unsaturated compounds other than the compound represented by the formula (1) include Kayarard TC-110S and TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.), V-158, and V-2311 under the trade names. (A) polymerizable unsaturated compound in (A) copolymer, such as unsaturated carboxylic acid diesters, such as Osaka Kagaku Kogyo Co., Ltd. or dimethyl maleate, diethyl maleate, etc., (b) The same thing as the compound illustrated with respect to a polymerizable unsaturated compound or (c) another polymerizable unsaturated compound is mentioned.

Subsequently, examples of other difunctional polymerizable unsaturated compounds include di (meth) acrylates of dihydric alcohols, preferably compounds represented by the following general formula (2), compounds represented by the following general formula (3), and compounds represented by the following general formula (4). Etc. can be mentioned.

Where

n and m are each an integer of 0 to 8,

Each R ² independently of one another represents a hydrogen atom or a methyl group,

E represents a linear or branched alkylene group having 2 to 8 carbon atoms,

i is an integer from 1 to 10,

Each R ² independently of one another represents a hydrogen atom or a methyl group,

Each M independently of one another represents a residue of a dihydric alcohol,

N represents a residue of a dibasic acid,

j is 0 or 1;

Specific examples of the compound represented by the formula (2) include trade names, such as Alonex M-210 (n = about 2, m = about 2, R ² = methyl group) (manufactured by Toa Kosei Chemical Industries, Ltd.), Kayarad R- 551 (n + m = about 4, R ² = methyl group), R-712 (n + m = about 4, R ² = H) (above, manufactured by Nippon Kayaku Co., Ltd.) and the like.

In addition, specific examples of the compound represented by the formula (3) in the trade name Alonics M-240 (R = -CH ₂ CH _2- , i = about 4), M-245 (R = -CH ₂ CH _2- , i = About 9) [above, manufactured by Toagosei Kagaku Kogyo Co., Ltd.], Kayarad HDDA (R =-(CH ₂ ) _6- , i = 1), NPGDA (R = -CH ₂ C (CH ₃ ) ₂ CH _2- , i = 1), TPGDA (R = -CH ₂ CH (CH ₃ )-, i = 1), PEG400DA (R = -CH ₂ CH _2- , i = about 8) [and above, Nippon Kayaku and the like (Co., Ltd.)], light acrylate-NDA 1.9 (, i 1 = R = - - (CH _{2) 8).}

In addition, specific examples of the compound represented by the general formula (4) under the trade name Alonics M-6100, M-6200, M-6250, M-6300, M-6400, M-6500 [above, Toagosei Kagaku Kogyo Co., Ltd. ) Production].

Moreover, as another bifunctional polymerizable unsaturated compound other than the above, the compound represented by following formula (5a) [brand name Kayarard HX-220, Nippon Kayaku Co., Ltd.], the compound represented by following formula (5b) HX-620, manufactured by Nippon Kayaku Co., Ltd. or trade name, Kayard R-526, R-604, MANDA [manufactured by Nippon Kayaku Co., Ltd.], V-260, V-312, V-335 HP Osaka Yuki Kagaku Kogyo Co., Ltd.] etc. are mentioned.

Where

p and q are each an integer of 0 to 2, p + q = 2,

r and s are each an integer of 0 to 4, and r + s = 4.

Subsequently, examples of other polyfunctional polymerizable unsaturated compounds include poly (meth) acrylates of trivalent or more alcohols, preferably compounds represented by the following formula (6), compounds represented by the following formula (7), and represented by the following formula (8). The compound, the compound represented by following formula (9), etc. are mentioned.

Where

n is an integer from 0 to 8,

R ³ represents a hydrogen atom, a hydroxyl group or a methyl group,

G represents an oxygen atom or a methylene group,

Each R ² independently of one another represents a hydrogen atom or a methyl group,

Each X independently of one another represents a residue of a trihydric alcohol,

Y represents a residue of a dibasic acid,

t is an integer from 0 to 15,

A represents CH ₂ = CHCO-,

u is 1 or 2,

a is an integer from 2 to 6,

b is an integer of 0 to 4,

a + b = 6.

Specific examples of the compound represented by the formula (6) in the trade name Alonics M-309 (n = 0, R = methyl group), M-310 (n = about 1, R = methyl group) [above, Doagosei Kagaku Kogyo ( Manufacture), Cayarad 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, Osaka Kagaku Kogyo Co., Ltd. product] etc. are mentioned.

In addition, examples of the compound represented by the general formula (7) include Alonics M-400 (manufactured by Toagosei Kagaku Kogyo Co., Ltd.).

In addition, specific examples of the compound represented by the formula (8) include, for example, Alonics M-7100, M-8030, M-8060, M-8100, M-9050 (above, manufactured by Toagosei Chemical Industries, Ltd.); Can be mentioned.

In addition, specific examples of the compound represented by the formula (9) in the trade name Kayadrad DPCA-20 (u = about 1, a = about 2, b = about 4), DPCA-30 (u = about 1, 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) Manufactured by Kayaku Co., Ltd., V-360, V-GPT, V-3PA, V-400 (above, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.).

Among the (B) polymerizable unsaturated compounds other than these (B1) polymerizable unsaturated compounds, other bifunctional polymerizable unsaturated compounds and other polyfunctional polymerizable unsaturated compounds are preferable, and more preferably, the compound represented by the formula (4), Compound to be displayed.

In the present invention, the polymerizable unsaturated compounds (B) other than the polymerizable unsaturated compounds (B1) may be used alone or in combination of two or more thereof.

The usage-amount of the (B) polymerizable unsaturated compound in this invention becomes like this. Preferably it is 5-150 weight part, More preferably, it is 10-100 weight part with respect to 100 weight part of (A) copolymers. Here, when the amount of the (B) polymerizable unsaturated compound is less than 5 parts by weight, not only the sensitivity is lowered when the radiation is irradiated, but also it may be difficult to obtain a desired lens shape. A) There is a possibility that the compatibility with the copolymer is poor and the film on the surface of the coating film becomes rough.

-(C) photoinitiator-

(C) component in this invention contains the photoinitiator which generate | occur | produces the active species (for example, radical etc.) which can start superposition | polymerization of (B) polymerizable unsaturated compound by radiation irradiation.

Examples of such (C) photopolymerization initiators include α-diketones such as benzyl and diacetyl; Acyl phosphorus such as benzoin; Acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; Thioxanthones such as thioxanthone, 2,4-diethyl thioxanthone and thioxanthone-4-sulfonic acid; Benzophenones such as benzophenone, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone; Acetophenones such as acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone and p-methoxyacetophenone; Quinones such as anthraquinone and 1,4-naphthoquinone; Halogen compounds such as phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butylperoxide; Acylphosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide; 1- (9-ethyl-6-benzoyl-9.H.-carbazol-3-yl) -nonane-1,2-nonane-2-oxime-O-benzoate, 1- (9-ethyl-6- Benzoyl-9.H.-carbazol-3-yl) -nonane-1,2-nonan-2-oxime-O-acetate, 1- (9-ethyl-6-benzoyl-9.H.-carbazole- 3-yl) -pentane-1,2-pentane-2-oxime-O-acetate, 1- (9-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-onoxime-O-acetate, 1- [9-ethyl-6- (1,3 , 5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9. H.-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1,2-octadione-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-octadione-1- [4- (methyl O- such as thio) phenyl] -2- (O-benzoyloxime) and 1,2-octadione-1- [4- (phenylthio) phenyl] -2- [O- (4-methylbenzoyloxime)] And acyl oximes.

In addition, as a commercial item of the (C) photoinitiator, it is a brand name Irgacure 184, 500, 651, 907, 369, 379, CG24-61 [above, Ciba Gaiji Corporation], rucillin LR8728, rucillin TPO [ As mentioned above, BASF Corporation], Darocure 1116, 1173 [above, Merck Corporation], Ubecryl p36 [UCB Corporation], etc. are mentioned.

Among these (C) photoinitiators, preferred ones are 2-methyl [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-mor Acetophenones such as polynophenyl) butan-1-one or phenacyl chloride, tribromomethylphenyl sulfone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide and the like.

In the present invention, the (C) photopolymerization initiator may be used alone or in combination of two or more thereof, or may be used in combination with one or more radiation sensitizers.

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, more preferably 0.5 to 40 parts by weight based on 100 parts by weight of the (B) polymerizable unsaturated compound. to be. Here, when the usage-amount of (C) photoinitiator is less than 0.01 weight part, there exists a tendency for a sensitivity to fall, and when it exceeds 100 weight part, it is compatible with (A) copolymer or (B) polymerizable unsaturated compound. There exists a tendency for this poor or the storage stability of the resin composition obtained to fall.

-additive-

A thermally polymerizable compound which is polymerized by heating but not polymerized by radiation can be added to the radiation-sensitive resin composition of the present invention.

Preferred as such thermally polymerizable compounds are those which are thermally polymerized at 80 to 250 ° C, more preferably 80 to 160 ° C, particularly preferably 100 to 150 ° C.

In the radiation sensitive resin composition for microlens formation, it is preferable to add a thermally polymerizable compound especially when forming a microlens by making the temperature of heat processing into 160 degreeC or less.

Although a thermally polymerizable compound is generally a monomer, there is no restriction | limiting in particular in the molecular weight, It may have a molecular weight about an oligomer.

As a thermally polymerizable compound, the compound which has one or more or more types of thermally polymerizable functional groups, for example, an epoxy group, an episulfide group, an oxetanyl group, etc. is mentioned in a molecule | numerator. However, the functional silane coupling agent which has an epoxy group is also contained in the thermally polymerizable compound which has an epoxy group in the adhesion | attachment adjuvant mentioned later.

Examples of the compound having one epoxy group in the thermally polymerizable compound include methylglycidyl ether, ethylglycidyl ether, n-propylglycidyl ether, i-propylglycidyl ether, n-butylglycidyl ether, alkyl glycidyl ethers such as sec-butylglycidyl ether and t-butylglycidyl ether; Alkylene glycol monoglycidyl ethers such as ethylene glycol monoglycidyl ether, propylene glycol monoglycidyl ether, 1,4-butanediol monoglycidyl ether, and 1,6-hexanediol monoglycidyl ether; Polyalkylene glycol monoglycidyl ethers such as polyethylene glycol monoglycidyl ether and polypropylene monoglycidyl ether; Phenylglycidyl ether, o-tolylglycidyl ether, m-tolylglycidyl ether, p-tolylglycidyl ether, o-ethylphenylglycidyl ether, m-ethylglycidyl ether, p-ethyl Compounds having glycidyl groups such as arylglycidyl ethers such as phenylglycidyl ether, or

[(3,4-epoxycyclohexyl) methyl] methyl ether, [(3,4-epoxycyclohexyl) methyl] ethyl ether, [(3,4-epoxycyclohexyl) methyl] n-propyl ether, [(3 , 4-epoxycyclohexyl) methyl] i-propyl ether, [(3,4-epoxycyclohexyl) methyl] n-butyl ether, [(3,4-epoxycyclohexyl) methyl] sec-butyl ether, [( [(3,4-epoxycyclohexyl) methyl] alkyl ethers such as 3,4-epoxycyclohexyl) methyl] 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) Alkylene glycol mono [(3,4-epoxycyclohexyl) methyl] ethers such as methyl] ether and 1,6-hexanediol mono [(3,4-epoxycyclohexyl) methyl] ether; Polyalkylene glycol mono [(3,4-epoxycyclohexyl) such as polyethylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether and polypropylene glycol mono [(3,4-epoxycyclohexyl) methyl] ether ) 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-ethylphenyl Compounds having 3,4-epoxycyclohexyl groups, such as [(3,4-epoxycyclohexyl) methyl] aryl ethers such as ether and [(3,4-epoxycyclohexyl) methyl] p-ethylphenylether Etc. can be mentioned.

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, and hydrogenated bisphenol F Diglycides of bisphenol compounds such as diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol S diglycidyl ether Dil ethers;

Ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl Polyglycidyl ethers of polyhydric alcohols such as dil ether;

Polyalkylene glycol diglycidyl ethers such as polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether;

Polyglycidyl ethers of polyether polyols obtained by adding one or two 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 epoxy resin; Bisphenol F type epoxy resin; Phenol novolac type epoxy resins; Cresol novolac type epoxy resins; Polyphenol type epoxy resins; Other alicyclic epoxy resins, other aliphatic polyglycidyl ethers, and polyglycidyl esters of higher polyvalent fatty acids; Epoxidized soybean oil, epoxidized linseed oil, or

When referred to by the following trade names, Epicoat 825, 828, 834, 1001, 1002, 1003, 1004, 1007, 1009, 1010, 8000, 8034 (above, manufactured by Japan Epoxy Resin Co., Ltd.) and the like; Epicoat 807 [Japan Epoxy Resin Co., Ltd.] etc. as bisphenol F-type epoxy resin; Epicoat 152, 154, 157S65 (above, manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.), etc. as a phenol novolak-type epoxy resin; EOCN102, 103S, 104S, 1020, 1025, 1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (made by Japan Epoxy Resin Co., Ltd.), etc. as cresol novolak-type epoxy resin; Epicoat 1032H60, XY-4000 [above, Japan epoxy resin Co., Ltd. product] etc. as polyphenol-type epoxy resin; As other alicyclic epoxy resins, CY-175, 177, 179, Araldite CY-182, 192, 184 (above, manufactured by Ciba Specialty Chemicals), ERL-4206, -4221, -4234,- 4299 [above, manufactured by UCC Corporation], Shodine 509 [manufactured by Showa Denko Co., Ltd.], Epiclone 200, 400 [above, manufactured by Dainippon Ink, Inc.], Epicoat 871, 872 [above, Japan epoxy resin Co., Ltd.], ED-5661, -5662 (above, Serrano Coating Co., Ltd. product), etc .; Other aliphatic polyglycidyl ethers include epolite 100MF (manufactured by Kyoesha Chemical Co., Ltd.), epiol TMP (manufactured by Nippon Yushi Co., Ltd.), and the like.

Examples of the compound having two or more 3,4-epoxycyclohexyl groups include [(3,4-epoxycyclohexyl) methyl] ester of 3,4-epoxycyclohexanecarboxylic acid and 2- (3,4-epoxycyclohexyl -5,5-spiro-3,4-epoxy) cyclohexanemethdioxane, bis [(3,4-epoxycyclohexyl) methyl] adipate, bis [(3,4-epoxy-6-methylcyclohexyl) Methyl] adipate, (3,4-epoxy-6-methylcyclohexyl) ester of 3,4-epoxy-6-methylcyclohexanecarboxylic acid, methylene bis (3,4-epoxycyclohexane), dicyclo Pentadiene diepoxide, bis [(3,4-epoxycyclohexyl) methyl] ether of ethylene glycol, bis (3,4-epoxycyclohexanecarboxylic acid) ester of ethylene glycol, 3,4-epoxycyclohexanecarboxyl Reaction products of [(3,4-epoxycyclohexyl) methyl] ester of acid and caprolactone;

Examples of the compound having an epoxy group and a 3,4-epoxycyclohexyl group include 1,2: 8,9-diepoxylimonene.

Moreover, as an example of the compound which has an episulfide group, the epoxy group in the compound which has one or two or more said epoxy groups is described by J. Org. Chem., Vol. 28, p. 229 (1963)] and the like converted to episulfide groups according to the method disclosed.

Examples of the compound having one oxetanyl group include 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-methoxymethyloxetane, 3-methyl-3-ethoxymethyloxetane, 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-butylamidomethoxy) oxetane, 3-ethyl-3- (Nn- Butyl amido methoxy) oxetane is mentioned.

In addition, examples of the compound having two or more oxetanyl groups include

3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 '-[1,3- (2-methylenyl) propanediyl bis (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-jade Cetanyl) methyl] ether, diethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, triethylene glycol bis [(3-ethyl-3-oxetanyl) methyl] ether, tetraethylene glycol Bis [(3-ethyl-3-oxetanyl) methyl] ether, dicyclopentenyl bis [(3-ethyl-3-oxetanyl) methyl] ether, 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-oxe Nil) 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) methyl] ether, dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether, dipentaerythritol pentakis [(3-ethyl -3-oxetanyl) methyl] ether, dipentaerythritol tetrakis [(3-ethyl-3-oxetanyl) methyl] ether,

Reaction product of dipentaerythritol hexakis [(3-ethyl-3-oxetanyl) methyl] ether with caprolactone, dipentaerythritol pentakis [(3-ethyl-3-oxetanyl) methyl] ether Reaction product of and caprolactone, ditrimethylolpropane tetrakis [(3-ethyl-3-oxetanyl) methyl] ether, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and ethylene Reaction product of oxide, bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] ether and reaction product of propylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl ] Reaction product of ether and ethylene oxide, hydrogenated bisphenol A bis [(3-ethyl-3-oxetanyl) methyl] reaction product of ether and propylene oxide, bisphenol F bis [(3-ethyl-3-jade Cetanyl) methyl] and the reaction product of ether and ethylene oxide.

Among these thermally polymerizable compounds, bisphenol A type epoxy resin, phenol novolak type epoxy resin, [(3,4-epoxycyclohexyl) methyl] ester of 3,4-epoxycyclohexanecarboxylic acid, and bis [(3-ethyl 3-oxetanyl) methyl] terephthalate, etc. are preferable.

The said thermally polymerizable compound may be used independently, or may mix and use 2 or more types.

The amount of the thermally polymerizable compound added is preferably 100 parts by weight or less, more preferably 50 parts by weight or less based on 100 parts by weight of the (A) copolymer. Here, when the addition amount of a thermopolymerizable compound exceeds 100 weight part, there exists a possibility that the developability of the resin composition obtained may be impaired.

A thermal polymerization inhibitor can be added to the radiation sensitive resin composition of this invention in order to suppress the developability deterioration by heat at the time of prefiring.

Examples of such thermal polymerization inhibitors are pyrogallol, benzoquinone, hydroquinone, methylene blue, t-butylcatechol, methylhydroquinone, n-amylquinone, n-amyloyloxyhydroquinone, n-butylphenol, phenol, hydroquinone mono -n-propylether, 4,4 '-[1- {4- (1- [4-hydroxyphenyl] -1-methylethyl) phenyl} ethylidene] diphenol, 1,1,3-tris (2 And 5-dimethyl-4-hydroxyphenyl) -3-phenylpropane.

These thermal polymerization inhibitors may be used alone or in combination of two or more thereof.

The amount of the thermal polymerization inhibitor added is preferably 5 parts by weight or less, more preferably 3 parts by weight or less based on 100 parts by weight of the thermally polymerizable compound.

Surfactant can be added to the radiation sensitive resin composition of this invention in order to improve applicability | paintability, antifoaming property, flatness, etc.

Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and the like.

Examples of the fluorine-based surfactants include BM-1000, -1100 (above, manufactured by BM CHIMIE Co., Ltd.), Megapack F142D, F172, F173, F183 (above, manufactured by Dainippon Ink Chemical Co., Ltd.), Flowride FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M Co., Ltd.), Supron 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 Co., Ltd. product) etc. are mentioned.

Examples of the silicone-based surfactants include SH-28PA, -190, -193, SZ-6032, SF-8428, DC-57, -190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), KP341 (made by Shin-Etsu Chemical Co., Ltd.), F-top EF301, EF303, EF352 (above, Shin-Kaida Kasei Co., Ltd. product) etc. are mentioned.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, etc. are mentioned.

In addition, examples of surfactants other than those mentioned above include polyflow Nos. 57 and No. 90 (above, manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants may be used alone or in combination of two or more thereof.

The amount of the surfactant added is preferably 5 parts by weight or less, more preferably 2 parts by weight or less based on 100 parts by weight of the (A) copolymer. Here, when the addition amount of surfactant exceeds 5 weight part, the film | membrane of a coating film tends to become rough easily at the time of application | coating.

An adhesive adjuvant can be added to the radiation sensitive resin composition of this invention in order to improve adhesiveness with a board | substrate.

As an example of such an adhesion | attachment adjuvant, the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is preferable, More specifically, a trimethoxysilyl benzoic acid, (gamma) -methacryloyloxy Propyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane, γ-isocyanatepropyl triethoxysilane, γ-glycidoxypropyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane etc. are mentioned.

These adhesion aids may be used independently, or may mix and use 2 or more types.

The addition amount of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less, More preferably, it is 10 weight part or less with respect to 100 weight part of (A) copolymers.

In order to adjust the solubility to the alkali developing solution of the (A) copolymer, a dissolution promoter and a dissolution control agent can be added to the radiation sensitive resin composition of this invention. That is, when the solubility of the (A) copolymer in an alkali developing solution is too low, a solubility promoter having the action of increasing its solubility and suitably increasing the dissolution rate of the (A) copolymer during alkali development can be blended. On the contrary, when the solubility of the (A) copolymer in the alkali developer is too high, the solubility control agent having the action of controlling the solubility and suitably reducing the dissolution rate of the (A) copolymer during alkali development can be blended. have.

Although there is no restriction | limiting in particular in the said dissolution promoter and the dissolution controller, The compound which does not change chemically at the time of processes, such as prefiring, exposure, and image development of a radiation sensitive resin composition, is 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.

In addition, 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 methylphenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone.

These dissolution accelerators and dissolution controllers may be used alone or in combination of two or more thereof.

Although the addition amount of a dissolution promoter and a dissolution controller can be adjusted suitably according to the kind of (A) copolymer used, Preferably it is 50 mass parts or less with respect to 100 mass parts of (A) copolymers, More preferably, Is 30 mass parts or less.

To the radiation-sensitive resin composition of the present invention, a compound having a carboxyl group and / or a carboxylic anhydride group (hereinafter, referred to as a "carboxylic acid-based additive") can be added to finely adjust the solubility in an alkaline developer.

Examples of the carboxylic acid additive include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid and cinnamic acid; Lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-hydroxycinnamic acid, m-hydroxycinnamic acid, p-hydroxycinnamic acid, 5 Hydroxy monocarboxylic acids such as hydroxyisophthalic acid and lysine formic acid; Oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2,4-cyclohexanetricar Acid, trimellitic acid, pyromellitic acid, 1,2,3,4-butanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,5,8-naphthalenetetra Polyvalent carboxylic acids such as carboxylic acid; Itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanylic acid, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic acid anhydride, phthalic anhydride, pyromellitic anhydride, Trimellitic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 3,4,3 ', 4'-benzophenone And acid anhydrides such as tetracarboxylic dianhydride, ethylene glycol bis (trimelitate) dianhydride, and glycerin tris (trimelitate) dianhydride.

These carboxylic acid additives may be used alone or in combination of two or more thereof.

The amount of the carboxylic acid additive added is preferably 10 parts by weight or less, more preferably 5 parts by weight or less based on 100 parts by weight of the (A) copolymer.

Further, the radiation-sensitive resin composition of the present invention is a range in which a filler, a colorant, a viscosity modifier, etc. do not impair the original properties of the radiation-sensitive resin composition, and preferably a range of 50% by weight or less of the entire composition to which the total amount is added. Can also be added from.

Examples of the filler include silica, alumina, talc, bentonite, zirconium silicate, powder glass and the like.

These fillers may be used alone or in combination of two or more thereof.

In addition, examples of the colorant include extender pigments such as alumina bag, clay, barium carbonate and barium sulfate; Inorganic pigments such as zincation, lead white, sulfur lead, iron group, ultramarine blue, royal blue, titanium oxide, zinc chromate, red iron oxide, and carbon black; Organic pigments such as brilliant carmine 6B, permanent red 6B, permanent red R, benzidine yellow, phthalocyanine blue, phthalocyanine green; Basic dyes such as magenta and rhodamine; Direct dyes such as direct scarlet and direct orange; Acid dyes, such as roserine and methyl yellow, etc. are mentioned.

These colorants may be used alone, or may be used by mixing two or more kinds.

In addition, examples of the viscosity modifier include bentonite, silica gel, aluminum powder and the like.

These viscosity modifiers may be used independently, or may mix and use 2 or more types.

The radiation sensitive resin composition of this invention mixes (A) copolymer, (B) polymerizable unsaturated compound, (C) photoinitiator, and the additive used as needed uniformly, and apply | coating to a board | substrate. It is preferable to make it a liquid composition by diluting with an organic solvent for the purpose of easily performing.

As said organic solvent, it is preferable that each component which comprises a radiation sensitive resin composition can be melt | dissolved or disperse | distributed uniformly, does not react with each said component, and has suitable volatility.

Examples of such organic solvents include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, and N-methyl in addition to the same organic solvent as the solvent exemplified in connection with the polymerization for preparing the copolymer (A). Acetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, benzylethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1 And high boiling point solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate and ethylene glycol monophenyl ether acetate.

Among these organic solvents, in view of solubility, reactivity with each component, and ease of coating film formation, alkyl ethers of polyhydric alcohols such as ethylene glycol monoethyl ether and diethylene glycol monomethyl ether; Alkyl ether acetates of polyhydric alcohols such as ethylene glycol monoethyl ether acetate; Other esters such as ethyl lactate, methyl 3-methoxypropionate and ethyl 3-ethoxypropionate; Ketones, such as diacetone alcohol, are preferable.

The said organic solvent may be used independently, or may mix and use 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 the filler or pigment is not added during the preparation of the radiation-sensitive resin composition of the present invention, stirring and mixing may be performed in a conventional manner. When adding the filler or pigment, dispersers such as a dissol bar, a homogenizer and a triaxial roll mill may be used. What is necessary is just to carry out dispersion mixing. Moreover, the radiation sensitive resin composition of this invention can also be used, filtering as needed through a mesh, a membrane filter, etc. after manufacture.

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

Microlens

The microlens of this invention is formed from the radiation sensitive resin composition for microlens formation of this invention, and is manufactured.

The microlenses of the present invention are very preferably used for liquid crystal display devices such as various OA devices, liquid crystal televisions, mobile phones, projectors, and imaging optical systems and optical fiber connectors of on-chip color filters such as facsimile machines, electronic copiers and solid-state imaging devices. Can be used.

Radiation  Dry film

The radiation-sensitive dry film of the present invention is produced by laminating a radiation-sensitive layer made of the radiation-sensitive resin composition of the present invention on a base film, preferably a flexible base film.

The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition on the base film as a liquid composition, and then drying the film.

As an example of the base film of a radiation sensitive dry film, the synthetic resin film, such as a polyethylene terephthalate (PET) film, polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used. Moreover, in order to have moderate mold release property, what apply | coated or baked the silicone type mold release agent to the said film surface can be used.

The thickness of the base film is suitably in the range of 15 to 125 mu m.

Although there is no restriction | limiting in particular in the coating method at the time of laminating a radiation sensitive layer on a base film, For example, the appropriate method, such as an applicator coating method, a bar coating method, a roll coating method, a curtain flow coating method, can be used.

As for the film thickness of the radiation sensitive layer obtained, about 10-30 micrometers is preferable.

In addition, a radiation sensitive dry film can also be laminated | stacked and preserve | saved further on the radiation sensitive layer at the time of nonuse.

The 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 a suitable release property so that it cannot be peeled off when not in use, and can be peeled off easily when in use. As an example of a cover film that satisfies these conditions, a film obtained by coating or baking a silicone-based release agent on the surface of a synthetic resin film such as PET film, polypropylene film, polyethylene film, polyvinyl chloride, or the like may be used.

The thickness of the cover film is usually about 25 m.

Formation method of microlens

The method for forming a microlens of the present invention includes at least the following steps (a) to (d) in the order of the following description.

(A) process of forming the film of the radiation sensitive resin composition for microlens formation of this invention on a board | substrate,

(B) irradiating (hereinafter referred to as "exposure") at least a part of the coating film,

(C) developing the film after exposure;

(D) A step of heating the film after development (hereinafter referred to as "firing").

Hereinafter, these processes are demonstrated.

(A) Process

In this process, both the method of using a radiation sensitive resin composition as a liquid composition or the method of using it as a radiation sensitive dry film (henceforth a "dry film method") can be used.

When using a radiation sensitive resin composition as a liquid composition, a film is formed by apply | coating the said liquid composition on a board | substrate and performing prebaking.

As a substrate which can be used, a glass substrate, a resin substrate, a silicon wafer, or the board | substrate with which various metal layers were formed in these surfaces, etc. are mentioned.

There is no particular limitation on the method of applying the liquid composition, but for example, a suitable method such as spray coating, roll coating, rotary coating, bar coating or the like can be used.

The prefiring conditions vary depending on the type of the constituent components of the radiation-sensitive resin composition, the use ratio, and the like, but are usually about 30 seconds to 15 minutes at 60 to 130 ° C.

As for the film thickness of the film obtained, about 10-30 micrometers is preferable as a value after prebaking.

In the case of the dry film method, in the case where the cover film is laminated, the pressure-sensitive dry film is subjected to atmospheric pressure hot roll pressing, vacuum hot roll pressing, and vacuum thermopressing pressing so that the radiation-sensitive dry film is the substrate side. By pressing an appropriate heat and pressure on a board | substrate, using a suitable crimping method, such as these, a radiation sensitive layer is transferred to a board | substrate surface, and the film of a radiation sensitive resin composition is formed on a board | substrate.

-(B) process-

In this process, at least a part of the film of the formed radiation sensitive resin composition is exposed. When exposing part of a film, it exposes normally through the photomask of a predetermined pattern.

There is no restriction | limiting in particular in the radiation used for exposure, For example, ultraviolet-rays, such as g-ray (wavelength 436 nm) or i-ray (wavelength 365 nm), KrF excimer laser, etc., depending on the kind of (C) photoinitiator used, etc. Although X-rays, such as far ultraviolet rays, and synchrotron radiation, and charged particle beams, such as an electron beam, can be selected suitably, ultraviolet-ray is preferable among these radiations, and especially radiation containing g-rays and / or i-rays is preferable.

In addition, the exposure dose is preferably about 50 to 10,000 J / m ² .

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 peeled off after exposure and before development.

-(C) process-

In this step, the exposed film is developed with a developer, preferably an alkaline developer, to remove the unexposed portion, thereby forming a pattern of a predetermined shape.

Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di-n-propylamine, triethylamine , Methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene And aqueous solutions of basic compounds such as 1,5-diazabicyclo [4.3.0] -5-nonene.

A suitable amount of water-soluble organic solvents or surfactants, such as methanol and ethanol, can also be added to the aqueous solution of the said basic compound.

Moreover, after image development with alkaline developing solution, it wash | cleans normally, for example by running water washing | cleaning.

Moreover, in the case of the radiation sensitive resin composition which does not contain insoluble components, such as a pigment or a filler, various organic solvent which melt | dissolves each component which comprises the said composition can also be used as a developing solution.

There is no restriction | limiting in particular in the developing method, The appropriate method, such as a puddle method, the dipping method, the rocking dipping method, the shower method, can be used.

Although development time changes with the composition of a radiation sensitive resin composition etc., it is about 30 to 300 second normally at normal temperature.

In the conventional radiation-sensitive resin composition used for the formation of the microlenses, when the developing time exceeds about 20 to 25 seconds from the optimum condition, since the peeling occurs in the formed pattern, it was necessary to strictly control the developing time. In the case of the radiation sensitive resin composition for microlens formation of the present invention, even if the excess time from the optimum developing time is 30 seconds or more, a good pattern can be formed, which is advantageous in terms of product yield.

-(D) process-

In this step, the film after development is baked, for example, by a heating apparatus such as a hot plate or an oven, and the microfilm can be formed by melting and flowing the film in a predetermined lens shape while curing the film.

The firing conditions vary depending on the kind or proportion of the components of the radiation-sensitive resin composition, the desired pattern shape, the heating device, etc., but in the case of a high temperature plate, for example, about 1 to 30 minutes at 150 to 240 ° C., and an oven In the case of 3 to 90 minutes at 150 to 240 ℃. When using a board | substrate with low heat resistance, such as a resin substrate, it is preferable to make baking temperature into 160 degrees C or less, Preferably it is 100-150 degreeC. In addition, the step type baking method etc. which heat-process twice or more at the time of baking can also be used.

[ Example ]

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to a following example.

Synthesis Example 1

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux machine, 4.0 g of 2,2'- azobisisobutyronitrile as a radical polymerization initiator, 100.0 g of diethylene glycol dimethyl ether as a solvent, and diethylene glycol monomethyl ether 50.0 g was added and stirred until the radical polymerization initiator dissolved. Subsequently, 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 The mixture was slowly started to stir. Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-1).

Synthesis Example 2

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux group, 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 150.0 g of ethyl lactate was added and stirred until the radical polymerization initiator was dissolved. Then 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 then added. The mixture was slowly started to stir. Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-2).

Synthesis Example 3

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux group, 4.0 g of 2,2'-azobisisobutyronitrile was added as a radical polymerization initiator and 150.0 g of diacetone alcohol as a solvent, and the radical polymerization initiator was dissolved. Stir until. Subsequently, 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 added thereto and slowly stirred. . Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-3).

Synthesis Example 4

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux group, 4.0 g of 2,2'- azobis (2,4-dimethylvaleronitrile) as a radical polymerization initiator and 150.0 g of ethyl 3-ethoxypropionate as a solvent Was added and stirred until the radical polymerization initiator was dissolved. Subsequently, 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 added thereto and slowly stirred. . Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-4).

Synthesis Example 5

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux group, 4.0 g of 2,2'- azobisisobutyronitrile was added as a radical polymerization initiator, and 150 g of methyl 3-methoxypropionate was added as a solvent, and a radical polymerization initiator was added. Stir until dissolved. Subsequently, 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 added slowly. Agitation was started. Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-5).

Synthesis Example 6

After nitrogen-substituting the flask equipped with the dry ice / methanol reflux group, 4.0 g of 2,2'- azobisisobutyronitrile was added as a radical polymerization initiator, and 150 g of methyl 3-methoxypropionate was added as a solvent, and a radical polymerization initiator was added. Stir until dissolved. Subsequently, 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 slowly added thereto. Agitation was started. Then, 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 was added dropwise into a large amount of methanol to coagulate the reaction product. The obtained coagulated product was washed with water, and then dissolved in tetrahydrofuran of the same weight as the coagulated product, and further dropped into a large amount of methanol to coagulate. After a total of three such redissolution-solidification operations, the reaction product was vacuum dried at 40 ° C. for 48 hours to obtain (A) copolymer.

This (A) copolymer was referred to as copolymer (A-6).

<Example 1>

Preparation of Liquid Composition

As the component (A), 10.0 g of the copolymer (A-1) was dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of anlonix M8100 and Kaya 1.0 g of lard R-526, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as (C) component, and 3-methoxy is further added. Methyl propionate was added to make a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-1) of the radiation-sensitive resin composition.

Evaluation of preservation stability

The liquid composition (S-1) was stored in an oven at 40 ° C. for 1 week, and the viscosity increase rate (%) before and after storage was evaluated. When the viscosity increase rate is less than 5%, it can be said that storage stability is favorable. The evaluation results are shown in Table 1 below.

Pattern  Formation of a thin film

After apply | coating a liquid composition (S-1) using a spinner on a glass substrate, it pre-baked for 5 minutes on the high temperature plate of 100 degreeC, and formed the film.

Subsequently, the obtained film was exposed to ultraviolet rays having a wavelength of 365 nm and intensity of 200 W / m ² through a photomask having a predetermined pattern for 5 seconds. Subsequently, shower development was carried out at 25 ° C. for 2 minutes with 0.5 wt% aqueous tetramethylammonium hydroxide solution, followed by washing with pure water for 1 minute to form a pattern. Subsequently, the film was baked and cured in an oven at 220 ° C. for 60 minutes to obtain a patterned thin film having a film thickness of 19.4 μm.

Next, evaluation was performed in the following way. The evaluation results are shown in Table 1.

Resolution evaluation

(Circle) when the pattern of the line / space = 10 micrometer / 10 micrometers is resolved with respect to a pattern-shaped thin film, and (triangle | delta) when the pattern of the line / space = 20 micrometer / 20 micrometers is resolved, The case without was evaluated as x.

-Evaluation of pattern shape

For 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 of the shapes shown in FIG. 1. In the case of a semi-convex lens shape as shown 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 film thickness reduction rate (%) before and after heating. When the film thickness reduction rate is within 5%, it can be said that heat resistance is favorable.

Evaluation of Transparency

The transmittance | permeability (%) in wavelength 450nm was measured and measured about the patterned thin film by the spectrophotometer 150-20 type double beam (made by Hitachi Seisakusho Co., Ltd.). When this transmittance | permeability is 89% or more, it can be said that transparency is favorable.

Evaluation of heat discoloration

The patterned thin film was heated in an oven at 220 ° C. for 60 minutes, and the transmittance at a wavelength of 450 nm was measured with a spectrophotometer 150-20 type double beam [manufactured by Hitachi Seisakusho Co., Ltd.] for the patterned thin film before and after heating. It measured and evaluated by the reduction rate (%) of a transmittance | permeability. When the rate of decrease in transmittance is within 5%, it can be said that heat discoloration resistance is good.

Evaluation of solvent resistance

The glass substrate in which the patterned thin film was formed was immersed in 50 degreeC N-methylpyrrolidone for 15 minutes, and the film thickness change rate (%) of the patterned thin film before and after immersion [= (film thickness after immersion-film thickness before immersion) ) X 100 / film thickness before immersion]. When the film thickness change rate is within ± 5%, it can be said that solvent resistance is favorable.

<Example 2>

As the component (A), 10.0 g of the copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of cayarad HDDA and Kaya 1.0 g of lard R-526, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as (C) component, and 3-methoxy is further added. Methyl propionate was added to make a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-2) of the radiation-sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 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 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 3>

As the component (A), 10.0 g of the copolymer (A-1) was dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of anlonix M309 and Kaya 1.0 g of lard R-526, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651, and 2.0 g of Epicoat 828 as additives are added as (C) component. Further, methyl 3-methoxypropionate was added to prepare a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-3) of the radiation-sensitive resin composition. .

Subsequently, storage stability was evaluated similarly to Example 1 except having used the liquid composition (S-3) of a radiation sensitive resin composition instead of the liquid composition (S-1) of a radiation sensitive resin composition, and obtained the pattern shape A 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 4>

As the component (A), 10.0 g of the copolymer (A-2) is dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate and 1.9-NDA 2.0 of light acrylate g and 1.0 g of Kayarard R-526, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 as (C) components, further 3 Methyl methoxypropionate was added to make a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-4) of the radiation sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (S-4) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A 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 5

As the component (A), 10.0 g of the copolymer (A-3) was dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of anlonix M8100 and Kaya 1.0 g of lard MANDA, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as components (C), and methyl 3-methoxypropionate is further added. Was added to form a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 μm to prepare a liquid composition (S-5) of the radiation sensitive resin composition.

Subsequently, storage stability was evaluated similarly to Example 1 except having used the liquid composition (S-5) of a radiation sensitive resin composition instead of the liquid composition (S-1) of a radiation sensitive resin composition, and obtained the pattern shape A 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 6>

As the component (A), 10.0 g of the copolymer (A-4) was dissolved in 10.0 g of methyl 3-methoxypropionate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of Kayarard NPGDA, and Kaya 1.0 g of lard HX-220, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as (C) component, and 3-methoxy is further added. Methyl propionate was added to make a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-6) of the radiation sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (S-6) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A 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 7>

As the component (A), 10.0 g of the copolymer (A-5) was dissolved in 10.0 g of methyl 3-methoxypropanoate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate and 2.0 g of cayarad DPCA-20 And 1.0 g of Cayarad HX-620, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphineoxide (trade name Lucillin TPO) as a component (C) and 1.0 g of Irgacure 651, 3,4-epoxy as an additive 2.0 g of [(3,4-epoxycyclohexyl) methyl] ester of cyclohexanecarboxylic acid was added, followed by addition of methyl 3-methoxypropionate to give a solution having a solid content of 50% by weight, followed by pore size 5 Filtration was performed with a membrane filter to prepare a liquid composition (S-7) of the radiation sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (S-7) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A 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 8>

As the component (A), 10.0 g of the copolymer (A-6) was dissolved in 10.0 g of methyl 3-methoxypropanoate, and as the component (B), 2.0 g of tricyclodecanyl methacrylate, 2.0 g of anlonix M9050 and Kaya 1.0 g of lard R-604, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) as a component (C) and 1.0 g of Irgacure 651, bis [(3-ethyl- 2.0 g of 3-oxetanyl) methyl] terephthalate was added, followed by addition of methyl 3-methoxypropionate to give a solution having a solid content of 50% by weight, followed by filtration with a membrane filter having a pore diameter of 5 μm. The liquid composition (S-8) of the resin composition was prepared.

Subsequently, storage stability was evaluated like Example 1 except having used the liquid composition (S-8) of a radiation sensitive resin composition instead of the liquid composition (S-1) of a radiation sensitive resin composition, and obtained the pattern shape A 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 9

The liquid composition (S-1) 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 have a film thickness of 25 μm. A radiation sensitive dry film was prepared. Subsequently, the radiation-sensitive layer of the radiation-sensitive dry film was superposed on the surface of the glass substrate so as to be in contact with each other.

Subsequently, after peeling off the base film from the radiation-sensitive dry film on a board | substrate, it carried out similarly to Example 1, and formed and evaluated the patterned thin film.

In addition, the transferability was evaluated in the following way.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Evaluation of transcription

When the radiation-sensitive dry film was transferred to the glass substrate and the substrate film was peeled off, the case where the radiation layer could be uniformly transferred onto the glass substrate was left at the point where the radiation layer remained partially on the substrate film, or The case where the radiation sensitive layer could not be uniformly transferred to a glass substrate like the radiation sensitive layer not adhered to the glass substrate surface was evaluated as "x".

<Example 10>

A radiation sensitive dry film was produced 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 in Example 9 It was.

Subsequently, after peeling off and removing a base film from the radiation-sensitive dry film on a board | substrate, it carried out similarly to Example 1, formed and evaluated the patterned thin film, and evaluated transferability similarly to Example 9.

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 baked on a hot plate at 150 ° C. for 5 minutes. Except having hardened | cured and hardened | cured, it carried out similarly to Example 1, evaluated storage stability, and formed and evaluated the patterned thin film.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

<Example 12>

A radiation sensitive resin in the same manner as 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) in Example 1. A liquid composition (S-9) of the composition was prepared.

Subsequently, the liquid composition (S-9) 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 have a film thickness of 25. A radiation sensitive dry film having a thickness was prepared. Subsequently, the radiation-sensitive layer of the radiation-sensitive dry film was superposed on the surface of the glass substrate so as to be in contact with each other, and the thermal radiation-sensitive dry film was transferred to the glass substrate by pressing by thermocompression bonding.

Subsequently, after peeling off and removing a base film from the radiation-sensitive dry film on a board | substrate, it carried out similarly to Example 1, formed and evaluated the patterned thin film, and evaluated transferability similarly to Example 9.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Example 13

A radiation sensitive resin in the same manner as in Example 7, except that in Example 7, 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 the composition was prepared.

Subsequently, 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 give a film thickness of 25. A radiation sensitive dry film having a thickness was prepared. Subsequently, the radiation-sensitive layer of the radiation-sensitive dry film was superposed on the surface of the glass substrate so as to be in contact with each other.

Subsequently, after peeling off and removing a base film from the radiation-sensitive dry film on a board | substrate, it carried out similarly to Example 1, formed and evaluated the patterned thin film, and evaluated transferability similarly to Example 9.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

<Example 14>

As the component (A), 10.0 g of the copolymer (A-1) was dissolved in 10.0 g of methyl 3-methoxypropionate, and as the component (B), 4.4 g of tricyclodecanyl methacrylate, 0.4 g of anlonix M8100 and Kaya 0.2 g of Rad R-526, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 are added as a component (C), and 3-methoxy is further added. Methyl propionate was added to make a solution having a solid content of 50% by weight, and then filtered through a membrane filter having a pore diameter of 5 µm to prepare a liquid composition (S-11) of the radiation-sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (S-11) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A 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 15>

As the component (A), 10.0 g of the copolymer (A-6) is dissolved in 10.0 g of methyl 3-methoxypropinate, and as the component (B), 4.4 g of tricyclodecanyl methacrylate, 0.4 g of anlonix M9050 and Kaya 0.2 g of lard R-604, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) as a component (C) and 1.0 g of Irgacure 651, bis [(3-ethyl- 2.0 g of 3-oxetanyl) methyl] terephthalate was added, followed by addition of methyl 3-methoxypropionate to give a solution having a solid content of 50% by weight, followed by filtration with a membrane filter having a pore diameter of 5 μm. The liquid composition (S-12) of the resin composition was prepared.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (S-12) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A thin film was formed and evaluated.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Comparative Example 1

(A) As a component, 10.0 g of copolymers (A-1) are dissolved in 10.0 g of methyl 3-methoxypropinate, and as the polymerizable unsaturated compound, 2.0 g of Alonix M8100 and 1.0 g of Cayarrad R-526, (C) As a component, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added, and methyl 3-methoxypropionate was further added to give a solid content of 50% by weight. After making it into% solution, it filtered with the membrane filter of 5 micrometers of pore diameters, and produced the liquid composition (s-1) of a radiation sensitive resin composition.

Subsequently, the storage stability was evaluated in the same manner as in Example 1 except that the liquid composition (s-1) of the radiation sensitive resin composition was used instead of the liquid composition (S-1) of the radiation sensitive resin composition. A thin film was formed and evaluated.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

Comparative Example 2

As a component (A), 10.0 g of copolymer (A-1) is dissolved in 10.0 g of methyl 3-methoxypropinate, and as a polymerizable unsaturated compound, 2.0 g of Cayarrad HDDA and 1.0 g of Cayarrad R-526, (C) As a component, 2.0 g of 2,4,6-trimethylbenzoyl diphenylphosphine oxide (trade name Lucillin TPO) and 1.0 g of Irgacure 651 were added, and methyl 3-methoxypropionate was further added to give a solid content of 50% by weight. After making it into% solution, it filtered with the membrane filter of 5 micrometers of pore diameters, and produced the liquid composition (s-2) of a radiation sensitive resin composition.

Subsequently, except for using the liquid composition (s-2) of a radiation sensitive resin composition instead of the liquid composition (S-1) of a radiation sensitive resin composition, it carried out similarly to Example 9, and produced a radiation sensitive dry film and Transferred to the substrate.

Subsequently, after peeling off and removing a base film from the radiation-sensitive dry film on a board | substrate, it carried out similarly to Example 1, formed and evaluated the patterned thin film, and evaluated transferability similarly to Example 9.

The evaluation results are shown in Table 1 together with the film thickness of the patterned thin film.

The radiation-sensitive resin composition of the present invention can form a high-precision microlens and a microlens array having high resolution, excellent storage stability, coating property, and the like, and excellent balance of properties.

In addition, the microlenses of the present invention are excellent in balance of characteristics such as film thickness, resolution, pattern shape, transparency, heat resistance, heat discoloration resistance, solvent resistance, and the like, and in particular, liquid crystal displays of various OA devices, liquid crystal televisions, mobile phones, projectors, and the like. It can be used very preferably for an element.

In addition, according to the method for forming a microlens of the present invention, a high precision microlens and a microlens array having excellent characteristics can be formed by a simple process. Moreover, in the formation method of the microlens of this invention by a dry film method, time to produce | generate the conditions for obtaining predetermined | prescribed film thickness is unnecessary, and there is no environmental problem, such as volatilization of an organic solvent.

Claims (9)

(A) 10 to 50% by weight of a polymerizable unsaturated compound having an acidic functional group, (b) 20 to 60% by weight of a polymerizable unsaturated compound having an alicyclic hydrocarbon group and no acidic functional group, and (c) another polymerizable property. Alkali-soluble copolymer obtained by superposing | polymerizing 5-40 weight% of unsaturated compounds (it is (a) + (b) + (c) = 100 weight%), (B) a polymerizable unsaturated compound having as an essential component a polymerizable unsaturated compound having an alicyclic hydrocarbon group and not having an acidic functional group, and (C) photoinitiator A radiation-sensitive resin composition comprising a. The radiation sensitive resin composition of Claim 1 which further contains (D) a thermally polymerizable compound. The radiation sensitive resin composition of Claim 1 or 2 for microlens formation. The microlens formed and manufactured from the radiation sensitive resin composition of Claim 3. The radiation sensitive dry film manufactured by laminating | stacking the radiation sensitive layer which consists of a radiation sensitive resin composition of 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 of the following description. (A) process of forming the film of the radiation sensitive resin composition of Claim 3 on a board | substrate, (B) irradiating at least a portion of the coating with radiation, (C) developing the film after irradiation; (D) Process of heat-processing the film after image development. The method for forming a microlens according to claim 6, wherein the heat treatment temperature in the step (d) is 160 ° C or lower. The radiation sensitive layer of the radiation sensitive dry film of Claim 5 is transferred to the board | substrate surface at the (a) process, and the film of a radiation sensitive resin composition is formed on a board | substrate in Claim 6 or 7. A method of forming a microlens. The liquid crystal display element manufactured with the microlens of Claim 4.

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