KR20100011902A - Radiation sensitive resin composition, spacer for liquid crystal display device and method for forming the same, and liquid crystal display device - Google Patents

Abstract

PURPOSE: A radiation-sensitive resin composition is provided to obtain an enough spacer form with an exposure dose of 1,000 J/m^2 or less, and to ensure elastic recoverability, rubbing resistance, adhesion with a transparent substrate and heat resistance. CONSTITUTION: A radiation-sensitive resin composition comprises (A) a copolymer of (a1) at least one kind selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride and (a2) unsaturated compounds excluding (a1), (B) a polymerizable unsaturated compound, and (C) a compound represented by chemical formula 1.

Description

Radiation-sensitive resin composition, spacer for liquid crystal display element, method for forming the same, and liquid crystal display element TECHNICAL FIELD

BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a radiation sensitive resin composition, a spacer for a display panel and a display panel, and more particularly, a radiation sensitive resin suitable as a material for forming a spacer used for a display panel such as a liquid crystal display panel or a touch panel. It relates to a composition, a display panel spacer formed from the composition, and a display panel comprising the spacer.

In the liquid crystal display device, a method of forming a spacer by photolithography for maintaining a constant gap (cell gap) between two substrates is mainstream. In this method, the radiation-sensitive resin composition is applied onto a substrate, and developed by exposing ultraviolet light through a predetermined mask, for example, to form a dot or stripe spacer, and a predetermined place other than the pixel formation region. Only the spacer can be formed.

In view of the large area of the liquid crystal display element, the improvement of productivity, etc., the enlargement of the mother glass substrate (for example, 1,500 * 1,800mm, and about 1,870 * 2,200mm) is progressing. However, in the conventional substrate size, since the substrate size is smaller than the mask size, it is possible to cope with the batch exposure method. However, in a large substrate, it is almost impossible to produce a mask size equivalent to this substrate size. Is difficult to respond.

Therefore, a step exposure method is proposed as an exposure method that can cope with a large substrate. However, in the step exposure method, since it is exposed several times on a single substrate and requires time for positioning and step movement for each exposure, the throughput is reduced as compared with the package exposure method, so that it is necessary to compensate for it. High sensitivity to the radioactive resin composition is required.

Applicant has recently shown that in Patent Document 1, it is possible to achieve a sufficient spacer shape and film thickness with an exposure dose of 1,200 J / m 2 or less, but recently, due to the demand for larger substrates and increased throughput, Further high sensitivity to the radioactive resin composition, for example, a sensitivity capable of forming a good spacer at an exposure amount of 1,000 J / m 2 or less is required.

By the way, in the above exposure process, ultraviolet light called "Type 1" which has a fairly strong emission line in 300 nm, 315 nm vicinity, and 340 nm vicinity besides the light of wavelength 365nm showing maximum intensity is used, for example. It is common to do However, the use of light exhibiting strong bright lines in a wavelength region of 340 nm or less with strong energy is not preferable because the exposure machine is easily damaged, and thus, "Type 2" and "Type 3" in which the intensity of light of these short wavelengths are suppressed. The use of so-called light sources is preferred, and furthermore, the use of light sources called "Type 4" which do not contain these short wavelengths of light tends to be preferred. However, when the radiation sensitive resin composition known conventionally is applied to the light source of Type 2 to Type 4, it turns out that the radiation sensitivity is inadequate.

Therefore, even when Type 2 to Type 4 which is good for an exposure machine are used as a light source, a radiation sensitive resin composition showing high radiation sensitivity is greatly desired.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2007-84809

Therefore, an object of the present invention is high sensitivity even when using a light source having a short wavelength cut, and a sufficient spacer shape can be obtained even at an exposure amount of 1,000 J / m 2 or less, for example, elastic recovery, rubbing resistance, and a transparent substrate. It is providing the radiation sensitive resin composition which can form the spacer for liquid crystal display elements excellent also in adhesiveness and heat resistance.

Another object of the present invention is to provide a spacer for a liquid crystal display device excellent in elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, and the like and a method of manufacturing the same.

Still another object of the present invention is to provide a liquid crystal display device excellent in display quality and reliability.

According to this invention, the said objective and advantage of this invention are 1st,

(A) Copolymer of (a1) at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and (a2) unsaturated compounds other than said (a1) (henceforth a copolymer (A)). ,

(B) a polymerizable unsaturated compound, and

(C) a compound represented by the following formula (1)

It is achieved by the radiation sensitive resin composition containing these.

(In formula 1, R <^1> , R <^2> and R <^3> respectively independently represents R <^11> , OR <^11> , COR <^11> , SR <^11> , CONR <^12> R <^13> or CN, and R <^11> , R <^12> And R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and represents an alkyl group, an aryl group, and an aryl; The hydrogen atom of the alkyl group and the heterocyclic group may also be OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C (= N-OR ²¹ ) -R ²² , -C (= N-OCOR ²¹ ) -R ²² , CN, halogen atom, -CR ²¹ = CR ²² R ²³ , -CO-CR ²¹ = CR ²² R ²³ , substituted with carboxyl group, epoxy group R ²¹ , R ²² and R ²³ may each independently be a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a complex having 2 to 20 carbon atoms. The methylene group of the alkylene moiety of the substituents represented by the above-mentioned R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ^22, and R ²³ is an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond , Amide Sum or it may be interrupted 1 to 5 times, the alkyl portion of the substituent of the urethane bond may be a branched side chain may be, may be a cyclic alkyl, unsaturated alkyl terminal of the substituents bond, and, R ¹² And R ¹³ And R ²² and R ²³ may each form a ring together, and R ³ may form a ring together with an adjacent benzene ring. R ⁴ And R ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN , A halogen atom or a hydroxyl group, a and b are each independently 0 to 3).

According to this invention, the said objective and advantage of this invention are 2nd,

It is achieved by the spacer for liquid crystal display elements formed with said each radiation sensitive resin composition.

According to this invention, the said objective and advantage of this invention are 3rd,

At least the following steps are included in the order described below. A method of forming a spacer for a liquid crystal display device is achieved.

(A) forming a film of a radiation sensitive resin composition for forming a spacer for the liquid crystal display element on a substrate;

(B) exposing to at least a portion of the coating,

(C) developing the film after exposure, and

(D) The process of heating the said film after image development.

According to this invention, the said objective and advantage of this invention are 4th,

It is achieved by the liquid crystal display element provided with the said liquid crystal display element spacer.

The radiation-sensitive resin composition of the present invention is highly sensitive even when using a light source having a short wavelength cut, and a sufficient pattern shape can be obtained even at an exposure amount of 1,000 J / m 2 or less, for example, excellent in developability and elastic recovery. The liquid crystal display element spacer excellent also in rubbing tolerance, adhesiveness with a transparent substrate, heat resistance, etc. can be formed.

The liquid crystal display element of this invention is equipped with the spacer which is excellent in various performances, such as a sensitivity, developability, elastic recovery property, rubbing tolerance, adhesiveness with a transparent substrate, and heat resistance, and can implement | achieve high reliability over a long term.

(The best form to carry out invention)

Hereinafter, the present invention will be described in detail.

Radiation  Resin composition

Copolymer (A)

The copolymer (A) contained in the radiation-sensitive resin composition of the present invention is at least one selected from the group consisting of (a1) unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter referred to as "compound (a1)") And a copolymer of (a2) another unsaturated compound (hereinafter referred to as "compound (a2)").

In this invention, a copolymer (A) will not be specifically limited if it has solubility with respect to the alkaline developing solution used at the image development process of the radiation sensitive resin composition containing the said component.

Moreover, it is more preferable that the copolymer (A) in this invention has a reactive functional group, As an reactive functional group, an epoxy group, a (meth) acryloyl group, etc. are mentioned, for example. When a reactive functional group is an epoxy group, it can obtain by copolymerizing the radically polymerizable monomer which has an epoxy group, and another radically polymerizable monomer. When a reactive functional group is a (meth) acryloyl group, after copolymerizing a hydroxyl-containing radically polymerizable monomer and another radically polymerizable monomer, it can obtain by making a hydroxyl group in a polymer react with a (meth) acryloyl-group containing isocyanate compound. .

As (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride, acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryl Monocarboxylic acids such as royloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And acid anhydrides of the dicarboxylic acids.

Among these compounds (a1), acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, and maleic acid from the viewpoint of copolymerization reactivity and solubility in an alkali developer of a polymer or copolymer obtained. Acid anhydrides are preferable.

In a copolymer (A), a compound (a1) can be used individually or in mixture of 2 or more types. In the copolymer (A), the content rate of the repeating unit derived from the compound (a1) is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, particularly preferably 8 to 40 mass%. . When the content rate of the repeating unit derived from a compound (a1) is 5-60 mass%, the radiation sensitive resin composition which has various characteristics, such as radiation sensitivity, developability, and storage stability of a radiation sensitive resin composition, at a higher level. Is obtained.

(a2) As another unsaturated compound, the (a2-1) epoxy group containing unsaturated compound (henceforth a compound (a2-1)) is mentioned first, As a compound (a2-1), glycidyl acrylate and acrylic acid 2 -Methylglycidyl, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, 2,3-epoxypropyl acrylic acid Epoxy alkyl acrylate; Glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3, 4- epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylic acid, 3, 4- epoxy methacrylic acid Methacrylic acid epoxyalkyl esters such as cyclohexyl, methacrylic acid 3,4-epoxycyclohexylmethyl, methacrylic acid 2,3-epoxypropyl; α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl α-alkyl acrylates such as α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl Alkyl ester; o- vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether m-, p- vinylbenzyl glycidyl and the like can be mentioned glycidyl ethers such as ether.

Moreover, as another radically polymerizable monomer which has an epoxy group, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) 2-methyloxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) oxetane Acrylic acid ester which has oxetanyl groups, such as these, etc. are mentioned. 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3 -Oxetanyl such as (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3-ethyl oxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane Methacrylic acid ester etc. which have group are mentioned.

In a copolymer (A), a compound (a2-1) can be used individually or in mixture of 2 or more types. In the copolymer (A), the content rate of the repeating unit derived from the compound (a2-1) is preferably 0.5 to 70 mass%, more preferably 1 to 60 mass%, particularly preferably 3 to 50 mass %to be. When the content rate of the repeating unit derived from a compound (a2-1) is 0.5-70 mass%, the radiation-sensitive radiation which has various characteristics, such as heat resistance of a copolymer, storage stability of a copolymer, and a radiation sensitive resin composition, at a higher level The resin composition is obtained.

The copolymer (A) may contain, in addition to the compound (a2-1), an unsaturated compound having other radical polymerizability (hereinafter also referred to as compound (a2-2)).

First, as a specific example of a compound (a2-2), the unsaturated compound containing one or more hydroxyl groups in 1 molecule is mentioned. Examples of the unsaturated compound containing one or more hydroxyl groups in one molecule include acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester and acrylic acid 4-hydroxymethyl-cyclo. Acrylic acid hydroxyalkyl esters such as hexyl methyl ester; methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, methacrylic acid 5-hydroxypentyl ester Methacrylic acid hydroxyalkyl such as methacrylic acid 6-hydroxyhexyl ester, methacrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, methacrylic acid 4-hydroxymethyl-cyclohexylmethyl ester Ester etc. are mentioned.

The unsaturated compound containing one or more hydroxyl groups in these 1 molecules can be made to react with the isocyanate compound which has a (meth) acryloyl group after copolymer formation.

From the viewpoint of copolymerization reactivity and reactivity with the isocyanate compound, as the unsaturated compound containing one or more hydroxyl groups in one molecule, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester and the like are preferable.

As an isocyanate compound made to react with the unsaturated compound containing the said hydroxyl group, acrylic acid and methacrylic acid derivatives, such as 2-acryloyloxyethyl isocyanate and 2-methacryloyl oxyethyl isocyanate, are mentioned, for example.

In addition, as a commercial item of 2-acryloyloxyethyl isocyanate, as a commercial item of Karenz AOI (made by SHOWA DENKO KK) and 2-methacryloyl oxyethyl isocyanate in a brand name, Carlens MOI (Showa Denko Co., Ltd. product) is mentioned as a brand name.

Specific examples of other compounds (a2-2) include alkyl acrylates such as methyl acrylate and i-propyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and meta Methacrylic acid alkyl esters, such as t-butyl acrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo acrylate [5.2.1.0 ^2,6 ] decane-8-yl, 2- (tricyclo [5.2] .1.0 ^2,6 ] acrylic acid alicyclic esters such as decane-8-yloxy) ethyl and isobornyl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0] Methacrylic acid alicyclic esters such as ^2,6 ] decane-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl, and isoboronyl methacrylate;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate; aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate; dialkyl dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Unsaturated hetero 5- and 6-membered ring methacrylic acid esters containing one atom of oxygen such as methacrylic acid tetrahydrofurfuryl, methacrylic acid tetrahydrofuryl, and methacrylic acid tetrahydrofuran-2-methyl;

4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4 -Acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacrylo Unsaturated hetero 5-membered ring methacrylic acid esters containing oxygen 2-atoms such as yloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane;

Vinylaromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and 4-isopropenylphenol; N-substituted maleimide such as N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate and N-succinimidyl-4-maleimide butyrate mid;

Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, etc. are mentioned besides conjugated diene type compounds, such as 1, 3- butadiene, isoprene, and 2, 3- dimethyl- 1, 3- butadiene.

Of these compounds (a2-2), styrene, 4-isopropenylphenol, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (tricyclodecanyl methacrylate), tetramethacrylate Hydrofurfuryl, 1,3-butadiene, acrylic acid 2-hydroxyethyl ester, methacrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, 4-acryloyloxymethyl-2-methyl-2- Ethyl-1,3-dioxo, N-cyclohexyl maleimide, N-phenylmaleimide, etc. are preferable from a copolymerization reactivity and developability viewpoint.

In a copolymer (A), a compound (a2-2) can be used individually or in mixture of 2 or more types. In the copolymer (A), the content rate of the repeating unit derived from the compound (a2-2) is preferably 1 to 70% by mass, more preferably 3 to 60% by mass, particularly preferably 5 to 50% by mass. to be. When the content rate of the repeating unit derived from a compound (a2-2) is 1-70 mass%, the radiation-sensitive radiation which has various characteristics, such as heat resistance of a copolymer, storage stability of a copolymer, and a radiation sensitive resin composition at a higher level, The resin composition is obtained.

The preparation of the copolymer can be produced by polymerizing monomers of the constituents in a suitable solvent in the presence of a radical polymerization initiator. As the solvent used for the polymerization, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate ester and the like are preferable. These solvent can be used individually or in mixture of 2 or more types.

Moreover, it does not specifically limit as said radical polymerization initiator, For example, 2,2'- azobisisobutyronitrile, 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2 , 2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2 Azo compounds such as -methyl propionate) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used individually or in mixture of 2 or more types.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the copolymer is preferably 2,000 to 30,000, and more preferably 3,000 to 20,000. When Mw of a copolymer is 2,000-30,000, the radiation sensitive resin composition by which heat resistance, developability, radiation sensitivity, etc. were balanced to a higher level is obtained.

-(B) polymerizable unsaturated compound-

(B) A polymerizable unsaturated compound consists of an unsaturated compound which superposes | polymerizes by exposure of the radiation in presence of a radiation sensitive polymerization initiator.

Although it does not specifically limit as such (B) polymerizable unsaturated compound, For example, the monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has good copolymerizability and the strength of the spacer which can be obtained improves. It is preferable at the point which becomes.

As said monofunctional (meth) acrylic acid ester, For example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, Isoboroyl acrylate, isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, (omega) -carboxy polycaprolactone monoacrylate, etc. are mentioned. As a commercial item, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd. make) are branded, for example; KAYARAD 'TC-110S, East's TC-120S (above, manufactured by NIPPON KAYAKU CO., LTD.); Viscoat 158, East 2311 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) (OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)), Etc. are mentioned.

As said bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetra Ethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1,9-nonanedioldimethacrylate, b Phenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, etc. are mentioned. As a commercial item in a brand name, for example, Aronix M-210, copper M-240, copper M-6200 (above, Toagosei Co., Ltd.), KAYARAD 'HDDA, copper HX-220, copper' R-604 (more, Nippon) Kayaku Co., Ltd.), Viscoat 260, copper 312, copper 335 HP (above, Osaka Yukikagaku Kogyo Co., Ltd.), light acrylate (LIGHT ACRYLATE) 1,9-NDA (Kyoeisha Kagaku Co., Ltd.) ) Manufactured by KYOEISHA CHEMICAL CO., LTD.

As said trifunctional or more than (meth) acrylic acid ester, a trimethylol propane triacrylate, a trimethylol propane trimethacrylate, a pentaerythritol triacrylate, a pentaerythritol trimethacrylate, a pentaerythritol tetraacrylate, a penta, for example Erythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri ( In addition to 2-methacryloyloxyethyl) phosphate, a compound having a linear alkylene group and an alicyclic structure and having at least two isocyanate groups, at least one hydroxyl group in the molecule, and having three, four or five Sulfuryl having acryloyloxy group and / or methacryloyloxy group It is obtained by reacting water and the like functional urethane acrylate compound.

As a commercial item of (meth) acrylic acid ester more than trifunctional, in a brand name, for example, Aronix M-309, copper M-400, copper M-405, copper M-450, copper M-7100, copper M-8030, copper M-8060, T1-1450 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, TDP DPHA, TDP DP-20, TDP DP-30, TDP DP-60, TDP DP-120 (above, Nippon Kayaku As a commercial item containing Viscoat 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) and a polyfunctional urethane acrylate compound, New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) have.

Among these monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher (meth) acrylic acid esters are more preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and pentaerythritol tetraacrylate are particularly preferred. , A commercial product containing dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and a polyfunctional urethane acrylate compound is preferable.

The said monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester can be used individually or in mixture of 2 or more types.

In the radiation-sensitive resin composition of the present invention, the amount of the (B) polymerizable unsaturated compound used is preferably 1 to 300 parts by mass, more preferably 10 to 200 parts by mass based on 100 parts by mass of the copolymer (A). It is wealth. When the usage-amount of (B) polymerizable unsaturated compound is less than 1 mass part, there exists a possibility that image development residue may occur at the time of image development, and when it exceeds 300 mass parts, there exists a tendency for the adhesiveness of the spacer obtained to fall.

-(C) the compound represented by the formula (1)-

The compound represented by the said General formula (1) in the radiation sensitive resin composition of this invention is a compound which functions as a radiation sensitive polymerization initiator.

Although the compound represented by the said Formula (1) exists, the geometric isomer by the double bond of an oxime exists, it does not distinguish these, The said Formula (1) and the below-mentioned exemplary compound show a mixture or both of both, and showed the isomer. It is not limited to a structure.

In the formula (1), examples of the alkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isono Neyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, isocyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, vinyl group, allyl group, butenyl group , Ethynyl group, propynyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, pentyloxyethyl group, octyloxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, propoxyoxyethyl group, methoxypropyl group, 2-methoxy-1-methylethyl group etc. are mentioned. As the aryl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ , for example, a phenyl group, tolyl group, xylyl group, ethylphenyl group, chlorophenyl group, naphthyl group, anthryl group, And phenanthrenyl groups, substituted phenyl groups substituted with one or more of the alkyl groups, substituted biphenylyl groups, substituted naphthyl groups, substituted anthryl groups, and the like. As the arylalkyl group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ , for example, a benzyl group, chlorobenzyl group, α-methylbenzyl group, α, α-dimethylbenzyl group, phenyl Ethyl group, a phenylethenyl group, etc. are mentioned. As a heterocyclic group represented by R <^11> , R <^12> , R <^13> , R <^21> , R <^22> and R <^23> , For example, a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, Benzoxazol-2-yl group, tetrahydropyranyl group, pyrrolidyl group, imidazolidil group, pyrazolidyl group, thiazolidyl group, isothiazolidyl group, oxazolidyl group, isoxoxazolidyl group, piperidyl group, pipe 5-7 membered heterocyclic groups, such as a ferazyl group and a morpholinyl group, are mentioned preferably. Moreover, as a ring which R <^12> and R <^13> may form together, the ring which R <^22> and R <^23> may form together, and a ring which R <^3> may form with an adjacent benzene ring, For example, cyclopene 5-7 membered rings, such as a cyclic ring, a cyclohexane ring, a cyclopentine ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, are mentioned. Moreover, as a halogen atom which can substitute R <^11> , R <^12> , R <^13> , R <^21> , R <^22> and R <^23> and the halogen atom represented by R <^4> , R <^5> , fluorine, chlorine, bromine, iodine etc. are mentioned. have.

The alkylene moiety of the substituent may be interrupted 1 to 5 times by unsaturated bonds, ether bonds, thioether bonds, ester bonds, thioester bonds, amide bonds or urethane bonds. It may be a group of two or more species, or two or more groups may be stopped continuously if the group can be stopped continuously. In addition, the alkyl moiety of the substituent may have a branched side chain, cyclic alkyl, or the alkyl terminal of the substituent may be an unsaturated bond.

Among the compounds represented by Formula 1, in Formula 1, R ¹ is an alkyl group having 11 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, a heterocyclic group having 2 to 20 carbon atoms, OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ Or CN, R ³ is an alkyl group having 1 to 12 carbon atoms interrupted 1 to 5 times by an ether bond or ester bond, an alkyl group having 13 to 20 carbon atoms, OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN is, in particular, R ¹ is an alkyl group having 11 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, or R ³ is 1 to 5 times the methylene group of the alkylene moiety of the alkyl group as an ether bond or ester bond. A branched alkyl group having 8 or more carbon atoms which may be interrupted; methylene group of the alkylene moiety of the alkyl group is an alkyl group having 13 or more carbon atoms which may be interrupted 1 to 5 times by an ether bond or an ester bond; R ³ is 1 by an ether bond Being an alkyl group suspended for 5 to 5 times; R ³ is an alkyl group suspended for 1 to 5 times by an ester bond, the synthesis being easy, the sensitivity is high, and the sensitivity in the radiation-sensitive resin composition of the present invention Radioactive When used as an initiator, is preferred in that a high solubility in solvents.

The compound represented by the formula (1) may be dimerized through R ¹ or R ² , as represented by the following formula.

(In said formula, R <^1> -R <^5> and a and b are as having defined in the said General formula (1), respectively.)

Therefore, as a preferable specific example of the compound represented by the said General formula (1), the compound represented by each of following compound No.1-No.71 is mentioned.

In the present invention, the compounds represented by the above formula (1) can be used alone or in combination of two or more thereof.

In this invention, another radiation sensitive polymerization initiator (henceforth simply "another initiator") can also be used together with the compound represented by said (C) said Formula (1).

As such a radiation sensitive polymerization initiator, an O-acyl oxime type compound, an acetophenone type compound, a biimidazole type compound, a benzoin type compound, a benzophenone type compound etc. are mentioned, for example.

Specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1- Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9- n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, ethanone-1- [9-ethyl-6- (2- Methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetra Hydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- Dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. have.

Among them, preferred O-acyl oxime compounds include 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl ) -9H-carbazol-3-yl] -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3 -Dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) is mentioned. These O-acyl oxime compounds can be used individually or in mixture of 2 or more types.

As said acetophenone compound, the (alpha)-amino ketone compound and the (alpha)-hydroxy ketone compound are mentioned, for example.

Specific examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1 -(4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned.

Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

Of these acetophenone compounds, α-aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4 -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one This is particularly preferred.

Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-ratio. Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichloro Phenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

In the radiation-sensitive resin composition of the present invention, when a biimidazole compound is used as a radiation-sensitive polymerization initiator, an aliphatic or aromatic compound having a dialkylamino group in order to sensitize it (hereinafter referred to as "amino sensitizer") Can be added.

As an amino-type sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned, for example. Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable.

Moreover, in the radiation sensitive resin composition of this invention, when using a biimidazole compound and an amino sensitizer together, a thiol compound can be added as a hydrogen radical donor. The biimidazole compound is sensitized and cleaved by an amino-based sensitizer to generate imidazole radicals, but the high polymerization initiation capacity is not expressed as it is, and the pattern upper part of the spacer obtained is large and the lower part of the pattern is preferable. There may be a shape that is not. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, a hydrogen radical is donated from a thiol compound to an imidazole radical. As a result, while the imidazole radical is converted into neutral imidazole, the component which has a sulfur radical with high polymerization initiation power generate | occur | produces, and the shape of a spacer can be made into a more preferable shape by this.

As said thiol compound, For example, aromatic thiol compounds, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, and 2-mercapto-5-methoxybenzothiazole; Aliphatic monothiol compounds such as 3-mercaptopropionic acid and 3-mercaptopropionic acid; And bifunctional or higher aliphatic thiol compounds such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate). Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

When using a biimidazole compound and an amino sensitizer together, the addition amount of an amino sensitizer becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, it is 1-20 mass It is wealth. When the addition amount of an amino sensitizer is 0.1-50 mass parts, the shape of the spacer obtained becomes favorable.

Moreover, when using a biimidazole compound, an amino sensitizer, and a thiol compound together, as an addition amount of a thiol compound, it is 0.1-30 mass parts with respect to 100 mass parts of biimidazole compounds, More preferably, 1 It is -20 mass parts. When the addition amount of a thiol compound is 0.1-30 mass parts, the shape and adhesiveness of a spacer become the best.

The total use ratio of the component (C) is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass with respect to 100 parts by mass of the copolymer (A). (C) When the usage-amount of a radiation sensitive polymerization initiator is 0.1-50 mass parts, the radiation sensitive resin composition of this invention can form the spacer which has high hardness and adhesiveness even in the case of low exposure amount.

(Other additives)

You may mix | blend additives, such as (D) adhesion | attachment adjuvant and (E) surfactant, with the radiation sensitive resin composition of this invention in the range which does not impair the desired effect.

(D) Adhesion Aids

Next, as (D) adhesion | attachment adjuvant (henceforth also called (D) component), the functional silane coupling agent which has a reactive substituent can be used, for example. As said reactive substituent, a carboxyl group, methacryloyl group, an isocyanate group, an epoxy group, etc. are mentioned, for example.

As a specific example, for example, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ- Glycidoxy propyl trimethoxysilane, (gamma)-glycidoxy propyl tri ethoxysilane, (beta)-(3, 4- epoxy cyclohexyl) ethyl trimethoxysilane, etc. are mentioned.

Such (D) component becomes like this. Preferably it is 0.1-50 mass parts with respect to 100 mass parts of copolymers (A), More preferably, it is 1-40 mass parts. (D) When the usage-amount of an adhesion | attachment adjuvant is 0.1-50 mass parts, the adhesiveness of the spacer obtained becomes the best.

(E) surfactant

The resin composition of this invention can contain (E) surfactant further (henceforth (E) component) in order to improve application | coating performance.

As such (E) component, a fluorochemical surfactant and silicone type surfactant are mentioned, for example.

As said fluorine-type surfactant, BM CHEMIE company brand names: BM-1000, BM-1100, Dainippon Inky Kagaku Kogyo Co., Ltd. (DIC CORPORATION) brand names: Megapack F142D, copper F172, Commercial products, such as F173, F183, and NEOS COMPANY LIMITED, brand name: FTX-218 is mentioned.

As said silicone type surfactant, Dow Corning Silicon Co., Ltd. make, for example, are brand names: SH-28PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190, Shin-Etsu Chemical Co., Ltd. brand name: KP341 etc. can be mentioned.

Such (E) component becomes like this. Preferably it is 0.01-10 mass parts, More preferably, it is 0.05-5 mass parts with respect to 100 mass parts of copolymers (A). When the usage-amount of (E) component is 0.01-10 mass parts, generation | occurrence | production of a rough film at the time of forming a coating film on a board | substrate can be suppressed.

The radiation sensitive resin composition used by this invention mixes and melts a copolymer (A), (B) component, (C) component, etc. in a solvent. Among the solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among these, for example, benzyl alcohol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, methyl methoxy propionate, ethyl ethoxy propionate, and 3-methoxybutyl acetate can be particularly preferably used.

Moreover, in order to improve the in-plane uniformity of a film thickness with the said solvent, you may use a high boiling point solvent together. As a high boiling point solvent which can be used together, N-methylpyrrolidone, benzyl ethyl ether, isophorone, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, a propylene carbonate, etc. are mentioned. Of these, N-methylpyrrolidone and γ-butyrolactone are preferable.

(Formation method of spacer)

-(A) film formation process

When forming a film by the apply | coating method, after apply | coating the solution of the radiation sensitive resin composition of this invention on a transparent conductive film, a film can be formed by heating (pre-baking) a coating surface. Solid content concentration of the composition solution used for a coating method becomes like this. Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%, More preferably, it is 15-35 mass%. The coating method of the composition solution is not particularly limited, and suitable methods such as spraying, roll coating, spin coating (spin coating), slit die coating and bar coating may be adopted. And, in particular, spin coating or slit die coating.

In particular, the radiation-sensitive resin composition of the present invention is particularly suitable for the slit die coating method, and does not generate coating unevenness even when the moving speed of the slit die is set to 150 mm / sec.

On the other hand, the dry film used when forming a film by the dry film method laminates the radiation sensitive layer which consists of the photosensitive resin composition of this invention on a base film, Preferably, a flexible base film, (Hereinafter referred to as "radiation-sensitive dry film").

The said radiation sensitive dry film can be formed by laminating a radiation sensitive layer by apply | coating the photosensitive resin composition of this invention as a composition solution on a base film, Preferably, after removing a solvent. Solid content concentration of the composition solution used for laminating | stacking the radiation sensitive layer of a radiation sensitive dry film becomes like this. Preferably it is 5-50 mass%, More preferably, it is 10-50 mass%, More preferably, it is 20-50 It is mass% and it is especially preferable that it is 30-50 mass%. As a base film of a radiation sensitive dry film, the film of synthetic resins, such as polyethylene terephthalate (PET), polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. As for the thickness of a base film, the range of 15-125 micrometers is suitable. As for the thickness of a radiation sensitive layer, about 1-30 micrometers is preferable.

The radiation-sensitive dry film can also be stored by laminating a cover film on the radiation-sensitive layer when not in use. It is preferable that this cover film has an appropriate release property so that it cannot be peeled off when not in use and can be peeled off easily when used. As a cover film which satisfies these conditions, the film which apply | coated the silicone mold release agent to the surface of synthetic resin films, such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, a polyurethane film, or baked, can be used, for example. Can be. As for the thickness of a cover film, about 5-30 micrometers is preferable. These cover films can also be set as the laminated cover film which laminated | stacked two layers or three layers.

A film can be formed by laminating such a dry film on the transparent conductive film of a transparent substrate by a suitable method, such as a thermocompression method.

The film thus formed is then preferably prebaked. Although the conditions of prebaking differ also according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 10 minutes at 70-120 degreeC.

The film thickness after prebaking of a film becomes like this. Preferably it is 0.5-10.0 micrometers, More preferably, it is about 1.0-5.0 micrometers.

(B) Exposure process

Next, it exposes to at least one part of the formed film. In this case, when exposing part of a film, it exposes normally through the photomask which has a predetermined pattern.

As the radiation used for exposure, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly includes ultraviolet rays of 365 nm. Radiation is preferred.

In the present invention, there is an advantage that the pattern can be formed with high sensitivity even when a light source of Type 2, Type 3, or Type 4 in which short wavelength light is cut during this exposure is used.

The exposure amount is a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) of the intensity at a wavelength of 365 nm of the radiation to be exposed, preferably 100 to 10,000 J / m 2, more preferably 500 It is -1,500 J / m <2>. Since the radiation sensitive resin composition of this invention is very sensitive, even when an exposure amount is 1,000 J / m <2> or less and 700 J / m <2> or less, a spacer of a favorable shape and a film thickness can be formed.

(C) Developing process

Next, by developing the film after exposure, an unnecessary part is removed and a predetermined pattern is formed.

As a developing solution used for image development, alkaline developing solution is preferable, As an example, Inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia; The aqueous solution of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, is mentioned.

In addition, an aqueous solution of the alkaline compound may be used by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant.

The developing method may be any of a puddle method, a dipping method, a shower method and the like, and the developing time is preferably about 10 to 180 seconds.

After the development, for example, washing with running water for 30 to 90 seconds, and then drying with, for example, compressed air or compressed nitrogen, a desired pattern is formed.

-(D) heat treatment process-

Subsequently, the obtained pattern is heated at a predetermined temperature, for example, 150 to 250 ° C. for a predetermined time, for example, on a hot plate for 5 to 30 minutes by a heating device such as a hot plate or an oven, for example. The spacer can be obtained by heating (post baking) for 30 to 180 minutes.

The film thickness of the spacer thus obtained is preferably 0.3 to 9.0 µm, more preferably about 0.5 to 4.0 µm.

Liquid crystal display element

The liquid crystal display element of this invention is equipped with the spacer of this invention formed as mentioned above.

Although it does not specifically limit as a structure of the liquid crystal display element of this invention, For example, as shown in FIG. 1, two alignment films which form a color filter layer and a spacer on a transparent substrate, and are arrange | positioned through a liquid crystal layer, The structure which has an opposing transparent electrode, an opposing transparent substrate, etc. is mentioned. Moreover, as shown in FIG. 1, you may form a protective film on a polarizing plate or a color filter layer as needed.

As shown in FIG. 2, a TN-TFT type liquid crystal display device may be formed by forming a color filter layer and a spacer on a transparent substrate and opposing a thin film transistor (TFT) array via an alignment film and a liquid crystal layer. have. Also in this case, a protective film may be formed on a polarizing plate or a color filter layer as needed.

(Example)

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

Preparation of (co) polymer

Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate were added, followed by 18 parts by mass of methacrylic acid and tricycle of methacrylic acid. After 25 mass parts of rho [5.2.1.0 ^2,6 ] decane-8-yl, 5 mass parts of styrene, 30 mass parts of methacrylic acid 2-hydroxyethyl ester, and 22 mass parts of benzyl methacrylate were substituted for nitrogen, While stirring slowly, the temperature of the solution was raised to 80 ° C. and maintained at this temperature for 5 hours to obtain a copolymer [α-1] solution having a solid content concentration of 28.8% by mass. The weight average molecular weight of the obtained copolymer [α-1] was measured using GPC (gel permeation chromatography) GPC-101 (brand name, the product made by SHOWA DENKO KK) , 13,000.

Subsequently, 14 parts by mass of 2-methacryloyloxyethyl isocyanate (trade name Carens MOI, manufactured by Showa Denko Co., Ltd.) and 0.1 parts by mass of 4-methoxyphenol were added to the copolymer [α-1] solution. After the addition, the mixture was stirred at 40 ° C for 1 hour and further at 60 ° C for 2 hours to react. Progress of reaction of the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer [α-1] was confirmed by IR (infrared absorption) spectrum. Derived from isocyanate group of 2-methacryloyloxyethyl isocyanate in IR spectrum of copolymer [α-1] solution, solution after 1 hour reaction and solution after reaction at 40 ° C for 1 hour and further at 60 ° C for 2 hours The peak in the vicinity of 2270 cm ^-1 was confirmed to decrease. The copolymer (A-1) solution of 30.0 mass% of solid content concentration was obtained.

Synthesis Example 2

14 mass parts of 2-acryloyloxyethyl isocyanate (brand name Carenz AOI, Showa Denko Co., Ltd. product) and 4-methoxy phenol in the said copolymer [(alpha) -1] solution similarly to the synthesis example 1 After 0.1 mass part was added, it stirred for 1 hour at 40 degreeC, and also reacted at 60 degreeC for 2 hours. The copolymer (A-2) solution of 30.5 mass% of solid content concentration was obtained.

Synthesis Example 3

17 parts by mass of 4-methacryloyloxybutyl isocyanate (trade name Carens MOI-C4, manufactured by Showa Denko Co., Ltd.) and 4- in the copolymer [α-1] solution in the same manner as in Synthesis example 1. 0.1 mass part of methoxyphenols were added, and it stirred for 1 hour at 40 degreeC, and also made it react at 60 degreeC for 2 hours. The copolymer (A-3) solution of 31.0 mass% of solid content concentration was obtained.

Synthesis Example 4

To a flask equipped with a cooling tube and a stirrer, 5 parts by mass of 2,2'-azobisisobutyronitrile, 125 parts by mass of 3-methoxybutyl acetate and 125 parts by mass of propylene glycol monomethyl ether acetate were added, and then methacryl was added. 18 parts by mass of acid, 25 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 5 parts by mass of styrene, 5 parts by mass of 1,3-butadiene, 2- (6-hydroxy methacrylate) Roxyhexanoyloxy) ethyl ester (brand name PLACCEL FM1D (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.)) 25 parts by mass and methacrylic acid tetrahydrofuran-2-yl 22 parts by mass, nitrogen replacement Then, while stirring slowly, the solution temperature was raised to 80 degreeC, this temperature was hold | maintained for 5 hours, and superposition | polymerization was obtained, and the copolymer [(alpha) -2] solution of 29.1 mass% of solid content concentration was obtained.

About the obtained copolymer [(alpha) -2], it was 18,000 when Mw was measured using GPC (gel permeation chromatography) GPC-101 (brand name, Showa Denko Co., Ltd. product).

Subsequently, 14 mass parts of 2-methacryloyloxyethyl isocyanate (brand name Carens MOI, Showa Denko Co., Ltd. product), and 0.1 mass part of 4-methoxy phenols are added to the said copolymer [alpha-2] solution. After that, the mixture was stirred at 40 ° C for 1 hour and further stirred at 60 ° C for 2 hours to obtain a copolymer (A-4) solution having a solid content concentration of 31.0 mass%.

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of diethylene glycol ethylmethyl ether were added. Then, 40 mass parts of glycidyl methacrylate, 32 mass parts of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 18 mass parts of methacrylic acid, 5 mass parts of styrene, and 1, 5 parts by mass of 3-butadiene was added, and after nitrogen replacement, stirring was started slowly. The solution temperature was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [β-1]. Solid content concentration of the obtained polymer solution was 31.0 mass%. The weight average molecular weight of the obtained polymer was 11,000.

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. 20 parts by mass of styrene, 18 parts by mass of methacrylic acid, 20 parts by mass of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 3-ethyl-3-methacryloyloxymethyloxetane 42 mass parts were put in, nitrogen-substituted, and stirring was started slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing a copolymer [β-2]. Solid content concentration of the obtained polymer solution was 33.0 mass%, and when Mw was measured using GPC (gel permeation chromatography) and GPC-101 (brand name, Showa Denko Co., Ltd.), it was 24,000.

Synthesis Example 7

In a flask equipped with a cooling tube and a stirrer, 3 parts by mass of 2,2'-azobisisobutyronitrile and 200 parts by mass of 3-methoxybutyl acetate were added, followed by 18 parts by mass of methacrylic acid and tricyclo methacrylate. [5.2.1.0 ^2,6 ] 25 parts by mass of decane-8-yl, 5 parts by mass of styrene, 30 parts by mass of methacrylic acid 2-hydroxyethyl ester and 22 parts by mass of benzyl methacrylate were added, followed by nitrogen substitution. The solution of the copolymer [α-3] of 33.5 mass% of solid content concentration was obtained by raising the temperature of the solution to 80 degreeC, stirring slowly, and superposing | polymerizing by holding this temperature for 6 hours.

It was 30,000 when Mw was measured about the obtained copolymer [(alpha) -3] using GPC (gel permeation chromatography) GPC-101 (brand name, Showa Denko Co., Ltd. product).

Subsequently, 15 mass parts of 2- (2-isocyanate ethoxy) ethyl methacrylic acid (brand name Carenz MOI-EG, Showa Denko Co., Ltd. product) and 4-methoxy are added to the said copolymer [alpha-3] solution. 0.1 mass part of phenols were added, and it stirred for 1 hour at 40 degreeC, and also made it react at 60 degreeC for 2 hours. The copolymer (A-5) solution of 36.0 mass% of solid content concentration was obtained.

(Example 1)

Radiation  Preparation of Resin Composition

As the component [A], 100 parts by mass of the copolymer (A-1) solution obtained in Synthesis Example 1 was used, and as the component [B], dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 100 5 parts by mass of Compound No. 33 as a mass part, 10 parts by mass of 1,9-nonanediacrylate (trade name Light Acrylate 1,9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.), [C] component, 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (brand name Irgacure 907, Chiba Specialty Chemicals, Inc.) as another polymerization initiator (CIBA JAPAN) KK) production) 5 parts by mass and 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole'5 parts by mass, as an amino sensitizer 5 parts by mass of 4,4'-bis (diethylamino) benzophenone # 5, 2.5 parts by mass of 2-mercaptobenzothiazole as a thiol compound, 5 parts by mass of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, and a surfactant As FTX-218 ( 0.5 mass part of a brand name, the Neos Corporation) were mixed, it melt | dissolved in propylene glycol monomethyl ether acetate so that solid content concentration might be 30 mass%, and it filtered by the Millipore filter of 0.5 micrometer of pore diameters, and it carried out radiation sensitive resin composition (S -1) was prepared The spacer was formed and evaluated as follows using this radiation sensitive resin composition (S-1) The evaluation result was shown in Table 2.

Spacer  formation

After applying the radiation sensitive resin composition (S-1) prepared above using a spinner on an alkali free glass substrate, it prebaked for 3 minutes on a 100 degreeC hotplate, and the film of 3.5 micrometers of film thicknesses Was formed (coating method).

Subsequently, using the high pressure mercury lamp (Type 1 light source) which has the spectral distribution of Type 1 shown in FIG. 4, the obtained film was exposed through the photomask of the afterimage pattern of a 10 micrometer square with a variable exposure amount. did. Then, after developing at 25 degreeC using 0.05 mass% aqueous solution of potassium hydroxide, it wash | cleaned with pure water for 1 minute, and also heated (postbaked) for 30 minutes in 230 degreeC oven, and formed the spacer. .

(1) evaluation of sensitivity

In formation of the said spacer, the minimum exposure amount which the residual film ratio (film thickness after postbaking x 100 / film | membrane thickness after post-baking) after postbaking becomes 90% or more was made into the sensitivity. When this exposure amount is 600 J / m <2> or less, it can be said that a sensitivity is favorable.

(2) evaluation of elastic recovery rate

For a spacer obtained at an exposure amount corresponding to the sensitivity irradiated in the above (1), using a micro compression tester (trade name DUH-201, manufactured by Shimadzu Seisakusho Co., Ltd.), using a planar indenter having a diameter of 50 μm. , Load and unload speed are 2.6mN / sec, load up to 50mN, hold for 5 seconds and unload, load-strain curve under load and load-strain under load Created a curve. At this time, as shown in FIG. 3, the elastic recovery rate was computed by following formula (1), making the deformation amount in load 50mN into L1, and the deformation amount under unloading as L2.

Elastic recovery rate (%) = L2 × 100 / L1 (1)

When the deformation amount L1 is 0.2 µm or more, flexibility can be said to be good, and when the elastic recovery rate is 65% or more, it can be said that the elastic recovery rate is high.

(3) evaluation of rubbing resistance

After applying AL3046 (trade name, manufactured by JSR Corporation) as a liquid crystal aligning agent, onto a substrate having a spacer at an exposure amount corresponding to the sensitivity irradiated with the above (1) with a liquid crystal aligning film coating machine It heated at 180 degreeC for 1 hour, and formed the coating film of the liquid crystal aligning agent with a film thickness of 0.05 micrometer.

Then, the rubbing process was performed by the rubbing machine which has the roll which wound the cloth made from polyamide to this coating film at the rotation speed of 500 rpm and the moving speed of 1 cm / sec of a stage. At this time, the presence or absence of the peeling of the pattern was evaluated.

(4) Evaluation of adhesiveness

Except not using a photomask, it carried out similarly to formation of the said spacer, and formed the cured film by the exposure amount corresponded to the sensitivity irradiated by said (1). About this cured film, it evaluated by the 8.5 * 2 checker scale tape method in the adhesion test of JISK5400 (1900) 8.5. The value shown in Table 2 is the number of remaining checkerboard scales among 100 checkerboard scales at this time.

(5) Evaluation of heat resistance

Except not using a photomask, it carried out similarly to formation of the said spacer, and formed the cured film by the exposure amount corresponded to the sensitivity irradiated by said (1). About this cured film, it heated further in 60 degreeC oven for 60 minutes, measured the film thickness before and behind further heating, and evaluated by calculating | requiring the residual film ratio (film thickness after additional heating x 100 / film thickness before additional heating).

(6) Evaluation of sensitivity according to change of exposure wavelength

In the above (1), in place of the light source of Type 1, a high-pressure mercury lamp (light sources of Type 2 to Type 4) having respective spectral distributions of Type 2, Type 3, and Type 4 shown in Figs. Sensitivity evaluation was performed similarly to said (1) except having used. As the light source becomes from Type 1 to Type 2, Type 3, and Type 4, light in the short wavelength region is gradually cut. Even when these light sources are used, when the sensitivity is 1,000 J / m 2 or less, the sensitivity can be said to be good.

(Examples 2 to 30 and Comparative Example 1)

The radiation sensitive resin compositions (S-2) to (S-30) and (in the same manner as in Example 1 except that the types and amounts of the respective components of the radiation sensitive resin composition were as shown in Table 1, respectively) s-1) was prepared and evaluated, respectively. The evaluation results are shown in Table 2.

(Example 31)

The radiation sensitive resin composition (S) was carried out similarly to Example 1 except having set the kind and quantity of each component of a radiation sensitive resin composition as Table 1, respectively, and having made solid content concentration into 50 mass%. -31) was prepared.

This composition (S-31) was performed by the dry film method instead of the coating method in formation of a film. The detail is as follows.

Spacer  formation

Radiation radiation by apply | coating the liquid composition (S-31) of a radiation sensitive resin composition using an applicator on a polyethylene terephthalate (PET) film of 38 micrometers in thickness as a base film, and heating a coating film at 100 degreeC for 5 minutes. A radiation sensitive dry film having a thickness of 4 µm having a transfer layer was produced. Next, the radiation sensitive dry film was overlaid on the surface of the glass substrate so that the surface of the radiation sensitive transfer layer abutted, and the radiation sensitive transfer layer was transferred to the glass substrate by a thermocompression bonding method. In addition, after peeling and removing a base film, it carried out similarly to Example 1, and formed the spacer by exposure, image development, washing | cleaning, and post-baking.

Except the above, various evaluations were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

(Comparative Example 2)

The radiation sensitive resin composition (s-2) was prepared and evaluated similarly to Example 31 except having changed the kind and quantity of each component of a radiation sensitive resin composition as Table 1, respectively. The evaluation results are shown in Table 2.

In Table 1, each component other than [A] copolymer is as follows.

[B] component

B-1: dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd. make, brand name "KAYARAD DPHA")

B-2: Commercial item (Nippon Kayaku Co., Ltd. make, brand name "KAYARAD DPHA-40H") containing polyfunctional urethane acrylate compound

B-3: ω-carboxy polycaprolactone monoacrylate (Toagosei Co., Ltd. make, brand name "Aronix M-5300")

B-4: 1,9-nonane diacrylate (Kyoeisha Chemical Co., Ltd. make, brand name "light acrylate 1,9-NDA")

[C] component

C-1 ： Compound No.33

C-2 ： Compound No.37

C-3 ： Compound No.50

C-4 ： Compound No.54

C-5 ： Compound No.69

C-6 ： Compound No.1

C-7 ： Compound No.27

C-8 ： Compound No.29

C-9 ： Compound No.43

C-10 ： Compound No.62

Other polymerization initiators, amino sensitizers and thiol compounds

c-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethan-1-one-oxime-O-acetate (Chiba Specialty Chemicals Co., Ltd.) ), A brand name "IRGACURE OX02")

c-2: 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one (Ciba specialty chemicals make, brand name "IRGACURE 907")

c-3: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (Ciba specialty chemicals Co., Ltd. product, a brand name) IRGACURE 379 '')

c-4: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole

c-5: 4,4'-bis (diethylamino) benzophenone

c-6: 2-mercaptobenzothiazole

1 is a schematic view of an example for explaining the structure of a liquid crystal display element.

It is a schematic diagram of another example for demonstrating the structure of a liquid crystal display element.

3 is a load-strain curve under load and under load in the evaluation of the elastic recovery rate.

4 is a spectral distribution diagram of a type 1 light source.

5 is a spectral distribution diagram of a type 2 light source.

6 is a spectral distribution diagram of a type 3 light source.

7 is a spectral distribution diagram of a type 4 light source.

Claims (5)

(A) (a1) copolymer of at least 1 sort (s) chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and (a2) unsaturated compounds other than said (a1), (B) a polymerizable unsaturated compound, and (C) a compound represented by the following formula (1) A radiation-sensitive resin composition comprising a.           (Formula 1)

(In formula 1, R <^1> , R <^2> and R <^3> respectively independently represents R <^11> , OR <^11> , COR <^11> , SR <^11> , CONR <^12> R <^13> or CN, and R <^11> , R <^12> And R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and represents an alkyl group, an aryl group, and an aryl; The hydrogen atom of the alkyl group and the heterocyclic group is also OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -NCOR ²² -OCOR ²³ , -C (= N-OR ²¹ ) -R ²² , -C (= N-OCOR ²¹ ) -R ²² , CN, halogen atom, -CR ²¹ = CR ²² R ²³ , -CO-CR ²¹ = CR ²² R ²³ , substituted with carboxyl group, epoxy group Could be R ²¹ , R ²² And R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms, and R ¹¹ and R The methylene group of the alkylene moiety of the substituent represented by ¹² , R ¹³ , R ²¹ , R ²² and R ²³ is 1 by an unsaturated bond, ether bond, thioether bond, ester bond, thioester bond, amide bond or urethane bond. May be interrupted ˜5 times, the alkyl moiety of the substituent may have a branched side chain, a cyclic alkyl, the alkyl terminus of the substituent may be an unsaturated bond, and R ¹² and R ¹³ And R ²² and R ²³ may each form a ring, and R ³ may form a ring together with an adjacent benzene ring. R ⁴ And R ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , OCSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN , A halogen atom or a hydroxyl group, a and b are each independently 0 to 3). The method of claim 1, The radiation sensitive resin composition used for formation of the spacer for liquid crystal display elements. The liquid crystal display element spacer formed from the radiation sensitive resin composition of Claim 2. The formation method of the spacer for liquid crystal display elements containing at least the following processes in the order described below. (A) forming a film of the radiation sensitive resin composition according to claim 2 on a substrate; (B) exposing to at least a portion of the coating, (C) developing the film after exposure, and (D) A step of heating the film after development. The liquid crystal display element provided with the spacer of Claim 3.

Images