JP5051371B2 - Radiation-sensitive resin composition, spacer and protective film for liquid crystal display element, and liquid crystal display element - Google Patents

Description

  The present invention relates to a radiation-sensitive resin composition, a spacer and a protective film of a liquid crystal display element, and a liquid crystal display element.

  Of the members used in the liquid crystal display element, many spacers, protective films and the like are formed by photolithography (see, for example, Patent Document 1 and Patent Document 2). In this method, a radiation-sensitive resin composition is applied on a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form a dot or stripe pattern. In addition, according to this method, there is an advantage that it is easy to control the cell gap width of the spacer by controlling the coating film thickness of the radiation-sensitive resin composition.

By the way, in the manufacture of a liquid crystal display panel, the substrate size has been increased from the viewpoint of improving productivity and adapting to a large screen. Substrate size is 300mm × 400mm first generation, 370mm × 470mm second generation, 620mm × 750mm third generation, 960mm × 1,100mm fourth generation, then 1,100mm × 1,300mm fifth Generations are now mainstream. Further, the sixth generation of 1,500 mm × 1,850 mm, the seventh generation of 1,850 mm × 2,100 mm, and the eighth generation of 2,200 mm × 2,600 mm will be further increased in the future.
When the substrate size is small, for example, 370 mm × 470 mm or less, the radiation-sensitive resin composition is dropped onto the substrate in the center and applied by a spin coating method. This method has a drawback that a large amount of radiation-sensitive resin composition solution is required for coating, and it cannot be applied to a large substrate.
When the substrate size is 960 mm × 1,100 mm or less, the coating is performed by the slit and spin method for the purpose of saving the radiation-sensitive resin composition solution. In this method, a radiation-sensitive resin composition solution is applied to the substrate surface from a slit nozzle, and then the substrate is rotated to form a uniform coating film. This method is effective for saving liquid, but it is difficult to cope with the substrate size from the fifth generation onward.

From such a background, as the substrate size increases, coating by a slit die coater has been performed. However, in the case of a slit die coater, streak-like unevenness, haze unevenness, substrate transfer arms and pins, suction pad marks (pin marks), and non-uniform film thickness at the edge of the substrate are likely to occur.
For these reasons, there has been a strong demand for the development of a radiation-sensitive resin composition solution having a uniform film thickness and no unevenness in the slit die coater method.
JP-A-5-165214 JP 2001-261761 A

  Accordingly, an object of the present invention is to provide a radiation-sensitive resin composition suitable for forming a coating film having a uniform film thickness and no unevenness by a slit die coater method, a spacer or a protective film formed therefrom, and the same. The object is to provide a liquid crystal display element.

  Still other objects and advantages of the present invention will become apparent from the following description.

In accordance with the present invention, the above objects and advantages of the present invention are primarily as follows:
(A) (a1) a copolymer of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and (a2) a copolymer of another unsaturated compound different from (a1) above,
(B) a polymerizable unsaturated compound,
This is achieved by a radiation-sensitive resin composition comprising (C) a radiation-sensitive polymerization initiator and (D) a solvent represented by the following formula (1).

Wherein (1), _{R 1} is an alkyl group having 1 to 9 carbon atoms. ]

  Secondly, the above objects and advantages of the present invention are achieved by a spacer or a protective film of a liquid crystal display element formed from the radiation sensitive resin composition.

  Thirdly, the above objects and advantages of the present invention are achieved by a liquid crystal display device comprising a spacer or a protective film formed from the radiation sensitive resin composition.

  The radiation sensitive resin composition of the present invention can provide a coating film having a uniform film thickness and no unevenness, and is suitable for the slit die coater method.

<Radiation sensitive resin composition>
Hereinafter, each component of the radiation sensitive resin composition of this invention is explained in full detail.

[A] Copolymer The [A] copolymer contained in the radiation-sensitive resin composition of the present invention is, for example, selected from the group consisting of (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. It is a copolymer of at least one (hereinafter referred to as “compound (a1)”) and another unsaturated compound different from (a2) and (a1) (hereinafter referred to as “compound (a2)”). In the present invention, [A] copolymer includes [A1] compound (a1) and an unsaturated compound having at least one hydroxyl group in one molecule (hereinafter referred to as “compound (a2-1)”). A polymer (hereinafter referred to as “[A] polymer”) obtained by reacting a copolymer (hereinafter referred to as “copolymer [α]”) with an unsaturated isocyanate compound, and a compound [A2] A group consisting of (a1) and a copolymer (hereinafter referred to as “copolymer [β]”) of an unsaturated compound having an oxiranyl group or oxetanyl group (hereinafter referred to as “compound (a2-2)”). At least one selected from is preferred.

As the compound (a1), for example,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.
Of these compounds (a1), acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity, solubility of the resulting polymer and copolymer in an alkaline developer, and easy availability. .

In the copolymer [α] and the copolymer [β], the compound (a1) can be used alone or in admixture of two or more.
In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from the compound (a1) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 ~ 30% by weight. If the content of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility of the resulting polymer in an alkaline developer tends to be reduced, whereas if it exceeds 50% by weight, the alkali of the polymer There is a possibility that the solubility in the developer becomes too large.

  In addition, when a compound (a1) has a carboxyl group, after protecting a carboxyl group, it uses for superposition | polymerization, Then, you may reproduce | regenerate a carboxyl group by deprotecting. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known protecting group for the carboxyl group can be used. For example, a trialkylsilyl group, 1-alkoxyalkyl group, cyclic 1-alkoxyalkyl group and the like can be mentioned. More specifically, for example, trimethylsilyl group, dimethylbutylsilyl group, 1-ethoxyethyl group, 1-propoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, triphenylmethyl group and the like can be mentioned.

Examples of the compound (a2-1) include (meth) acrylic acid 2-hydroxyethyl ester, (meth) acrylic acid 3-hydroxypropyl ester, (meth) acrylic acid 4-hydroxybutyl ester, and (meth) acrylic. Acid 5-hydroxypentyl ester, (meth) acrylic acid 6-hydroxyhexyl ester, (meth) acrylic acid 7-hydroxyheptyl ester, (meth) acrylic acid 8-hydroxyoctyl ester, (meth) acrylic acid 9-hydroxynonyl ester (Meth) acrylic acid hydroxyalkyl esters such as (meth) acrylic acid 10-hydroxydecyl ester, (meth) acrylic acid 11-hydroxyundecyl ester, (meth) acrylic acid 12-hydroxydodecyl ester;
Furthermore, (meth) acrylic acid 4-hydroxy-cyclohexyl ester, (meth) acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, (meth) acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, (meth) acrylic acid 3-hydroxy -Bicyclo [2.2.1] hept-5-en-2-yl ester, (meth) acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, (Meth) acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, (meth) acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5 -En-2-yl ester, (meth) acrylic acid 2-hydroxy-octahydro-4,7-methanoin N-yl ester, (meth) acrylic acid 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, (meth) acrylic acid 2-hydroxyethyl-octahydro-4,7-methano -Inden-5-ylethyl ester, (meth) acrylic acid 3-hydroxy-adamantan-1-yl ester, (meth) acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, (meth) acrylic acid 3- (Meth) acrylic acid hydroxyalkyl ester having an alicyclic structure such as hydroxyethyl-adamantan-1-ylethyl ester;
(Meth) acrylic acid 1,2-dihydroxyethyl ester, (meth) acrylic acid 2,3-dihydroxypropyl ester, (meth) acrylic acid 1,3-dihydroxypropyl ester, (meth) acrylic acid 3,4-dihydroxybutyl ester Esters, (meth) acrylic acid dihydroxyalkyl esters such as 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester;
Acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, acrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, acrylic acid 5- ( 6-hydroxyhexanoyloxy) pentyl ester, acrylic acid (6-hydroxyhexanoyloxy) alkyl ester such as acrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester;
Methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, methacrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, methacrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, methacrylic acid 5- ( 6-hydroxyethylhexanoyloxy) pentyl ester, methacrylic acid (6-hydroxyhexanoyloxy) alkyl ester such as methacrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester, etc. (hereinafter referred to as (meth) acrylic acid) (6-hydroxyhexanoyloxy) alkyl ester may be referred to as “other compound (a2-1)”.

  Of these compounds (a2-1), from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, Methacrylic acid 2-hydroxyethyl ester, Methacrylic acid 3-hydroxypropyl ester, Methacrylic acid 4-hydroxybutyl ester, Acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Acrylic acid 2, 3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester, other compounds (a2-1) and the like are preferable.

  Of the compounds (a2-1), the other compound (a2-1) is particularly preferable from the viewpoint of improving developability and improving the compression performance of the resulting spacer. Among other compounds (a2-1), acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester are preferable, and methacrylic acid 2- (6 As a commercial product of a mixture of -hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2-hydroxyethyl ester, PLACEL FM1D, FM2D (manufactured by Daicel Chemical Industries, Ltd.) and the like can be given as trade names.

In the copolymer [α], the compound (a2-1) can be used alone or in admixture of two or more.
In the copolymer [α], the content of the repeating unit derived from the compound (a2-1) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, particularly preferably 5 to 30% by weight. is there. If the content of the repeating unit derived from the compound (a2-1) is less than 1% by weight, the introduction rate of the unsaturated isocyanate compound into the polymer tends to be lowered, and the sensitivity tends to be lowered, while 50% by weight is reduced. When it exceeds, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound to fall.

Examples of the compound (a2-2) in the copolymer [β] include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meta ) 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. ) Epoxy (cyclo) alkyl esters of acrylic acid;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -3 -Ethyloxy Tan, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxy) Ethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxyethyl) -2 Methacrylic acid esters such as 1,2,4,4-tetrafluorooxetane;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra Acrylic esters such as fluorooxetane are mentioned.

Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methyl-3-methacryloyloxymethyloxetane, 3-ethyl- 3-Methacryloyloxymethyloxetane and the like are preferable from the viewpoint of polymerizability.
In the copolymer [β], the compound (a2-2) can be used alone or in admixture of two or more.
In the copolymer [β], the content of the repeating unit derived from the compound (a2-2) is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, and particularly preferably 3 to 50% by weight. %. When the content of the repeating unit derived from the compound (a2-2) is less than 0.5% by weight, the heat resistance of the resulting copolymer tends to be reduced. On the other hand, when the content exceeds 70% by weight, Storage stability tends to decrease.

Further, in the copolymer [α] and the copolymer [β], the compound (a2) other than the compound (a2-1) and the compound (a2-2) “hereinafter referred to as“ compound (a2-3) ”. Can be used as a component of the copolymer. Specific examples thereof include alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these, from the viewpoint of copolymerization reactivity, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, Styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferable.

In copolymer [α] and copolymer [β], compound (a2-3) can be used alone or in admixture of two or more.
In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from the compound (a2-3) is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably. Is 30 to 50% by weight. When the content of the repeating unit of the compound (a2-3) is less than 10% by weight, the molecular weight of the copolymer tends to decrease. On the other hand, when the content exceeds 70% by weight, the compound (a1) and the compound (a2-1) And the effect which a compound (a2-2) ingredient shows falls.
Copolymer [α] and copolymer [β] can be produced by polymerization in a suitable solvent in the presence of a radical polymerization initiator.

As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, i-propanol;
Ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,
Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, methoxyacetic acid -Propyl, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, n-butyl ethoxyacetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propyloxyacetate n-propyl, n Examples include other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-propyl n-butoxyacetate, n-butyl n-butoxyacetate, and the like.

Of these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetate, and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In addition, the radical polymerization initiator is not particularly limited. 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-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, etc. And organic peroxides such as hydrogen peroxide.
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.
The copolymer [α] and the copolymer [β] thus obtained can be used in the production of the [A] polymer as they are in solution, or once separated from the solution, You may use for manufacture.

The polystyrene-converted weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [α] and the copolymer [β] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably. Is 5,000 to 50,000. If the Mw is less than 2,000, the resulting film may be deteriorated in alkali developability, residual film ratio, or the like, or may be damaged in pattern shape, heat resistance, or the like. , There is a possibility that the resolution is lowered or the pattern shape is damaged.
The [A] polymer in the present invention is obtained by reacting the copolymer [α] with an unsaturated isocyanate compound.

Examples of unsaturated isocyanate compounds include:
2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyloxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyloxydecyl isocyanate,
2- (2-isocyanatoethoxy) ethyl acrylate,
2- [2- (2-isocyanatoethoxy) ethoxy] ethyl acrylate,
2- {2- [2- (2-isocyanatoethoxy) ethoxy] ethoxy} ethyl acrylate, 2- (2-isocyanatopropoxy) ethyl acrylate,
Acrylic acid derivatives such as acrylic such as 2- [2- (2-isocyanatopropoxy) propoxy] ethyl acrylate;
2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, 10-methacryloyloxydecyl isocyanate 2- (2-isocyanatoethoxy) )ethyl,
2- [2- (2-isocyanatoethoxy) ethoxy] ethyl methacrylate,
2- {2- [2- (2-isocyanatoethoxy) ethoxy] ethoxy} ethyl methacrylate,
2- (2-isocyanatopropoxy) ethyl methacrylate,
And methacrylic acid derivatives such as 2- [2- (2-isocyanatopropoxy) propoxy] ethyl methacrylate.

Moreover, as a commercial item of 2-acryloyloxyethyl isocyanate, it is a trade name, Karenz AOI (made by Showa Denko KK), and as a commercial item of 2-methacryloyloxyethyl isocyanate, it is a brand name, Karenz MOI (Showa Denko). As a commercial product of 2- (2-isocyanatoethoxy) ethyl methacrylate, a product name, Karenz MOI-EG (manufactured by Showa Denko KK) can be mentioned.
Among these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate, methacrylic acid 2- (2) from the viewpoint of reactivity with the copolymer [α]. -Isocyanatoethoxy) ethyl and the like are preferred.
[A] In the polymer, unsaturated isocyanate compounds can be used alone or in admixture of two or more.

  In the present invention, the reaction between the copolymer [α] and the unsaturated isocyanate compound is, for example, a copolymer containing a catalyst such as di-n-butyltin (IV) dilaurate and a polymerization inhibitor such as p-methoxyphenol. It can be carried out by adding the unsaturated isocyanate compound to the combined [α] solution while stirring at room temperature or under heating.

[A] The amount of the unsaturated isocyanate compound used in producing the polymer is preferably 0.1 to 95 mol% with respect to 1 equivalent of the hydroxyl group of the compound (a2-1) in the copolymer [α]. More preferably, it is 1.0-80 mol%, Most preferably, it is 5.0-75 mol%. When the amount of the unsaturated isocyanate compound used is less than 0.1 mol%, the effect of improving the sensitivity, heat resistance and elastic properties is small. On the other hand, when it exceeds 95 mol%, an unreacted unsaturated isocyanate compound remains, The storage stability of the resulting polymer solution and radiation sensitive resin composition tends to decrease.
[A] The polymer and the copolymer [β] can be used alone, respectively, but can further improve the storage stability of the resulting radiation-sensitive resin composition, and the strength and heat resistance of the spacer. In view of the possibility, it is more preferable to use the [A] polymer and the copolymer [β] in combination.

  In the present invention, when the [A] polymer and the copolymer [β] are used in combination, the amount of the copolymer [β] used is preferably 0.5 to 50 with respect to 100 parts by weight of the [A] polymer. Part by weight, more preferably 1 to 40 parts by weight, and particularly preferably 3 to 30 parts by weight. When the amount of the copolymer [β] used is less than 0.5 parts by weight, the effect of improving the strength and heat resistance of the spacer is small. On the other hand, when it exceeds 50 parts by weight, the storage stability of the radiation-sensitive resin composition is lowered. There is a tendency to make it.

[B] Polymerizable unsaturated compound [B] The polymerizable unsaturated compound comprises an unsaturated compound that is polymerized by exposure to radiation in the presence of a radiation-sensitive polymerization initiator.
Such a [B] polymerizable unsaturated compound is not particularly limited. For example, a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester has good copolymerizability. From the viewpoint of improving the strength of the obtained spacer.

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3- Examples include methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω-carboxypolycaprolactone monoacrylate. be able to. As a commercial product, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S ( As mentioned above, Nippon Kayaku Co., Ltd.); Biscoat 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6- Examples include hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange methacrylate.

    Moreover, as a commercial item of bifunctional (meth) acrylate, for example, Aronix M-210, M-215, M-220, M-240, M-260, M-270, M-1200 , M-1600, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (manufactured by Nippon Kayaku Co., Ltd.), Art Resin UN-9000PEP, UN-9200A, UN-7600, UN-33 3, UN-1003, UN-1255, UN-6060PTM, UN-6060P (manufactured by Negami Kogyo Co., Ltd.), SH-500B, Biscote 260, 215, 312, 335HP (and above) , Manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BEPG-A, HPP-A, light ester G-201P, epoxy ester 40EM, 70PA, 80MFA, 3002M, 3002A (Kyoeisha Chemical Co., Ltd.) ), Denacol Acrylate DA-721, DA-722, DM-201 (above, manufactured by Nagase ChemteX Corporation), BMI-70, BMI-80 (above, manufactured by KEI Kasei Co., Ltd.), etc. Can be mentioned.

  Furthermore, as the tri- or higher functional (meth) acrylic acid ester, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, 9 or more functionalities As (meth) acrylic acid esters, linear alkylene groups and alicyclic structures And a compound having two or more isocyanate groups and a compound having one or more hydroxyl groups in the molecule and having three, four or five acryloyloxy groups and / or methacryloyloxy groups The polyfunctional urethane acrylate type compound etc. which are obtained by making it react with can be mentioned.

  Examples of commercially available trifunctional or higher functional (meth) acrylates include Aronix M-309, M-315, M-350, M-400, M-402, M-405, and M-408. , M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8530, M-8530, M-8560 , M-9050, Aronix TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, GPO-303, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA- 120, MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemicals Co., Ltd.) Made of), and as a urethane acrylate compound, New Frontier R-1150, R-1303, R-1304, R-1305, R-1306, R-1308 (Daiichi Kogyo Seiyaku Co., Ltd.) , KAYARAD DPHA-40H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), Art Resin UN-9000H, UN-3320HA, UN-3320HB, UN-3320HC, UN-3320HS, UN-3904, UN- 901T (manufactured by Negami Kogyo Co., Ltd.).

Among these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher functional (meth) acrylic acid esters are more preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and commercial products containing polyfunctional urethane acrylate compounds are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters can be used alone or in admixture of two or more.

  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 weight, more preferably 10 to 100 parts by weight of the [A] copolymer. 200 parts by weight. [B] If the amount of the polymerizable unsaturated compound used is less than 1 part by weight, there may be a residual image during development, while if it exceeds 300 parts by weight, the adhesiveness of the resulting pattern tends to decrease.

[C] Radiation-sensitive polymerization initiator [C] The radiation-sensitive polymerization initiator is a component that generates an active species capable of initiating polymerization of the [B] polymerizable unsaturated compound in response to radiation.
Examples of such [C] radiation-sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, and polynuclear quinone compounds. , Xanthone compounds, phosphine compounds, triazine compounds, and the like.

As the O-acyloxime compound, 9. H. A carbazole-based O-acyloxime polymerization initiator is preferred. For example, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate,
Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2 -Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime),
1- [9-Ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate,
1- [9-Butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate,
1- [9-Ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate and the like.

  Among these O-acyloxime compounds, in particular, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-Ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) is preferred.

The O-acyloxime compounds can be used alone or in admixture of two or more. In the present invention, by using an O-acyloxime compound, it is possible to obtain a radiation-sensitive resin composition having sufficient sensitivity and adhesion even with an exposure amount of 1,500 J / m ² or less.
Examples of the acetophenone compound include an α-hydroxyketone compound and an α-aminoketone compound.

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like. Examples of the α-aminoketone compound include 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4- And methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one. The Examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-Morpholinophenyl) -butan-1-one is preferred.

In the present invention, the sensitivity, spacer shape and compressive strength can be further improved by using an acetophenone compound in combination.
Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole. 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2-bromophenyl) -4,4', 5,5'-tetrafe 1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferred, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole Imidazole is preferred.

In the present invention, it is possible to further improve sensitivity, resolution and adhesion by using a biimidazole compound in combination.
When a biimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) may be added to sensitize it. it can.
Examples of amino sensitizers include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, p-dimethylamino. Examples include i-amyl benzoate.
Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.

  Further, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino sensitizer to generate an imidazole radical, but as it is, high polymerization initiating ability is not expressed, and the resulting spacer has an unfavorable shape such as a reverse taper shape. In many cases. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is neutral imidazole. In addition, a component having a sulfur radical having a high polymerization initiating ability is generated, whereby the spacer can have a more preferable forward taper shape.

Examples of the thiol compound include aromatics such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole. Compounds: aliphatic monothiols such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, Bifunctional or higher aliphatic thiols such as pentaerythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified.
Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

Further, when the biimidazole compound and the amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the biimidazole compound. Preferably it is 1-20 weight part. If the addition amount of the amino sensitizer is less than 0.1 parts by weight, the effect of improving the sensitivity, resolution and adhesion tends to be reduced. On the other hand, if it exceeds 50 parts by weight, the shape of the resulting spacer tends to be impaired. There is.
In addition, when a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the biimidazole compound. 1 to 20 parts by weight. If the amount of the thiol compound added is less than 0.1 parts by weight, the effect of improving the spacer shape tends to be reduced or the film tends to be reduced. There is a tendency to be damaged.

[C] A radiation-sensitive cationic polymerization initiator can also be used as the radiation-sensitive polymerization initiator. Specific examples thereof include onium salts such as phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trifluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium-p-toluenesulfonate. 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazonium trifluoroacetate, 4- Methoxyphenyldiazonium-p-tolue Sulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarsenate, 4-ter-butylphenyldiazonium trifluoromethanesulfonate, 4- diazonium salts such as ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, tri Phenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trif Oroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium Trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4- Phenylthiophenyl diphenyl hexafluoroarsenate 4 phenylthiophenyldiphenylsulfonium trifluoromethane sulfonate, 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, sulfonium salts such as 4-phenylthiophenyldiphenylsulfonium -p- toluenesulfonate;
Examples include iodonium salts such as bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate and (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate.

Examples of the metallocene compound include (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-).
Commercially available products of these radiation-sensitive cationic polymerization initiators include, for example, Adeka Ultra Set PP-33 (made by Asahi Denka Kogyo Co., Ltd.) which is a diazonium salt, OPTOMER SP-150 and 170 (both Asahi Denka) which are sulfonium salts. Kogyo Co., Ltd.) and Irgacure 261 (Ciba Specialty Chemicals Co., Ltd.), which is a metallocene compound.
Said radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types.

  In the radiation sensitive resin composition of the present invention, the proportion of [C] radiation sensitive polymerization initiator used is preferably 1 to 50 parts by weight, more preferably 100 parts by weight of [A] copolymer. Is 3 to 40 parts by weight.

[D] Solvent The radiation-sensitive resin composition of the present invention is characterized by containing a solvent represented by the formula (1). In formula (1), R ₁ is an alkyl group having 1 to 9 carbon atoms. Such an alkyl group may be linear, branched or cyclic.

Examples of the compound represented by the formula (1) include propylene glycol dimethyl ether, propylene glycol methyl ethyl ether, propylene glycol methyl propyl ether, propylene glycol methyl isopropyl ether, propylene glycol methyl butyl ether, propylene glycol methyl isobutyl ether, propylene glycol methyl pentyl. Examples include ether, propylene glycol methylcyclopentyl ether, propylene glycol methyl hexyl ether, propylene glycol methyl cyclohexyl ether, propylene glycol methyl heptyl ether, and propylene glycol methyl octyl ether.
Of these, propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl pentyl ether, propylene glycol methyl isopropyl ether, and propylene glycol methyl isobutyl ether are preferably used.

In addition to the solvent represented by Formula (1), other solvents can be used in combination with the composition of the present invention.
The content of the compound represented by the formula (1) in the solvent is preferably in the range of 10% by weight or more, more preferably 15% by weight or more, and further preferably 20% by weight or more based on the total amount of the solvent.
As another solvent different from the compound represented by Formula (1), a solvent that dissolves or disperses each component of the composition and does not react with each component is preferably used.
Examples of such other solvents include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propio. Nates, aromatic hydrocarbons, ketones, esters and the like.

Specific examples of these other solvents include, for example, alcohol, methanol, ethanol, benzyl alcohol and the like;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
As ethylene glycol alkyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, etc .;
As diethylene glycol monoalkyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .;
As diethylene glycol dialkyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, etc .;
As propylene glycol monoalkyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, etc .;
As propylene glycol alkyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, etc .;
As propylene glycol alkyl ether propionate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene and xylene;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, and the like;
As esters, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methylpropion Ethyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, 3- Butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxy Propyl acetate, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl acetate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, 2-butoxypropionic acid Methyl, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Propyl toxipropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxy Examples include ethyl propionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, respectively. It is done.

  Of these, alcohol, diethylene glycol, propylene glycol alkyl acetate, ethylene glycol alkyl ether acetate, diethylene glycol dialkyl ether are preferred, and in particular, benzyl alcohol, diethylene glycol ethyl methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol diethyl ether are preferred.

[D] The amount of the solvent (including other solvents when used in combination) is the total solid content in the composition of the present invention (excluding the amount of the solvent from the total amount of the composition including the solvent). The amount is preferably in the range of 5 to 50% by weight, more preferably 10 to 50% by weight.
A high boiling point solvent can be used in combination with the above [D] solvent (including other solvents). Here, examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, Benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, carbonic acid Examples include propylene and phenyl cellosolve acetate.
The amount of the high-boiling solvent used in combination is preferably 70% by weight or less, more preferably 60% by weight or less based on the total amount of the solvent.

[E] Surfactant The radiation-sensitive resin composition of the present invention preferably contains [E] a surfactant. Preferred examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant.

  The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain, and examples thereof include 1,1,2,2 -Tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1, 1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2, 2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n- Til) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10 -Decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoro Examples thereof include alkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Moreover, as a commercial item of the said fluorosurfactant, BM-1000, BM-1100 (above, the product made from BM CHEMIE), MegaFack F142D, F172, F173, F183, F178, F178, F191, for example F471, F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, Sumitomo 3M Limited), Surflon S- 112, -113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, Asahi Glass (Manufactured by Co., Ltd.), F-top EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), FT-100, -110, -14 A, the same -150, the same -250, the same -251, the same -300, the same -310, the same -400S, the tergent FTX-218, the same -251 (above, manufactured by Neos Co., Ltd.) and the like. .

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF -8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (The above-mentioned, GE Toshiba Silicone Co., Ltd. product) etc. can be mentioned what is marketed.

  Moreover, as surfactants other than the above, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n -Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured), (meth) acrylic acid copolymer polyflow No. 57, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is preferably 1.0 part by weight or less, and more preferably 0.5 part by weight or less with respect to 100 parts by weight of the [A] copolymer. When the amount of the surfactant exceeds 1.0 part by weight, film unevenness tends to occur.

Other optional additives In the radiation-sensitive resin composition of the present invention, optional additives other than those described above, for example, an adhesion aid, a storage stabilizer, and heat resistance, as long as they do not impair the effects of the present invention. An improver etc. can also be mix | blended.
The adhesion aid is a component used to improve the adhesion between the formed pattern and the substrate.

As such an adhesion assistant, for example, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an epoxy group is preferable. Examples thereof include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
These adhesion assistants can be used alone or in admixture of two or more.
The compounding amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that development residue is likely to occur.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-. Examples include phenylhydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.
The blending amount of the storage stabilizer is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. When the amount of the storage stabilizer exceeds 3.0 parts by weight, the sensitivity may be lowered and the pattern shape may be deteriorated.

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.
Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycoluril. N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N ′ -Tetra (n-butoxymethyl) glycoluril, N, N, N ′, N′-tetra (t-butoxymethyl) glycoluril and the like can be mentioned.
Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is preferred.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′, N '', N ''-hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ′ , N ″, N ″ -hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N, N Examples include ', N', N ″, N ″ -hexa (t-butoxymethyl) melamine.
Of these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred. -2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

The radiation-sensitive resin composition of the present invention comprises the above-mentioned [A] copolymer, [B] component, [C] component, [D] component and [E] component and other optional additions as described above. Prepared by mixing the ingredients uniformly. The radiation sensitive resin composition of the present invention comprises [A] copolymer, [B] component, [C] component, [D] component and [E] component, and other components optionally added. By mixing in the ratio, it can be prepared as a radiation sensitive resin composition in a solution state.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

<Method for forming spacer and protective film>
Next, a method for forming a spacer or a protective film using the radiation sensitive resin composition of the present invention will be described.

The method for forming a spacer or protective film of the present invention is performed by carrying out the following steps in the order described below.
(1) The process of forming the film of the radiation sensitive resin composition of this invention on a board | substrate.
(2) A step of irradiating at least a part of the coating with radiation.
(3) A step of developing the film after irradiation.
(4) A step of heating the film after development.
Hereinafter, each of these steps will be described sequentially.

(1) The process of forming the coating film of the radiation sensitive resin composition of this invention on a board | substrate Forming a transparent conductive film on the single side | surface of a transparent substrate, and the radiation sensitive resin composition of this invention on this transparent conductive film Form a coating.
Examples of the transparent substrate used here include glass substrates and resin substrates. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, and polyether. Examples thereof include a resin substrate made of a plastic such as sulfone, polycarbonate, and polyimide.
As the transparent conductive film provided on one surface of the transparent substrate, for example, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), ITO made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), or the like. A film etc. can be mentioned.
As a method for forming the film, a coating method or a dry film method can be used.

When a coating film is formed by a coating method, the coating film can be formed by heating (pre-baking) the coating surface after coating the solution of the radiation-sensitive resin composition of the present invention on the transparent conductive film. . The solid content concentration of the composition solution used in the coating method is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and further preferably 15 to 35% by weight. The method for applying the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method is adopted. In particular, a spin coating method or a slit die coating method is preferable.
On the other hand, the dry film used in the case of forming a film by the dry film method is obtained 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. (Hereinafter referred to as “radiation-sensitive dry film”).

  The radiation-sensitive dry film is formed by laminating a radiation-sensitive layer on the base film by applying the radiation-sensitive resin composition of the present invention, preferably as a composition solution, and then removing the solvent. Can do. The solid content concentration of the composition solution used for laminating the radiation-sensitive layer of the radiation-sensitive dry film is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, and still more preferably. It is 20 to 50% by weight, and particularly preferably 30 to 50% by weight. As the base film of the radiation-sensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the radiation sensitive layer is preferably about 1 to 30 μm.

  The radiation-sensitive dry film can be stored by laminating a cover film on the radiation-sensitive layer when not in use. The cover film preferably has an appropriate releasability so that it does not peel off when not in use and can be easily peeled off when in use. As a cover film satisfying such conditions, for example, a film obtained by applying or baking a silicone release agent on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polyurethane film is used. can do. The thickness of the cover film is preferably about 5 to 30 μm. These cover films may be a laminated cover film in which two or three layers are laminated.

A film can be formed by laminating such a dry film on a transparent conductive film of a transparent substrate by an appropriate method such as a thermocompression bonding method.
The coating thus formed is then preferably pre-baked. Prebaking conditions vary depending on the type of each component, the blending ratio, etc., but are preferably about 70 to 120 ° C. for about 1 to 15 minutes.
The film thickness after pre-baking of the film is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least a part of the coating film Next, radiation is applied to at least a part of the formed coating film. At this time, when irradiating only a part of the film, for example, the irradiation can be performed through a photomask having a predetermined pattern.
Examples of radiation used for irradiation include visible light, ultraviolet light, and far ultraviolet light. Of these, radiation having a wavelength in the range of 250 to 550 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.
The radiation irradiation amount (exposure amount) is preferably 100 to 5,000 J / m ² as a value measured with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of irradiated radiation. more preferably 200~3,000J / ^{m 2.}

(3) Step of developing the film after radiation irradiation Next, by developing the film after radiation irradiation, unnecessary portions are removed to form a predetermined pattern.

  Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; aliphatic primary amines such as ethylamine and n-propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8 -Alicyclic tertiary amines such as diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene; aromatics such as pyridine, collidine, lutidine, quinoline Tertiary amine; dimethylethanolamine, methyldi Ethanolamine, alkanolamines such as triethanolamine; tetramethylammonium hydroxide, the aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethyl ammonium hydroxide may be used. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.

As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds at room temperature.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern can be obtained by, for example, air drying with compressed air or compressed nitrogen.

(4) Step of heating the film after development Next, the obtained patterned film is heated at a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, with a suitable heating device such as a hot plate or oven. The desired spacer or protective film can be obtained by heating (post-baking) for 5 to 30 minutes in the above and 30 to 180 minutes in the oven.

  As described above, a spacer or protective film excellent in various properties such as compressive strength, resistance to the rubbing process of the liquid crystal alignment film, and adhesion to the substrate can be obtained.

<Liquid crystal display element>
The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b).

  (A) First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates. A spacer and / or a protective film is formed according to the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and the spacer or protective film of these substrates. These substrates are arranged to face each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Can be obtained.

  (B) First, a pair of transparent substrates on which a transparent conductive film, a spacer, a protective film, or both of them and an alignment film are formed are prepared in the same manner as in the first method. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both substrates are sealed by irradiating the above-mentioned sealant part with ultraviolet rays using a high-pressure mercury lamp. Finally, the liquid crystal display element of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal, etc. are used. In addition, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate, and trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.) are sold as these liquid crystals. It can also be used by adding a chiral agent or the like. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
In addition, the polarizing plate used outside the liquid crystal cell is composed of a polarizing plate in which a polarizing film called an H film that has absorbed iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
In the following synthesis examples, the weight average molecular weight Mw of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.

<Measurement of molecular weight of copolymer by gel permeation chromatography>
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid

<Synthesis Example of (A) Copolymer>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobis (isobutyronitrile) and 220 parts by weight of diethylene glycol dimethyl ether, followed by 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, and methacrylic acid. Charge 30 parts by weight of benzyl, 20 parts by weight of n-butyl methacrylate and 20 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane, and after purging with nitrogen, further add 5 parts by weight of 1,3-butadiene. While gently stirring, the temperature of the solution was raised to 80 ° C., and this temperature was maintained for 4 hours for polymerization to obtain a copolymer solution (A) having a solid content concentration of 29.9% by weight. This is referred to as [A-1] polymer.
The obtained [A-1] polymer was measured using Mw by GPC and found to be 12,400.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol ethyl methyl ether, followed by 20 parts by weight of methacrylic acid and methacrylic acid. After charging 35 parts by weight of glycidyl, 5 parts by weight of styrene and 35 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and substituting with nitrogen, 5 parts by weight of 1,3-butadiene is further added. The temperature of the solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 4 hours for polymerization to obtain a resin solution containing [A] copolymer (solid content concentration = 29.5). % By weight). This is referred to as [A-2] polymer. Mw of the obtained [A] copolymer was 13,000.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobis (isobutyronitrile) and 220 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of acrylic acid and benzyl methacrylate 35. First, 5 parts by weight, 5 parts by weight of styrene and 40 parts by weight of butyl methacrylate were added, and after nitrogen substitution, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was raised to 80 ° C. while gently stirring. This temperature was maintained for 5 hours for polymerization to obtain a resin solution containing [A] copolymer (solid content concentration = 28.6% by weight). This is referred to as [A-3] polymer. Mw of the obtained [A] copolymer was 12,000.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2,2′-azobis (isobutyronitrile), 110 parts by weight of propylene glycol methyl butyl ether and 110 parts by weight of diethylene glycol ethyl methyl ether, followed by 20 parts of methacrylic acid. Parts by weight, 20 parts by weight of tetrahydrofurfuryl methacrylate, 5 parts by weight of styrene and 50 parts by weight of benzyl methacrylate, and after purging with nitrogen, further 5 parts by weight of 1,3-butadiene were added and gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain a resin solution (solid concentration = 29.2% by weight) containing the [A] copolymer. This is designated as [A-4] polymer. Mw of the obtained [A] copolymer was 13,200.

Examples 1-7 and Comparative Examples 1-2
(I) Preparation of Radiation Sensitive Resin Composition Polymer (A) obtained in Synthesis Examples 1 to 4, components (B), (C) and (E) described below, and γ-glycol as an adhesion assistant After 5 parts by weight of Sidoxypropyltrimethoxysilane and 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer were mixed and dissolved in the component (D) so that the solid content concentration became 23% by weight, The composition solution was prepared by filtering through a 2 μm Millipore filter. The amount of each component is shown in Table 1.

(B) Component B-1: Dipentaerythritol hexaacrylate B-2: 1,9-nonanediol diacrylate B-3: ω-carboxypolycaprolactone monoacrylate (trade name Aronix M-5300 (manufactured by Toagosei Co., Ltd.) )

(C) Component C-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name Irgacure OXE02, Ciba Specialty Chemicals)
C-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)
C-3: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole C-4: Ethanone, 1- [9-ethyl-6 -[2-Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (N-1919 manufactured by ADEKA)

(D) Component D-1: Propylene glycol methyl propyl ether D-2: Propylene glycol methyl butyl ether D-3: Diethylene glycol dimethyl ether D-4: Diethylene glycol ethyl methyl ether D-5: Propylene glycol monomethyl ether acetate

(E) Component E-1: MegaFuck F178 (Dainippon Ink Chemical Co., Ltd.)
E-2: Torre Silicone SH28PA (Toray Dow Corning Silicone Co., Ltd.)
E-3: TSF-4460 (manufactured by GE Toshiba Silicone Co., Ltd.)
Evaluation The composition prepared as described above was evaluated as follows. The evaluation results are shown in Table 2.

(I) Evaluation of applicability (muscle unevenness, haze unevenness, pin mark) The prepared composition solution was applied on a 550 × 650 mm chromium-deposited glass using a slit die coater. After drying under reduced pressure to 0.5 Torr, pre-baking on a hot plate at 100 ° C. for 2 minutes to form a coating film, and further exposing at an exposure amount of 2,000 J / m ² , the upper surface of the chromium film-forming glass A film having a thickness of 4 μm was formed.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. Straight lines (one or more straight lines that can be applied in the direction of application or crossing it), haze unevenness (cloud-like unevenness), pin marks (dot-shaped unevenness on the substrate support pins) are clearly confirmed When it was possible, it was evaluated as “X”, when it was slightly confirmed, “△”, when it could hardly be confirmed, “◯”, when it was not able to confirm any streaks, haze, and pin marks, “◎”.

(II) Evaluation of applicability (uniformity) The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact type measuring instrument (AS200 manufactured by KLA Tencor).
The uniformity was calculated from the film thickness at nine measurement points. The nine measurement points are X (mm) and Y (mm) when the short axis direction of the substrate is X and the long axis direction is Y (275, 20), (275, 30), (275, 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).
The uniformity calculation formula is expressed by the following formula (3). In the following formula (3), FT (X, Y) max is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, and FT (X, Y Y) avg is an average value in the film thickness at nine measurement points. When the uniformity is less than 2%, ◎ when 2% or more and less than 3%, ◯ when 3% or more and less than 5%, and △ when 5% or more.
Uniformity (%) = {FT (X, Y) max−FT (X, Y) min} × 100 / {2 × FT (X, Y) avg} (3)

(III) Measurement of viscosity It measured at 25 degreeC using the E-type viscosity meter (The Toki Sangyo Co., Ltd. product VISCONIC ELD.R).

Claims (6)

(A) (a1) a copolymer of at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and (a2) a copolymer of another unsaturated compound different from (a1) above,
(B) a polymerizable unsaturated compound,
(C) a radiation-sensitive polymerization initiator, and (D) a solvent represented by the following formula (1) , and
The radiation-sensitive resin composition characterized Rukoto used to form the spacers or protective film of a liquid crystal display device.

Wherein (1), _{R 1} is an alkyl group having 1 to 9 carbon atoms. ] (A) component is (A1) a polymer obtained by reacting an unsaturated isocyanate compound with a copolymer of an unsaturated compound having at least one hydroxyl group in one molecule of (a1) and (a2-1), And (A2) the radiation sensitive resin according to claim 1, which is at least one selected from the group consisting of a copolymer of an unsaturated compound having (a1) and (a2-2) oxiranyl group or oxetanyl group. Composition. The radiation-sensitive resin composition according to claim 1 or 2, wherein the content of the solvent represented by the formula (1) is at least 10% by weight based on the total solvent. The solvent represented by the formula (1) is at least one selected from the group consisting of propylene glycol methyl propyl ether, propylene glycol methyl butyl ether, propylene glycol methyl pentyl ether, propylene glycol methyl isopropyl ether and propylene glycol methyl isobutyl ether. The radiation sensitive resin composition in any one of Claims 1-3. The spacer or protective film of the liquid crystal display element formed from the radiation sensitive resin composition in any one of Claims 1-4 . A liquid crystal display device comprising the spacer or protective film according to claim 5 .