KR20080085760A - Radiation sensitive resin composition, spacer for liquid crystal display device and method for manufacturing the same - Google Patents

Abstract

A radiation-sensitive resin composition is provided to form a sufficient spacer shape with high sensitivity even by an exposure amount of 1,000 J/m^2 or less, and to be superior in elastic recovery, rubbing resistance, and adhesiveness with a transparent substrate. A radiation-sensitive resin composition includes [A1] a polymer obtained by reacting a copolymer of (a1) at least one selected from the group comprising unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a2) an unsaturated compound containing at least one hydroxyl group in a molecule, with an isocyanate group-containing unsaturated compound represented by the following formula 1, and [A2] a copolymer of (a1) at least one selected from the group comprising unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a2) an unsaturated compound having an oxylanyl group or oxetanyl group. In the formula 1, R^1 is a hydrogen atom or methyl group, and n is an integer of 1-12.

Description

Spacer for radiation sensitive resin composition and liquid crystal display element, and its manufacturing method {RADIATION SENSITIVE RESIN COMPOSITION, SPACER FOR LIQUID CRYSTAL DISPLAY DEVICE AND METHOD FOR MANUFACTURING THE SAME}

The present invention relates to a radiation-sensitive resin composition comprising a side chain unsaturated polymer which is very suitable for formation of a spacer in a liquid crystal display device, a spacer, a method for forming the same, and a liquid crystal display device.

Conventionally, spacers, such as glass beads and plastic beads, having a predetermined particle size, have been used in the liquid crystal display element in order to maintain a constant gap (cell spacing) between two substrates. Since these spacers are randomly scattered on transparent substrates such as glass substrates, when spacers exist in the pixel formation region, there is a problem that contrast as a liquid crystal display element is reduced due to occurrence of projection phenomenon of the spacers and scattering of incident light. there was.

Therefore, in order to solve such a problem, the method of forming a spacer by photolithography has been adopted. In this method, the radiation-sensitive resin composition is applied onto a substrate, and is developed after exposing ultraviolet light through a predetermined mask, for example, to form a dot or stripe spacer, and the predetermined place other than the pixel formation region. Since only the spacer can be formed, the above-described problem is basically solved.

Moreover, in recent years, the mother glass substrate was enlarged, for example, 1,500 * 1,800 mm, and also about 1,870 * 2,200 mm in terms of the large area of a liquid crystal display element, the improvement of productivity, etc. were advanced. 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, for a large substrate, it is almost impossible to manufacture a mask size that is about the same as the substrate size. It is difficult to respond by exposure method.

Therefore, the step exposure method is proposed as an exposure method compatible with a large substrate. However, in the step exposure method, since it is exposed to a single substrate several times and requires time for position alignment and step movement for each exposure, the throughput is reduced as compared with the batch exposure method. There was a demand for high sensitivity to the resin composition.

In addition, although the exposure amount of about 3,000 J / m <2> is possible with the package exposure system, each exposure amount needs to be lowered by the step exposure system, and it is 1,000 J in the conventional radiation sensitive resin composition used for formation of a spacer. It was difficult to achieve sufficient spacer shape and film thickness with an exposure amount of / m 2 or less.

In addition, when defects occur in the process as the substrate is enlarged, it is necessary to peel off and reuse the alignment film formed on the color filter. The peeling liquid of an alkali aqueous liquid type | system | group is used for peeling of an orientation film, The spacer needs tolerance with respect to this peeling liquid. That is, when the alignment layer is peeled off, it is preferable that the lower spacer does not have a change in film thickness due to swelling or dissolution, and the physical properties such as elastic properties also need to exhibit the same properties as before peeling.

In JP-A-2000-105456, JP-A-2000-171804 and JP-A-2000-298339, in (meth) acryloyloxy to copolymerizable resin which has a hydroxyl group in the photosensitive resin composition. By using the copolymerizable resin which has a photopolymerizable functional group which made the alkylisocyanate compound react as a structural unit, performance improvement as a spacer and protective film, such as high sensitivity and chemical resistance, is attained. The novolak type epoxy resin which has 2 or more epoxy groups in a molecule | numerator is used for the purpose of improving the heat resistance of a spacer and a protective film, adhesiveness with a board | substrate, chemical-resistance, especially an orientation film peeling liquid, and the resistance to aqueous alkali solution. . However, deterioration of the solubility to the developing solution of the photosensitive resin composition is concerned by adding this epoxy resin.

Moreover, in acrylic resin type and novolak-type epoxy resin, since the molecular structure of each other differs greatly, compatibility between resins is low, and uneven surface roughness may generate | occur | produce on the spacer surface formed. If uneven surface roughness occurs on the surface of the spacer, it is difficult to precisely control the cell gap, and as a result, the quality of the liquid crystal display element may be reduced.

As mentioned above, in the conventional radiation sensitive resin composition, although addition of a novolak-type epoxy resin compound can improve adhesiveness with a board | substrate, chemical resistance, for example, alignment film peeling-resistance resistance, it is solubility to a developing solution, The surface roughness of the pattern is concerned.

Accordingly, an object of the present invention is to achieve a spacer shape with a high sensitivity, even at an exposure dose of 1,000 J / m 2 or less, and excellent in elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, and the like, and excellent developability. Then, it is providing the radiation sensitive resin composition which can form the spacer for liquid crystal display elements which does not have uneven surface roughness on the obtained pattern surface.

Another object of the present invention is to provide a liquid crystal display spacer formed of the radiation-sensitive resin composition and a liquid crystal display device having the same.

Another object of the present invention is to provide a method for forming the liquid crystal display spacer.

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

According to the present invention, the above objects and advantages of the present invention,

[A1] (a1) A copolymer of at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a2) unsaturated compounds containing at least one hydroxyl group in one molecule is represented by the following formula (1): A polymer obtained by reacting an isocyanate group-containing unsaturated compound represented, and

(A2) A copolymer comprising (a1) at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a3) unsaturated compounds having an oxylanyl group or an oxetanyl group. It is achieved by a radiation sensitive resin composition.

(Wherein R ¹ is a hydrogen atom or a methyl group, n is an integer from 1 to 12)

Here, it is preferable that the component (a2) of [A1] is an unsaturated compound which has a hydroxyl group represented by following formula (2).

(Wherein R ² is a hydrogen atom or a methyl group, l is an integer from 1 to 12, m is an integer from 1 to 6)

According to the present invention, the above objects and advantages of the present invention,

The radiation sensitive resin composition used for formation of the spacer for liquid crystal display elements in which the said radiation sensitive resin composition contains a [B] polymerizable unsaturated compound and a [C] radiation sensitive polymerization initiator further (hereinafter, "liquid crystal display Radiation sensitive resin composition for device spacers).

According to the present invention, the above objects and advantages of the present invention,

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

According to the present invention, the above objects and advantages of the present invention,

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 the radiation-sensitive resin composition for spacers for liquid crystal display elements on the substrate;

(B) exposing to at least a portion of the film;

(C) developing the film after exposure; and

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

According to the present invention, the above objects and advantages of the present invention,

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

According to the present invention, a sufficient spacer shape is obtained even at an exposure amount of 1,000 J / m 2 or less with high sensitivity, and excellent in elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, and the like, and excellent in developability, The radiation sensitive resin composition which can form the spacer for liquid crystal display elements which does not have uneven surface roughness on the obtained pattern surface can be provided.

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

[A] polymer-

The composition of the present invention is a mixture of one or more selected from the group consisting of [A1] (a1) unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a2) an unsaturated compound containing one or more hydroxyl groups in one molecule. A polymer obtained by reacting an isocyanate compound (hereinafter, referred to as an "unsaturated isocyanate compound (1)") represented by the formula (1) with a copolymer (hereinafter referred to as "copolymer [α]") (hereinafter "[A] Polymer "),

[A2] A copolymer of (a1) at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a3) unsaturated compounds having an oxylanyl group or an oxetanyl group (hereinafter referred to as "copolymer [ β] ").

Among the components constituting the copolymer [α] and the copolymer [β], (a1) unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter, collectively referred to as "(a1) unsaturated carboxylic acid compound") As, for example

Acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid Monocarboxylic acids such as;

Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid;

Acid anhydride of the said dicarboxylic acid, etc. are mentioned.

Among these (a1) unsaturated carboxylic acid compounds, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoint of copolymerization reactivity, solubility in an alkali developer of the obtained polymer and copolymer, and availability.

In the copolymer [α] and the copolymer [β], the (a1) unsaturated carboxylic acid compound can be used alone or in combination of two or more thereof.

In the copolymer [α] and the copolymer [β], the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, Especially preferably, it is 15-30 weight%. When the content rate of the repeating unit derived from (a1) unsaturated carboxylic acid compound is less than 5 weight%, there exists a tendency for the solubility to the alkali developing solution of the polymer obtained by reaction with an unsaturated isocyanate compound (1) to fall, while 50 When it exceeds weight%, there exists a possibility that the solubility of the said polymer in alkaline developing solution may become large too much.

As the unsaturated compound containing one or more hydroxyl groups in one molecule (a2), for example, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, and acrylic acid 5-hydroxy Hydroxypentyl ester, acrylic acid 6-hydroxyhexyl ester, acrylic acid 7-hydroxyheptyl ester, acrylic acid 8-hydroxyoctyl ester, acrylic acid 9-hydroxynonyl ester, acrylic acid 10-hydroxydecyl ester, acrylic acid 11-hydroxyound Acrylic acid hydroxyalkyl esters such as silester and acrylic acid 12-hydroxydodecyl ester;

Methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, methacrylic acid 5-hydroxypentyl ester, methacrylic acid 6-hydroxyhexyl ester, Methacrylic acid 7-hydroxyheptyl ester, methacrylic acid 8-hydroxyoctyl ester, methacrylic acid 9-hydroxynonyl ester, methacrylic acid 10-hydroxydecyl ester, methacrylic acid 11-hydroxyundecyl ester Methacrylic acid hydroxyalkyl esters such as methacrylic acid 12-hydroxydodecyl ester;

Moreover, 4-hydroxy cyclohexyl ester of acrylic acid, 4-hydroxymethyl cyclohexyl methyl ester of acrylic acid, 4-hydroxyethyl cyclohexyl ethyl ester of acrylic acid, 3-hydroxy-bicyclo acrylate [2.2.1] hept -5-en-2-ylester, acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethylester, acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] Hept-5-en-2-ylethylester, acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-ylester, acrylic acid 2-hydroxy-octahydro-4,7-metha No-inden-5-ylester, acrylic acid 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, acrylic acid 2-hydroxyethyl-octahydro-4,7-methano Inden-5-ylethyl ester, acrylic acid 3-hydroxy-adamantane-1-yl ester, acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, acrylic acid 3-hydroxyethyl-adamant Tan-1- Acrylic acid hydroxyalkyl ester which has an alicyclic structure like monoethyl ester;

Methacrylic acid 4-hydroxy-cyclohexyl ester, methacrylic acid 4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid 4-hydroxyethyl-cyclohexylethyl ester, methacrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5-en-2-ylester, methacrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethylester, methacrylic acid 3-hydride Hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, methacrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-ylester, methacryl Acid 2-hydroxy-octahydro-4,7-methano-inden-5-ylester, methacrylic acid 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, Methacrylic acid 2-hydroxyethyl-octahydro-4,7-methano-inden-5-ylethyl ester, methacrylic acid 3-hydroxy-adamantane-1-yl ester, methacrylic acid 3-hydroxy Roxymethyl-adamantan-1-ylmethyl ester, methacrylic acid 3- De-hydroxyethyl-adamantyl methacrylate hydroxyalkyl ester having an alicyclic structure such as a carbon-1-yl ethyl ester;

1,2-dihydroxyethyl ester, acrylic acid 2,3-dihydroxypropyl ester, acrylic acid 1,3-dihydroxypropyl ester, acrylic acid 3,4-dihydroxybutyl ester, acrylic acid 3- [3- Acrylic acid dihydroxyalkyl esters such as (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester;

Methacrylic acid 1,2-dihydroxyethyl ester, methacrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 1,3-dihydroxypropyl ester, methacrylic acid 3,4-dihydroxybutyl Methacrylic acid dihydroxy alkyl esters, such as ester and methacrylic acid 3- [3- (2,3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester, etc. are mentioned. have.

Among unsaturated compounds containing at least one hydroxyl group in these one molecule, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, in terms of copolymerization reactivity and reactivity with isocyanate compounds, Methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid 4-hydroxymethyl -Cyclohexyl methyl ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3-dihydroxypropyl ester and the like are preferable.

Moreover, the unsaturated compound which has a hydroxyl group represented by the said Formula (2) among component (a2) is especially preferable at the point of the improvement of developability, and the improvement of the compression performance of the spacer obtained.

Specific examples thereof include acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, acrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester and acrylic acid Acrylic acid (6-hydroxyhexanoyloxy) alkyl esters such as 5- (6-hydroxyhexanoyloxy) pentyl ester and 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 (6-hydroxyhexanoyloxy) alkyl, such as methacrylic acid 5- (6-hydroxyethylhexanoyloxy) pentyl ester, methacrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester ester;

Among these, acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester are preferable, and methacrylic acid 2- (6-hydroxyhexa) As a commercial item of the mixture of noyloxy) ethyl ester and methacrylic acid 2-hydroxyethyl ester, PLACCEL FM1D, FM2D (made by Daicel Chemical Industries, Ltd.) etc. are mentioned by brand name.

In the copolymer [α], the unsaturated compound containing one or more hydroxyl groups in one molecule of (a2) can be used alone or in combination of two or more thereof.

In the copolymer [α], the content of the repeating unit derived from an unsaturated compound containing at least one hydroxyl group in one molecule of (a2) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight. Especially preferably, it is 5-30 weight%.

(a2) When the content rate of the repeating unit derived from the unsaturated compound containing one or more hydroxyl groups in 1 molecule is less than 1 weight%, the introduction ratio of an unsaturated isocyanate compound (1) to a polymer will fall and a sensitivity will fall On the other hand, when it exceeds 50 weight%, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound (1) to fall.

Moreover, as an unsaturated compound which has the oxylanyl group or oxetanyl group of (a3) in copolymer [(beta)], for example, glycidyl acrylate, 2-methylglycidyl acrylate, and 4-hydroxybutyl acrylate Acrylic acid epoxy (cyclo) alkyl esters such as glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and 3,4-epoxycyclohexyl acrylate;

Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid Methacrylic acid epoxy (cyclo) alkyl esters such as acid 3,4-epoxycyclohexylmethyl;

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 Α-alkylacrylic acid epoxy (cyclo) alkyl esters, etc .;

glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl 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-ethyl Oxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) 2-pentafluoroethyl oxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (Methacryloyl When ethyl) 2,2,4-trifluoro oxetane, 3- (methacryloyloxyethyl) methacrylic acid esters such as -2,2,4,4- tetrafluoroethane oxetane;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyl Oxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (Acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyl oxymethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl)- 2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acrylic Loyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acrylic Loyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluoro Looxetane, 3- ( And acrylic acid esters such as acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane.

Among these, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methyl-3- (meth) acryloyloxymethyloxetane, 3- Ethyl-3- (meth) acryloyloxymethyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane and the like are preferable in view of polymerizability.

In a copolymer [(beta)], (a3) can be used individually or in mixture of 2 or more types.

In the copolymer [β], the content of the repeating unit derived from (a3) is preferably 0.5 to 70% by weight, more preferably 1 to 60% by weight, particularly preferably 3 to 50% by weight. When the content rate of the repeating unit derived from (a3) is less than 0.5 weight%, there exists a tendency for the heat resistance of the copolymer obtained to fall, and when it exceeds 70 weight%, there exists a tendency for the storage stability of a copolymer to fall.

In the copolymer [α] and the copolymer [β], other unsaturated compounds different from (a1), (a2) and (a3) can be used as components 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, and t-butyl methacrylate ester;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxy) ethyl acrylate Acrylic alicyclic esters such as isoboroyl acrylate;

Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid 2- (tricyclo [5.2.1.0 ^2,6 ] Methacrylic acid alicyclic esters such as decan-8-yloxy) ethyl and methacrylic acid isoboroyl;

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 and diethyl itaconic acid;

Acrylic esters having an oxygen-containing hetero five-membered ring or an oxygen-containing hetero six-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate and 2-methyltetrahydropyran-2-yl acrylate;

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, etc. Methacrylic acid esters;

Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxystyrene;

In addition to conjugated diene-based compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,

Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate

Etc. can be mentioned.

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

In the copolymer [α] and the copolymer [β], other unsaturated compounds different from (a1), (a2) and (a3) can be used alone or in combination of two or more thereof.

In the copolymer [α] and the copolymer [β], the content rate of the repeating unit derived from other unsaturated compounds different from (a1), (a2) and (a3) is preferably 10 to 70% by weight, moreover. Preferably it is 20-50 weight%, Especially preferably, it is 30-50 weight%. When the content rate of this repeating unit is less than 10 weight%, there exists a tendency for the molecular weight of a copolymer to fall, and when it exceeds 70 weight%, the effect of (a1), (a2), and (a3) components will fall.

Copolymer [alpha] and copolymer [beta] can be manufactured by superposing | polymerizing in presence of a radical polymerization initiator in a suitable solvent.

As a solvent used for the said superposition | polymerization, for example,

Alcohols such as methanol, ethanol, n-propanol and 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 and 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, and ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionate, such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, and ethylene glycol mono-n-butyl ether propionate Nate;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and 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 and 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, and 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, and propylene glycol mono-n-butyl ether acetate;

Propylene glycol monoalkyl ether propionate, such as propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, and propylene glycol mono-n-butyl ether propionate Nate;

Aromatic hydrocarbons such as toluene and xylene;

Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, and 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, 2-methoxy ethylpropionate, n-propyl 2-methoxypropionic acid, n-butyl 2-methoxypropionic acid, octyl methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2- N-propyl ethoxypropionate, n-butyl 2-ethoxypropionate, methyl 2-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, 2-n-propionate Foxypropionate n-butyl, 2-n-butoxypropionate methyl, 2-n-butoxypropionate ethyl, 2-n-butoxypropionate n-propyl, 2-n-butoxypropionate n-butyl, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, n-propyl 3-methoxypropionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate , 3-ethoxypropionate n-butyl, 3-n-propoxypropionate methyl, 3-n-propoxypropionate ethyl, 3-n-prop Foxypropionate n-propyl, 3-n-propoxypropionate n-butyl, 3-n-butoxypropionate methyl, 3-n-butoxypropionate ethyl, 3-n-butoxypropionic acid n-propyl, 3-n- Alkoxy alkoxypropionate, such as butoxy propionate n-butyl,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, hydroxyacetic acid n-propyl, hydroxyacetic acid n-butyl, 4-methoxybutyl acetate, acetic acid 3- Methoxybutyl, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-hydroxybutyl acetate, methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate , Ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionic acid, n-butyl 3-hydroxypropionic acid, 2-hydroxy-3 Methyl butyrate methyl, methoxyacetic acid methyl, methoxyacetic acid ethyl, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid n-propyl, ethoxyacetic acid N-butyl acid, n-propoxyacetic acid methyl, n-propoxyacetic acid ethyl, n-propoxyacetic acid n-propyl, n-propoxyacetic acid n-butyl, n-butoxyacetic acid methyl, n-butoxyacetic acid ethyl esters such as n-butoxyacetic acid n-propyl, n-butoxyacetic acid n-butyl

Etc. can be mentioned.

Among these solvents, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, acetic acid ester and the like are preferable.

The said 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); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxy pivalate and 1,1-bis (t-butylperoxy) cyclohexane; Hydrogen peroxide etc. are mentioned, for example.

In addition, when using a peroxide as a radical polymerization initiator, it can also be used together with a reducing agent and can be used as a redox type initiator.

These radical polymerization initiators can be used individually or in mixture of 2 or more types.

The copolymer [α] thus obtained may be used for the production of the polymer [A] as a solution, or may be separated from the solution once and used for the production of the [A] polymer.

The polystyrene reduced 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 5,000 to 50,000. If Mw is less than 2,000, alkali developability, residual film ratio, etc. of the resulting film may be lowered, and pattern shape, heat resistance, and the like may be impaired. On the other hand, if Mw is more than 100,000, resolution is reduced or pattern shape is damaged. There is a concern.

The polymer [A] in the present invention is obtained by reacting an unsaturated isocyanate compound (1) with a copolymer [α].

As unsaturated isocyanate compound (1), for example

2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyloxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyl jade Acrylic acid derivatives such as cedyl isocyanate;

2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, Methacrylic acid derivatives, such as 10-methacryloyl oxydecyl isocyanate, are mentioned.

In addition, as a commercial item of 2-acryloyloxyethyl isocyanate, Kalenz AOI (manufactured by Showa Denko Co., Ltd.) and 2-methacryloyloxyethyl isocyanate are commercially available products of Kalenz MOI (Showa). Denko Co., Ltd.) is mentioned.

Among these unsaturated isocyanate compounds (1), 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 4-methacryloyloxybutyl isocyanate, etc. are preferable from the viewpoint of reactivity with the copolymer [α]. Do.

In the polymer (A), the unsaturated isocyanate compound (1) can be used alone or in combination of two or more thereof.

In the present invention, the reaction between the copolymer [α] and the unsaturated isocyanate compound (1) is, for example, a catalyst such as dilauric di-n-butyltin (IV) or a polymerization inhibitor such as p-methoxyphenol. It can carry out by inject | pouring an unsaturated isocyanate compound (1) to the copolymer [(alpha]) solution containing containing, stirring at room temperature or heating.

The amount of the unsaturated isocyanate compound (1) used in the production of the polymer (A) is preferably 1 equivalent of the hydroxyl group of the unsaturated compound containing one or more hydroxyl groups in one molecule of (a2) in the copolymer [α]. 0.1-95 mol%, More preferably, it is 10-80 mol%, Especially preferably, it is 15-75 mol%. When the amount of the unsaturated isocyanate compound (1) used is less than 0.1 mol%, the effect on the sensitivity, the heat resistance improvement and the elastic property improvement is small, while when it exceeds 95 mol%, the unreacted unsaturated isocyanate compound (1) remains. There exists a tendency for the storage stability of the obtained polymer solution and a radiation sensitive resin composition to fall.

The polymer (A) has a carboxyl group and / or a carboxylic anhydride group and a polymerizable unsaturated bond, has a suitable solubility in an alkaline developer, and can be easily cured by exposure and heating, and an epoxy group By using together with the acryl-type copolymer [(beta)] which does not have phase separation with a polymer [A], it does not generate pattern surface roughness and makes it possible to improve the intensity | strength of a spacer, having excellent developability. The radiation sensitive resin composition containing the polymer [A] and the copolymer [β] can easily form a spacer having a predetermined shape without developing developing residue and film reduction when developing.

The amount of the copolymer [β] to 100 parts by weight of the polymer (A) is preferably 0.5 to 50 parts 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] is less than 0.5 part by weight, the effect of improving the strength and heat resistance of the spacer is small. On the other hand, when the amount of the copolymer [β] is more than 50 parts by weight, the storage stability of the radiation-sensitive resin composition tends to be reduced.

-Radiation-sensitive resin composition-

The radiation sensitive resin composition of this invention contains a polymer [A] and a copolymer [β] as mentioned above, Preferably it contains a [B] polymerizable unsaturated compound and a [C] radiation sensitive polymerization initiator. Can be.

-[B] polymerizable unsaturated compound-

The polymerizable unsaturated compound (B) includes an unsaturated compound which is polymerized by exposure to radiation in the presence of a radiation sensitive polymerization initiator.

Although it does not specifically limit as such a [B] polymerizable unsaturated compound, For example, a monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester has good copolymerizability, and since the strength of the spacer obtained improves. desirable.

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, iso Boronyl acrylate, Isoboroyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, ( 2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, (omega) -carboxypolycaprolactone monoacrylate, etc. are mentioned. As a commercial item, It is a trade name, for example, Aronix M-101, M-111, M-114, M-5300 (above, Toagosei Co., Ltd. product); KAYARAD TC-110S, TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.); Biscoat 158, East 2311 (above, Osaka Yuki Chemical Co., Ltd. make) etc. are mentioned.

Moreover, as said bifunctional (meth) acrylic acid ester, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, Tetraethylene glycol dimethacrylate, 1,6-hexanedioldiacrylate, 1,6-hexanedioldimethacrylate, 1,9-nonanedioldiacrylate, 1,9-nonanedioldimethacrylate, Bisphenoxy ethanol 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. product), KAYARAD HDDA, copper HX-220, copper R-604 (or more, Nippon Kayaku Co., Ltd.), biscot 260, east 312, east 335 HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.), light acrylate 1,9-NDA (Kyoeisha Co., Ltd.) Etc. can be mentioned.

Moreover, as said trifunctional or more than (meth) acrylic acid ester, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetra Acrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acrylic) Loyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, or a compound having 9 or more functional (meth) acrylic acid esters having a linear alkylene group and an alicyclic structure, and having two or more isocyanate groups; , Having at least one hydroxyl group in the molecule, and also having three, four or five acryloyloxy And polyfunctional urethane acrylate compounds obtained by reacting a compound having a group and / or a methacryloyloxy group.

As a commercial item of the trifunctional or more than trifunctional (meth) acrylic acid ester, 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, copper TO-1450 (above, Toa Kosei Co., Ltd.), KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120 (more, Nippon Kayaku (Manufactured by Co., Ltd.), biscoat 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (above, manufactured by Osaka Yuki Chemical Co., Ltd.) and commercially-containing products containing a polyfunctional urethane acrylate compound As New Frontier R-1150 (made by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

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 tetraacrylic acid are particularly preferred. A commercial item containing a latex, 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 polymerizable unsaturated compound [B] is preferably 1 to 120 parts by weight, more preferably 3 to 100 parts by weight based on 100 parts by weight of the polymer [A]. to be. When the usage-amount of a polymerizable unsaturated compound (B) is less than 1 weight part, there exists a possibility that image development residue may arise at the time of image development, and when it exceeds 120 weight part, there exists a tendency for the adhesiveness of the spacer obtained to fall.

-[C] radiation sensitive polymerization initiator-

The radiation sensitive polymerization initiator (C) generates active species capable of initiating polymerization of the polymerizable unsaturated compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet rays, charged particle beams, and X-rays. Contains ingredients to make.

As such a [C] 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, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xan Tone type compound, a phosphine type compound, a triazine type compound, etc. are mentioned.

As the O-acyl oxime compound, an O-acyl oxime type polymerization initiator of 9.H.-carbazole type is preferable. For example, 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9- Ethyl-6-benzoyl-9.H.-carbazol-3-yl] -nonan-1,2-nonan-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-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-benzoate , 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl ) -9.H.-Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9 .H.- Rbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxo Yl) methoxybenzoyl} -9.H.-carbazol-3-yl] -1- (O-acetyloxime), and the like.

Among these O-acyl oxime compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1 -[9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone- 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9.H.-carbazol-3-yl] -1 -(O-acetyl oxime) is preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof. In the present invention, by using the O-acyl oxime compound, a spacer having sufficient sensitivity and adhesion even at an exposure amount of 1,000 J / m 2 or less can be obtained.

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

As said (alpha)-hydroxy ketone type compound, 1-phenyl- 2-hydroxy- 2-methyl-propan- 1-one, 1- (4-i-propylphenyl) -2-hydroxy- 2-methyl, for example Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, and the like. As the system compound, for example, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl ) -Butan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one, and the like. As a compound other than these, 2, 2- dimethoxy acetophenone, 2, 2- diethoxy acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, etc. are mentioned, for example.

Among these acetophenone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and 2- (4-methylbenzoyl) -2- (dimethylamino) -1 -(4-morpholinophenyl) -butan-1-one is preferred.

In this invention, by using an acetophenone type compound together, it becomes possible to further improve a sensitivity, a spacer shape, and compressive strength.

Moreover, as said biimidazole type compound, 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'-biimi Dazole, 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'-tetraphenyl-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, etc. are 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, in particular 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole is preferred.

In this invention, it becomes possible to further improve a sensitivity, a resolution, and adhesiveness by using a biimidazole type compound together.

In addition, when using a biimidazole type compound together, in order to sensitize it, the aliphatic type or aromatic type compound which has a dialkylamino group (henceforth "amino type sensitizer") can be added.

As an amino-type sensitizer, N-methyl diethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylamino benzoate, for example, p-dimethylaminobenzoic acid i-amyl etc. are mentioned.

Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable.

The said amino type sensitizer can be used individually or in mixture of 2 or more types.

In addition, when using a biimidazole type compound and an amino sensitizer together, a thiol type compound can be added as a hydrogen donor compound. When the biimidazole compound is sensitized and cleaved by the amino-based sensitizer to generate imidazole radicals, the high polymerization initiation capacity is not expressed as it is, and the spacer obtained has an undesirable shape such as an inverse taper shape. There are many. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, the hydrogen radical is donated from the thiol compound to the imidazole radical, and the imidazole radical is converted into a neutral imidazole. At the same time, a component having a sulfur radical having a high polymerization initiation capacity is generated, whereby the shape of the spacer can be made a more preferable forward taper shape.

As said thiol type compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto, for example Aromatic compounds such as -5-methoxybenzoimidazole; Aliphatic monothiols such as 3-mercaptopropionic acid, 3-mercaptopropionic acid methyl, 3-mercaptopropionic acid ethyl, and 3-mercaptopropionic acid octyl; And bifunctional or higher aliphatic thiols such as 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), and the like. .

Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

In the radiation-sensitive resin composition of the present invention, the use ratio of the other radiation-sensitive polymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less based on 100 parts by weight of the total radiation-sensitive polymerization initiator. Especially preferably, it is 60 weight part or less. When the use ratio of another radiation sensitive polymerization initiator exceeds 100 weight part, the desired effect of this invention may be impaired.

In addition, when using a biimidazole type compound and an amino sensitizer together, the addition amount of an amino type sensitizer becomes like this. Preferably it is 0.1-50 weight part, More preferably, 1 with respect to 100 weight part of nonimidazole type compounds. To 20 parts by weight. When the amount of the amino sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, resolution, and adhesion tends to decrease, while when the amount of the amino sensitizer exceeds 50 parts by weight, the shape of the spacer to be obtained tends to be damaged.

In addition, when using a biimidazole type compound and an amino sensitizer together, the addition amount of a thiol type compound becomes like this. Preferably it is 0.1-50 weight part, More preferably, it is 1-1 with respect to 100 weight part of biimidazole type compounds. 20 parts by weight. When the amount of the thiol compound added is less than 0.1 part by weight, the effect of improving the shape of the spacer is lowered or the film tends to be reduced. On the other hand, when the amount is more than 50 parts by weight, the shape of the spacer obtained is damaged. .

- additive -

To the radiation-sensitive resin composition of the present invention, additives such as surfactants, adhesion aids, storage stabilizers, heat resistance enhancers, etc. may be added to the radiation-sensitive resin composition of the present invention in addition to the above components, as necessary, within the range of not impairing the desired effects of the present invention. It may be.

The said surfactant is a component which has the effect | action which improves applicability, and a fluorine-type surfactant and a silicone type surfactant are preferable.

As said fluorine-type surfactant, the compound which has a fluoroalkyl group or a fluoroalkylene group in at least one site | part of a terminal, a main chain, and a side chain is preferable, As a specific example, 1,1,2,2- tetrafluorooctyl ( 1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycoldi (1,1,2 , 2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycoldi (1,1,2, 2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, 1,1,2,2,3,3 Hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, perfluoro-n-dodecylsulfonic acid sodium, Sodium fluoroalkylbenzenesulfonic acid, sodium fluoroalkylphosphonic acid, sodium fluoroalkylcarboxylic acid, fluoroalkylpol Oxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodido, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoro A roalkyl alkoxylate, a fluorine-type alkyl ester, etc. are mentioned.

Moreover, as a commercial item of a fluorine-type surfactant, in a brand name, for example, BM-1000, copper-1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191, Copper F471, Copper F476 (above, manufactured by Dainippon Ink & Chemicals Co., Ltd.), Fluoride FC170C, Copper FC-171, Copper FC-430, Copper FC-431 (above, Sumitomo Three M Co., Ltd.) Suplon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC- 104, east SC-105, east SC-106 (above, Asahi Glass Co., Ltd.), f-top EF301, east EF303, east EF352 (above, Shin Akita Kasei Co., Ltd.), plant FT-100, east FT-110, East FT-140 A, East FT-150, East FT-250, East FT-251, East FTX-251, East FTX-218, East FT-300, East FT-310, East FT-400S As mentioned above, Neos Corporation) etc. are mentioned.

As said silicone type surfactant, it is a commercial item from a brand name, for example, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ- 6032, copper SF-8428, copper DC-57, copper DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, copper-4300, copper-4445, copper-4446, copper-4460, copper -4452 (above, GE Toshiba Silicone Co., Ltd.), etc. are mentioned.

Moreover, as surfactant other than the above, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; As nonionic surfactants, such as polyoxyethylene dialkyl esters, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and a commercial item, it is a brand name, for example, KP341 (Shin-Etsu Chemical Co., Ltd. make). ), Polyflow no. 57, East No. 95 (the Kyoeisha Chemical Co., Ltd. product) etc. are mentioned.

The said surfactant can be used individually or in mixture of 2 or more types.

The compounding quantity of surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less based on 100 parts by weight of the polymer [A]. When the compounding quantity of surfactant exceeds 5 weight part, it exists in the tendency for a film roughness to arise at the time of application | coating.

The said adhesion | attachment adjuvant is a component which has the effect | action which further improves adhesiveness of a spacer and a base, and a functional silane coupling agent is preferable.

As said functional silane coupling agent, the compound which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is mentioned, for example, More specifically, trimethoxysilyl benzoic acid and (gamma)- Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4- Epoxy cyclohexyl) ethyl trimethoxysilane etc. are mentioned.

These adhesion aids can be used individually or in mixture of 2 or more types.

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less, More preferably, it is 10 weight part or less with respect to 100 weight part of [A] polymers. When the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, there exists a tendency for image development residue to occur easily.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and the like. More specifically, 4-methoxyphenol and N-nitroso-N-phenyl Hydroxylamine aluminum etc. are mentioned.

These storage stabilizers can be used individually or in mixture of 2 or more types.

The compounding quantity of a storage stabilizer is 3 weight part or less with respect to 100 weight part of [A] polymers, More preferably, it is 0.001-0.5 weight part. When the compounding quantity of a storage stabilizer exceeds 3 weight part, there exists a possibility that a sensitivity may fall and a pattern shape may be damaged.

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.

Among these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril is particularly preferable.

As the N- (alkoxymethyl) melamine compound, for example, 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 ', N ", N", N "-hexa (t-butoxymethyl) melamine and the like can be given.

Among these N- (alkoxymethyl) melamine compounds, in particular, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable, and as the commercially available product, under the trade name, for example, Nika Rock N-2702, copper MW-30M (above, Sanwa Chemical Co., Ltd. product), etc. are mentioned.

The said heat resistance improving agent can be used individually or in mixture of 2 or more types.

The compounding quantity of a heat resistance improving agent becomes like this. Preferably it is 30 weight part or less, More preferably, it is 20 weight part or less with respect to 100 weight part of [A] polymers. When the compounding quantity of a heat resistance improving agent exceeds 30 weight part, there exists a tendency for the storage stability of a radiation sensitive resin composition to fall.

It is preferable to use the radiation sensitive resin composition of this invention as a composition solution melt | dissolved in the suitable solvent.

As said solvent, what melt | dissolves each component which comprises a radiation sensitive resin composition uniformly, does not react with each component, and has a suitable volatility is used, The solvent of each component, the reactivity with each component, and the coating film formation In view of ease, alcohols, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, dipropylene glycol alkyl ethers, alkoxypropionic acid alkyls, acetic acid esters and the like are preferred. In particular, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol ethyl methyl ether, propylene glycol monomethyl Etc. Thermal acetate, propylene glycol monomethyl ether acetate, dipropylene glycol dimethyl ether acetate, 3-methoxybutyl acetate, 2-methoxyethyl are preferable.

The said solvent can be used individually or in mixture of 2 or more types.

In this invention, a high boiling point solvent can also be used together with the said solvent.

As said high boiling point solvent, for example, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, Dimethyl sulfoxide, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, oxalic acid di Ethyl, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

In addition, the composition solution prepared as mentioned above can also be used, filtering using a Millipore filter etc. about 0.5 micrometer of pore diameters.

The radiation sensitive resin composition of this invention can be used especially suitably for formation of the spacer for liquid crystal display elements.

<Spacer formation method>

Next, the method of forming the spacer of this invention using the radiation sensitive resin composition of this invention is demonstrated.

Formation of the spacer of the present invention includes at least the following steps in the order described below.

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

(B) exposing to at least a portion of the film;

(C) developing the film after exposure; and

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

Hereinafter, each of these steps will be described in order.

-(A) Process-

A transparent conductive film is formed on one surface of a transparent substrate, and after a radiation sensitive resin composition is apply | coated on the said transparent conductive film as a composition solution, Preferably, a coating film is formed by heating, ie, prebaking.

As a transparent substrate used for formation of a spacer, a glass substrate, a resin substrate, etc. are mentioned, for example, More specifically, glass substrates, such as a soda-lime glass and an alkali free glass; And resin substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide.

Examples of the transparent conductive film provided on one surface of the transparent substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG Co., Ltd.) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be used.

As a coating method of a composition solution, as a method of forming the film of the radiation sensitive resin composition of this invention, (1) coating method and (2) dry film method can be used, for example.

As the coating method of the composition solution, for example, a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet coating method, or the like can be adopted, and in particular, spin coating. The method and the slit die coating method are preferable.

Moreover, when forming the film of the radiation sensitive resin composition of this invention, when (2) dry film method is employ | adopted, the said dry film is a persimmon of this invention on a base film, Preferably a flexible base film It is what laminates the radiation sensitive layer containing a radioactive resin composition (henceforth "a radiation sensitive dry film").

The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition of the present invention on the base film as a liquid composition, and then drying the coating. 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 the radiation sensitive layer obtained, about 1-30 micrometers is preferable.

In addition, a radiation sensitive dry film can also be laminated | stacked and preserve | saved further on the radiation sensitive layer at the time of nonuse. This cover film needs to have a suitable mold release property so that it may not peel at the time of nonuse, and can peel easily at the time of use. As a cover film which satisfies such conditions, a film can be used by apply | coating or baking a silicone type mold release agent to the surface of synthetic resin films, such as a PET film, a polypropylene film, a polyethylene film, and a polyvinyl chloride film, for example. The thickness of the cover film is usually about 25 m.

In addition, although the conditions of prebaking differ according to the kind, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-120 degreeC.

-(B) 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 365 nm ultraviolet rays. Radiation is preferred.

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 To 1,500 J / m 2.

-(C) 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; 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-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Alkanolamines such as ethanol dimethylamine, methyl diethanolamine and triethanolamine; The aqueous solution of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, is mentioned.

In addition, a suitable amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the aqueous solution of the alkaline compound.

The developing method may be any of a puddle method, an immersion 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) Process-

Subsequently, the obtained pattern is heated by a heating device such as a hot plate or an oven at a predetermined temperature, for example, 100 to 230 ° C. for a predetermined time, for example, 5 to 30 minutes on a hot plate, and 30 to 30 in an oven. The predetermined spacer can be obtained by heating, post-baking, for 180 minutes.

In the radiation-sensitive resin composition of the present invention, the conventional radiation-sensitive resin composition used for formation of the spacer cannot exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to 230 ° C or higher, but in the radiation-sensitive resin composition of the present invention, The heating temperature can be lower than that of the prior art, and as a result, a spacer excellent in various performances such as compressive strength, rubbing resistance at the time of liquid crystal alignment, and adhesion to a transparent substrate can be formed without causing yellowing or deformation of the resin substrate. have.

<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 element of this invention, For example, as shown in FIG. 1, the 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, oppose each other. The structure which has a transparent electrode, an opposing transparent substrate, etc. is mentioned. In addition, as shown in FIG. 1, a protective film can also be formed on a polarizing plate and a color filter layer as needed.

As shown in FIG. 2, a TN-TFT type liquid crystal display device can 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.

As described above, the radiation-sensitive resin composition of the present invention has a high sensitivity and a high resolution, and a sufficient pattern shape is obtained even at an exposure amount of 1,000 J / m 2 or less, which is excellent in developability, elastic recovery, rubbing resistance, and a transparent substrate. It is also excellent in adhesiveness, heat resistance, etc., and can form the spacer for liquid crystal display elements without surface roughness on the obtained pattern surface, and does not cause yellowing or deformation of a resin substrate.

The liquid crystal display element of this invention is excellent in various performances, such as a sensitivity, developability, elastic recovery property, rubbing tolerance, adhesiveness with a transparent substrate, heat resistance, etc., and is provided with the spacer which does not have an uneven surface roughness on a pattern surface, High reliability can be realized over a long period of time.

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. Where parts and% are based on weight.

Synthesis Example 1

To a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobisisobutyronitrile and 250 parts of 3-methoxybutyl acetate were charged, followed by 18 parts of methacrylic acid and tricyclomethacrylate [5.2. 1.0 ^2,6 ] 25 parts of decane-8-yl, 5 parts of styrene, 30 parts of 2-hydroxyethyl ester of methacrylic acid and 22 parts of benzyl methacrylic acid were added, and after nitrogen-substitution, the temperature of the solution was slowly stirred. The copolymer [α-1] solution with a solid content concentration of 28.8% was obtained by raising the temperature to 80 ° C. and maintaining the temperature for 5 hours to polymerize.

About the obtained copolymer [(alpha) -1], it was 13,000 when Mw was measured using GPC (gel permeation chromatography) GPC-101 (brand name, the Showa Denko Corporation make).

Subsequently, after adding 14 parts of 2-methacryloyl oxyethyl isocyanate (trade name Carens MOI, the Showa Denko Co., Ltd. product) and 0.1 part of 4-methoxyphenol to the said copolymer [alpha-1] solution, The reaction was stirred at 40 ° C for 1 hour and further at 60 ° C for 2 hours. Reaction of the isocyanate group derived from 2-methacryloyloxyethyl isocyanate group, and the hydroxyl group of copolymer [alpha-1] was confirmed by IR (infrared absorption) spectrum. 2270 cm derived from an isocyanate group of 2-methacryloyloxyethyl isocyanate in the IR spectrum of each of the polymer solution [α-1], the solution after 1 hour reaction and the solution after 1 hour reaction at 40 ° C and 2 hours at 60 ° C. The peak around ^-1 was confirmed to be reduced. [A] polymer solution of 30.0% of solid content concentration was obtained. This polymer [A] is referred to as polymer (A-1).

Synthesis Example 2

14 parts of 2-acryloyloxyethyl isocyanate (brand name Carenz AOI, the Showa Denko Co., Ltd. product) and 4-methoxyphenol 0.1 were carried out similarly to the synthesis example 1 in the said copolymer [alpha-1] solution. After the addition, the reaction was stirred at 40 ° C for 1 hour and at 60 ° C for 2 hours. [A] polymer solution of 30.5% of solid content concentration was obtained. This polymer [A] is referred to as polymer (A-2).

Synthesis Example 3

17 parts of 4-methacryloyloxybutyl isocyanate (brand name Carens MOI-C4, the Showa Denko Co., Ltd. product) and 4-meth are carried out to the said copolymer [alpha-1] solution similarly to the synthesis example 1. After 0.1 part of oxyphenol was added, the mixture was stirred at 40 ° C for 1 hour and further at 60 ° C for 2 hours to react. [A] polymer solution of 31.0% of solid content concentration was obtained. This polymer [A] is referred to as polymer (A-3).

Synthesis Example 4

To the flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobisisobutyronitrile, 125 parts of 3-methoxybutyl acetate and 125 parts of propylene glycol monomethyl ether acetate were added, followed by 18 parts of methacrylic acid. , 25 parts of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 5 parts of styrene, 5 parts butadiene, methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester 25 parts of PLACCEL FM1D (manufactured by Daicel Chemical Industries, Ltd.) and 22 parts of tetrahydrofuran-2-yl methacrylate were added thereto, and after nitrogen-substituting, the temperature of the solution was raised to 80 ° C while stirring slowly. By maintaining this temperature for 5 hours and polymerizing, a copolymer [α-2] solution having a solid content concentration of 29.1% 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, the Showa Denko Corporation make).

Subsequently, after adding 14 parts of 2-methacryloyl oxyethyl isocyanate (brand name CARENS MOI, Showa Denko Co., Ltd.), and 0.1 part of 4-methoxy phenols to the said copolymer [alpha-2] solution, And [A] polymer solution of 31.0% of solid content concentration was obtained by making it react by stirring at 40 degreeC for 1 hour and 60 degreeC for 2 hours. This polymer [A] is referred to as polymer (A-4).

Synthesis Example 5

To a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methylethyl ether were added, followed by 18 parts of methacrylic acid and methacrylic acid. 34 parts of acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 5 parts of styrene, 5 parts of butadiene, and 40 parts of glycidyl methacrylates were added, and after nitrogen-substituting, the temperature of the solution was slowly stirred. The copolymer [β-1] solution having a solid content concentration of 31.0% was obtained by raising the temperature to 70 ° C. and maintaining the temperature for 5 hours to polymerize. The obtained copolymer [β-1] was 11,000 when Mw was measured using GPC (gel permeation chromatography) GPC-101 (trade name, Showa Denko Co., Ltd.).

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were charged. Subsequently, after adding 19 parts of styrene, 38 parts of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 13 parts of methacrylic acid, and 30 parts of methyl methacrylate, and nitrogen-substituted, Stirring was started slowly. The temperature of the solution was raised to 70 ° C, and this temperature was maintained for 7 hours to obtain a polymer solution containing a copolymer [β-2]. Solid content concentration of the obtained polymer solution was 32.9%. The obtained copolymer [β-2] was 12,000 when Mw was measured using GPC (gel permeation chromatography) GPC-101 (trade name, Showa Denko Co., Ltd.).

Synthesis Example 7

To a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methylethyl ether were added, followed by 18 parts of methacrylic acid and methacrylic acid. 34 parts of acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 5 parts of styrene, 5 parts of butadiene, 20 parts of methacrylic acid 3,4-epoxycyclohexylmethyl and tetrahydrofuran-2-methacrylate 20 parts of one part was added, and after nitrogen-substituting, the temperature of a solution was raised to 70 degreeC, stirring slowly, and this copolymer was hold | maintained for 5 hours and superposed | polymerized, and the copolymer [beta-3] solution of 30.0% of solid content concentration was obtained. . The obtained copolymer [β-3] was 11,000 when Mw was measured using GPC (gel permeation chromatography) GPC-101 (trade name, Showa Denko Co., Ltd.).

Synthesis Example 8

In a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 250 parts of propylene glycol monomethyl ether acetate were charged. Subsequently, 5 parts of styrene, 18 parts of methacrylic acid, 17 parts of methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 3- (methacryloyloxymethyl) -3-ethyloxetane 40 20 parts of methacrylic acid tetrahydrofuran-2-yl were added and nitrogen-substituted, and stirring was slowly started. 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-4]. Solid content concentration of the obtained polymer solution was 29.0%, and the weight average molecular weight of the polymer measured using GPC (gel permeation chromatography) GPC-101 (brand name, the Showa Denko Corporation make) was 14,000.

Example 1

Preparation of Composition Solution

As the component [A], 100 parts of the polymer solution [A] obtained in Synthesis Example 1 as the polymer (A-1), 10 parts of the copolymer [β-1] obtained in Synthesis Example 5 and the component [B] were used. 100 parts of pentaerythritol hexaacrylate (brand name KAYARAD DPHA, Nippon Kayaku Co., Ltd. product) and [C] component are 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-car Bazol-3-yl] -ethane-1-onoxime-O-acetate (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals) 5 parts, 2,2'-bis (2-chlorophenyl) -4,4 ', 5 5 parts of 5'-tetraphenyl-1,2'-biimidazole, 5 parts of 4,4'-bis (diethylamino) benzophenone, 2.5 parts of 2-mercaptobenzothiazole, as an adhesion aid, -5 parts of glycidoxypropyl trimethoxysilane, 0.5 parts of FTX-218 (trade name, manufactured by Neos) as a surfactant, and 0.5 parts of 4-methoxyphenol as a storage stabilizer are mixed, and the solid content concentration is 30%. Dissolved in propylene glycol monomethyl ether acetate so that the pore size was 0.5 Filtration with a μm Millipore filter produced a composition solution.

In Table 1, each component other than a polymer is as follows.

[B] component

B-1: dipentaerythritol hexaacrylate (brand name KAYARAD DPHA)

B-2: Commercial item containing a polyfunctional urethane acrylate type compound (brand name KAYARAD DPHA-40H)

B-3: pentaerythritol tetraacrylate (brand name Aronix M-450 (Toa Kosei Co., Ltd. product))

B-4: ω-carboxy polycaprolactone monoacrylate (brand name Aronix M-5300 (Toa Kosei Co., Ltd. product))

B-5: 1,9-nonane diacrylate (brand name light acrylate 1,9-NDA (Kyoeisha Co., Ltd. product))

[C] component

C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate (trade name IRGACURE OX02, Ciba Specialty) Chemicals company)

C-2: ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9.H.-carr Bazol-3-yl] -1- (O-acetyl oxime) (N-1919 by ADEKA Corporation)

C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one (brand name Irgacure 907, the Ciba specialty chemicals company make)

C-4: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)

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

C-6: 4,4'-bis (diethylamino) benzophenone

C-7: 2-mercaptobenzothiazole

[D] component

D-1: Polyfunctional novolak-type epoxy resin (Epicoat 152 by a brand name Japan epoxy resin Co., Ltd. product)

In Examples 2 to 16 and Comparative Examples 1 to 5, a composition solution was prepared in the same manner as in Example 1. The results are shown in Table 1 below.

In addition, Example 17 and the comparative example 6 were implemented by the dry film method.

Formation of spacers

Examples 2-16 and Comparative Examples 1-5 were apply | coated to the board | substrate using the spinner, and the spacer was formed. The detail is shown below.

After the said composition solution was apply | coated using the spinner on the alkali free glass substrate, it prebaked for 3 minutes on the 100 degreeC hotplate, and the film of 3.5 micrometers of film thicknesses was formed.

Subsequently, the obtained film was exposed through the photomask of a residual pattern of 10 micrometers angle. Then, after developing at 25 degreeC with 0.05 weight% aqueous solution of potassium hydroxide, it wash | cleaned for 1 minute with pure water, and heated for 30 minutes in 230 degreeC oven, and formed the spacer.

In addition, Example 15 formed the spacer by the dry film method. The details are shown below.

Example 17

Except having produced the coating film from the liquid composition (S-17) of the radiation sensitive resin composition by the dry film method, it carried out similarly to Examples 1-14, and formed and evaluated the patterned thin film. Each component is shown in Table 1. In addition, peeling removal of the base film was performed before the exposure process. The evaluation results are shown in Table 2 below. In addition, the evaluation results of the following transferability are also shown in Table 2.

The manufacture and transfer of a dry film were performed as follows.

On the 38-micrometer-thick polyethylene terephthalate (PET) film, the liquid composition (S-17) of a radiation sensitive resin composition was apply | coated using an applicator, and a coating film was heated at 100 degreeC for 5 minutes, and the thickness of 4 micrometers was sensed. The radioactive dry film (J-1) was produced. Next, the radiation sensitive transfer dry film was superposed so that the surface of a radiation sensitive transfer layer might contact the surface of a glass substrate, and the radiation sensitive dry film (J-1) was transferred to the glass substrate by the thermocompression bonding method.

-Evaluation of transferability of dry film to glass substrate-

When the radiation-sensitive dry film was transferred onto the glass substrate by thermocompression bonding, the case where the dry film could be uniformly transferred onto the glass substrate was indicated by "o", and the dry film remained on the base film or the glass substrate partially. The case where the dry film was not able to be transferred uniformly on the glass substrate, such as the dry film is not in close contact with each other, was referred to as "x".

Comparative Example 6

In Example 17, except having used the liquid composition (S-6) of a radiation sensitive resin composition instead of the liquid composition (S-17) of a radiation sensitive resin composition, it carried out similarly to Example 17, and it is radiation-sensitive After producing the dry dry film (J-2), a patterned thin film was formed and evaluated. Each component is shown in Table 1. The evaluation results are shown in Table 2. In addition, the evaluation results of the transferability are also shown in Table 2.

Subsequently, various evaluation was performed in the following way. The evaluation results are shown in Table 2.

(1) Evaluation of developing time

The developing time was made into 30, 40, 50, 60, 70, 80, 90, and 100 second, and the residue of the unexposed part was observed with the optical microscope in each developing time. In each developing time, the shortest developing time when it was confirmed that there was no residue in an unexposed part is shown in Table 2. It can be judged that developability is so favorable that developing time is short.

(2) evaluation of sensitivity

In the same manner as the formation of the spacer, when the spacer was formed, the exposure amount at which the residual film ratio (film thickness after post-baking x 100 / post-exposure film thickness after post-baking) became 90% or more was used as the sensitivity. When this exposure amount is 1,000 J / m <2> or less, it can be said that a sensitivity is favorable.

(3) Evaluation of elastic recovery rate

With respect to the obtained spacer, using a micro-compression tester (trade name DUH-201, manufactured by Shimadzu Corporation), a planar indenter having a diameter of 50 µm allowed both the load speed and the unloading speed to be 2.6 mN / sec. The load to mN was loaded and held for 5 seconds, and then unloaded to prepare a load-strain curve at load and a load-strain curve at unload. At this time, as shown in Fig. 3, the amount of deformation at 50 mN under load is L1, and the difference between the amount of deformation at 50 mN under load and the amount of deformation at load 5 mN is L2. By this, the elastic recovery rate was calculated.

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

Table 2 shows the elastic recovery rate (%) and the deformation amount L1 (µm).

(4) evaluation of rubbing resistance

After apply | coating AL3046 (brand name, JSR Corporation make) to the board | substrate with a spacer as a liquid crystal aligning agent with the printer for liquid crystal aligning film application, it dries at 180 degreeC for 1 hour, and the coating film of the liquid crystal aligning agent of thickness 0.05micrometer Formed.

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

(5) Evaluation of adhesiveness

Except not having used a photomask, it carried out similarly to formation of the said spacer, and after forming a cured film, it evaluated by the 8.5 * 2 checker scale tape method in the adhesion test of JISK-5400 (1900) 8.5. At this time, Table 2 shows the number of remaining checkerboard ticks among the 100 checkerboard ticks.

(6) evaluation of heat resistance

Except not using a photomask, after forming a cured film similarly to the formation of the said spacer, it heats further for 60 minutes in an oven of 240 degreeC, the film thickness before and after further heating was measured, and the residual film rate (after Film thickness x 100 / film thickness before additional heating).

(7) Evaluation of the surface of the spacer pattern

The surface of the obtained spacer was observed with the scanning electron microscope. The case where surface roughness of uneven | corrugated phase was observed was evaluated as x and the case where it was not observed as (circle). The results are shown in Table 2.

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram of an example for demonstrating the structure of a liquid crystal display element.

2 is a schematic view of another example for explaining the structure of a liquid crystal display element.

3 is a diagram illustrating load-strain curves under load and under load in evaluation of elastic recovery rate.

Claims (7)

[A1] (a1) A copolymer of at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides and (a2) unsaturated compounds containing at least one hydroxyl group in one molecule is represented by the following formula (1): A polymer obtained by reacting an isocyanate group-containing unsaturated compound represented, and [A2] (a1) A copolymer of an unsaturated compound having one or more selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and (a3) an oxylanyl group or an oxetanyl group, characterized by containing Radiation-sensitive resin composition. <Formula 1>

(Wherein R ¹ is a hydrogen atom or a methyl group, n is an integer from 1 to 12) The radiation sensitive resin composition of Claim 1 whose said (a2) component is an unsaturated compound represented by following General formula (2). <Formula 2>

(Wherein R ² is a hydrogen atom or a methyl group, l is an integer from 1 to 12, m is an integer from 1 to 6) The radiation sensitive resin composition of Claim 1 or 2 which further contains a [B] polymerizable unsaturated compound and a [C] radiation sensitive polymerization initiator. The radiation sensitive resin composition of any one of Claims 1-3 used for formation of the spacer for liquid crystal display elements. The liquid crystal display element spacer formed from the radiation sensitive resin composition in any one of Claims 1-3. The formation method of the spacer for liquid crystal display elements containing at least the following processes in the order described below. (A) process of forming the film of the radiation sensitive resin composition of Claim 1 on a board | substrate, (B) exposing to at least a portion of the film; (C) developing the film after exposure; and (D) The process of heating the said film after image development. The liquid crystal display element provided with the spacer of Claim 5.

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