KR20070024399A - Side chain unsaturated polymer, radiation sensitive resin composition and spacer for liquid crystal display element - Google Patents

Abstract

A radiation sensitive composition for fabricating a spacer for crystal display device is provided to form the spacer which exhibits high sensitivity, excellent flexibility, elastic recovery, rubbing resistance, adhesiveness to a transparent wafer and heat resistance, and gives desired shape of the spacer even with small exposure dose. The composition includes a polymer obtained by reacting a copolymer comprising: (a1) unsaturated carboxylic acid and carboxylic anhydride; (a2) an unsaturated compound containing hydroxyl group, which is represented by any one selected from formulae(1) to (4); and (a3) polymer obtained by reacting copolymer of another unsaturated compound except the compounds(a1) and (a2) with isocyanate compound represented by a formula(5). The composition further contains a polymeric unsaturated compound and a radiation sensitive polymerization initiator.

Description

Side Chain Unsaturated Polymer, Radiation Sensitive Resin Composition and Spacer for Liquid Crystal Display Element}

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

2 is a schematic diagram showing another example of the structure of a liquid crystal display element.

3 is an infrared spectral diagram of the polymer solution [α-1] of Synthesis Example 1. FIG.

4 is an infrared spectral diagram of a solution after 1 hour reaction at 60 ° C. of the polymer solution [α-1].

5 is an infrared spectral diagram of a solution after reaction at 60 ° C. of the polymer solution [α-1] for 2 hours.

6 is a schematic diagram illustrating a cross-sectional shape of a spacer.

FIG. 7 is a diagram illustrating load-strain curves at the time of loading and removal of load in the evaluation of the elastic recovery rate. FIG.

[Patent Document 1] Japanese Unexamined Patent Publication No. 2003-173025

This invention relates to the side chain unsaturated polymer which is especially preferable for formation of the spacer in a liquid crystal display element, the radiation sensitive resin composition containing it, a spacer, its formation method, and a liquid crystal display element.

Conventionally, in the liquid crystal display device, spacers such as glass beads and plastic beads having a predetermined particle diameter are used to maintain a constant gap between two substrates, that is, a cell gap, but these spacers are formed on a transparent substrate such as a glass substrate. Because of the random scattering on the substrate, if the spacer is present in the pixel formation region, there is a problem that the spacer is stamped out or the incident light is scattered and the contrast as the liquid crystal display element is lowered.

Therefore, in order to solve this problem, the method of forming a spacer by photolithography was adopted. In this method, a radiation sensitive resin composition is apply | coated on a board | substrate, it develops, for example, after exposing ultraviolet-ray through a predetermined mask, and forms a spacer of a dot form or a stripe, and predetermined place other than a pixel formation area | region Only because the spacer can be formed, the above problem is basically solved.

Moreover, in view of the large area of a liquid crystal display element, the improvement of productivity, etc., the enlargement of a mother glass substrate, for example, 1,500 * 1,800mm, and about 1,870 * 2,200mm is advancing in recent years. However, in the conventional substrate size, since the substrate size is smaller than the mask size, it is possible to cope with the batch exposure method. However, in the case of large substrates, it is almost impossible to manufacture the mask size that is about the same as the substrate size. It is difficult.

Therefore, the step exposure method was proposed as an exposure method that can cope with a large substrate. However, in the step exposure method, since a single substrate is exposed several times and time alignment and step movement are required for each exposure, a reduction in the throughput is problematic compared to the batch exposure method.

In addition, although the exposure amount of about 3,000 J / m <^2> is possible in the package exposure system, it is necessary to lower each exposure amount in the step exposure system, and it is 1,200 as a 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 dose of J / m ² or less.

Moreover, from the viewpoint of productivity improvement, the process technology "ODF (One Drop Fil1) method" which introduce | transduces a liquid crystal material on the glass surface before bonding the glass of a liquid crystal panel was introduced.

This method can save a great deal of time. For example, in the conventional method, it takes about five days to fill a liquid crystal in a 30-inch panel, but when the ODF method is introduced, it takes only two hours, so that a significant productivity improvement can be achieved.

In the conventional bonding method, since a load is applied when bonding the TFT array and the color filter, the spacer is evenly pressed by the load, thereby maintaining the height uniformity of the spacer. However, in the ODF method, the initial bonding load is smaller than that of the conventional method, because the bonding is performed only by the weight of the substrate and the atmospheric pressure. Therefore, it is said that it is important to express height uniformity by being pressed evenly even if the spacer is pressed with a small load. This required the flexibility of the spacers. If the height of the spacer becomes uneven, the uniformity of the cell spacing cannot be maintained, and a gap occurs in the cell, which causes display unevenness. Therefore, a spacer material having both flexibility and high recovery rate due to the compression load was required.

In Japanese Unexamined Patent Publication No. 2003-173025, a copolymerizable having a photopolymerizable functional group as a structural unit obtained by reacting a (meth) acryloyloxyalkyl isocyanate compound with a copolymerizable resin having an imide group and a hydroxyl group in the photosensitive resin composition. By using resin, it was disclosed that performance improvement as a spacer, such as high sensitivity and high recovery rate, can be achieved. However, no flexibility is considered.

As described above, in the conventional radiation-sensitive resin composition, high sensitivity and high recovery rate can be achieved by using a copolymerizable resin having a photopolymerizable functional group as a structural unit. It could not be said that the material provided the spacer which had further combined.

Therefore, the subject of this invention is high sensitivity, and sufficient spacer shape is obtained even in the exposure amount of 1,200 J / m <^2> or less, and it forms the spacer for liquid crystal display elements excellent in flexibility, high recovery rate, rubbing tolerance, adhesiveness with a transparent substrate, heat resistance, etc. It is providing the radiation sensitive resin composition which can be performed.

Another object of the present invention is to provide a side chain unsaturated polymer or the like which is useful as a resin component of the radiation-sensitive resin composition.

Another object of the present invention is to provide a liquid crystal display spacer formed from 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.

According to the present invention, the problem is firstly

(a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides,

(a2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by formulas (1) to (4), and

(a3) unsaturated compounds other than (a1) and (a2)

It is achieved by a polymer (hereinafter referred to as "[A] polymer") obtained by reacting a copolymer of the isocyanate compound represented by the following formula (5).

(In formula, R represents a hydrogen atom or a methyl group, and a is an integer of 5 or more.)

(In formula, R represents a hydrogen atom or a methyl group, and b and c are the integers of 1-12 each independently.)

(Wherein R represents a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 12.)

(Wherein R represents a hydrogen atom or a methyl group, f and g each independently represent an integer of 0 to 6, and W has any of the alicyclic structures represented by the following formulas (I) to (IV)): It represents a divalent group.)

(In formula, R represents a hydrogen atom or a methyl group, h is an integer of 1-12.)

According to the invention, the problem is second

It is achieved by the radiation sensitive resin composition characterized by containing a polymer (A), a polymerizable unsaturated compound (B), and a radiation sensitive polymerization initiator (C).

According to the present invention, the problem is third

It is achieved by the radiation sensitive resin composition (henceforth "the radiation sensitive resin composition for spacers for liquid crystal display elements") used for formation of the liquid crystal display element spacer containing the said radiation sensitive resin composition.

According to the present invention, the problem is the fourth

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

According to the present invention, the problem is the fifth

It is achieved by the formation method of the spacer for liquid crystal display elements characterized by including at least the following processes in the order described below.

(A) process of forming the film of the radiation sensitive resin composition for spacers for liquid crystal display elements 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.

According to the present invention, the sixth problem

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

Best Mode for Carrying Out the Invention

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

Radiation  Resin composition

-[A] polymer-

The polymer of the present invention comprises at least one compound selected from the group consisting of (a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides, and (a2) hydroxyl group-containing unsaturated compounds represented by each of Formulas 1 to 4 above. And (a3) an isocyanate compound represented by the above formula (5) in a copolymer (hereinafter referred to as "copolymer [α]") consisting of other unsaturated compounds other than (a1) and (a2) (hereinafter referred to as "unsaturated isocyanate compound"). (5) "), and the polymer (henceforth" the [A] polymer ") obtained by reacting is included.

Examples of the (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride (hereinafter, collectively referred to as "(a1) unsaturated carboxylic acid compound") in each component constituting the copolymer [α] include For example, acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydro Monocarboxylic acids such as phthalic acid;

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

Anhydride of the said dicarboxylic acid, etc. are mentioned.

Acrylic acid, methacrylic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, etc. from the point of the copolymerization reactivity in these (a1) unsaturated carboxylic acid type compounds, the solubility to the alkali developing solution of the obtained [A] polymer, and an acquisition are easy. This is preferred.

In a copolymer [(alpha)], (a1) unsaturated carboxylic acid type compound can be used individually or in mixture of 2 or more types.

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

(A2) As the hydroxyl group-containing unsaturated compound selected from the group consisting of unsaturated compounds represented by each of the above formulas (1) to (4), for example, the compound represented by the above formula (1) may be acrylic acid 5-hydroxypentyl ester or 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-hydroxy undecyl ester, acrylic acid 12- Acrylic acid hydroxyalkyl esters such as hydroxydodecyl 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 hydroxyalkyl esters, such as methacrylic acid 10-hydroxydecyl ester, methacrylic acid 11-hydroxy undecyl ester, and methacrylic acid 12-hydroxy dodecyl ester, etc. are mentioned.

As the compound represented by the above formula (2), for example, acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, acrylic acid 4- (6- Acrylic acid (6-hydroxyhexanoyloxy) such as hydroxyhexanoyloxy) butyl ester, acrylic acid 5- (6-hydroxyhexanoyloxy) pentyl ester, acrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester Alkyl esters;

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-hydroxyhexanoyloxy) pentyl ester, methacrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester Ester is mentioned.

In addition, as a commercial item of the mixture of a (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester and methacrylic acid 2-hydroxyethyl ester, it is PLACCEL FM1D, FM2D (made by Daicel Chemical Industries, Ltd.) under a brand name. ), And the like.

Moreover, as a compound represented by the said General formula (3), For example, acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, acrylic acid 3- (3-hydroxy-2, 2-dimethyl-propoxycarbonyloxy) -propyl ester, acrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, acrylic acid 5- (3-hydroxy-2, Acrylic acid (3-hydroxy-2,2, such as 2-dimethyl-propoxycarbonyloxy) -pentyl ester, acrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester -Dimethyl-propoxycarbonyloxy) -alkyl ester,

Methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, methacrylic acid 3- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -Propyl ester, methacrylic acid 4- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -butyl ester, methacrylic acid 5- (3-hydroxy-2,2-dimethyl-propoxy Methacrylic acid (3-hydroxy-2,2-dimethyl, such as carbonyloxy) -pentyl ester, methacrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester -Propoxycarbonyloxy) -alkyl ester, etc. are mentioned.

In addition, as a commercial item of the mixture of (meth) acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -alkyl ester and methacrylic acid 2-hydroxyethyl ester, it is a brand name HEMAC1 (di Cell Chemical Industries, Ltd.) etc. are mentioned.

As the compound represented by the above formula (4), for example, 4-hydroxy-cyclohexyl ester of acrylic acid, 4-hydroxymethyl-cyclohexylmethyl ester of acrylic acid, 4-hydroxyethyl-cyclohexylethyl ester of acrylic acid, and acrylic acid 3 -Hydroxy-bicyclo [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-methanoinden-5-ylester, 2-hydroxymethyl-octahydro-4,7-methanoinden-5-ylmethylester, 2-hydroxyethyl acrylate -Octahydro-4,7-methanoinden-5-ylethyl ester, acrylic acid 3-hydroxy-adamantane-1-yl ester, acrylic acid 3-hydroxymethyl-adamantane-1-ylme Acrylic acid hydroxyalkyl esters having an alicyclic structure such as tilester and 3-hydroxyethyl-adamantan-1-ylethyl 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-methanoinden-5-ylester, methacrylic acid 2-hydroxymethyl-octahydro-4,7-methanoinden-5-ylmethyl ester, methacryl Acid 2-hydroxyethyl-octahydro-4,7-methanoinden-5-ylethyl ester, methacrylic acid 3-hydroxy-adamantane-1-yl ester, methacrylic acid 3-hydroxymethyl- Adamantane-1-ylmethyl ester, methacrylic acid 3-hi Hydroxyethyl-adamantyl methacrylate hydroxyalkyl ester having an alicyclic structure such as a carbon-1-yl ethyl ester;

Among these hydroxyl group-containing unsaturated compounds represented by formulas (1) to (4) above, acrylic acid 6-hydroxyhexyl ester, methacrylic acid 6-hydroxyhexyl ester, and acrylic acid 2- ( 6-hydroxyethylhexanoyloxy) ethyl ester, methacrylic acid 2- (6-hydroxyethylhexanoyloxy) ethyl ester, acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy ) -Ethyl ester, methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester, acrylic acid 4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid 4-hydroxy Hydroxymethyl-cyclohexyl methyl ester, acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, methacrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester and the like are preferable.

In a copolymer [(alpha)], (a2) hydroxyl-containing unsaturated compound can be used individually or in mixture of 2 or more types.

In the copolymer [α], the content of the repeating unit derived from the hydroxyl group-containing unsaturated compound (a2) is preferably 1 to 50% by weight, more preferably 3 to 40% by weight, based on the copolymer [α], More preferably, it is 5-30 weight%, Especially preferably, it is 10-30 weight%. (a2) When the content rate of the repeating unit derived from a hydroxyl-containing unsaturated compound is less than 1 weight%, the introduction rate of an unsaturated isocyanate compound (5) to a polymer will fall and a sensitivity will fall, and 50 weight% When it exceeds, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound (5) to fall.

Moreover, as (a3) another unsaturated compound, it is, for example

Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, 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 ester;

Glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate Same acrylic acid epoxy (cyclo) alkyl esters;

Meta such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate Crylic acid epoxy (cyclo) alkyl ester;

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-epoxycyclohex Other α-alkylacrylic acid epoxy (cyclo) alkyl esters such as yarn:

glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

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

Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate, benzyl acrylate:

Aryl esters or aralkyl esters of methacrylic acid, such as phenyl methacrylate and benzyl methacrylate;

Acrylic acid hydroxyalkyl esters such as acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester and acrylic acid 3-hydroxybutyl ester;

Methacrylic acid hydroxyalkyl esters such as methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxypropyl ester, methacrylic acid 3-hydroxybutyl ester:

Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;

Acrylate esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing complex 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;

Meta having an oxygen-containing hetero five-membered ring or an oxygen-containing hetero six-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, or 2-methyltetrahydropyran-2-yl methacrylate Acrylate esters;

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

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

Acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate, etc. are mentioned.

N-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, methacrylic acid from the point of copolymerization reactivity in these (a3) other unsaturated compounds, and the solubility to the aqueous alkali solution of the obtained [A] polymer. Acidtricyclo [5.2.1.0 ^2,6 ] decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like are preferred.

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

In the copolymer [α], the content of the repeating unit derived from the other unsaturated compound (a3) is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, especially due to the copolymer [α]. Preferably it is 30-50 weight%. (a3) When the content rate of the repeating unit derived from another unsaturated compound is less than 10 weight%, there exists a tendency for the storage stability of the polymer obtained by reaction with an unsaturated isocyanate compound (5) to fall, while exceeding 70 weight%, There exists a tendency for the solubility with respect to the alkaline developing solution of the said polymer to fall. Moreover, when using (meth) acrylic-acid epoxy (cyclo) alkyl ester, 10 weight% or less of content rate is preferable, and there exists a tendency for storage stability to fall that it is 10 weight% or more.

The copolymer [α] can be produced, for example, by polymerizing (a1) unsaturated carboxylic acid compound, (a2) hydroxyl group-containing unsaturated compound and (a3) other unsaturated compound in the presence of a radical polymerization initiator in a suitable solvent.

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

Ethers such as tetrahydrofuran, 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-propylether acetate, ethylene glycol mono-n-butylether acetate;

Ethylene glycol monoalkyl ether propionate such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propylether propionate, ethylene glycol mono-n-butylether propionate Nate;

Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl 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, dipropylene glycol methylethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propylether acetate, propylene glycol mono-n-butylether acetate;

Propylene glycol monoalkyl ether propionate such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propylether propionate, propylene glycol mono-n-butylether propionate Nate;

Aromatic hydrocarbons such as toluene and xylene;

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

2-Methoxypropionate, 2-methoxyethylpropionate, 2-methoxypropionic acid n-propyl, 2-methoxypropionic acid n-butyl, 2-ethoxypropionate methyl, 2-ethoxypropionate, 2-e N-propyl oxypropionate, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionic acid, 2-n-propoxy N-butyl propionate, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionic acid, n-butyl 2-n-butoxypropionic acid, 3-methoxypropionic acid Methyl, 3-methoxypropionate, 3-methoxypropionic acid n-propyl, 3-methoxypropionic acid n-butyl, 3-ethoxypropionic acid methyl, 3-ethoxypropionic acid, 3-ethoxypropionic acid n-propyl, 3-ethoxypropionate n-butyl, 3-n-propoxypropionate, 3-n-ethylpropoxypropionate, 3-n-propoxyprop N-propyl on-acid, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, ethyl 3-n-butoxypropionate, n-propyl 3-n-butoxypropionate, 3-n-part Alkoxy alkoxypropionate like n-butyl oxypropionate,

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, 3-acetic acid 3- Methoxybutyl, 2-methoxybutyl acetate, 3-ethoxybutyl acetate, 3-hydroxybutyl acetate, methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, 2-hydroxy-2-methylpropionate , 2-hydroxy-2-methylpropionate, 3-hydroxypropionate, methyl 3-hydroxypropionate, 3-hydroxypropionic acid n-propyl, 3-hydroxypropionic acid n-butyl, 2-hydroxy-3 Methyl methyl butyrate, methyl methoxyacetate, ethyl methoxyacetate, methoxyacetic acid n-propyl, methoxyacetic acid n-butyl, ethoxyacetic acid methyl, ethoxyacetic acid ethyl, ethoxyacetic acid n-propyl, ethoxyacetic acid n-part , n-propoxy acetate, n-propoxy acetate, n-propoxy acetate n-propyl, n-propoxy acetate n-butyl, n-butoxy acetate, n-butoxy acetate, n-part Other esters such as oxyacetic 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, acetate 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-methylprop Azo compounds such as cionate) 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 and the like.

In addition, when using a peroxide as a radical polymerization initiator, it can also be used together with a reducing agent 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 as it is for the production of the polymer [A], or may be separated from the solution once and used for the production of the polymer [A].

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") by gel permeation chromatography (GPC) of the copolymer [α] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. In this case, when Mw is less than 2,000, alkali developability, residual film ratio, etc. of the obtained film may fall, or pattern shape, heat resistance, etc. may be impaired. On the other hand, when Mw exceeds 100,000, resolution may be reduced or pattern shape may be damaged. There is concern.

The polymer [A] in the present invention is obtained by reacting an unsaturated isocyanate compound (5) with a copolymer [α].

As unsaturated isocyanate compound (5), 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 cydecyl isocyanate;

2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, And methacrylic acid derivatives such as 10-methacryloyloxydecyl isocyanate.

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

Among these unsaturated isocyanate compounds (5), 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, etc. are preferable at the point of reactivity with copolymer [α].

In the polymer (A), the unsaturated isocyanate compound (5) 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 (5) includes a catalyst such as dilauric di-n-butyltin (IV) or a polymerization inhibitor such as p-methoxyphenol. It can carry out by adding the unsaturated isocyanate compound (5) dropwise to the copolymer [α] solution to be stirred at room temperature or under heating.

[A] The amount of the unsaturated isocyanate compound (5) used in preparing the polymer is the amount of the (a2) hydroxyl group-containing unsaturated compound in the copolymer [α], or (a3) when the compound containing a hydroxyl group is used as another unsaturated compound. The amount is preferably 0.1 to 90% by weight, more preferably 10 to 80% by weight, particularly preferably 25 to 75% by weight based on the total amount of the amount thereof and the amount of the hydroxyl group-containing unsaturated compound. When the amount of the unsaturated isocyanate compound (5) is less than 0.1% by weight, the effect on improving the sensitivity and elastic properties is small. On the other hand, when the amount of the unsaturated isocyanate compound (5) is more than 90% by weight, the polymer solution obtained by remaining of the unreacted unsaturated isocyanate compound (5) or There exists a tendency for the storage stability of 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 suitable solubility in an alkaline developer, and can be easily cured by heating without using a special curing agent. The radiation sensitive resin composition containing the polymer (A) can easily form a spacer having a predetermined shape without causing development residue and film reduction when developing.

The radiation sensitive resin composition of this invention contains a [A] polymer, a [B] polymerizable unsaturated compound, and a [C] radiation sensitive polymerization initiator as an essential component.

-[B] polymerizable unsaturated compound-

The polymerizable unsaturated compound (B) contains an unsaturated compound which polymerizes by exposure of 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, monofunctional, bifunctional, or trifunctional or more (meth) acrylic acid ester is preferable at the point which copolymerizability is favorable and the intensity | strength of the spacer obtained improves. .

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, ω-carboxypolycaprolactone monoacrylate, etc. are mentioned, Also as a commercial item, it is an alloy M-101, copper M by brand name, for example. -111, copper M-114, copper M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.); Biscoat 158, Copper 2311 (above, Osaka Kagaku Kogyo Co., Ltd. product) 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-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, Bisphenoxy ethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, etc. are mentioned, Furthermore, as a commercial item, it is a brand name, for example, Alonics M-210, copper M-240, copper M -6200 (above, Doa Kosei Co., Ltd.), KAYARAD HDDA, East HX-220, East R-604 (above, Nippon Kayaku Co., Ltd.), Biscot 260, East 312, East 335 HP (above, Osaka Yuki Kagaku Kogyo Co., Ltd.) All.

Moreover, as said (meth) acrylic acid ester more than trifunctional, for example, trimethylolpropane triacrylate, trimethylolpropane 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 a linear alkylene group and an alicyclic structure, and also having two or more isocyanate groups, and having at least one hydroxyl group in the molecule Having dog, four or five acryloyloxy groups and / or methacryloyloxy groups It is obtained by reacting a compound, and the like functional urethane acrylate compound.

As a commercial item of the trifunctional or more than trifunctional (meth) acrylic acid ester, for example, alonics M-309, copper M-400, copper M-405, copper M-450, copper M-7100, copper M-8030, copper M by brand name -8060, copper TO-1450, copper TO-1382 (above, manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120 (more , Nippon Kayaku Co., Ltd.), biscot 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (above, manufactured by Osaka Yuki Chemical Co., Ltd.), and polyfunctional urethane acrylate-based compound Examples of commercially available products include New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like.

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

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

In the radiation-sensitive resin composition of the present invention, the amount of the polymerizable unsaturated compound [B] is preferably 1 to 200 parts by weight, more preferably 3 to 180 parts by weight based on 100 parts by weight of the polymer [A]. . If the amount of the polymerizable unsaturated compound (B) is less than 1 part by weight, developing residues may occur at the time of development. On the other hand, when the amount of the polymerizable unsaturated compound is more than 200 parts by weight, the adhesiveness of the spacer obtained 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 polymerizable unsaturated compound [B] by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, charged particle beam, or X-ray. It includes.

As such a [C] radiation sensitive polymerization initiator, a 0-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 xanthone type A 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 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.-ylcarbazol-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, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-benzo Ate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6 -(1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O- benzoate, 1- [9-butyl-6- (2-ethyl Benzoyl) -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.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, etc. are mentioned.

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-0-acetate is preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof. By using a 0-acyl oxime compound in this invention, it becomes possible to obtain the spacer which has sufficient sensitivity and adhesiveness even in the exposure amount of 1,200 J / m <^2> or less.

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-hydroxycyclohexylphenyl ketone, and the like. Moreover, as said (alpha)-amino ketone type compound, 2-methyl-1- (4-methylthio phenyl) -2-morpholino propane- 1-one, 2-benzyl-2- dimethylamino-1- ( 4-morpholinophenyl) -butan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned. Examples of the compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

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

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'-tetra Phenyl-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 amino sensitizers may be used alone or in combination of two or more thereof.

Moreover, when using a biimidazole type compound and an amino sensitizer together, a thiol type compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino-based sensitizer to generate imidazole radicals, but the high polymerization initiation capacity is not expressed as it is, and the spacer obtained is in an undesirable shape such as an inverse taper shape. There are many cases. However, by adding a thiol-based compound to a system in which a biimidazole-based compound and an amino-based sensitizer coexist, the hydrogen radical from the thiol-based compound is donated 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 amount of the [C] polymerization initiator to be used is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 30 parts by weight based on 100 parts by weight of the [A] polymer. If it is less than 0.05 part by weight, the developing residual film ratio may be insufficient at the time of development, while if it exceeds 30 parts by weight, the shape of the spacer obtained tends to be damaged.

In the radiation-sensitive resin composition of the present invention, the use ratio of other radiation-sensitive polymerization initiators 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. In this case, 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, it is 1-1 with respect to 100 weight part of biimidazole type compounds. 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 1-20 with respect to 100 weight part of biimidazole type compounds. 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 of the thiol compound is more than 50 parts by weight, the shape of the obtained spacer tends to be damaged.

-additive-

In addition to the said component, additives, such as surfactant, an adhesion | attachment adjuvant, a storage stabilizer, and a heat resistance improving agent, can also be mix | blended with the radiation sensitive resin composition of this invention as needed in the range which does not impair the desired effect of this invention.

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

As said fluorine-type surfactant, the compound which has a fluoroalkyl group or a fluoroalkylene group in at least any 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 glycol di (1,1,2,2- Tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (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-hexa Fluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, perfluoro-n-dodecylsulfonic acid sodium fluoro Sodium alkylbenzenesulfonate, sodium fluoroalkylphosphonate, sodium fluoroalkylcarboxylic acid, fluoroalkylpolyoxye Len ether, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoro Alkyl alkoxylate, fluorine-type alkyl ester, etc. are mentioned.

In addition, as a commercial item of a fluorine-type surfactant, for example, BM-1000, the same 1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191, copper F471 , East F476 (above, Dai Nippon Ink Chemical Co., Ltd.), Florade FC170C, East FC-171, East FC-430, East FC-431 (above, Sumitomo 3M Co., Ltd.), Saffron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, S SC-105, copper SC-106 (above, manufactured by Asahi Glass Co., Ltd.), F-top EF301, copper EF303, copper EF352 (more, manufactured by Kasei Kasei Co., Ltd.), pgentant FT-100, copper FT-110 , FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S Neo product) etc. can be mentioned.

As said silicone type surfactant, it is a commercial item, For example, Toray silicone DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ- 6032, SF-8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, copper-4300, copper-4445, copper-4446, copper-4460 And 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; Nonionic surfactants, such as polyoxyethylene dialkyl esters, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and a commercial item, are brand name, for example, KP341 (made by Shin-Etsu Chemical Co., Ltd.). , Polyflow 57, the 95 (Kyoesha Chemical Co., Ltd. product) etc. are mentioned.

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

The blending amount of the surfactant is preferably 5 parts by weight or less, 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 gas, 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, and an epoxy group, is mentioned, for example. More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyl Trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

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 polymers [A]. 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, nitronitrosol 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 blending amount of the storage stabilizer is preferably 3 parts by weight or less, and more preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polymer [A]. 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, N- (alkoxymethyl) melamine compounds, and the like.

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, etc. are mentioned.

Among these N- (alkoxymethyl) melamine compounds, especially N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable, and as a commercial item thereof, for example by brand name, Nikarak N-2702, 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 polymers [A]. 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. Alcohol, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, from the viewpoint of solubility of each component, reactivity with each component, and ease of coating film formation, Dipropylene glycol alkyl ether, alkyl alkoxypropionate, acetate ester, etc. are preferable, and benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butylether acetate, diethylene glycol monoethyl ether Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, acetic acid 2-methoxy on The like 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, dioxalic acid 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 described above may be used after filtration using a Millipore filter having a pore size of about 0.5 μm.

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 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.

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 apply | coating a radiation sensitive resin composition on this transparent conductive film as a composition solution, it forms a film by heating (prebaking) a coating surface.

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 made of plastic 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 made of tin oxide (SnO ₂ ) (registered trademark of PPG, USA), an ITO film made of indium tin oxide (In ₂ O ₃ -SnO ₂ ), and the like. Can be used.

As a coating method of a composition solution, although suitable methods, such as the spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet coating method, can be employ | adopted, for example, spin The coating method and the slit die coating method are preferable.

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

Instead of the coating method, a dry film method may be employed to form a coating.

When using the dry film method, the said dry film is what laminates the photosensitive layer which consists of the photosensitive resin composition of this invention on a base film, Preferably a flexible base film (henceforth "photosensitive dry film"). .

The photosensitive dry film may be formed by laminating a photosensitive layer by coating the photosensitive resin composition of the present invention on the base film as a liquid composition, and then drying. As a base film of a photosensitive dry film, the film of synthetic resins, such as polyethylene terephthalate (PET), polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. The thickness of the base film is suitably in the range of 15 to 125 mu m. As for the thickness of the photosensitive layer obtained, about 1-30 micrometers is preferable.

In addition, a photosensitive dry film can also be laminated | stacked and preserve | saved further on the photosensitive layer at the time of nonuse. This cover film does not need to be peeled off when not in use, and needs to have appropriate release property so that it can be easily peeled off when used. As a cover film which satisfies such conditions, the film which apply | coated or baked the silicone type mold release agent to the surface of synthetic resin films, such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, and a polyurethane film, for example Can be used. As for the thickness of a cover film, about 5-30 micrometers is preferable normally. As these cover films, two or three layers can be laminated | stacked and used as needed.

-(B) process-

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

As radiation used for exposure, visible light, an ultraviolet-ray, an ultraviolet ray, an electron beam, X-rays, etc. can be used, for example, Although radiation whose wavelength is 190-450 nm is preferable, especially the ultraviolet-ray of 365 nm is included. Radiation is preferred.

The exposure dose is a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) of the intensity of the exposed radiation at a wavelength of 365 nm, preferably 100 to 10,000 J / m ^2, but the radiation of the present invention The exposure resin composition can use the exposure amount of 1,200 J / m <^2> or less, for example, can form a desired pattern also in the exposure amount of 500-1,200 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, n-propylamine; Aliphatic secondary amines such as diethylamine, di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine, 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, quinoline; Alkanolamines such as ethanoldimethylamine, methyldiethanolamine, triethanolamine; The aqueous solution of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, is mentioned.

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

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

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

-(D) process-

Subsequently, the obtained pattern is heated at a predetermined temperature, for example, 80 to 160 ° C. for a predetermined time, for example, on a hot plate for 5 to 30 minutes by a heating device such as a hot plate or an oven, for example, 30 to 180 in an oven. For a minute, a predetermined spacer can be obtained by heating (postbaking).

In the conventional radiation-sensitive resin composition used for formation of the spacer, the obtained spacer cannot exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to about 200 ° C. or higher, but in the radiation-sensitive resin composition of the present invention, the heating temperature is increased. It can be made at a lower temperature than before, and as a result, a spacer excellent in various performances such as compressive strength, rubbing resistance at the time of liquid crystal alignment, adhesion with a transparent substrate, and the like can be formed without causing yellowing or deformation of the resin substrate.

Liquid crystal display device

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 color filter layer and a spacer are formed on a transparent substrate, and two alignment films arrange | positioned through a liquid crystal layer, opposing transparent electrodes, and opposing The structure which has a transparent substrate etc. to mention is mentioned. Moreover, as shown in FIG. 1, you may form a protective film on a polarizing plate or a color filter layer as needed.

In addition, as shown in FIG. 2, a color filter layer and a spacer are formed on a transparent substrate, and it can also be set as a TN-TFT type liquid crystal display element by opposing a thin-film transistor (TFT) array through an alignment film and a liquid crystal layer. 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 high sensitivity and high resolution, and a sufficient pattern shape is obtained even at an exposure amount of 1,200 J / m ² or less, and excellent in elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, and the like. The liquid crystal display element spacer can be formed, and post-baking temperature after development at the time of spacer formation can be lowered, and yellowing and deformation of the resin substrate are not caused.

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

<Example>

EMBODIMENT OF THE INVENTION Hereinafter, embodiment is given and embodiment of this invention is described more concretely. Where parts and% are by 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 added, followed by 18 parts of methacrylic acid and tricyclo methacrylate [5.2.1.0 ^{2 , 6]} decan-8-one (30 parts), and then 5 parts of styrene, 5 parts of butadiene, methacrylic acid, 6-hydroxy-hexyl ester 25 parts, methacrylic acid tetrahydro-furan-2-one In 17 parts, and purged with nitrogen The copolymer [α-1] solution having a solid content concentration of 27.5% by raising the temperature of the solution to 80 ° C. and gradually maintaining the temperature for 4 hours, then raising the temperature to 100 ° C., then maintaining the temperature for 1 hour and polymerization. Got.

It was 14,000 when Mw was measured about the obtained copolymer [(alpha-1)] using GPC (gel permeation chromatography) HLC-8020 (brand name, Tosoh Corporation make).

Subsequently, after adding 14 parts of 2-methacryloyloxyethyl isocyanate (brand name Carens MOI, the Showa Denko Co., Ltd. product), and 0.08 part of 4-methoxyphenol to the said copolymer [α-1] solution, The reaction was stirred at 2 ° C. for 2 hours. Progress of reaction of the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group of the copolymer [α-1] was confirmed by IR (infrared absorption) spectrum. IR spectra of the polymer solution [α-1], the solution after 1 hour reaction and the solution after 2 hour reaction at 60 ° C. are shown in Figs. 3, 4 and 5, respectively. As the reaction proceeded, it was confirmed that the peak around 2,270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate decreased. [A] polymer solution of 30.5% of solid content concentration was obtained. This polymer [A] is called a polymer (A-1).

Synthesis Example 2

After adding 14 parts of 2-acryloyloxyethyl isocyanate (brand name Carenz AOI, the Showa Denko Co., Ltd. product) and 0.08 part of 4-methoxy phenol to 100 parts of said copolymer [alpha-1] solutions, 60 degreeC It stirred for 2 hours and made it react, and the polymer solution [A] of 30.5% of solid content concentration was obtained. This polymer [A] is called a polymer (A-2).

Synthesis Example 3

7.5 parts of 2,2'- azobisisobutyronitrile, 100 parts of 3-methoxybutyl acetate, and 100 parts of propylene glycol monomethyl ether acetate were added to the flask equipped with a cooling tube and a stirrer, followed by 18 parts of methacrylic acid, meta Tricyclo acrylate [5.2.1.0 ^2,6 ] decane-8-yl 30 parts, styrene 5 parts, butadiene 5 parts, 2- (6-hydroxyhexanoyloxy) ethyl ester (trade name PLACCEL FM1D 25 parts of Kogyo Co., Ltd.) and 17 parts of tetrahydrofuran-2-yl methacrylate were added thereto, and after nitrogen substitution, the temperature of the solution was raised to 80 ° C. while gradually stirring to maintain this temperature for 4 hours. Then, the mixture was raised to 100 ° C. and maintained at this temperature for 1 hour to obtain a copolymer [α-2] solution having a solid content concentration of 33.0%.

Mw was 15,000 when the obtained copolymer [α-2] was measured using GPC.

Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the solution of the copolymer [α-2] in the same manner as in Synthesis example 1. In the same manner as in Synthesis example 1, reaction of an isocyanate group and a copolymer was confirmed by IR spectrum. [A] polymer solution of 35.0% of solid content concentration was obtained. This polymer [A] is called a polymer (A-3).

Synthesis Example 4

2-acryloyloxyethyl isocyanate was reacted with 100 parts of the copolymer [α-2] solution in the same manner as in Synthesis example 2 to obtain a polymer solution [A] having a solid content concentration of 35.0%. This polymer [A] is called a polymer (A-4).

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate were added, followed by 18 parts of methacrylic acid and tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl 30 parts, styrene 5 parts, butadiene 5 parts, methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester and methacrylic acid 25 parts of a mixture of 2-hydroxyethyl ester (brand name HEMAC1 (manufactured by Daicel Chemical Industries, Ltd.)) and 17 parts of tetrahydrofuran-2-yl methacrylate were added thereto, and after nitrogen substitution, the solution was slowly stirred. The temperature was raised to 80 ° C. to maintain this temperature for 4 hours, then to 100 ° C., and then maintained at this temperature for 1 hour to polymerize to obtain a copolymer [α-3] solution having a solid content concentration of 28.2%.

Mw was 15,000 when the obtained copolymer [α-3] was measured using GPC.

Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-3] solution in the same manner as in Synthesis example 1. In the same manner as in Synthesis example 1, reaction of an isocyanate group and a copolymer was confirmed by IR spectrum. [A] polymer solution of 31.0% of solid content concentration was obtained. This polymer [A] is called a polymer (A-5).

Synthesis Example 6

2-acryloyloxyethyl isocyanate was reacted with 100 parts of the copolymer [α-3] solution in the same manner as in Synthesis example 2 to obtain a polymer solution [A] having a solid content concentration of 31.0%. This polymer [A] is called a polymer (A-6).

Synthesis Example 7

To a flask equipped with a cooling tube and a stirrer, 5 parts of 2,2'-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate were added, followed by 18 parts of methacrylic acid and tricyclo methacrylate [5.2.1.0 ^{2 , 6} ] decane-8-yl 10 parts, styrene 5 parts, butadiene 5 parts, methacrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester 25 parts, methacrylic acid tetrahydrofuran-2-yl 37 parts were added, and after nitrogen-substituting, the temperature of a solution was raised to 80 degreeC, stirring gradually, this temperature was kept for 4 hours, and it raised to 100 degreeC after that, and this temperature was maintained for 1 hour and superposed | polymerized, and solid content concentration 28.2% Copolymer [α-4] was obtained.

Mw was 17,000 when the obtained copolymer [α-4] was measured using GPC.

Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the solution of the copolymer [α-4] in the same manner as in Synthesis example 1. In the same manner as in Synthesis example 1, reaction of an isocyanate group and a copolymer was confirmed by IR spectrum. [A] polymer solution of 32.0% of solid content concentration was obtained. This polymer [A] is called a polymer (A-7).

Synthesis Example 8

2-acryloyloxyethyl isocyanate was reacted with 100 parts of the copolymer [α-4] solution in the same manner as in Synthesis example 2 to obtain a polymer solution [A] having a solid content concentration of 32.0%. This polymer [A] is called a polymer (A-8).

Synthesis Example 9

5 parts of 2,2'-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 18 parts of methacrylic acid and tricyclo methacrylate [5.2.1.0 ^{2 , 6]} decan-8-one (10 parts), and then 5 parts of styrene, 5 parts of butadiene, methacrylic acid 2-hydroxyethyl ester, 25 parts of methacrylic acid tetrahydro-furan-2-one In 37 parts, and purged with nitrogen The temperature of the solution was raised to 80 DEG C while gradually stirring, and the temperature was maintained for 4 hours. Then, the temperature was increased to 100 DEG C, and then maintained at this temperature for 1 hour to polymerize, thereby obtaining a copolymer [α-5] solution having a solid content concentration of 28.8%. Got.

Mw was 17,000 when the obtained copolymer [α-5] was measured using GPC.

Next, 2-methacryloyloxyethyl isocyanate was reacted with the solution of the copolymer [α-5] in the same manner as in Synthesis example 1. In the same manner as in Synthesis example 1, reaction of an isocyanate group and a copolymer was confirmed by IR spectrum. [A] polymer solution of 32.0% of solid content concentration was obtained. This polymer [A] is called a polymer (A-9).

Synthesis Example 10

2-acryloyloxyethyl isocyanate was reacted with 100 parts of the copolymer [α-5] solution in the same manner as in Synthesis example 2 to obtain a polymer solution [A] having a solid content concentration of 32.0%. This polymer [A] is called a polymer (A-10).

Synthesis Example 11

7.5 parts of 2,2'- azobisisobutyronitrile, 100 parts of 3-methoxybutyl acetate, and 100 parts of propylene glycol monomethyl ether acetate were added to the flask equipped with a cooling tube and a stirrer, followed by 18 parts of methacrylic acid, meta Tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl 30 parts, styrene 5 parts, butadiene 5 parts, methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester and methacrylic acid 2- 25 parts of mixtures with a hydroxyethyl ester (brand name PLACCEL FM1D (manufactured by Daicel Chemical Industries, Ltd.), 17 parts of tetrahydrofuran-2-yl methacrylate) were added thereto, and after nitrogen substitution, the solution was gradually stirred. The temperature was raised to 80 ° C. to maintain this temperature for 4 hours, then to 100 ° C., and then maintained at this temperature for 1 hour to polymerize to obtain a copolymer [α-6] solution having a solid content concentration of 33.5%.

Mw was 16,000 when the obtained copolymer [α-6] was measured using GPC.

Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the solution of the copolymer [α-6] in the same manner as in Synthesis example 1. In the same manner as in Synthesis example 1, reaction of an isocyanate group and a copolymer was confirmed by IR spectrum. [A] polymer solution of 36.0% of solid content concentration was obtained. This polymer [A] is called a polymer (A-11).

Example 1

Preparation of Composition Solution

The polymer solution [A] obtained in Synthesis Example 1 as the component [A] was 100 parts as the polymer (A-1) and dipentaerythritol hexaacrylate (trade name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) as the component [B]. ) 80 parts, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate as a [C] component CGI-242, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one 10 parts of Cure 379, manufactured by Ciba Specialty Chemicals Co., Ltd., 5 parts of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, 0.5 parts of FTX-218 (trade name, manufactured by Neos) as a surfactant, and storage 0.5 parts of 4-methoxyphenol was mixed as a stabilizer, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30%, and then filtered through a Millipore filter having a pore size of 0.5 µm for the composition. A liquid was prepared.

(1) evaluation of sensitivity

After the said composition solution was apply | coated using the spinner on the alkali free glass substrate with an ITO film | membrane, it prebaked for 3 minutes on the 90 degreeC hotplate, and formed the film of 4.0 micrometers in thickness.

Subsequently, the obtained film was exposed by changing the exposure time by the ultraviolet-ray whose intensity | strength at 365 nm is 250 W / m <^2> through the photomask of the residual pattern of 15 micrometers ring. Then, after developing at 25 degreeC for 60 second with 0.05 weight% aqueous solution of potassium hydroxide, it wash | cleaned for 1 minute with pure water, and also heated for 60 minutes in 220 degreeC oven, and formed the spacer. At this time, the minimum exposure amount whose residual film rate after development (film thickness after development x 100 / initial film thickness. When this exposure amount is 1,200 J / m <^2> or less, it can be said that a sensitivity is favorable.

(2) evaluation of resolution

In the above "(1) Sensitivity Evaluation", a photomask having a line-and-space pattern of various sizes is used as the photomask, and the exposure amount is set to an exposure amount corresponding to the sensitivity determined in "(1) Sensitivity Evaluation". The pattern was formed on the board | substrate similarly except having carried out. At this time, the resolution of the minimum pattern size resolved was called resolution.

(3) formation of spacers

A spacer having a height of 3.5 µm was formed in the same manner as in the above "(1) Sensitivity Evaluation" except that the exposure amount was set to an exposure amount corresponding to the sensitivity determined in "(1) Sensitivity Evaluation".

(4) Evaluation of Cross-sectional Shape

The cross-sectional shape of the obtained spacer was observed with the scanning electron microscope, and it evaluated by which of A-D shown in FIG. At this time, as in A or B, when the pattern edge is a forward taper or vertical shape, it can be said that a cross-sectional shape is favorable. On the other hand, as shown in C, when the sensitivity is insufficient, the residual film ratio is low, the cross-sectional dimension is small compared to A and B, and the bottom is a planar semiconvex lens image, the cross-sectional shape is poor, and as shown in D, Likewise, even in the case of the reverse taper shape (the reverse triangular shape in which the side of the film surface is longer than the side of the substrate in the cross-sectional shape), the cross-sectional shape is poor because the possibility of the pattern peeling off during the subsequent rubbing treatment becomes very large.

(5) evaluation of compression characteristics

With respect to the obtained spacer, using a micro compression tester (trade name FISCHER SCOPE H100C, manufactured by Fischer Instruments), the load speed and the load removal rate were both 2.6 mN / sec and 50 mN by a planar indenter having a diameter of 50 µm. After the load was kept for 5 seconds and the load was removed, the load-strain curve at the time of the load and the load-strain curve at the time of the load removal were prepared. At this time, as shown in Fig. 7, the difference between the deformation amount at the load 50 mN and the deformation amount at the load 5 mN is L1, and the deformation amount at the load 50 mN and the load 5 mN at the time of removing the load is L1. Assuming that the difference with the deformation amount is L2, the elastic recovery rate was calculated by the following equation.

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

In addition, when L1 is large, it can be said that there is flexibility.

(6) Evaluation of rubbing resistance and adhesion

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

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

(7) evaluation of heat resistance

Except not using a photomask, a cured film was formed in the same manner as the formation of the spacer, and then heated in an oven at 240 ° C. for 60 minutes to measure the film thickness before and after heating, and the remaining film ratio (film thickness after heating × 100 / Initial film thickness).

Examples 2 to 22 and Comparative Examples 1 to 7

Each component shown in Table 1 of Example 1 was made into 5 parts of gamma-glycidoxy propyl trimethoxysilane as an adhesion | attachment adjuvant, 0.5 parts of FTX-218 as a surfactant, and 0.5 parts of 4-methoxyphenol as a storage stabilizer, The mixture was dissolved, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30%, and filtered through a Millipore filter having a pore size of 0.5 µm to prepare a composition solution. Thereafter, a spacer was formed in the same manner as in Example 1, and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 23

A patterned thin film was formed in the same manner as in Examples 1 to 22, except that the coating film was manufactured by the dry film method of the liquid composition (S-23) of the radiation-sensitive resin composition instead of applying the film using a spinner. Evaluated. 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. In addition, the evaluation results of the following transferability are also shown in Table 2.

Preparation and transfer of a dry film were performed as follows.

A liquid composition (S-1) of the radiation-sensitive resin composition was applied onto a polyethylene terephthalate (PET) film having a thickness of 38 μm using an applicator, and the coating film was heated at 100 ° C. for 5 minutes to provide radiation of 4 μm thickness. The dry film (J-1) was produced. Next, the radiation sensitive transfer dry film was laminated so that the surface of the radiation sensitive transfer layer could contact the surface of the glass substrate, and the radiation sensitive dry film (J-1) was transferred to the glass substrate by thermocompression bonding.

-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 was able to be uniformly transferred onto the glass substrate was indicated by "o", partially leaving the dry film on the base film or the glass substrate. The case where the dry film was not able to be transferred uniformly on the glass substrate, such as the dry film was not in close contact, was referred to as "x".

Example 24

A radiation sensitive dry film (J-2) was prepared in the same manner as in Example 23 except that the liquid composition of the radiation sensitive resin composition shown in Table 1 was used instead of the liquid composition of the radiation sensitive resin composition used in Example 23. Evaluation was made after preparation. 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.

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)

[C] component

C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate (trade name CGI-242, Ciba ㆍ Specialty Chemicals Co., Ltd.)

C-2: 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-0- acetate

C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one (brand name Irugacure 907, the product made by Ciba specialty chemicals company)

C-4: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (brand name Irugacure 379, the Ciba specialty chemicals company make) )

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

The radiation-sensitive resin composition of the present invention has a high sensitivity and a sufficient spacer shape is obtained even at an exposure amount of 1,200 J / m ² or less, and has excellent flexibility and high recovery rate, rubbing resistance, adhesion to a transparent substrate, heat resistance, and the like. Can be formed.

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

Claims (7)

(a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides, (a2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by formulas (1) to (4), and (a3) unsaturated compounds other than (a1) and (a2) The polymer obtained by making the copolymer of react with the isocyanate compound represented by following formula (5). <Formula 1>

(In formula, R represents a hydrogen atom or a methyl group, and a is an integer of 5 or more.) <Formula 2>

(In formula, R represents a hydrogen atom or a methyl group, and b and c are the integers of 1-12 each independently.) <Formula 3>

(Wherein R represents a hydrogen atom or a methyl group, and d and e each independently represent an integer of 1 to 12.) <Formula 4>

(Wherein R represents a hydrogen atom or a methyl group, f and g each independently represent an integer of 0 to 6, and W has any of the alicyclic structures represented by the following formulas (I) to (IV)): It represents a divalent group.)

<Formula 5>

(In formula, R represents a hydrogen atom or a methyl group, h is an integer of 1-12.) The compound according to claim 1, which is selected from the group consisting of (a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides, and (a2) hydroxyl group-containing unsaturated compounds represented by each of the formulas (1) to (1). A method for producing a polymer comprising reacting an isocyanate compound represented by the formula (5) according to claim 1 with a copolymer of at least one compound and unsaturated compounds other than (a3) (a1) and (a2). [A] A radiation sensitive resin composition comprising the polymer according to claim 1, a [B] polymerizable unsaturated compound and a [C] radiation sensitive polymerization initiator. The radiation sensitive resin composition used for formation of the spacer for liquid crystal display elements containing the radiation sensitive resin composition of Claim 3. The liquid crystal display element spacer formed from the radiation sensitive resin composition of Claim 3. At least (A) process of forming the film of the radiation sensitive resin composition of Claim 3 on a board | substrate, (B) exposing to at least a portion of the film; (C) developing the film after exposure; and (D) heating the film after development It comprises in the order described above, The method for forming a spacer for a liquid crystal display element. The liquid crystal display element provided with the spacer of Claim 5.

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