JP2007084809A - Polymer having unsaturated side chain, radiation-sensitive resin composition and spacer for liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having high sensitivity, forming a sufficient spacer form even by the exposure rate of ≤1,200 J/m<SP>2</SP>and giving a spacer for a liquid crystal display element having excellent softness, high recovery rate, rubbing resistance, adhesiveness to a transparent substrate, heat resistance, etc. <P>SOLUTION: The radiation-sensitive resin composition contains a polymer produced by reacting an isocyanate compound to a copolymer of (a1) an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride, (a2) a hydroxy-containing unsaturated compound containing one hydroxy group in the molecule and (a3) an unsaturated compound other than the compounds (a1) and (a2). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a side chain unsaturated polymer, particularly suitable for forming a spacer in a liquid crystal display device, a radiation-sensitive resin composition containing the polymer, a spacer, a method for forming the spacer, and a liquid crystal display device.

Conventionally, spacers such as glass beads and plastic beads having a predetermined particle diameter have been used for liquid crystal display elements in order to keep the distance (cell gap) between two substrates constant. Is randomly distributed on a transparent substrate such as a glass substrate, so if there is a spacer in the pixel formation area, the spacer will be reflected, or the incident light will be scattered and the contrast of the liquid crystal display element will be reduced. There was a problem to do.
Therefore, in order to solve such a problem, a method of forming a spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate, exposed to, for example, ultraviolet rays through a predetermined mask, and then developed to form a dot-like or stripe-like spacer. Since the spacer can be formed only at a predetermined place other than the above, the above-described problem is basically solved.

In recent years, the mother glass substrate has been increased in size (for example, about 1,500 × 1,800 mm, further about 1,870 × 2,200 mm) from the viewpoint of increasing the area of the liquid crystal display element and improving productivity. . However, with the conventional substrate size, the substrate size is smaller than the mask size, so it was possible to cope with the batch exposure method. However, with a large substrate, it is almost impossible to produce a mask size comparable to this substrate size. It is possible, and it is difficult to cope with the batch exposure method.
Therefore, a step exposure method has been proposed as an exposure method that can be applied to a large substrate. However, in the step exposure method, since a single substrate is exposed several times, and each exposure requires time for alignment and step movement, reduction of throughput is regarded as a problem compared to the batch exposure method. .
Further, in the batch exposure method, an exposure amount of about 3,000 J / m ² is possible, but in the step exposure method, it is necessary to lower the exposure amount each time, and the conventional exposure method used for forming the spacer is used. In the radiation sensitive resin composition, it has been difficult to achieve a sufficient spacer shape and film thickness with an exposure amount of 1,200 J / m ² or less.

Further, from the viewpoint of improving productivity, a process technique “ODF (One Drop Fill) method” in which a liquid crystal material is put on the glass surface before the glass of the liquid crystal panel is laminated is introduced.
This approach can save a lot of time. For example, in the conventional method, it takes about 5 days to fill the liquid crystal for a 30-inch panel. However, if the ODF method is introduced, only 2 hours are required, and the productivity can be greatly improved.
In the conventional bonding method, since a load is applied when the TFT array and the color filter are bonded together, the spacer is pressed evenly by the load, and the height uniformity of the spacer is maintained. However, in the ODF method, the initial bonding load is smaller than the conventional method because the bonding is performed only by the load due to the weight of the substrate and the atmospheric pressure. Therefore, even if the spacer is pushed with a small load, it is important to develop height uniformity by being pushed evenly. For this purpose, the flexibility of the spacer is required. If the height of the spacer is not uniform, the cell gap cannot be kept uniform, causing a gap in the cell and causing display unevenness. Therefore, a spacer material having both flexibility due to compressive load and a high recovery rate is required.

In Patent Document 1, the photosensitive resin composition has, as a structural unit, a photopolymerizable functional group obtained by reacting a (meth) acryloyloxyalkyl isocyanate compound with a copolymerizable resin having an imide group and a hydroxyl group. It has been disclosed that the use of a copolymerizable resin can achieve improved performance as a spacer, such as higher sensitivity and higher recovery rate. However, no consideration is given to flexibility.
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. In addition to increasing the recovery rate and increasing the recovery rate, it cannot be said that it is a material that gives a spacer having more flexibility.
JP 2003-173025 A

Therefore, the object of the present invention is to obtain a sufficient spacer shape with high sensitivity and an exposure amount of 1,200 J / m ² or less, flexibility and high recovery rate, rubbing resistance, adhesion to a transparent substrate, and heat resistance. It is providing the radiation sensitive resin composition which can form the spacer for liquid crystal display elements excellent in these.

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

  Still another object of the present invention is to provide a liquid crystal display spacer formed from the above radiation sensitive resin composition and a liquid crystal display element including the same.

  Still another object of the present invention is to provide a method for forming the above-mentioned liquid crystal display spacer.

According to the present invention, the problem is firstly
(A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by the following formulas (1) to (4), and (a3) other unsaturation other than (a1) and (a2) This is achieved by a polymer obtained by reacting an isocyanate compound represented by the following formula (5) with a copolymer of the compound (hereinafter referred to as “[A] polymer”).

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

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

(In the formula, R represents a hydrogen atom or a methyl group, and d and e are each independently an integer of 1 to 12.)

(In the formula, R represents a hydrogen atom or a methyl group, f and g are each independently an integer of 0 to 6, and W is an alicyclic structure represented by each of the following formulas (I) to (IV)). A divalent group having any of

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

According to the present invention, the problem is secondly,
It is achieved by a radiation sensitive resin composition comprising [A] a polymer, [B] a polymerizable unsaturated compound, and [C] a radiation sensitive polymerization initiator.

According to the present invention, the problem is thirdly,
This is achieved by a radiation-sensitive resin composition (hereinafter referred to as “a radiation-sensitive resin composition for spacers for liquid crystal display elements”) used for forming a spacer for liquid crystal display elements, comprising the radiation-sensitive resin composition.

According to the present invention, the problem is fourthly,
This is achieved by a liquid crystal display element spacer formed from a radiation-sensitive resin composition for a liquid crystal display element spacer.

According to the present invention, fifthly, the problem is as follows:
This is achieved by a method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a coating of a radiation sensitive resin composition for spacers for liquid crystal display elements on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.

According to the present invention, the object is achieved sixth by a liquid crystal display device comprising the liquid crystal display device spacer.

The radiation-sensitive resin composition of the present invention has high sensitivity and high resolution, and a sufficient pattern shape can be obtained even with an exposure amount of 1,200 J / m ² or less. Elastic recovery, rubbing resistance, adhesion to a transparent substrate It is possible to form spacers for liquid crystal display elements with excellent heat resistance, etc., and at the time of spacer formation, the post-baking temperature after development can be lowered, which can cause yellowing or deformation of the resin substrate. Absent.
The liquid crystal display element of the present invention comprises a spacer having excellent performance such as pattern shape, elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, etc., and expresses high reliability over a long period of time. be able to.

Hereinafter, the present invention will be described in detail.
Radiation-sensitive resin composition- [A] polymer-
The polymer of the present invention comprises (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, and (a2) a hydroxyl group-containing unsaturated compound represented by each of the above formulas (1) to (4). A copolymer (hereinafter referred to as “copolymer [α]”) composed of at least one selected compound and other unsaturated compounds other than (a3), (a1), and (a2) is represented by the above formula (5). ) (Hereinafter referred to as “unsaturated isocyanate compound (5)”), and a polymer (hereinafter referred to as “[A] polymer”).
Among the components constituting the copolymer [α], (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter these are collectively referred to as “(a1) unsaturated carboxylic acid compound”. ), 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, itaconic acid;
The anhydride of the said dicarboxylic acid etc. can be mentioned.
Among these (a1) unsaturated carboxylic acid-based compounds, copolymerization reactivity, solubility of the resulting [A] polymer in an alkaline developer, and easy availability, acrylic acid, methacrylic acid, 2- Methacryloyloxyethyl hexahydrophthalic acid is preferred.

In the copolymer [α], the (a1) unsaturated carboxylic acid compound can be used alone or in admixture of two or more.
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 based on the copolymer [α]. % By weight, particularly preferably 10 to 30% by weight. (A1) If the content of the repeating unit derived from the unsaturated carboxylic acid compound is less than 1% by weight, the solubility of the polymer obtained by the reaction with the unsaturated isocyanate compound (5) in an alkaline developer is lowered. On the other hand, if it exceeds 50% by weight, the solubility of the polymer in an alkaline developer may be too high.

Moreover, (a2) As a hydroxyl-containing unsaturated compound chosen from the group which consists of an unsaturated compound represented by each of said Formula (1)-(4), for example, as a compound represented by said Formula (1) Are acrylic acid 5-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 hydroxyalkyl esters such as acrylic acid 11-hydroxyundecyl ester, acrylic acid 12-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 10-hydroxydecyl ester, methacrylic acid Examples include 11-hydroxyundecyl ester and methacrylic acid hydroxyalkyl ester such as methacrylic acid 12-hydroxydodecyl ester.

Examples of the compound represented by the formula (2) include acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, acrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, and acrylic acid 4 Acrylic acid (6-hydroxy such as 6- (6-hydroxyhexanoyloxy) butyl ester, acrylic acid 5- (6-hydroxyhexanoyloxy) pentyl ester, acrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester Hexanoyloxy) alkyl ester;
Methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, methacrylic acid 3- (6-hydroxyhexanoyloxy) propyl ester, methacrylic acid 4- (6-hydroxyhexanoyloxy) butyl ester, methacrylic acid 5- ( Mention may be made of methacrylic acid (6-hydroxyhexanoyloxy) alkyl esters such as 6-hydroxyhexanoyloxy) pentyl ester and methacrylic acid 6- (6-hydroxyhexanoyloxy) hexyl ester.
Moreover, as a commercial item of the mixture of (meth) acrylic acid (6-hydroxyhexanoyloxy) alkyl ester and methacrylic acid 2-hydroxyethyl ester, it is a brand name and PLACEL FM1D and FM2D (made by Daicel Chemical Industries Ltd.). Etc.

Examples of the compound represented by the formula (3) include acrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester and 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-2,2-dimethyl) Acrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) such as -propoxycarbonyloxy) -pentyl ester, acrylic acid 6- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -hexyl ester -Alkyl esters,
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-propoxycarbonyloxy) -pentyl ester, methacrylic acid 6- (3-hydroxy And methacrylic acid (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -alkyl ester such as -2,2-dimethyl-propoxycarbonyloxy) -hexyl ester.
Moreover, 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, HEMAC1 (Daicel Chemical Industries) For example).

Furthermore, examples of the compound represented by the formula (4) include acrylic acid 4-hydroxy-cyclohexyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, and acrylic acid. 3-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, Acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept-5-en-2-ylethyl ester, 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl acrylate Esters, acrylic acid 2-hydroxy-octahydro-4,7-methano-inden-5-yl esters, 2-hydroxymethyl-octahydro-4,7-methano-inden-5-ylmethyl ester, 2-hydroxyethyl-octahydro-4,7-methano-inden-5-ylethyl acrylate, acrylic acid 3- Hydroxyalkyl acrylates having an alicyclic structure such as hydroxy-adamantan-1-yl ester, 3-hydroxymethyl-adamantan-1-ylmethyl acrylate, 3-hydroxyethyl-adamantan-1-ylethyl acrylate ester;
Methacrylic acid 4-hydroxy-cyclohexyl ester, Methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Methacrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, Methacrylic acid 3-hydroxy-bicyclo [2.2.1] Hept-5-ene 2-yl ester, methacrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, methacrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept- 5-En-2-ylethyl ester, methacrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, methacrylic acid 2-hydroxy-octahydro-4,7-methano-indene -5-yl ester, 2-hydroxymethyl methacrylate-octahi B, 7-Methano-inden-5-ylmethyl ester, 2-hydroxyethyl methacrylate-octahydro-4,7-methano-inden-5-ylethyl ester, 3-hydroxy-adamantan-1-yl methacrylate Methacrylic acid hydroxyalkyl esters having an alicyclic structure such as esters, methacrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, methacrylic acid 3-hydroxyethyl-adamantan-1-ylethyl ester;

  Among these hydroxyl group-containing unsaturated compounds represented by the above formulas (1) to (4), from the viewpoint of copolymerization reactivity and reactivity with isocyanate compounds, acrylic acid 6-hydroxyhexyl ester, methacrylic acid 6-hydroxyhexyl ester, 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 Methyl-cyclohex Methyl ester, acrylic acid 3-hydroxymethyl - adamantan-1-yl methyl ester, methacrylic acid 3-hydroxymethyl - adamantan-1-yl methyl ester, and the like are preferable.

In the copolymer [α], the hydroxyl group-containing unsaturated compound (a2) can be used alone or in admixture of two or more.
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 3, based on the copolymer [α]. It is 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 10 to 30% by weight. (A2) If the content of the repeating unit derived from the hydroxyl group-containing unsaturated compound is less than 1% by weight, the introduction rate of the unsaturated isocyanate compound (5) into the polymer tends to decrease, and the sensitivity tends to decrease. On the other hand, when it exceeds 50% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (5) tends to be lowered.

Moreover, as (a3) other unsaturated compounds, 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;
Acrylic epoxies such as glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate (Cyclo) alkyl esters;
Methacrylic acid epoxy (cyclo) alkyl esters such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;

Glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl or aralkyl esters of acrylic acid such as phenyl acrylate, benzyl acrylate;
Aryl or aralkyl esters of methacrylic acid such as phenyl methacrylate or benzyl methacrylate;
Acrylic acid hydroxyalkyl esters such as acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, 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, diethyl itaconate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylate esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these (a3) other unsaturated compounds, n-butyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid, from the viewpoint of copolymerization reactivity and solubility of the obtained [A] polymer in an alkaline aqueous solution. Preferred are benzyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like.

In the copolymer [α], (a3) other unsaturated compounds can be used alone or in admixture of two or more.
In the copolymer [α], (a3) the content of repeating units derived from other unsaturated compounds is preferably 10 to 70% by weight, more preferably 20 to 60%, based on the copolymer [α]. % By weight, particularly preferably 30 to 50% by weight. (A3) When the content of the repeating unit derived from another unsaturated compound is less than 10% by weight, the storage stability of the polymer obtained by the reaction with the unsaturated isocyanate compound (5) tends to decrease, If it exceeds 70% by weight, the solubility of the polymer in an alkaline developer tends to be lowered. Further, when (meth) acrylic acid epoxy (cyclo) alkyl esters are used, the content is preferably 10% by weight or less, and if it is 10% by weight or more, the storage stability tends to decrease.
The copolymer [α] may be prepared by, for example, using (a1) an unsaturated carboxylic acid compound, (a2) a hydroxyl group-containing unsaturated compound, and (a3) another unsaturated compound as a radical polymerization initiator in a suitable solvent. It can be produced by polymerizing in the presence.

As the solvent used for the polymerization, for example,
Ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;
Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate;
Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;
Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,
Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, 4-methoxybutyl acetate, 3-methoxybutyl acetate, acetic acid 2 -Methoxybutyl, 3-ethoxybutyl acetate, 3-proxybutyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2-methyl Ethyl propionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, n-butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, Ethoxy methoxyacetate, n-propyl methoxyacetate Pill, n-butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, n-propyl ethoxy acetate, n-butyl ethoxy acetate, methyl n-propoxyacetate, ethyl n-propoxyacetate, n-propoxyacetate n-propyl, n- Other esters such as n-butyl propoxyacetate, methyl n-butoxyacetate, ethyl n-butoxyacetate, n-butoxyacetate, n-butyloxybutoxyacetate and the like can be mentioned.

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

In addition, the radical polymerization initiator is not particularly limited. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 , 2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane And organic peroxides such as hydrogen peroxide.
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The copolymer [α] thus obtained may be used as it is in the production of the [A] polymer, or once separated from the solution and used in the production of the [A] polymer.
The polystyrene equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer [α] by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50, 000. In this case, if the Mw is less than 2,000, there is a risk that the alkali developability, the remaining film ratio, etc. of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. If it exceeds 1, the resolution may be reduced, or the pattern shape may be impaired.

The [A] polymer in the present invention can be obtained by reacting the unsaturated isocyanate compound (5) with the copolymer [α].
As unsaturated isocyanate compound (5), for example,
Acrylic acid derivatives such as 2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyloxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyloxydecyl isocyanate;
Mention may be made of methacrylic acid derivatives such as 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, 10-methacryloyloxydecyl isocyanate. it can.
Moreover, as a commercial item of 2-acryloyloxyethyl isocyanate, it is a trade name, Karenz AOI (made by Showa Denko KK), and as a commercial item of 2-methacryloyloxyethyl isocyanate, it is a brand name, Karenz MOI (Showa Denko) (Made by Co., Ltd.).

Of these unsaturated isocyanate compounds (5), 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and the like are preferable from the viewpoint of reactivity with the copolymer [α].
[A] In the polymer, the unsaturated isocyanate compound (5) can be used alone or in admixture of two or more.

  In the present invention, the reaction between the copolymer [α] and the unsaturated isocyanate compound (5) is carried out, for example, by a catalyst such as di-n-butyltin (IV) dilaurate or a polymerization inhibitor such as p-methoxyphenol. The unsaturated isocyanate compound (5) can be added to the copolymer [α] solution containing, while stirring at room temperature or under heating.

  [A] The amount of the unsaturated isocyanate compound (5) used in producing the polymer is the amount of the (a2) hydroxyl group-containing unsaturated compound in the copolymer [α], or (a3) other unsaturated compounds. When a compound containing a hydroxyl group is used as the compound, it is preferably 0.1 to 90% by weight, more preferably 10 to 80%, based on the total amount of the amount and the amount of the (a2) hydroxyl group-containing unsaturated compound. % By weight, particularly preferably 25 to 75% by weight. When the amount of the unsaturated isocyanate compound (5) used is less than 0.1% by weight, the effect of improving the sensitivity and elastic properties is small. On the other hand, when it exceeds 90% by weight, the unreacted unsaturated isocyanate compound (5) Remain and the storage stability of the resulting polymer solution and radiation-sensitive resin composition tends to decrease.

[A] The polymer has a carboxyl group and / or a carboxylic anhydride group and a polymerizable unsaturated bond, has an appropriate solubility in an alkali developer, and is used in combination with a special curing agent. Can be easily cured by heating, and [A] the radiation-sensitive resin composition containing the polymer has a predetermined-shaped spacer without developing residue and film loss during development. It can be formed easily.
The radiation-sensitive resin composition of the present invention contains [A] a polymer, [B] a polymerizable unsaturated compound, and [C] a radiation-sensitive polymerization initiator as essential components.

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

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3- Examples include methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, and ω-carboxypolycaprolactone monoacrylate. In addition, as commercial products, for example, Aronix M-101, M-111, M-114, M-5300 ( KAYARAD TC-110S, TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.); Biscote 158, 2311 (above, made by Osaka Organic Chemical Co., Ltd.), etc. Can be mentioned.

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6- Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, etc. Moreover, as a commercial item, it is a brand name, for example, Aronix M-210, M-240, M-6200 (above, east Synthetic Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.), Biscote 260, 312, 335HP (Osaka Organic Chemical Co., Ltd.) And the like.

  Furthermore, as the trifunctional or higher functional (meth) acrylic acid ester, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, linear alkylene Group and alicyclic structure, and having two or more isocyanate groups Polyfunctional urethane acrylate compound obtained by reacting a compound with a compound having one or more hydroxyl groups in the molecule and having three, four or five acryloyloxy groups and / or methacryloyloxy groups Etc.

  Commercially available products of tri- or higher functional (meth) acrylic acid esters are trade names, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M -8030, M-8060, TO-1450, TO-1382 (manufactured by Toa Gosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.) and polyfunctional urethane acrylate New frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.), KAYAARAD DPHA-40H (Nippon Kayaku Co., Ltd.) And the like.

Among these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, trifunctional or higher functional (meth) acrylic acid esters are more preferable, and in particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and commercial products containing polyfunctional urethane acrylate compounds are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters can be used alone or in admixture of two or more.
In the radiation sensitive resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound used is preferably 1 to 200 parts by weight, more preferably 3 to 180 parts per 100 parts by weight of the [A] polymer. Parts by weight. [B] If the amount of the polymerizable unsaturated compound used is less than 1 part by weight, there may be a residual image during development. On the other hand, if it exceeds 200 parts by weight, the adhesion of the resulting spacer tends to decrease.

-[C] Radiation sensitive polymerization initiator-
[C] Radiation sensitive polymerization initiator generates [B] active species capable of initiating polymerization of polymerizable unsaturated compounds upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray. It consists of the component to do.
Examples of such [C] radiation sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples include xanthone compounds, phosphine compounds, triazine compounds, and the like.

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

Of these O-acyloxime 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 is preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more. In the present invention, the use of an O-acyloxime compound makes it possible to obtain a spacer having sufficient sensitivity and adhesion even with an exposure amount of 1,200 J / m ² or less.

Examples of the acetophenone compound include an α-hydroxyketone compound and an α-aminoketone compound.
Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -On, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like can be mentioned. Examples of the α-aminoketone compound include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). ) -Butan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one, etc., and other compounds Examples thereof include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.
Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-Morpholinophenyl) -butan-1-one is preferred.
In the present invention, the sensitivity, spacer shape and compressive strength can be further improved by using an acetophenone compound in combination.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole. 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2-bromophenyl)- , 4 ′, 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 and the like can be mentioned. .

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

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

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

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

The amount of the [C] polymerization initiator used in the radiation sensitive resin composition of the present invention is preferably 0.05 to 30 parts by weight, more preferably 0.1 to 100 parts by weight of the [A] polymer. -30 parts by weight. If the amount is less than 0.05 parts by weight, the residual film ratio may be insufficient during development, whereas if it exceeds 30 parts by weight, the shape of the resulting spacer may be impaired.
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 with respect to 100 parts by weight of the total radiation-sensitive polymerization initiator. Part or less, particularly preferably 60 parts by weight or less. In this case, if the use ratio of the other radiation-sensitive polymerization initiator exceeds 100 parts by weight, the intended effect of the present invention may be impaired.

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

-Additives-
In the radiation-sensitive resin composition of the present invention, a surfactant, an adhesion assistant, a storage stabilizer, a heat resistance, in addition to the above components, if necessary, within a range that does not impair the intended effect of the present invention. Additives such as property improvers can also be blended.
The said surfactant is a component which has the effect | action which improves coating property, and a fluorine-type surfactant and a silicone type surfactant are preferable.

  The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group at at least one of the terminal, main chain and side chain, and specific examples thereof include 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- Nethyl) ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, Sodium perfluoro-n-dodecyl sulfonate, sodium fluoroalkylbenzene sulfonate, sodium fluoroalkyl phosphonate, sodium fluoroalkyl carboxylate, fluoroalkyl polyoxyethylene ether, diglycerin tetrakis (fluoroalkyl polyoxyethylene ether), fluoroalkyl Ammonium iodide, fluoroalkyl betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, fluorine alkyl ester and the like can be mentioned.

  Moreover, as a commercial item of a fluorine-type surfactant, it is a brand name, for example, BM-1000, the same -1100 (above, the product made from BM CHEMIE), MegaFuck F142D, the same F172, the same F173, the same F183, the same F178. F191, F471, F476 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC 170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M Limited) ), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-103 104, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), F-top EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), lid Agent FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, manufactured by Neos Co., Ltd.) and the like.

  The silicone-based surfactant is a commercially available product, for example, Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193. SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, -4300, -4445, -4446 -4460, -4442 (above, manufactured by GE Toshiba Silicone Co., Ltd.), and the like.

Furthermore, as surfactants other than the above, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dilaurate and polyoxyethylene dialkyl esters such as polyoxyethylene distearate, and commercially available products under the trade name, for example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
The surfactants can be used alone or in admixture of two or more.

  The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the polymer [A]. When the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening tends to occur during coating.

The adhesion assistant is a component having an effect of further improving the adhesion between the spacer and the substrate, and a functional silane coupling agent is preferable.
Examples of the functional silane coupling agent include compounds having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group. More specifically, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like can be mentioned.
These adhesion assistants can be used alone or in admixture of two or more.

  The blending amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue tends to occur.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenyl. Examples include hydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.

  The blending amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, with respect to 100 parts by weight of the [A] polymer. When the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity may be lowered and the pattern shape may be impaired.

  Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.

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

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′. , N ″, N ″ -hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N , N ′, N ′, N ″, N ″ -hexa (t-butoxymethyl) melamine and the like.
Among these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is particularly preferable. For example, Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.
The heat resistance improvers can be used alone or in admixture of two or more.
The blending amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. When the blending amount of the heat resistance improver exceeds 30 parts by weight, the storage stability of the radiation sensitive resin composition tends to be lowered.

The radiation-sensitive resin composition of the present invention is preferably used as a composition solution dissolved in an appropriate solvent.
As the solvent, a solvent that dissolves each component constituting the radiation-sensitive resin composition uniformly, does not react with each component, and has appropriate volatility is used. From the viewpoints of solubility of each component, reactivity with each component, and ease of film formation, alcohol, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, Propylene glycol alkyl ether, alkoxypropionate alkyl, acetic acid ester and the like are preferable, and 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 Le, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In the present invention, a high boiling point solvent may be used in combination with the solvent.
Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, Examples thereof include ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.
These high boiling point solvents can be used alone or in admixture of two or more.

In addition, the composition solution prepared as described above can be filtered for use with a Millipore filter or the like having a pore diameter of about 0.5 μm.
Especially the radiation sensitive resin composition of this invention can be used very suitably for formation of the spacer for liquid crystal display elements.

Method of forming spacers Next, a method of forming a spacer of the present invention will be described with reference to radiation-sensitive resin composition of the present invention.
The spacer forming method of the present invention includes at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition of the present invention on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.
Hereinafter, each of these steps will be described sequentially.

-(I) Process-
A transparent conductive film is formed on one surface of a transparent substrate, and a radiation-sensitive resin composition is applied onto the transparent conductive film, preferably as a composition solution, and then the coated surface is heated (prebaked) to form a coating film. Form.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, a glass substrate such as soda lime glass and alkali-free glass; polyethylene terephthalate, polybutylene terephthalate, Examples thereof include a resin substrate made of a plastic such as polyethersulfone, polycarbonate, and polyimide.
Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of US PPG) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used.
As a coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method can be employed. However, the spin coating method and the slit die coating method are particularly preferable.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., Preferably it is about 1 to 15 minutes at 70-120 degreeC.
Moreover, it can replace with the said coating method and can also employ | adopt a dry film method, and can also form coating | cover.
When the dry film method is employed, the dry film is formed by laminating a photosensitive layer comprising the photosensitive resin composition of the present invention on a base film, preferably a flexible base film (hereinafter referred to as “ It is referred to as a “photosensitive dry film”.

The photosensitive dry film can be formed by laminating a photosensitive layer on the base film by applying the photosensitive resin composition of the present invention, preferably as a liquid composition, and then drying. As a base film of the photosensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.
Moreover, the photosensitive dry film can also be preserve | saved by laminating | stacking a cover film on the photosensitive layer at the time of unused. This cover film needs to have an appropriate releasability so that it does not peel off when not in use and can be easily peeled off when in use. As a cover film satisfying such conditions, for example, a film obtained by applying or baking a silicone mold release agent on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polyurethane film is used. can do. The thickness of the cover film is usually preferably about 5 to 30 μm. As these cover films, two or three layers can be laminated as required.

-(B) Process-
Next, at least a part of the formed film is exposed. In this case, when exposing a part of the film, the exposure is usually performed through a photomask having a predetermined pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. However, radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly radiation containing 365 nm ultraviolet light. Is preferred.
The exposure amount is preferably 100 to 10,000 J / m ² as a value obtained by measuring the intensity of the exposed radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI OpticalAssociates Inc.). The radiation sensitive resin composition can be used even at an exposure amount of 1,200 J / m ² or less, and for example, a desired pattern can be formed even at an exposure amount of 500 to 1,200 J / m ² .

-(C) Process-
Subsequently, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
The developer used for development is preferably an alkali developer, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine, n- Aliphatic primary amines such as propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole, piperidine and N-methyl Alicyclic tertiary amines such as piperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene; pyridine , Aromatic tertiary amines such as collidine, lutidine, quinoline; Examples include aqueous solutions of alkaline compounds such as ethanoldimethylamine, methyldiethanolamine, alkanolamines such as triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

In addition, an appropriate 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.
As the developing method, for example, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is preferably about 10 to 180 seconds.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

-(2) Process-
Next, the obtained pattern is heated at a predetermined temperature, for example, 80 to 160 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, for 30 to 180 minutes in the oven, by a heating device such as a hot plate or an oven. A predetermined spacer can be obtained by heating (post-baking).
The conventional radiation-sensitive resin composition used for the formation of the spacer cannot obtain sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 ° C. or higher. In the radiation-sensitive resin composition, the heating temperature can be made lower than before, and as a result, without causing yellowing or deformation of the resin substrate, compressive strength, rubbing resistance during liquid crystal alignment, adhesion to the transparent substrate It is possible to form a spacer excellent in various properties such as properties.

Liquid crystal display element The liquid crystal display element of the present invention comprises the spacer of the present invention formed as described above.
The structure of the liquid crystal element of the present invention is not particularly limited. For example, as shown in FIG. 1, a color filter layer and a spacer are formed on a transparent substrate, and the liquid crystal element 2 is disposed via the liquid crystal layer. A structure having two alignment films, opposing transparent electrodes, opposing transparent substrates, and the like can be given. 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 are opposed to a thin film transistor (TFT) array through an alignment film and a liquid crystal layer, whereby a TN-TFT type liquid crystal display. It can also be an element. Also in this case, a protective film may be formed on the polarizing plate or the color filter layer as necessary.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, parts and% are based on weight.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobisisobutyronitrile and 250 parts of 3-methoxybutyl acetate, followed by 18 parts of methacrylic acid and tricyclomethacrylate [5.2. 1.0 ^2,6 ] 30 parts of decan-8-yl, 5 parts of styrene, 5 parts of butadiene, 25 parts of 6-hydroxyhexyl methacrylate and 17 parts of tetrahydrofuran-2-yl methacrylate While stirring gently, the temperature of the solution is raised to 80 ° C., this temperature is kept for 4 hours, then raised to 100 ° C., and this temperature is kept for 1 hour to polymerize, whereby the solid content concentration becomes 27. A 5% copolymer [α-1] solution was obtained.
For the obtained copolymer [α-1], Mw was 14,000 as measured using GPC (gel permeation chromatography) HLC-8020 (trade name, manufactured by Tosoh Corporation). .
Subsequently, 14 parts of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.08 part of 4-methoxyphenol were added to the copolymer [α-1] solution, and then 60 parts. The reaction was stirred for 2 hours at ° C. The progress of the reaction between 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 at 60 ° C., and the solution after 2 hours reaction are shown in FIG. 3, FIG. 4 and FIG. 5, respectively. It was confirmed that the peak near 2,270 cm ⁻¹ derived from the isocyanate group of 2-methacryloyloxyethyl isocyanate decreased with the progress of the reaction. A [A] polymer solution having a solid concentration of 30.5% was obtained. Let this [A] polymer be a polymer (A-1).

Synthesis example 2
After adding 14 parts of 2-acryloyloxyethyl isocyanate (trade name Karenz AOI, Showa Denko KK) and 0.08 part of 4-methoxyphenol to 100 parts of the copolymer [α-1] solution, 60 parts are obtained. By stirring and reacting at 2 ° C. for 2 hours, a [A] polymer solution having a solid content concentration of 30.5% was obtained. This [A] polymer is referred to as polymer (A-2).

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7.5 parts of 2,2′-azobisisobutyronitrile, 100 parts of 3-methoxybutyl acetate and 100 parts of propylene glycol monomethyl ether acetate, followed by methacrylic acid 18 Parts, 30 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 5 parts of styrene, 5 parts of butadiene, 2- (6-hydroxyhexanoyloxy) ethyl methacrylate (trade name) After charging 25 parts of PLACCEL FM1D (manufactured by Daicel Chemical Industries, Ltd.) and 17 parts of tetrahydrofuran-2-yl methacrylate, the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was increased. Is kept for 4 hours and then raised to 100 ° C., and this temperature is kept for 1 hour for polymerization to obtain a solid content concentration. A 33.0% copolymer [α-2] solution was obtained.
When the obtained copolymer [α-2] was measured using GPC, Mw was 15,000.
Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-2] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. An [A] polymer solution having a solid content concentration of 35.0% was obtained. Let this [A] polymer be a polymer (A-3).

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

Synthesis example 5
In a flask equipped with a condenser and a stirrer, 5 parts of 2,2′-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate were charged, followed by 18 parts of methacrylic acid, tricyclomethacrylate [5.2. 1.0 ^2,6 ] 30 parts decan-8-yl, 5 parts styrene, 5 parts butadiene, methacrylic acid 2- (3-hydroxy-2,2-dimethyl-propoxycarbonyloxy) -ethyl ester and methacrylic acid 2 -Hydroxyethyl ester mixture (trade name HEMAC1 (manufactured by Daicel Chemical Industries, Ltd.) 25 parts, tetrahydrofuran-2-yl methacrylate 17 parts were charged, and after nitrogen substitution, the temperature of the solution was adjusted while gently stirring. Increase to 80 ° C and hold this temperature for 4 hours, then increase to 100 ° C and hold this temperature for 1 hour. The copolymer [α-3] solution having a solid content concentration of 28.2% was obtained by polymerization.
When the obtained copolymer [α-3] was measured using GPC, Mw was 15,000.
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, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. A [A] polymer solution having a solid concentration of 31.0% was obtained. Let this [A] polymer be a polymer (A-5).

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

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate, followed by 18 parts of methacrylic acid and tricyclomethacrylate [5.2. 1.0 ^2.6 ] 10 parts decan-8-yl, 5 parts styrene, 5 parts butadiene, 25 parts 3-hydroxymethyl-adamantan-1-yl methyl ester methacrylate, 37 parts tetrahydrofuran-2-yl methacrylate After charging and replacing with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring, and this temperature is maintained for 4 hours, then raised to 100 ° C., and this temperature is maintained for 1 hour for polymerization. As a result, a copolymer [α-4] solution having a solid concentration of 28.2% was obtained.
When the obtained copolymer [α-4] was measured using GPC, Mw was 17,000.
Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-4] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. A [A] polymer solution having a solid content concentration of 32.0% was obtained. This [A] polymer is referred to as a polymer (A-7).

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

Synthesis Example 9
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobisisobutyronitrile and 250 parts of propylene glycol monomethyl ether acetate, followed by 18 parts of methacrylic acid and tricyclomethacrylate [5.2. 1.0 ^2.6 ] 10 parts decan-8-yl, 5 parts styrene, 5 parts butadiene, 25 parts 2-methacrylic acid 2-hydroxyethyl ester, 37 parts tetrahydrofuran-2-yl methacrylate, and nitrogen-substituted While stirring gently, the temperature of the solution is raised to 80 ° C., this temperature is kept for 4 hours, then raised to 100 ° C., and this temperature is kept for 1 hour to polymerize, whereby a solid concentration of 28. An 8% copolymer [α-5] solution was obtained.
When the obtained copolymer [α-5] was measured using GPC, Mw was 17,000.

Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-5] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. A [A] polymer solution having a solid content concentration of 32.0% was obtained. This [A] polymer is referred to as a polymer (A-9).
Synthesis Example 10
In the same manner as in Synthesis Example 2, 100 parts of the copolymer [α-5] solution was reacted with 2-acryloyloxyethyl isocyanate to obtain an [A] polymer solution having a solid content concentration of 32.0%. This [A] polymer is referred to as a polymer (A-10).

Synthesis Example 11
A flask equipped with a condenser and a stirrer was charged with 7.5 parts of 2,2′-azobisisobutyronitrile, 100 parts of 3-methoxybutyl acetate and 100 parts of propylene glycol monomethyl ether acetate, followed by methacrylic acid 18 Parts, 30 parts of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 5 parts of styrene, 5 parts of butadiene, 2- (6-hydroxyhexanoyloxy) ethyl methacrylate and methacrylic acid A mixture with 2-hydroxyethyl ester (trade name PLACEL FM1D (manufactured by Daicel Chemical Industries)), 17 parts of tetrahydrofuran-2-yl methacrylate, charged with nitrogen, and then gently stirred while stirring. The temperature of this is raised to 80 ° C, this temperature is maintained for 4 hours, and then raised to 100 ° C. The copolymer [α-6] solution having a solid content concentration of 33.5% was obtained by polymerization while maintaining the temperature of 1 hour.
When the obtained copolymer [α-6] was measured using GPC, Mw was 16,000.
Subsequently, 2-methacryloyloxyethyl isocyanate was reacted with the copolymer [α-6] solution in the same manner as in Synthesis Example 1. In the same manner as in Synthesis Example 1, the reaction between the isocyanate group and the copolymer was confirmed by IR spectrum. An [A] polymer solution having a solid content concentration of 36.0% was obtained. This [A] polymer is referred to as polymer (A-11).

Example 1
Preparation of Composition Solution As component [A], 100 parts of polymer solution [A] obtained in Synthesis Example 1 was used as polymer (A-1), and dipentaerystol hexaacrylate (trade name as component [B]. KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.) 80 parts, [C] component, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals), 2- (4-methylbenzoyl) -2- (dimethylamino) ) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals), γ-glycidoxypropyltrimethoxysilane 5 as an adhesion aid Part, 0.5 part FTX-218 (trade name, manufactured by Neos Co., Ltd.) as a surfactant and 0.5 part 4-methoxyphenol as a storage stabilizer are mixed to a solid content concentration of 30%. Thus, it melt | dissolved in propylene glycol monomethyl ether acetate, Then, it filtered with the Millipore filter with the hole diameter of 0.5 micrometer, and prepared the composition solution.

(1) Evaluation of sensitivity After applying the composition solution on a non-alkali glass substrate with an ITO film using a spinner, pre-baking on a hot plate at 90 ° C. for 3 minutes to form a film having a film thickness of 4.0 μm. Formed.
Next, the obtained film was exposed with ultraviolet light having an intensity of 365 W / m ² at 365 nm through a photomask having a 15 μm round pattern, leaving the exposure time as a variable. Thereafter, development was performed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by washing with pure water for 1 minute, and further heating in an oven at 220 ° C. for 60 minutes to form a spacer. At this time, the minimum exposure amount at which the remaining film ratio after development (film thickness after development × 100 / initial film thickness; the same applies hereinafter) is 90% or more was defined as sensitivity. When this exposure amount is 1,200 J / m ² or less, it can be said that the sensitivity is good.

(2) Resolution Evaluation In the above “(1) Sensitivity Evaluation”, a photomask having a line and space pattern of various sizes is used as a photomask, and the exposure amount is “(1) Sensitivity Evaluation”. A pattern was formed on the substrate in the same manner except that the exposure amount corresponding to the determined sensitivity was used. The minimum pattern size resolved at this time was taken as the resolution.

(3) Formation of spacer In the above “(1) Evaluation of sensitivity”, the exposure amount was set in the same manner except that the exposure amount was equivalent to the sensitivity determined in “(1) Evaluation of sensitivity”. A 5 μm spacer was formed.

(4) Evaluation of cross-sectional shape The cross-sectional shape of the obtained spacer was observed with a scanning electron microscope and evaluated according to which of A to D shown in FIG. At this time, when the pattern edge is forward tapered or vertical like A or B, it can be said that the cross-sectional shape is good. On the other hand, as shown in C, when the sensitivity is insufficient, the remaining film rate is low, the cross-sectional dimension is small compared to A and B, and the bottom surface is a semi-convex lens shape with a flat surface, the cross-sectional shape is Also, as shown in D, the pattern may be peeled off during the subsequent rubbing process even in the case of an inversely tapered shape (in the cross-sectional shape, an inverted triangular shape in which the side of the film surface is longer than the side on the substrate side). Since it became very large, the cross-sectional shape was regarded as defective.

(5) Evaluation of compression characteristics About the obtained spacer, using a micro compression tester (trade name: FISCHER SCOPE H100C, manufactured by Fisher Instruments Co., Ltd.), a flat indenter with a diameter of 50 μm was used to adjust the loading speed and unloading speed. In both cases, the load was set to 2.6 mN / sec, and a load up to 50 mN was applied and held for 5 seconds, followed by unloading, and a load-deformation curve and a load-deformation curve during unloading were created. At this time, as shown in FIG. 7, the difference between the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN is L1, and the deformation amount at the load of 50 mN and the deformation amount at the load of 5 mN at unloading. The elastic recovery rate was calculated by the following formula, with the difference from
Elastic recovery rate (%) = L2 × 100 / L1
Moreover, if L1 is large, it can be said that there is flexibility.

(6) Evaluation of rubbing resistance and adhesion After applying AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent to a substrate on which a spacer is formed with a printing machine for applying a liquid crystal aligning film, 180 ° C. for 1 hour. It dried and formed the coating film of the liquid crystal aligning agent with a film thickness of 0.05 micrometer.
Thereafter, the coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a polyamide cloth was wound, with a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern shaving or peeling was evaluated.

(7) Evaluation of heat resistance A cured film was formed in the same manner as the spacer formation except that no photomask was used, and then heated in an oven at 240 ° C for 60 minutes, and the film thickness before and after heating was measured. The remaining film ratio (film thickness after heating × 100 / initial film thickness) was evaluated.

Examples 2 to 22 and Comparative Examples 1 to 7
In Example 1, each component shown in Table 1 was used as an adhesion assistant, 5 parts of γ-glycidoxypropyltrimethoxysilane, as a surfactant, 0.5 part of FTX-218, and as a storage stabilizer, 4 parts. -It mixed with 0.5 parts of methoxyphenol, 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 to prepare a composition solution. Thereafter, evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 23
Instead of coating using a spinner, evaluation was performed in the same manner as in Examples 1 to 22, except that the liquid composition of the radiation-sensitive resin composition shown in Table 1 was formed by a dry film method. . Each component is shown in Table 1. The base film was peeled and removed before the exposure process. The evaluation results are shown in Table 2. Table 2 also shows the evaluation results of the following transferability.

Dry film preparation and transfer were performed as follows.
On a 38 μm thick polyethylene terephthalate (PET) base film, a liquid composition (S-1) of a radiation sensitive resin composition was applied using an applicator, and the coating film was heated at 100 ° C. for 5 minutes to obtain a thickness. A 4 μm radiation-sensitive dry film (J-1) was produced. Next, the radiation-sensitive transfer dry film is superposed on the surface of the glass substrate so that the surface of the radiation-sensitive transfer layer is in contact, and the radiation-sensitive dry film (J-1) is laminated on the glass substrate by a thermocompression bonding method. Transcribed to.

-Evaluation of transferability of dry film to glass substrate-
When the radiation sensitive dry film is transferred onto the glass substrate by the thermocompression bonding method, the case where the dry film can be uniformly transferred onto the glass substrate is `` ○ '', and the dry film partially remains on the base film, The case where the dry film could not be uniformly transferred onto the glass substrate, such as when the dry film did not adhere to the glass substrate, was designated as “x”.

Example 24
Radiation sensitivity 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. After producing a dry film (J-2), it was evaluated. Each component is shown in Table 1. The evaluation results are shown in Table 2. Table 2 also shows the evaluation results of transferability.

In Table 1, each component other than the polymer is as follows.
[B] Component B-1: Dipentaerystol hexaacrylate (trade name KAYARAD DPHA)
B-2: Commercial product containing a polyfunctional urethane acrylate compound (trade name KAYARAD DPHA-40H)
[C] component C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name CGI-242, manufactured by Ciba Specialty Chemicals)
C-2: 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name Irgacure 907, Ciba Specialty Chemicals)
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

It is a schematic diagram which shows an example of the structure of a liquid crystal display element. It is a schematic diagram which shows the other example of the structure of a liquid crystal display element. 2 is an infrared spectrum diagram of a polymer solution [α-1] in Synthesis Example 1. FIG. It is an infrared spectrum figure of the solution after reaction at 60 degreeC of the polymer solution [(alpha) -1] for 1 hour. The infrared spectrum figure of the solution after reaction at 60 degreeC of the polymer solution [(alpha) -1] for 2 hours. It is a schematic diagram which illustrates the cross-sectional shape of a spacer. It is a figure which illustrates the load-deformation amount curve at the time of the load in evaluation of an elastic recovery factor, and a slow load.

Claims (7)

(A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) at least one compound selected from the group consisting of hydroxyl-containing unsaturated compounds represented by the following formulas (1) to (4), and (a3) other impurities other than (a1) and (a2) A polymer obtained by reacting a saturated compound copolymer with an isocyanate compound represented by the following formula (5).

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

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

(In the formula, R represents a hydrogen atom or a methyl group, and d and e are each independently an integer of 1 to 12.)

(In the formula, R represents a hydrogen atom or a methyl group, f and g are each independently an integer of 0 to 6, and W is an alicyclic structure represented by each of the following formulas (I) to (IV)). A divalent group having any of

(In the formula, R represents a hydrogen atom or a methyl group, and h is an integer of 1 to 12.)   (A1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) at least one compound selected from the group consisting of hydroxyl group-containing unsaturated compounds represented by the above formulas (1) to (4) And (a3) a copolymer of an unsaturated compound other than (a1) and (a2) is reacted with an isocyanate compound represented by the above formula (5). A method for producing a polymer.   [A] A radiation-sensitive resin composition comprising the polymer according to claim 1, [B] a polymerizable unsaturated compound, and [C] a radiation-sensitive polymerization initiator.   The radiation sensitive resin composition used for formation of the spacer for liquid crystal display elements which consists of a radiation sensitive resin composition of Claim 3.   The spacer for liquid crystal display elements formed from the radiation sensitive resin composition of Claim 3. A method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a film of the radiation-sensitive resin composition according to claim 3 on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.     A liquid crystal display device comprising the spacer according to claim 5.

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