JP2009258652A - Radiation-sensitive resin composition, spacer and production method of the same, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having an extremely little amount of a volatile component generated upon forming a spacer, and capable of responding to high-speed coating by a slit die coating method. <P>SOLUTION: The radiation-sensitive resin composition contains: [A] a polymer having at least one group selected from carboxyl groups and carboxylic acid anhydride groups, and a group derived from a specified polyvalent thiol compound represented by pentaerythritol tetrakis(3-mercaptopropionate), and having a ratio (Mw/Mn) of 1.0 to 2.8, which is a ratio of a weight average molecular weight (Mw) in terms of polystyrene to a number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography; [B] a polymerizable unsaturated compound; and [C] a radiation-sensitive polymerization initiator. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, a spacer, a method for producing the same, and a liquid crystal display device. More specifically, a radiation-sensitive resin composition suitable as a material for forming a spacer used in a display element such as a liquid crystal display panel or a touch panel, a display element spacer formed from the composition, and the spacer. The present invention relates to a liquid crystal display element.

Conventionally, spacer particles 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. Since these spacer particles are randomly distributed on a transparent substrate such as a glass substrate, if the spacer particles are present in the pixel formation region, the spacer particles may be reflected or incident light may be scattered, There was a problem that the contrast was lowered.
In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate to form a film, and the film is exposed to ultraviolet rays through a predetermined mask and then developed to form dot-like or stripe-like spacers. Since the spacer can be formed only at a predetermined place other than the pixel formation region, the above-described problem has been basically solved.
In recent years, the size of a mother glass substrate has been increased from about 680 × 880 mm to about 1,500 × 1,800 mm from the viewpoint of increasing the area of liquid crystal display elements and improving productivity. Usually, the production process of a liquid crystal display element is performed by applying a radiation-sensitive resin composition for spacer formation to a transparent substrate, baking on a hot plate to remove the solvent, and then exposing and developing to form a spacer. Yes. However, as the substrate size increases, the volatile components in the radiation-sensitive resin composition volatilize during the formation of the spacer, and the problem of contaminating the baking furnace and photomask causes a decrease in production tact and an increase in production cost. Has been a concern.

Moreover, when apply | coating a radiation sensitive resin composition to the large sized board | substrate after the 5th generation, although the slit-die application | coating method is used, the shortening of application | coating time is calculated | required from a viewpoint of production tact shortening. In order to shorten the coating time, it is necessary to increase the coating speed, but when the coating speed is increased, streaky coating unevenness often occurs on the coating surface. Therefore, there is a strong demand for the development of a radiation sensitive resin composition that does not cause coating unevenness even when the coating speed is increased.
In order to solve the above-mentioned problems, the applicant has already been able to suppress contamination of a baking furnace or an exposure mask due to sublimation of the photopolymerization initiator by adding a specific photopolymerization initiator to Patent Document 1. Show. Patent Document 2 shows that by defining the relationship between the viscosity of the radiation-sensitive resin composition and the solid content concentration, a coating film having a uniform thickness and no unevenness can be obtained in the slit die coating method. Yes. However, due to the recent demand for further improvement in production tact and reduction in production cost, the amount of volatile components generated during spacer formation is smaller than in the past, and the radiation-sensitive resin composition can be used for high-speed coating by the slit die coating method. Development of is strongly desired.

JP 2005-234362 A JP 2006-184841 A

Accordingly, an object of the present invention is to provide a radiation-sensitive resin composition that has an extremely small amount of volatile components generated during spacer formation and that can be applied to high-speed coating by a slit die coating method.
Another object of the present invention is to provide a spacer formed from the radiation-sensitive resin composition, a method for producing the same, and a liquid crystal display device excellent in display quality.
Still other objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages are firstly:
[A] At least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the following formula (1)

(In the formula (1), R ^I is a methylene group, an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, —CO—, —O—CO— ^* (where “*” is The bond attached to R ^I ) or —NHCO— ^* (where the bond attached with “*” binds to R ^I ), and n is an integer of 2 to 10 and X Is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or n is 3 and X is the following formula (2)

(In Formula (2), each R ^II independently represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond.)
The “+” represents a bond. )
The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is 1.0 to A polymer which is 2.8,
[B] It is achieved by a radiation-sensitive resin composition containing a polymerizable unsaturated compound and [C] a radiation-sensitive polymerization initiator.
According to the present invention, the above objects and advantages are secondly
This is achieved by a method for manufacturing a spacer for a display element including at least the following steps in the order described below.
(A) a step of forming a film of the radiation-sensitive resin composition,
(B) exposing at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development.
According to the present invention, the above objects and advantages are thirdly:
This is achieved by a display element spacer produced from the radiation-sensitive resin composition.
According to the present invention, the above objects and advantages are achieved by a liquid crystal display device comprising the spacer.

  The radiation-sensitive resin composition of the present invention has a very small amount of volatile components generated during the production of spacers, and can cause streaky unevenness in the resulting coating even when high-speed coating by a slit die coating method is employed. Absent. In addition, the radiation-sensitive resin composition of the present invention is highly sensitive and can produce a display element spacer having a sufficient remaining film ratio even with a low exposure amount.

Hereinafter, the present invention will be described in detail.
<Radiation sensitive resin composition>
The radiation-sensitive resin composition of the present invention comprises at least one group selected from the group consisting of at least [A] carboxyl group and carboxylic anhydride group, and an n-valent group represented by the above formula (1). And a ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is 1.0 to 2.8 ( Hereinafter referred to as “polymer [A]”).
[B] A polymerizable unsaturated compound (hereinafter referred to as “polymerizable compound [B]”) and [C] a radiation-sensitive polymerization initiator are contained.

[Polymer [A]]
The polymer [A] contained in the radiation-sensitive resin composition of the present invention is:
It has at least one group selected from the group consisting of a carboxyl group and a carboxylic acid anhydride group, and an n-valent group represented by the above formula (1).
The alkylene group having 2 to 10 carbon atoms ^{R I} in formula (1), preferably an alkylene group having 2 to 6 carbon atoms, 2 to 6 carbon atoms straight-chain alkylene group or the following formula (3)

(In Formula (3), R ^III is a methylene group or a linear alkylene group having 2 to 4 carbon atoms, and a bond marked with “*” is bonded to S.)
The group represented by these is preferable. The alkyl methylene group having 2 to 10 carbon atoms R ^I, the following formula (4)

The group represented by these is preferable.
Y in the formula (1) is preferably —O—CO— ^* (where a bond marked with “*” is bonded to R ^I ).
N in the above formula (1) is preferably an integer of 2 to 8, more preferably an integer of 2 to 6 or 8, and further preferably 2, 3, 4, 6 or 8. .
In the above formula (1), when n is 2, X is, for example, a linear or branched alkylene group having 2 to 10 carbon atoms, the following formula (5)

(Wherein (in ^{5), R IV} are each hydrogen atom or a methyl group, m1 is an integer of from 1 to 20, "*", respectively, indicating that a bond.)
A divalent group represented by:
X in the case where n is 3 is, for example, a trivalent group represented by the above formula (2), the following formula (6)

(In formula (6), “*” indicates a bond, respectively.)
A trivalent group represented by:
X in the case where n is 4, 6 or 8, for example, the following formula (7)

(In Formula (7), m2 is an integer of 0 to 2, and “*” represents a bond, respectively.)
4, 6 or 8 valent groups represented by the formula can be mentioned as preferred examples.
In addition to at least one group selected from the group consisting of a carboxyl group and a carboxylic acid anhydride group and an n-valent group represented by the above formula (1), the polymer [A] has a side chain. Furthermore, you may have a polymerizable unsaturated bond.
The content ratio of at least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group in the polymer [A] is preferably 0.1 to 10 mmol / g, more preferably 0.8. 5 to 5 mmol / g. The content ratio of the n-valent group represented by the above formula (1) in the polymer [A] is preferably 0.005 to 1 mmol / g, more preferably 0.01 to 0.5 mmol / g. g. When the polymer [A] has a polymerizable unsaturated bond in its side chain, the content of the polymerizable unsaturated bond in the polymer [A] is preferably 20 mmol / g or less, More preferably, it is 0.1-15 mmol / g, More preferably, it is 0.5-10 mmol / g.

The weight average molecular weight (hereinafter referred to as “Mw”) in terms of polystyrene of the polymer [A] is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. If the Mw is less than 2,000, the developability and remaining film ratio of the resulting film may be insufficient, or the pattern shape and heat resistance of the manufactured spacer may be impaired. On the other hand, if Mw exceeds 100,000, the resolution may be insufficient or the pattern shape of the manufactured spacer may be impaired. The molecular weight distribution (hereinafter referred to as “Mw / Mn”) of the polymer [A] defined as a value obtained by dividing Mw by Mn (polystyrene equivalent number average molecular weight) is 1.0 to 2.8, Preferably it is 1.0-2.5, More preferably, it is 1.0-2.3. If Mw / Mn exceeds 2.8, streaky unevenness may occur on the formed film when high-speed coating by the slit die coating method is adopted as the coating method.
The polymer [A] may be obtained by any method as long as it is a polymer as described above, but at least (a1) a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. At least one selected from the following (hereinafter referred to as “compound (a1)”).
An unsaturated compound containing the following formula (8)

(In the formula (8), X, Y, ^{R I} and n, respectively, the same meanings as X, Y, ^{R I} and n in the formula (1).)
It is preferable that it is a polymer obtained through the process of radical polymerization in presence of the compound represented by these. This polymer can be the polymer itself obtained through the above steps, or it can be a polymer having a polymerizable unsaturated bond introduced into the side chain of the polymer.
As a result of intensive studies, the inventors of the present invention can obtain an unsaturated compound by radical polymerization in the presence of a compound having two or more thiol groups in one molecule represented by the above formula (8). The molecular weight distribution of the polymer can be controlled, thereby finding that the conversion rate of the unsaturated compound subjected to radical polymerization to the polymer is improved, and the polymer [A] obtained by such a method is further sensed. It has been found that a radiation-sensitive resin composition that can be applied at a high speed by a slit die coating method can be obtained by incorporating it in a radiation-sensitive resin composition, and the amount of volatile components generated at the time of spacer formation is extremely small. .
The polymer [A] in the present invention is preferably the following polymer [A1], polymer [A2-1], or polymer [A2-2].

Polymer [A1]: Compound (a1),
At least one selected from the group consisting of an unsaturated compound having an oxiranyl group and an unsaturated compound having an oxetanyl group (hereinafter referred to as “compound (a2-1)”);
An unsaturated compound having a hydroxyl group (hereinafter referred to as “compound (a2-2)”) and an unsaturated compound other than the above compound (a1), compound (a2-1) and compound (a2-1) (hereinafter referred to as “compound”) (A2-3) ") a copolymer obtained by radical copolymerization of an unsaturated compound consisting of at least one selected from the group consisting of the compound represented by the above formula (8). .
Polymer [A2-1]: Compound (a1),
Obtained by radical copolymerization of an unsaturated compound comprising at least one selected from the group consisting of compound (a2-2) and compound (a2-3) in the presence of the compound represented by the above formula (8). A polymer which is a reaction product obtained by reacting the compound (a2-1) with a copolymer (hereinafter referred to as “precursor polymer [A2-1]”).
Polymer [A2-2]: Compound (a1),
Compound (a2-2),
Obtained by radical copolymerization of an unsaturated compound comprising at least one selected from the group consisting of compound (a2-1) and compound (a2-3) in the presence of the compound represented by the above formula (8). A polymer which is a reaction product obtained by reacting an unsaturated isocyanate compound with a copolymer obtained (hereinafter referred to as “precursor polymer [A2-2]”).
Hereinafter, the compound (a2-1), the compound (a2-1) and the compound (a2-3) may be collectively referred to as “compound (a2)”.

Specific examples of the compound (a1) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydro. Monocarboxylic acids such as phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid, and dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
Examples of unsaturated carboxylic acid anhydrides include the dicarboxylic acid anhydrides exemplified above.
Among these compounds (a1), an acrylic resin is used because it has good copolymerization reactivity, good solubility in an alkaline developer of a coating formed from the resulting radiation-sensitive resin composition, and easy availability. Acid, methacrylic acid, maleic anhydride or 2-methacryloyloxyethyl hexahydrophthalic acid is preferred.
Specific examples of the compound (a2-1) include, as unsaturated compounds having an oxiranyl group, for example, 4-methacryloyloxymethyl-2-cyclohexyl-1,3-dioxolane glycidyl acrylate, 2-methylglycidyl acrylate, Acrylic acid epoxy alkyl esters such as 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexylmethyl acrylate;
Methacrylic acid such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate Acid epoxy alkyl ester;
α-alkylacrylic acid epoxy alkyl esters such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl;
Examples thereof include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

Examples of unsaturated compounds having an oxetanyl group include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, and 3- (methacryloyloxy). Methyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2- Difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) oxetane 3 (Methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-penta Fluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, Methacrylic acid esters having an oxetanyl group such as 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra An acrylic acid ester having an oxetanyl group such as fluorooxetane can be exemplified.

Specific examples of the compound (a2-2) include, for example, acrylic acid 2-hydroxyethyl ester, acrylic acid 3-hydroxypropyl ester, acrylic acid 4-hydroxybutyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3- Hydroxypropyl ester, methacrylic acid 4-hydroxybutyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, acrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 2,3- Examples include dihydroxypropyl ester, acrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester, and methacrylic acid 2- (6-hydroxyhexanoyloxy) ethyl ester. Can.
Specific examples of the compound (a2-3) include alkyl acrylate esters such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-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) Decanoyl methacrylate) such as decan-8-yloxy) ethyl, isobornyl methacrylate;

Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Methacrylate esters having an unsaturated heterocyclic 5- or 6-membered ring containing one oxygen atom, such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydrofupyran-2-methyl methacrylate;
4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclohexyl- Oxygen such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Methacrylic acid ester having an unsaturated hetero five-membered ring containing 2 atoms;
4-acryloyloxymethyl-2, 2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Methacryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxy Acrylic acid ester having an unsaturated heterocyclic five-membered ring containing two oxygen atoms, such as orchids;

Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
In addition to conjugated dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples thereof include polar unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Examples of the compound (a2) used for producing the polymer [A1] include styrene, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (tricyclodecanyl methacrylate), methacrylic acid, Glycidyl acid, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-methacryloyloxymethyl oxetane Tetrahydrofurfuryl methacrylate, 1,3-butadiene, 2-hydroxyethyl acrylate, 2- (6-hydroxyethylhexanoyloxy) ethyl methacrylate and 4-acryloyloxymethyl-2-methyl-2-ethyl -1 It is preferable to use at least one selected from the group consisting of 1,3-dioxolane from the viewpoints of copolymerization reactivity, developability of the coating, and improvement of the compression performance of the resulting spacer.
The content of the repeating unit derived from the compound (a1) in the polymer [A1] is preferably 5 to 50% by weight, more preferably 5 to 40% by weight, based on the total of all the repeating units. Particularly preferably, it is 10 to 30% by weight. If the content of the repeating unit derived from the compound (a1) is less than 5% by weight, the solubility in an alkali developer tends to be insufficient, whereas if it exceeds 50% by weight, the solubility in an alkali developer is large. There is a risk of becoming too much.

The content of the repeating unit derived from the compound (a1) in the precursor polymer [A2-1] is preferably 10 to 60% by weight, and preferably 15 to 50% by weight, based on the total of all the repeating units. It is more preferable.
The content of the repeating unit derived from the compound (a1) in the precursor polymer [A2-2] is preferably 5 to 50% by weight, and preferably 10 to 40% by weight based on the total of all the repeating units. Is more preferable. The content of the repeating unit derived from the compound (a2-2) in the precursor polymer [A2-2] is preferably 5 to 60% by weight based on the total of all the repeating units, and is 10 to 50% by weight. More preferably. The content of the repeating unit derived from at least one selected from the group consisting of the compound (a2-1) and the compound (a2-3) in the precursor polymer [A2-2] is based on the total of all the repeating units. It is preferably 20 to 80% by weight, and more preferably 25 to 70% by weight.

The polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2] each represent an unsaturated compound as described above with a compound represented by the above formula (8) (hereinafter, “multiple” It can be produced by radical polymerization in the presence of a “valent thiol compound”), preferably in a suitable solvent, in the presence of a polymerization initiator.
The polyvalent thiol compound is a component that acts as a chain transfer agent in the synthesis of the polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2].
As the polyvalent thiol compound, for example, an esterified product of mercaptocarboxylic acid and polyhydric alcohol can be used.
Examples of the mercaptocarboxylic acid include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, and 3-mercaptopentanoic acid.
Examples of the polyhydric alcohol include ethylene glycol, tetraethylene glycol, butanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,3,5-tris (2-hydroxyethyl) cyanurate, sorbitol and the like. , Can be mentioned respectively.
Specific examples of preferable polyvalent thiol compounds used in the present invention include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3- Mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3- Mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like. .
The said polyvalent thiol compound can be used individually or in mixture of 2 or more types.

The ratio of the polyvalent thiol compound used in the synthesis of the polymer [A1], the precursor polymer [A2-1] and the precursor polymer [A2-2] is preferably 100 parts by weight of the total unsaturated compounds. It is 0.5-30 weight part, More preferably, it is 1-20 weight part, Especially preferably, it is 1.5-10 weight part. When the use ratio of the polyvalent thiol compound is less than 0.5 parts by weight, a desired molecular weight distribution may not be obtained. On the other hand, if it exceeds 30 parts by weight, it may be difficult to easily obtain a high polymerization conversion rate.
Examples of the solvent that can be used in producing the polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2] include alcohols, ethers, glycol ethers, and ethylene glycol alkyl ether acetates. , Diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, ketone, ester and the like. Specific examples thereof include alcohols such as methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, and 3-phenyl-1-propanol;
Ethers such as tetrahydrofuran;
Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;

Examples of ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate;
Examples of diethylene glycol include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether;
Examples of dipropylene glycol include dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, and dipropylene glycol ethyl methyl ether;
Examples of propylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
As propylene glycol alkyl ether propionate, for example, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate and the like;
As propylene glycol alkyl ether acetate, for example, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc .;
Aromatic hydrocarbons such as toluene, xylene, etc .;
Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like;

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxy Ethyl acetate, hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy -3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, 3-methoxybutyl acetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate Propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid Lopyl, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate , Esters of propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc. it can.

Of these, ethylene glycol alkyl ether acetate, diethylene glycol, dipropylene glycol, propylene glycol monoalkyl ether, and propylene glycol alkyl ether acetate are preferable. Among them, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol ethyl Methyl ether, propylene glycol methyl ether, propylene glycol methyl ether acetate or 3-methoxybutyl acetate is particularly preferred.
The said solvent can be used individually or in mixture of 2 or more types.
It does not specifically limit as a radical polymerization initiator which can be used when manufacturing polymer [A1], precursor polymer [A2-1], and precursor polymer [A2-2], for example, 2 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), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Azo compounds; organic peroxides such as benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane; It can be mentioned. Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox-type initiator combining this and a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

By polymerizing in this way, the molecular weight distribution of the resulting polymer can be controlled, and unreacted unsaturated compounds can be reduced. As a result, the conversion rate of the unsaturated compound subjected to radical polymerization of the polymer [A1], the precursor polymer [A2-1] and the precursor polymer [A2-2] (hereinafter referred to as “conversion rate”). .) Can be 95% by weight or more.
Here, the polymerization conversion rate is the actual charged weight of each component subjected to radical polymerization and the solid content concentration of the polymer solution after polymerization (synthesis of all components other than the solvent contained in the radiation-sensitive resin composition). The weight can be determined by the following formula from the ratio (% by weight) to the total weight of the composition. The solid content was measured by weighing the polymer solution obtained in an aluminum dish and heating it on a hot plate at 175 ° C. for 1 hour, and measuring the weight before and after heating (weight after heating × 100 / before heating). Weight).
Polymerization addition rate (% by weight) = solid content concentration of polymer solution after polymerization (% by weight) × actual total charge of all components / actual total charge of components other than solvent

In the production of the polymer [A2-1], the reaction of the precursor copolymer [A2-1] and the compound (a2-1) can be performed by a known method.
As the compound (a2-1) used here, at least one selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate is used. However, it is preferable from the viewpoint that the storage stability of the obtained radiation-sensitive resin composition is high, and the heat resistance and chemical resistance of the spacer produced therefrom can be further increased.
The ratio of the compound (a2-1) used when synthesizing the polymer [A2-1] is at least selected from the group consisting of a carboxyl group and an acid anhydride group contained in the precursor copolymer [A2-1]. Among the one kind, the group (unreacted group) that is not used for the reaction with the compound (a2-1) is set so that the alkali solubility of the obtained polymer [A2-1] remains appropriate. It is preferable. Specifically, the content of the repeating unit having a pre-reacted group in the polymer after the reaction (polymer [A2-1]) is 5 to 30% by weight based on the total of all the repeating units. Is preferable, and it is more preferable to set it as 10 to 20 weight%.

In the synthesis of the polymer [A2-2], the reaction of the precursor copolymer [A2-2] and the unsaturated isocyanate compound can be performed by a known method.
The unsaturated isocyanate compound is not particularly limited as long as it is an unsaturated compound having an isocyanate group. For example, 2-acryloyloxyethyl isocyanate, 3-acryloyloxypropyl isocyanate, 4-acryloyloxybutyl isocyanate, 6-acryloyl Acrylic acid derivatives such as oxyhexyl isocyanate, 8-acryloyloxyoctyl isocyanate, 10-acryloyloxydecyl isocyanate, 1,1- (bisacryloyloxymethyl) ethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl acrylate;
2-methacryloyloxyethyl isocyanate, 3-methacryloyloxypropyl isocyanate, 4-methacryloyloxybutyl isocyanate, 6-methacryloyloxyhexyl isocyanate, 8-methacryloyloxyoctyl isocyanate, 10-methacryloyloxydecyl isocyanate, 1,1- (bismethacryloyloxy And methacrylic acid derivatives such as methyl) ethyl isocyanate and 2- (2-isocyanatoethoxy) ethyl methacrylate.
Among these unsaturated isocyanate compounds, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) methacrylic acid from the viewpoint of reactivity with the precursor copolymer [A2-2]. ) Ethyl and the like are preferable. In the synthesis of the polymer [A2-2], unsaturated isocyanate compounds can be used alone or in admixture of two or more.
The ratio of the unsaturated isocyanate compound used in the production of the polymer [A2-2] is preferably 0.1 to 90 mol%, more preferably based on the hydroxyl group of the precursor copolymer [A2-2]. Is 10 to 80 mol%, particularly preferably 25 to 75 mol%. When the amount of the unsaturated isocyanate compound used is less than 0.1 mol%, the sensitivity of the resulting radiation-sensitive resin composition and the effect of improving the elastic properties of the spacer of the display device produced therefrom are small, while 90 wt. If it exceeds%, the unreacted unsaturated isocyanate compound remains in the reaction solution, and the storage stability of the resulting polymer solution or radiation-sensitive resin composition tends to be insufficient.

[Polymerizable compound [B]]
The polymerizable compound [B] in the radiation-sensitive resin composition of the present invention is a compound having a polymerizable unsaturated bond.
The polymerizable compound [B] is not particularly limited, but it is preferable to use a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester. This is preferable from the viewpoint of improving the strength.
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 thereof include methoxybutyl acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and ω-carboxypolycaprolactone monoacrylate. As these commercial products, for example, Aronix M-101, M-111, M-114, M-5300 (manufactured by Toagosei Co., Ltd.); KAYARAD TC-110S, TC-120S (Nippon Kayaku ( Biscoat 158, 2311 (produced by Osaka Organic Chemical Industry Co., Ltd.) and the like.

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, and 1,6-hexanediol. Examples include diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange methacrylate. As these commercial products, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (Nippon Kayaku Co., Ltd.) Product), Biscoat 260, 312 and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).
Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol And hexaacrylate. Or,
Reaction of a compound having an alkylene linear and alicyclic structure and two or more isocyanate groups in the molecule with a trifunctional, tetrafunctional or pentafunctional (meth) acrylate compound containing one or more hydroxyl groups in the molecule The urethane (meth) acrylate compound obtained by making it possible to mention is mentioned. This urethane (meth) acrylate compound is preferably a compound having 9 or more functional groups.

As a commercial item of the above-mentioned trifunctional or higher functional (meth) acrylic acid ester, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M-8030, M -8060, TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA-12 (Nippon Kayaku) (Made by Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.), etc.
In particular, examples of the above 9- or more functional urethane (meth) acrylate compound include New Frontier R-1150 (above, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD DPHA-40H (above, manufactured by Nippon Kayaku Co., Ltd.), and the like. be able to.
As the polymerizable compound [B] in the present invention, it is preferable to use a tri- or higher functional (meth) acrylic acid ester, and particularly preferable are trimethylolpropane triacrylate, pentaerythritol triacrylate, penta Mention may be made of erythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and ethylene oxide-modified dipentaerythritol hexaacrylate.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester can be used alone or in combination of two or more.
The ratio of the polymerizable compound [B] used in the radiation-sensitive resin composition of the present invention is preferably 50 to 200 parts by weight, more preferably 60 to 150 parts by weight with respect to 100 parts by weight of the polymer [A]. Part. If the amount of the polymerizable compound [B] used is less than 50 parts by weight, there may be a residual image during development, whereas if it exceeds 200 parts by weight, the adhesion of the resulting spacer to the substrate tends to be insufficient.

[[C] Radiation sensitive polymerization initiator]
[C] The radiation-sensitive polymerization initiator in the radiation-sensitive resin composition of the present invention is a polymer of the polymerizable compound [B] by irradiation with radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray. It consists of components that generate active species that can initiate Examples of such [C] radiation-sensitive polymerization initiators include a radiation-sensitive radical polymerization initiator and a radiation-sensitive cationic polymerization initiator. Examples of the radiation-sensitive radical polymerization initiator include O-acyl oxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, triazine compounds, and the like. Examples of the radiation-sensitive cationic polymerization initiator include onium salts and metallocene compounds.

Examples of the O-acyloxime compound include etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-octyloxime), 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- (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, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione- 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2- Octadion-1- [4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime) )) And the like.
Of these O-acyloxime compounds, in particular, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-octyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) are preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more.

Examples of the acetophenone compound include α-hydroxyketone compounds, α-aminoketone compounds, and other compounds.
Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one. 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like:
Examples of the α-aminoketone compound include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane. -1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one and the like;
Examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.
Of these acetophenone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4 -Morpholinophenyl) -butan-1-one is preferred.
These acetophenone compounds can be used alone or in admixture of two or more.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.
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 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ is particularly preferable. -Biimidazole.
The above biimidazole compounds can be used alone or in admixture of two or more.
By using these biimidazole compounds, it is possible to further improve the radiation sensitivity, resolution, and adhesion of the manufactured spacer to the substrate.

When a biimidazole compound is used as the [C] radiation sensitive polymerization initiator in the radiation sensitive resin composition of the present invention, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”). .) And at least one selected from thiol compounds can be added.
The amino sensitizer is a compound having a function of sensitizing the radiation sensitivity of the biimidazole compound and increasing the generation efficiency of the imidazole radical, and is formed by improving the sensitivity and resolution of the radiation-sensitive resin composition. It can be added for the purpose of further improving the adhesion of the spacer or the protective film to the substrate. Examples of such 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. These amino sensitizers can be used alone or in admixture of two or more.
The addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the biimidazole compound. 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 may be insufficient. On the other hand, if it exceeds 50 parts by weight, the shape of the spacer formed is It may be damaged.

The thiol compound is a compound having a function of donating a hydrogen radical to an imidazole radical and, as a result, generating a component having a sulfur radical. The ability to initiate polymerization of imidazole radicals generated by cleavage of a biimidazole compound upon irradiation is moderate and not very high. Therefore, if this is used as it is for forming a spacer of a liquid crystal display element, the cross section of the spacer The shape may be an undesirable shape with a reverse taper shape. However, by adding a thiol compound here, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is converted to neutral imidazole and has a higher sulfur radical with higher polymerization initiation ability. As a result, the spacer can be surely made into a more preferable forward tapered shape. Examples of such thiol compounds include aromatic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole. Aliphatic monothiol compounds such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, pentaerythritol Bifunctional or higher functional aliphatic thiol compounds such as stall tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be exemplified. Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.
The addition amount of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the biimidazole compound. If the addition amount of the thiol compound is less than 0.1 parts by weight, the effect of improving the spacer shape may be insufficient. On the other hand, if it exceeds 50 parts by weight, the shape of the spacer formed may be impaired. .
In the radiation-sensitive resin composition of the present invention, when a biimidazole compound is used as the [C] radiation-sensitive polymerization initiator, it is preferable to add both the amino sensitizer and the thiol compound.

  Examples of the onium salt in the radiation-sensitive cationic polymerization initiator include phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trifluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium. -P-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazonium Trifluoroacetate, 4-methoxyphenyl di Zonium-p-toluenesulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarsenate, 4-ter-butylphenyldiazonium trifluoro Diazonium salts such as romethanesulfonate, 4-ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate;

Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxy Phenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4 -Methoxy Phenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfone Examples thereof include sulfonium salts such as narate, 4-phenylthiophenyl diphenyl trifluoroacetate, and 4-phenylthiophenyl diphenyl-p-toluenesulfonate.
Examples of the metallocene compound include (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-).
The radiation-sensitive cationic polymerization initiators can be used alone or in admixture of two or more.

The use ratio of the [C] radiation sensitive polymerization initiator in the radiation sensitive resin composition of the present invention is preferably 0.01 to 120 parts by weight, more preferably 100 parts by weight of the polymer [A]. Is 1 to 100 parts by weight. [C] If the proportion of the radiation-sensitive polymerization initiator used is less than 0.01 parts by weight, the residual film ratio tends to be insufficient at the time of development. The solubility in the liquid may be insufficient.
In the radiation sensitive resin composition of this invention, it is preferable to contain an O-acyl oxime compound as a [C] radiation sensitive polymerization initiator. In the radiation sensitive resin composition of the present invention, a highly sensitive radiation sensitive resin composition can be obtained by using an O-acyloxime compound, and a spacer having good adhesion can be obtained. Become. In the radiation-sensitive resin composition of the present invention, when the O-acyloxime compound is used as the [C] radiation-sensitive polymerization initiator, the proportion of the O-acyloxime compound used is 100 parts by weight of the polymer [A]. On the other hand, it is preferably 0.01 to 30 parts by weight, and more preferably 0.05 to 20 parts by weight. If the amount of the O-acyloxime type polymerization initiator used is less than 0.01 parts by weight, the residual film rate during development may be insufficient. May be insufficient.
In the radiation sensitive resin composition of this invention, 1 or more types of other radiation sensitive polymerization initiators can be used together with an O-acyl oxime polymerization initiator as a [C] radiation sensitive polymerization initiator. The other radiation-sensitive polymerization initiator is preferably at least one selected from the group consisting of an acetophenone compound, a biimidazole compound, and a radiation-sensitive cationic polymerization initiator. In the radiation-sensitive resin composition of the present invention, when the O-acyloxime polymerization initiator and another radiation-sensitive polymerization initiator are used in combination, the use ratio of the other radiation-sensitive polymerization initiator is the total radiation-sensitive polymerization. In an initiator, Preferably it is 80 weight% or less, More preferably, it is 70 weight% or less. In the present invention, by using at least one selected from the group consisting of an acetophenone compound and a biimidazole compound as another polymerization initiator, it is possible to further improve the sensitivity, the shape of the obtained spacer, the compressive strength, etc. It becomes.

<Other additives>
The radiation-sensitive resin composition of the present invention contains the polymer [A], the polymerizable compound [B] and the [C] radiation-sensitive polymerization initiator as essential components as described above. In the range which does not impair the effect of, other additives other than the above may be contained as necessary.
Examples of such other additives include [D] surfactants, [E] adhesion assistants, [F] storage stabilizers, and [G] heat resistance improvers.
[[D] Surfactant]
The above [D] surfactant can be contained in the radiation-sensitive resin composition of the present invention in order to improve applicability. Examples of the [D] surfactant include a fluorine-based surfactant, a silicone-based surfactant, and other surfactants. As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain, and side chain can be suitably used. Specific examples thereof include, for example, 1,1, 2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, octaethylene glycol di (1,1,2,2-tetra Fluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, perfluorododecylsulfo Sodium 1,1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, sodium fluoroalkylbenzenesulfonate, fluoro Sodium alkylphosphonate, sodium fluoroalkylcarboxylate, fluoroalkylpolyoxyethylene ether, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, fluoroalkylpolyoxyethylene ether, perfluoroalkyl Examples include polyoxyethanol, perfluoroalkyl alkoxylates, and fluorine-based alkyl esters.

As these commercially available products, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, F471 (and above) , Manufactured by DIC Corporation), Florard FC 170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M Co., Ltd.), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, Asahi Glass Co., Ltd.) Manufactured), F-top EF301, 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), 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.), etc. Can be mentioned.
Examples of the silicone surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, what is marketed by brand names, such as Momentive Performance Materials Japan GK), can be mentioned.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl. Nonionic surfactants such as polyoxyethylene aryl ethers such as phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and commercially available products such as KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) ), Polyflow No. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
[D] The compounding 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]. [D] When the blending amount of the surfactant exceeds 5 parts by weight, film roughness tends to occur during coating.

[[E] Adhesion aid]
The governmental radiation resin composition of the present invention can contain [E] an adhesion assistant in order to further improve the adhesion between the spacer to be produced and the substrate.
As the [E] adhesion aid, a functional silane coupling agent can be preferably used. Examples thereof include a silane cup having a reactive functional group such as a carboxyl group, a methacryloyl group, an isocyanate group, and an epoxy group. A ring agent can be mentioned. More specifically, for example, trimethoxysilylbenzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
These adhesion assistants can be used alone or in admixture of two or more.
The blending ratio of [E] adhesion assistant in the radiation sensitive resin composition of the present invention 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 polymer [A]. is there. [E] If the blending amount of the adhesion assistant exceeds 20 parts by weight, there may be a case where a development residue is likely to occur.
[[F] Storage stabilizer]
The radiation sensitive resin composition of the present invention can contain a storage stabilizer [F] for the purpose of improving its storage stability. [F] Storage stabilizers include, for example, sulfur, quinone compounds, hydroquinone compounds, polyoxy compounds, amine compounds, nitronitroso compounds, 4-methoxyphenol, N-nitroso-N-phenylhydroxylamine aluminum, etc. Is preferred. In the radiation-sensitive resin composition of the present invention, the [F] storage stabilizer is preferably 3.0 parts by weight or less, more preferably 0.001 to 0.5 parts per 100 parts by weight of the polymer [A]. Used in parts by weight. When this value exceeds 3.0 parts by weight, sufficient radiation sensitivity cannot be obtained, and the pattern shape may deteriorate.

[[G] Heat resistance improver]
The radiation-sensitive resin composition of the present invention has an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound or a bifunctional or higher functional epoxy group in order to further improve the heat resistance of the produced spacer. A compound contained in one molecule can be added.
Specific examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycol. Uril, N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N Examples include '-tetra (n-butoxymethyl) glycoluril, N, N, N', N'-tetra (t-butoxymethyl) glycoluril, and the like. Of these, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is particularly preferable.
Specific 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 can be mentioned. Of these, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is particularly preferred. Examples of these commercially available products include Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.
Examples of the compound having a bifunctional or higher functional epoxy group in one molecule include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol di Examples include glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like. it can. Specific examples of these commercially available products include Epolite 40E, Epolite 100E, Epolite 200E, Epolite 70P, Epolite 200P, Epolite 400P, Epolite 40E, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Epolite 4000, Epolite 3002 (or more, Kyoeisha Chemical Co., Ltd.). These can be used alone or in combination of two or more.

[Radiation sensitive resin composition]
The radiation-sensitive resin composition of the present invention is prepared by dissolving the polymer [A], the polymerizable compound [B] and [C] the radiation-sensitive polymerization initiator and other optional components in an appropriate solvent. Thus, it is preferably prepared as a solution-like composition.
As a solvent used for the preparation of the composition solution, a solvent that uniformly dissolves each component constituting the radiation-sensitive resin composition and does not react with each component is used.
Examples of such a solvent include the same solvents as those exemplified as the solvent that can be used for producing the polymer [A1], the precursor polymer [A2-1], and the precursor polymer [A2-2]. be able to.
Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters, and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, and ease of film formation. It is done. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxypropionate, and -3-methoxybutyl acetate can be particularly preferably used.

Furthermore, in order to improve the in-plane uniformity of the film thickness of the formed film, a high boiling point solvent may be used in combination with the above solvent. Examples of the high boiling point solvent that can be used in combination here include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, and dimethyl. Sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenyl cellosolve acetate and the like. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.
The composition solution thus prepared may be filtered for use with a Millipore filter having a pore size of, for example, about 0.2 to 0.5 μm, if necessary.
The radiation sensitive resin composition of the present invention is particularly suitable as a material for forming spacers for display elements such as liquid crystal panels and touch panels.

<Method for producing display element spacer>
Next, a method for producing the spacer of the present invention using the radiation sensitive resin composition of the present invention will be described.
The production of the spacer of the present invention includes at least the following steps in the order described below.
(A) a step of forming a film of the radiation-sensitive resin composition of the present invention;
(B) exposing at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development.
Hereinafter, each of these steps will be described sequentially.

[(I) Process]
A transparent conductive film is formed on one side of the transparent substrate, and the radiation-sensitive resin composition of the present invention is applied on the transparent conductive film to form a film.
Examples of the transparent substrate used here include glass substrates and resin substrates. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, and polyether. Examples thereof include a resin substrate made of a plastic such as sulfone, polycarbonate, and polyimide.
As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) And so on.
As a method for forming the film, a coating method or a dry film method can be used.
In the case of forming a film by a coating method, after coating the radiation-sensitive resin composition of the present invention on the transparent conductive film, the coating surface is heated (prebaked) to remove the solvent, thereby forming the film. be able to. Solid content concentration of radiation-sensitive resin composition used in coating method (the ratio (% by weight) of the total weight of all components other than the solvent in the radiation-sensitive resin composition to the total weight of the radiation-sensitive resin composition) The same shall apply hereinafter) is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and even more preferably 15 to 35% by weight. Although it does not specifically limit as an application method, For example, appropriate methods, 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, an inkjet coating method, can be employ | adopted. In particular, a spin coating method or a slit die coating method is preferable.
The radiation-sensitive resin composition of the present invention is particularly suitable for the slit die coating method, and even when the moving speed of the slit die is 150 mm / second, coating unevenness does not occur.

On the other hand, the dry film used in the case of forming a film by the dry film method is obtained by laminating a radiation sensitive layer made of the radiation sensitive resin composition of the present invention on a base film, preferably a flexible base film. (Hereinafter referred to as “radiation-sensitive dry film”).
The radiation-sensitive dry film is formed by laminating a radiation-sensitive layer on the base film by applying the radiation-sensitive resin composition of the present invention, preferably as a solution-like composition, and then removing the solvent. can do. The solid content concentration of the composition solution used for laminating the radiation-sensitive layer of the radiation-sensitive dry film is preferably 5 to 50% by weight, more preferably 10 to 50% by weight, and still more preferably. It is 20 to 50% by weight, and particularly preferably 30 to 50% by weight. As the base film of the radiation-sensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the radiation sensitive layer is preferably about 1 to 30 μm.
The radiation-sensitive dry film can be stored by laminating a cover film on the radiation-sensitive layer when not in use. This cover film is preferably a material having an appropriate releasability so that it does not peel off when not in use (during storage) and can be easily peeled off during use. As a cover film satisfying such conditions, for example, a film obtained by applying or baking a silicone release agent on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, or a polyurethane film is used. can do. The thickness of the cover film is preferably about 5 to 30 μm. These cover films may be a laminated cover film in which two or three layers are laminated.
A film can be formed by laminating such a dry film on a transparent conductive film of a transparent substrate by an appropriate method such as a thermocompression bonding method.
The coating thus formed is then preferably pre-baked. Prebaking conditions vary depending on the type of each component, the blending ratio, etc., but are preferably about 70 to 120 ° C. for about 1 to 15 minutes.
The film thickness after pre-baking of the film is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

[(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 , more preferably 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 Optical Associates Inc.). Is 500 to 3,000 J / m ² .

[(C) Process]
Subsequently, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
As the developer used for development, an alkali developer is preferable, 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 and quinoline It can be exemplified an aqueous solution of an alkali compound such as tetramethyl ammonium hydroxide, quaternary ammonium salts such as tetraethylammonium hydroxide; ethanol dimethylamine, methyldiethanolamine, alkanolamines such as triethanolamine.
Further, 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.
The developing method may be any of a liquid filling method, a dipping method, a shower method, and the like, 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 desired spacer can be obtained by heating (post-baking) the obtained pattern at a predetermined temperature, for example, 100 to 230 ° C., using a heating device such as a hot plate or an oven. The heating time is preferably 5 to 30 minutes when the heating is performed using a hot plate, and 30 to 180 minutes when the heating is performed using an oven.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises a spacer produced from the radiation sensitive resin composition of the present invention as described above.
The liquid crystal display element of the present invention can be produced, for example, by the following method (a) or (b).
(A) First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates. A spacer is produced according to the method described above. Subsequently, an alignment film having liquid crystal alignment ability is formed on the transparent conductive film and spacers of these substrates. These substrates are arranged facing each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Can be obtained.
(B) First, in the same manner as in the method (a), a pair of transparent substrates on which a transparent conductive film, a spacer, and an alignment film are formed are prepared. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, then liquid crystal is dropped into a fine droplet using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both substrates are sealed by irradiating the above-mentioned sealant part with ultraviolet rays using a high pressure mercury lamp. Finally, the liquid crystal display element of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

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

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples.
In the following synthesis examples, Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate) methacrylate, 40 parts by weight of glycidyl methacrylate and After 2 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-1]. In this synthesis example, the conversion rate was 98%, the solid content concentration of the obtained polymer solution was 30.0% by weight, Mw of the polymer [A-1] was 15,000, and Mw / Mn was 2.1. Met.
Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate) methacrylate, 40 parts by weight of glycidyl methacrylate and After 4 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-2]. In this synthesis example, the conversion rate was 99%, the solid content concentration of the obtained polymer solution was 30.5% by weight, the polymer [A-2] had Mw of 12,000, and Mw / Mn was 1.9. Met.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 10 parts by weight of methacrylic acid, 4 parts by weight of acrylic acid, 31 parts by weight of benzyl methacrylate, 45 parts by weight of n-butyl methacrylate and 4 parts by weight of dipentaerythritol hexakis (3-mercaptopropionate) Was added, and the mixture was purged with nitrogen. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-3]. In this synthesis example, the conversion rate was 96%, the solid content concentration of the obtained polymer solution was 28.7% by weight, the polymer Mw was 12,000, and Mw / Mn was 1.7.
Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 12 parts by weight of methacrylic acid, 23 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate), 30 parts by weight of glycidyl methacrylate, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane (25 parts by weight) and pentaerythritol tetrakis (3-mercaptopropionate) (4 parts by weight) were charged with nitrogen, and then gently stirred. . The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-4]. In this synthesis example, the conversion was 96%, the polymer solution obtained had a solid content concentration of 29.8% by weight, the polymer Mw was 12,000, and Mw / Mn was 1.7.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate, followed by 18 parts by weight of methacrylic acid, tricyclomethacrylate [ 5.2.1.0 ^2,6 ] decan-8-yl 30 parts by weight, styrene 5 parts by weight, butadiene 5 parts by weight, methacrylic acid 2-hydroxyethyl ester 25 parts by weight, tetrahydrofuran-2-yl methacrylate 17 parts by weight And 2 parts by weight of trimethylolpropane tris (3-mercaptopropionate) were charged, and after nitrogen substitution, the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was maintained for 4 hours. Thereafter, the temperature was raised to 100 ° C., and this temperature was maintained for 1 hour for polymerization to obtain a polymer solution containing the precursor copolymer [a-5]. In the synthesis of the precursor copolymer [a-5], the conversion rate was 98%, and the solid content concentration of the obtained polymer solution was 29.5% by weight.
Next, after adding 14 parts by weight of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, Showa Denko KK) and 0.08 parts by weight of 4-methoxyphenol to the precursor copolymer [a-5] solution. The polymer solution containing the polymer [A-5] was obtained by stirring and reacting at 60 ° C. for 2 hours.
Here, the progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group derived from the precursor copolymer [a-5] was confirmed by IR (infrared absorption) spectrum. 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. Mw of the obtained polymer [A-5] was 12,000, and Mw / Mn was 1.9.

Synthesis Example 6
In Synthesis Example 5, instead of 2-methacryloyloxyethyl isocyanate, 2- (2-isocyanatoethoxy) ethyl methacrylate (trade name Karenz MOI-EG, Showa Denko Co., Ltd.) was added to the precursor copolymer [a-5] solution. )) After adding 15 parts by weight and 0.1 part by weight of 4-methoxyphenol, the polymer [A-6] is reacted by stirring at 40 ° C. for 1 hour and further at 60 ° C. for 2 hours. A polymer solution containing was obtained.
Here, the progress of the reaction between the isocyanate group derived from 2- (2-isocyanatoethoxy) ethyl methacrylate and the hydroxyl group derived from the precursor copolymer [a-5] was carried out in the same manner as in Synthesis Example 5 and IR (infrared absorption). Confirmed by spectrum. Mw of the obtained polymer “A-6” was 12,500, and Mw / Mn was 1.9.
Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 20 parts by weight of methacrylic acid, 38 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate) methacrylate, 3- (methacryloyloxymethyl) 10 parts by weight of -3-ethyloxetane, 30 parts by weight of 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane and 4 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) are charged, and nitrogen is added. After the replacement, stirring was started gently. The temperature of the solution was raised to 70, and this temperature was maintained for 4 hours to obtain a polymer solution containing the precursor copolymer (a-7). In this synthesis example, the conversion was 96%, the polymer solution obtained had a solid content concentration of 29.8% by weight, the polymer Mw was 12,000, and Mw / Mn was 1.7.
Next, 0.16 part by weight of triphenylphosphine and 0.08 part by weight of 4-methoxyphenol were added to the precursor copolymer (a-7) solution, and the temperature was raised to 90 ° C. Subsequently, after adding 7 weight part of glycidyl methacrylate, it stirred at 90 for 8 hours, and the polymer solution containing a polymer [A-7] was obtained.
Here, the progress of the reaction between the glycidyl group derived from glycidyl methacrylate and the carboxyl group derived from the precursor copolymer (a-7) was confirmed by IR (infrared absorption) spectrum. It confirmed that the peak of 800 cm < ^-1 > vicinity derived from the glycidyl group derived from glycidyl methacrylate decreased with progress of reaction.
Mw of the obtained polymer [A-7] was 13,000, and Mw / Mn was 2.0.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate) and 40 parts by weight of glycidyl methacrylate were added. After replacing the charged nitrogen, the stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-7]. In this synthesis example, the conversion was 94%, the polymer solution obtained had a solid content concentration of 28.8% by weight, the polymer [A-7] had an Mw of 15,000, and an Mw / Mn of 3.1. Met.
Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 10 parts by weight of methacrylic acid, 4 parts by weight of acrylic acid, 31 parts by weight of benzyl methacrylate, 45 parts by weight of n-butyl methacrylate and 4 parts by weight of α-methylstyrene dimer were charged, and after the nitrogen substitution, Stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-8]. In this synthesis example, the conversion is 92%, the solid content concentration of the obtained polymer solution is 27.5% by weight, the Mw of the polymer [A-8] is 12,000, and the Mw / Mn is 2.8. Met.

Comparative Synthesis Example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (isobutyronitrile) and 250 parts by weight of 3-methoxybutyl acetate, followed by 18 parts by weight of methacrylic acid, tricyclomethacrylate [ 5.2.1.0 ^2,6 ] decan-8-yl 30 parts by weight, styrene 5 parts by weight, butadiene 5 parts by weight, methacrylic acid 2-hydroxyethyl ester 25 parts by weight and tetrahydrofuran-2-yl methacrylate 17 parts by weight The temperature of the solution was raised to 80 ° C. while gently stirring, and the temperature was maintained for 4 hours, then increased to 100 ° C., and this temperature was maintained for 1 hour for polymerization. As a result, a polymer solution containing the precursor copolymer [a-9] was obtained. In the synthesis of the precursor copolymer [a-9], the conversion was 94%, and the solid content concentration of the obtained polymer solution was 29.0% by weight.
About the obtained precursor copolymer [a-9], when Mw was measured using GPC (gel permeation chromatography) HLC-8020 (trade name, manufactured by Tosoh Corporation), Mw was 14,000. Mw / Mn = 2.5.
Next, after adding 14 parts by weight of 2-methacryloyloxyethyl isocyanate (trade name Karenz MOI, manufactured by Showa Denko KK) and 0.08 part by weight of 4-methoxyphenol to the precursor copolymer [a-9] solution. The polymer solution containing the polymer [A-9] was obtained by stirring and reacting at 60 ° C. for 2 hours.
Here, in the same manner as in Synthesis Example 5, the progress of the reaction between the isocyanate group derived from 2-methacryloyloxyethyl isocyanate and the hydroxyl group derived from the precursor copolymer [a-9] was confirmed by IR (infrared absorption) spectrum. Mw of the obtained polymer [A-9] was 14,000, and Mw / Mn was 2.5.

Comparative Synthesis Example 4
A flask equipped with a condenser and a stirrer was charged with 8 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts by weight of 3-methoxybutyl acetate. Subsequently, 5 parts by weight of styrene, 16 parts by weight of methacrylic acid, 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (tricyclodecanyl methacrylate) methacrylate, 40 parts by weight of glycidyl methacrylate and After 0.5 parts by weight of pentaerythritol tetrakis (3-mercaptopropionate) was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer [A-10]. In this synthesis example, the conversion rate was 98%, the solid content concentration of the obtained polymer solution was 28.8% by weight, the Mw of the polymer [A-10] was 16,000, and Mw / Mn was 2.9. Met.

Example 1
<Preparation of radiation-sensitive resin composition>
An amount corresponding to 100 parts by weight in terms of the polymer [A] in the polymer solution containing the polymer [A-1] obtained in Synthesis Example 1 as the polymer [A], as a polymerizable compound [B] product KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) 100 parts by weight and [C] etanone as a radiation-sensitive polymerization initiator, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (Irgacure OX02 manufactured by Ciba Specialty Chemicals) and 2-dimethylamino-2- (4-methyl-benzyl) -1- 10 parts by weight of (4-morpholin-4-yl-phenyl) -butan-1-one (Irgacure 379 manufactured by Ciba Specialty Chemicals Co., Ltd.) in a propylene glycol monomethyl ether so that the solid content concentration is 21% by weight After dissolving in acetate, the mixture was filtered through a Millipore filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (S-1).
Evaluation was performed as follows using this radiation-sensitive resin composition (S-1). The evaluation results are shown in Table 2.

<Evaluation of radiation-sensitive resin composition>
(1) Evaluation of sensitivity Using a spinner on an alkali-free glass substrate, the radiation sensitive resin composition (S-1) was applied and then pre-baked on a 90 ° C. hot plate for 3 minutes to obtain a film thickness of 3.0 μm. The coating film was formed.
Next, the obtained coating film was exposed with ultraviolet light having an intensity at 365 nm of 250 W / m ² through a photomask having a round pattern with a diameter of 15 μm as an opening, with the exposure time as a variable. Then, after developing for 60 seconds at 25 ° C. with a 0.05 wt% aqueous solution of potassium hydroxide, the substrate was washed with pure water for 1 minute, and further post-baked in an oven at 230 ° C. for 20 minutes to form a spacer.
At this time, the sensitivity was defined as the minimum exposure amount at which the remaining film ratio after post-baking (film thickness after post-baking × 100 / film thickness after exposure) was 90% or more.

(2) Evaluation of the amount of volatile components After applying the radiation sensitive resin composition (S-1) on a silicon wafer using a spinner, the film thickness is 3 by pre-baking on a hot plate at 90 ° C. for 3 minutes. A coating film of 0.0 μm was formed.
After the substrate on which the coating film is formed is cut into strip-shaped sample pieces, headspace gas chromatography / mass spectrometry (headspace sampler: JHS-100A, gas analysis / mass spectrometer manufactured by Nihon Analytical Industries, Ltd.) JEOL JMS-AX505W type mass spectrometer). The purge condition was 100 ° C./10 min, and the peak area of the volatile component was determined. Octane was used as a standard substance (octane specific gravity: 0.701, octane injection amount: 0.02 μl), and the amount of all volatile components in terms of octane was calculated from the following formula based on the peak area.
Volatile component amount (μg) = (peak area of volatile component ÷ peak area of octane) × 0.02 × 0.701
(3) Evaluation of applicability by slit die coating method The radiation-sensitive resin composition (S-1) was applied on a 550 × 650 mm chromium-deposited glass using a slit die coater. The moving speed of the slit die and 150 mm / sec, after removal of dried solvent as reduced to 0.5 Torr, the coating film is formed by prebaking for 3 minutes in 100 ° C. clean oven, yet 2,000 J / ^{m 2} By exposing with an exposure amount, a film having a thickness of 3 μm from the upper surface of the chromium film-forming glass was formed.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. Applicability “x” (defect) when streaky irregularities (one or more straight irregularities in the direction in which the slit die travels or in the direction intersecting the slit die) are confirmed. “△” (slightly poor), and “◯” (good) when not confirmed.

Examples 2 to 13 and 15 and Comparative Examples 1 to 4
In Example 1, each composition solution was prepared in the same manner as in Example 1 except that the components and amounts contained in Table 1 were used as the components contained in the radiation-sensitive resin composition. And evaluated. Polymer [A] is used as a polymer solution, and the amount used (parts by weight) in Table 1 is a value converted to the weight of the polymer contained in the polymer solution used. Moreover, the addition amount of [B] polymeric compound and [C] radiation sensitive polymerization initiator is the quantity with respect to 100 weight part of polymer [A], respectively.
Further, when an amino sensitizer and a thiol compound were used in combination with the [C] radiation sensitive polymerization initiator, these were listed in the column of [C] radiation sensitive polymerization initiator in Table 1.
The evaluation results are shown in Table 2.

Example 14 and Comparative Example 5
<Preparation of radiation-sensitive resin composition>
As the polymer [A], [B] polymerizable compound and [C] radiation sensitive polymerization initiator, the types and amounts shown in Table 1 are used, respectively, so that the solid content concentration is 40% by weight. Radiation sensitive resin compositions (S-14) and (s-5) were prepared in the same manner as in Example 1 except that they were dissolved in propylene glycol monomethyl ether acetate.
<Evaluation of radiation-sensitive resin composition>
Using each of the radiation-sensitive resin compositions (S-14) and (s-5) prepared above, a dry film was produced as follows, and the transferability to the glass substrate was evaluated.
The evaluation results are shown in Table 2.
(4) Evaluation of transferability of dry film to glass substrate [Production of dry film]
By applying the radiation sensitive resin composition on a polyethylene terephthalate (PET) film having a thickness of 38 μm using an applicator, and heating the obtained coating film at 100 ° C. for 5 minutes to remove the solvent, PET is obtained. A radiation-sensitive dry film having a radiation-sensitive layer having a thickness of 4 μm thereon was produced.
[Evaluation of transferability to glass substrate]
Next, the radiation sensitive transfer dry film was overlaid on the surface of the glass substrate so that the surface of the radiation sensitive transfer layer was in contact with the glass substrate, and the radiation sensitive dry film was transferred to the glass substrate by a thermocompression bonding method.
At this time, when the dry film can be uniformly transferred onto the glass substrate, the transferability is “Good” (good), the dry film partially remains on the base film, or the dry film does not adhere to the glass substrate. The case where the dry film could not be uniformly transferred onto the glass substrate was determined as “x” (defective).

In Table 1, the abbreviation of each component indicates the following compound.
B-1: Dipentaerythritol hexaacrylate (trade name “KAYARAD DPHA”, manufactured by Nippon Kayaku Co., Ltd.)
B-2: A polymerizable unsaturated compound containing a polyfunctional urethane acrylate compound (trade name “KAYARAD DPHA-40H”, manufactured by Nippon Kayaku Co., Ltd.)
B-3: Pentaerystol tetraacrylate (trade name “Aronix M-450”, manufactured by Toagosei Co., Ltd.)
B-4: ω-carboxypolycaprolactone monoacrylate (trade name “Aronix M-5300”, manufactured by Toagosei Co., Ltd.)
B-5: 1,9-nonane diacrylate (trade name “Light acrylate 1,9-NDA”, manufactured by Kyoeisha Chemical Co., Ltd.)
C-1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (trade name “Irgacure OX02”, manufactured by Ciba Specialty Chemicals)
C-2: Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (trade name “N-1919”, manufactured by ADEKA Corporation)
C-3: 2-dimethylamino-2- (4-methyl-benzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one (trade name “Irgacure 379”, Ciba Special Made by Tea Chemicals)
C-4: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole C-5: 4,4′-bis (diethylamino) benzophenone C-6: 2-mercaptobenzothiazole C-7: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name “Irgacure 369”, Ciba Specialty Chemicals) Made)
C-8: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name “Irgacure 907”, manufactured by Ciba Specialty Chemicals)
D-1: Phenol novolac epoxy resin (trade name “Epicoat 152”, manufactured by Japan Epoxy Resin Co., Ltd.)
In Table 1, the “-” mark indicates that the component is not added.
In Table 2, "-" mark indicates that the evaluation is not performed.

Claims (7)

[A] At least one group selected from the group consisting of a carboxyl group and a carboxylic anhydride group, and the following formula (1)

(In the formula (1), R ^I is a methylene group, an alkylene group having 2 to 10 carbon atoms or an alkylmethylene group, and Y is a single bond, —CO—, —O—CO— ^* (where “*” is The bond attached to R ^I ) or —NHCO— ^* (where the bond attached with “*” binds to R ^I ), and n is an integer of 2 to 10 and X Is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or n is 3 and X is the following formula (2)

(In Formula (2), each R ^II independently represents a methylene group or an alkylene group having 2 to 6 carbon atoms, and “*” represents a bond.)
The “+” represents a bond. )
The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is 1.0 to A polymer which is 2.8,
[B] A radiation-sensitive resin composition comprising a polymerizable unsaturated compound and [C] a radiation-sensitive polymerization initiator. The unsaturated compound containing at least one selected from the group consisting of (a1) an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride is represented by the following formula (8):

(In the formula (8), X, Y, ^{R I} and n, respectively, the same meanings as X, Y, ^{R I} and n in the formula (1).)
The radiation sensitive resin composition of Claim 1 which is a polymer obtained through the process of radical-polymerizing in presence of the compound represented by these. Y in the formula (1) is -O-CO- * ^(However, bond marked with "*" is bonded to R ^I.) Is radiation-sensitive resin composition according to claim 1 or 2 object.   The radiation sensitive resin composition as described in any one of Claims 1-3 used for manufacture of the spacer for display elements. The manufacturing method of the spacer for display elements characterized by including the following processes at least in the order as described below.
(A) forming a film of the radiation sensitive resin composition according to claim 4;
(B) exposing at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development.   A spacer for a display element, which is manufactured from the radiation-sensitive resin composition according to claim 4.   A liquid crystal display element comprising the display element spacer according to claim 6.