JP4911304B2 - Radiation sensitive resin composition and spacer for liquid crystal display element - Google Patents

Description

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

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

In recent years, the mother glass substrate has been increased in size (for example, about 1,500 × 1,800 mm, further about 1,870 × 2,200 mm) from the viewpoint of increasing the area of the liquid crystal display element and improving productivity. Yes. However, with the increase in size of the substrate, problems that have not been surfaced, such as pre-baking furnaces and exposure mask contamination due to the radiation-sensitive resin composition in the pre-baking and exposure processes, have occurred and problems that further reduce productivity have occurred. is doing.
In addition, since the cost of the substrate is increased with the increase in size of the substrate, the substrate that has failed in the process is actively reused. As an example of the reuse, the color filter on which the alignment film is formed is subjected to alignment film peeling treatment with a peeling solution such as a strong alkaline aqueous solution. At this time, if the spacer has low peeling liquid resistance, the spacer may also be peeled off.
If the spacer is also peeled off, the spacer must be formed again, which increases the production cost.

  Therefore, the object of the present invention is to obtain a high sensitivity and sufficient spacer shape, to suppress the contaminants generated during the formation of the spacer, and to resist the stripping solution such as a strong alkaline aqueous solution at the time of reprocessing and adhere to the substrate. The object is to provide a radiation-sensitive resin composition capable of forming a spacer for a liquid crystal display element having excellent properties.

  Another object of the present invention is to provide a spacer for a liquid crystal display element formed from the radiation-sensitive resin composition of the present invention, a method for forming the spacer, and a liquid crystal display element containing the spacer.

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

According to the present invention, the above objects and advantages of the present invention are, firstly,
[A] a copolymer of (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and (a2) another unsaturated compound,
[B] polymerizable unsaturated compound,
[C] photopolymerization initiator and [D] oxiranyl group, oxetanyl group, episulfide group, vinyl group, allyl group, (meth) acryloyl group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, amino group, ureido group And a siloxane oligomer containing at least one functional group selected from the group consisting of a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, an amino group and a ureido group among styryl groups This is achieved by the resin composition.

Furthermore, the [D] component is preferably a siloxane oligomer obtained by cohydrolyzing an alkoxysilane represented by each of the following formula (1) and the following formula (2).
Si (R ¹ ) _l (R ² ) _m (OR ³ ) _n (1)
(Wherein R ¹ contains an epoxy group, oxetanyl group, episulfide group, vinyl group, allyl group, (meth) acryloyl group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, amino group, ureido group or styryl group. R ² and R ³ may be the same or different, each is a monovalent organic group, l and n are each an integer of 1 to 3, and m is an integer of 0 to 2. (However, l + m + n = 4.)
Si (R ⁴ ) _x (OR ⁵ ) _4-x (2)
(Here, R ⁴ and R ⁵ may be the same or different, and each is a hydrogen atom or a monovalent organic group, and x is an integer of 0 to 3.)

  According to the present invention, the above-mentioned objects and advantages of the present invention are secondly achieved by a spacer for a liquid crystal display element formed from the radiation-sensitive resin composition.

According to the present invention, the above objects and advantages of the present invention are thirdly achieved by a method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a coating of the radiation-sensitive resin composition for a spacer for a liquid crystal display element on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.

  According to the present invention, fourthly, the above objects and advantages of the present invention are achieved by a liquid crystal display element comprising the liquid crystal display element spacer.

The radiation-sensitive resin composition of the present invention provides a high sensitivity and sufficient spacer shape, can suppress contaminants generated at the time of spacer formation, prevents contamination of the prebaking furnace and the exposure mask, and at the time of reprocessing This makes it possible to form a spacer for a liquid crystal display element having excellent resistance to a stripping solution such as a strong alkaline aqueous solution and excellent adhesion to a substrate.
The liquid crystal display element of the present invention comprises a spacer having excellent performance such as sensitivity, elastic recovery, rubbing resistance, adhesion to a transparent substrate, heat resistance, etc., and realizes high reliability over a long period of time. Can do.

  Hereinafter, the present invention will be described in detail.

-[A] copolymer-
The copolymer in the present invention is a copolymer of (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and (a2) another unsaturated compound (hereinafter referred to as [A] copolymer). ).
[A] Among the components constituting the copolymer, (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter collectively referred to as “(a1) unsaturated carboxylic acid compound”). ), For example,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. can be mentioned.

These (a1) unsaturated carboxylic acid-based compounds undergo a crosslinking reaction with the [D] component when the later-described [D] component has an epoxy group, oxetanyl group, episulfide group, hydroxyl group, mercapto group or amino group. .
Among these (a1) unsaturated carboxylic acid-based compounds, copolymerization reactivity, solubility of the resulting [A] copolymer in an alkaline developer and ease of availability, acrylic acid, methacrylic acid, anhydrous Maleic acid and the like are preferred.
[A] In the copolymer, (a1) unsaturated carboxylic acid compounds may be used alone or in admixture of two or more.
[A] In the copolymer, the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is preferably 5 to 50% by weight, more preferably 10 to 40% by weight, and particularly preferably 15 to 30%. % By weight.

(A2) As another unsaturated compound, it is referred to as an unsaturated compound (hereinafter referred to as “compound (a2-1)”) that can undergo a crosslinking reaction with the [D] component, depending on the type of functional group possessed by the [D] component. ) Can be selected as appropriate.
When having [D] component turtles mercapto group, as the compound (a2-1), for example, can be selected allyl (meth) acrylate.

[D] component carboxyl group, a hydroxyl group, sometimes having a mercapto group, a ureido group or an amino group, the compound (a2-1), for example,
Acrylic acid epoxy such as glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate (Cyclo) alkyl esters;
Methacrylic acid epoxy (cyclo) alkyl esters such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
Glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether can be selected.

When the component [D] is an isocyanate group, examples of the compound (a2-1) include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxy acrylate. Pentyl ester, 6-hydroxyhexyl acrylate, 7-hydroxyheptyl acrylate, 8-hydroxy octyl acrylate, 9-hydroxy nonyl acrylate, 10-hydroxy decyl acrylate, 11-hydroxy undecyl acrylate Esters, acrylic acid hydroxyalkyl esters such as acrylic acid 12-hydroxydodecyl ester;
Methacrylic acid 2-hydroxyethyl ester, Methacrylic acid 3-hydroxypropyl ester, Methacrylic acid 4-hydroxybutyl ester, Methacrylic acid 5-hydroxypentyl ester, Methacrylic acid 6-Hydroxyhexyl ester, Methacrylic acid 7-Hydroxyheptyl ester, Methacrylic acid Methacrylic acid hydroxyalkyl esters such as 8-hydroxyoctyl ester, methacrylic acid 9-hydroxynonyl ester, methacrylic acid 10-hydroxydecyl ester, methacrylic acid 11-hydroxyundecyl ester, methacrylic acid 12-hydroxydodecyl ester;
Further, acrylic acid 4-hydroxy-cyclohexyl ester, acrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, acrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, acrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5 -En-2-yl ester, acrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, acrylic acid 3-hydroxyethyl-bicyclo [2.2.1] Hept-5-en-2-ylethyl ester, acrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, acrylic acid 2-hydroxy-octahydro-4,7-methano -Inden-5-yl ester, 2-hydroxymethyl-octaacrylate B-4,7-methano-inden-5-ylmethyl ester, 2-hydroxyethyl-octahydro-4,7-methano-inden-5-ylethyl acrylate, 3-hydroxy-adamantan-1-yl acrylate Acrylic acid hydroxyalkyl esters having an alicyclic structure such as esters, acrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, acrylic acid 3-hydroxyethyl-adamantan-1-ylethyl ester;
Methacrylic acid 4-hydroxy-cyclohexyl ester, Methacrylic acid 4-hydroxymethyl-cyclohexyl methyl ester, Methacrylic acid 4-hydroxyethyl-cyclohexyl ethyl ester, Methacrylic acid 3-hydroxy-bicyclo [2.2.1] hept-5-ene 2-yl ester, methacrylic acid 3-hydroxymethyl-bicyclo [2.2.1] hept-5-en-2-ylmethyl ester, methacrylic acid 3-hydroxyethyl-bicyclo [2.2.1] hept- 5-En-2-ylethyl ester, methacrylic acid 8-hydroxy-bicyclo [2.2.1] hept-5-en-2-yl ester, methacrylic acid 2-hydroxy-octahydro-4,7-methano-indene -5-yl ester, 2-hydroxymethyl methacrylate Octahydro-4,7-methano-inden-5-ylmethyl ester, 2-hydroxyethyl methacrylate-octahydro-4,7-methano-inden-5-ylethyl ester, 3-hydroxy-adamantan-1-yl methacrylate Methacrylic acid hydroxyalkyl esters having an alicyclic structure such as esters, methacrylic acid 3-hydroxymethyl-adamantan-1-ylmethyl ester, methacrylic acid 3-hydroxyethyl-adamantan-1-ylethyl ester;
Acrylic acid 1,2-dihydroxyethyl ester, acrylic acid 2,3-dihydroxypropyl ester, acrylic acid 1,3-dihydroxypropyl ester, acrylic acid 3,4-dihydroxybutyl ester, acrylic acid 3- [3- (2, 3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester and other acrylic acid dihydroxyalkyl esters;
Methacrylic acid 1,2-dihydroxyethyl ester, methacrylic acid 2,3-dihydroxypropyl ester, methacrylic acid 1,3-dihydroxypropyl ester, methacrylic acid 3,4-dihydroxybutyl ester, methacrylic acid 3- [3- (2, A dihydroxyalkyl ester of methacrylic acid such as 3-dihydroxypropoxy) -2-hydroxypropoxy] -2-hydroxypropyl ester or the like can be selected.

[A] In the copolymer, the compound (a2-1) can be used alone or in admixture of two or more.
[A] In the copolymer, the content of the repeating unit derived from the compound (a2-1) is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably 20 to 40% by weight. is there.

As the other unsaturated compound (a2), an unsaturated compound that does not show a crosslinking reaction with the component [D] (hereinafter referred to as “compound (a2-2)”) can also be selected. As the compound (a2-2), in addition to the compound (a2-1), for example,
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;
Aryl esters or aralkyl esters of acrylic acid such as phenyl acrylate and benzyl acrylate;
Aryl esters or aralkyl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate;
Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Acrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylic acid ester having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.

Among these compounds (a2-2), n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, from the viewpoint of copolymerization reactivity and solubility of the obtained [A] polymer in an alkaline aqueous solution, 3,4-epoxycyclohexylmethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3- Butadiene is preferred.

[A] In the copolymer, the compound (a2-2) can be used alone or in admixture of two or more.
[A] In the copolymer, the content of the repeating unit derived from the compound (a2-2) is preferably 10 to 70% by weight, more preferably 20 to 50% by weight, particularly preferably 30 to 50% by weight. is there. When the content rate of the repeating unit derived from a compound (a2-2) exceeds 70 weight%, the solubility with respect to the alkali developing solution of this polymer tends to fall.
[A] The copolymer is produced, for example, by polymerizing (a1) an unsaturated carboxylic acid compound and (a2) another unsaturated compound in a suitable solvent in the presence of a radical polymerization initiator. Can do.

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

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

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

[A] The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer by gel permeation chromatography (GPC) is preferably 2,000 to 100,000, more preferably 5,000 to 50, 000. If the Mw is less than 2,000, the resulting film may be deteriorated in alkali developability, residual film ratio, or the like, or may be damaged in pattern shape, heat resistance, or the like. , There is a possibility that the resolution is lowered or the pattern shape is damaged.
[A] The copolymer has a carboxyl group and / or a carboxylic acid anhydride group, has an appropriate solubility in an alkali developer, and [A] contains a copolymer. The radiation resin composition can easily form a spacer having a predetermined shape without developing residue and film loss during development.

-[B] polymerizable unsaturated compound-
[B] The polymerizable unsaturated compound comprises an unsaturated compound that is polymerized by exposure to radiation in the presence of a photopolymerization initiator. Moreover, when the [D] component mentioned later has a vinyl group, an allyl group, a (meth) acryloyl group, a mercapto group or a styryl group, it crosslinks with the [D] component by heat or radiation exposure.
Such a [B] polymerizable unsaturated compound is not particularly limited. For example, a monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid ester has good copolymerizability. From the viewpoint of improving the strength of the obtained spacer.

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

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6- Examples include hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, and bisphenoxyethanol full orange methacrylate. As commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toa Gosei Co., Ltd.), KAYARAD HDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.), Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.), Light Acrylate 1,9-NDA (Kyoeisha Co., Ltd.) and the like.

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

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

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

  In the radiation-sensitive resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound used is preferably 1 to 120 parts by weight, more preferably 3 to 100 parts by weight of the [A] copolymer. 100 parts by weight. [B] If the amount of the polymerizable unsaturated compound used is less than 1 part by weight, there is a possibility that a developing residue may be generated during development. On the other hand, if it exceeds 120 parts by weight, the adhesion of the resulting spacer tends to decrease.

-[C] Photopolymerization initiator-
[C] A photopolymerization initiator is a component that generates an active species capable of initiating polymerization of a polymerizable unsaturated compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, and X-ray. Consists of.
Examples of such [C] radiation sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples include xanthone compounds, phosphine compounds, triazine compounds, and the like.

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

  Of these O-acyloxime compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) is preferred.

The O-acyloxime compounds can be used alone or in admixture of two or more. In the present invention, the use of an O-acyloxime compound makes it possible to obtain a spacer having sufficient sensitivity and adhesion even with an exposure amount of 1,000 J / m ² or less.
Examples of the acetophenone compound include an α-hydroxyketone compound and an α-aminoketone compound.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -One, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone and the like. Examples of the α-aminoketone compound include 2 -Methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4- And methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one. wear. Examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

Among these acetophenone compounds, in particular, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-Morpholinophenyl) -butan-1-one is preferred.
In the present invention, the sensitivity, spacer shape and compressive strength can be further improved by using an acetophenone compound in combination.

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

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

In the present invention, it is possible to further improve sensitivity, resolution and adhesion by using a biimidazole compound in combination.
When a biimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) may be added to sensitize it. it can.

Examples of amino sensitizers include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, p-dimethylamino. Examples include i-amyl benzoate.
Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.

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

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

In the radiation-sensitive resin composition of the present invention, the use ratio of the other radiation-sensitive polymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, with respect to 100 parts by weight of the total photopolymerization initiator. Particularly preferred is 60 parts by weight or less. If the proportion of other photopolymerization initiator used exceeds 100 parts by weight, the intended effect of the present invention may be impaired.
Further, when the biimidazole compound and the amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the biimidazole compound. Preferably it is 1-20 weight part. If the addition amount of the amino sensitizer is less than 0.1 parts by weight, the effect of improving the sensitivity, resolution and adhesion tends to be reduced. On the other hand, if it exceeds 50 parts by weight, the shape of the resulting spacer tends to be impaired. There is.
In addition, when a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the biimidazole compound. 1 to 20 parts by weight. If the amount of the thiol compound added is less than 0.1 parts by weight, the effect of improving the spacer shape tends to be reduced or the film tends to be reduced. There is a tendency to be damaged.

-[D] siloxane oligomer-
The [D] component used in the present invention is a siloxane oligomer having a functional group that undergoes a crosslinking reaction with the above [A] copolymer component or [B] polymerizable unsaturated compound by heat or exposure to radiation, and an oxiranyl group , Oxetanyl group, episulfide group, vinyl group, allyl group, (meth) acryloyl group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, amino group, ureido group and styryl group carboxyl group, hydroxyl group, mercapto group And at least one functional group selected from the group consisting of an isocyanate group, an amino group and a ureido group .
[D] component used by this invention, Preferably, it can manufacture by cohydrolyzing the alkoxysilane represented by each of following formula (1) and each of following formula (2).
Si (R ¹ ) _l (R ² ) _m (OR ³ ) _n (1)
(Wherein R ¹ is an oxiranyl group, oxetanyl group, episulfide group, vinyl group, allyl group, (meth) acryloyl group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, amino group, ureido group or styryl group . Represents a substituent containing a carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, an amino group or a ureido group , and R ² and R ³ may be the same or different and are each a hydrogen atom or a monovalent organic group. , L and n are each an integer of 1 to 3, and m is an integer of 0 to 2. However, l + m + n = 4.
Si (R ⁴ ) _x (OR ⁵ ) _4-x (2)
(Here, R ⁴ and R ⁵ may be the same or different, each is a monovalent organic group, and x is an integer of 0 to 2.)
It is understood that the above hydrolyzate includes those in which all of the hydrolyzable parts in the raw material are hydrolyzed and those in which some of them are hydrolyzed and part of them remain without being hydrolyzed. Should.

  Specific examples of the compound (1) containing an oxiranyl group include 3-glycidoxymethyltrimethoxysilane, 3-glycidoxymethyltriethoxysilane, 3-glycidoxymethyltri-n-propyloxysilane, 3 -Glycidoxymethyltri-i-propyloxysilane, 3-glycidoxymethyltriacetoxysilane, 3-glycidoxymethylmethyldimethoxysilane, 3-glycidoxymethylmethyldiethoxysilane, 3-glycidoxymethyl Methyldi-n-propyloxysilane, 3-glycidoxymethylmethyldi-i-propyloxysilane, 3-glycidoxymethylmethyldiacetoxysilane, 3-glycidoxymethylethyldimethoxysilane, 3-glycidoxy Methylethyldiethoxysilane, 3-glycidoxymethylethyl -N-propyloxysilane, 3-glycidoxymethylethyldi-i-propyloxysilane, 3-glycidoxymethylethyldiacetoxysilane, 3-glycidoxymethylphenyldimethoxysilane, 3-glycidoxymethylphenyl Diethoxysilane, 3-glycidoxymethylphenyldi-n-propyloxysilane, 3-glycidoxymethylphenyldi-i-propyloxysilane, 3-glycidoxymethylphenyldiacetoxysilane, 3-glycidoxy Ethyltrimethoxysilane, 3-glycidoxyethyltriethoxysilane, 3-glycidoxyethyltri-n-propyloxysilane, 3-glycidoxyethyltri-i-propyloxysilane, 3-glycidoxyethyltri Acetoxysilane, 3-glycidoxyethylmethyl Methoxysilane, 3-glycidoxyethylmethyldiethoxysilane, 3-glycidoxyethylmethyldi-n-propyloxysilane, 3-glycidoxyethylmethyldi-i-propyloxysilane, 3-glycidoxyethyl Methyldiacetoxysilane, 3-glycidoxyethylethyldimethoxysilane, 3-glycidoxyethylethyldiethoxysilane, 3-glycidoxyethylethyldi-n-propyloxysilane, 3-glycidoxyethylethyldi- i-propyloxysilane, 3-glycidoxyethylethylacetoxysilane, 3-glycidoxyethylphenyldimethoxysilane, 3-glycidoxyethylphenyldiethoxysilane, 3-glycidoxyethylphenyldi-n-propyl Oxysilane, 3-glycidoxyethyl pheny Rudi-i-propyloxysilane, 3-glycidoxyethylphenyldiacetoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltri-n-propyl Oxysilane, 3-glycidoxypropyltri-i-propyloxysilane, 3-glycidoxypropyltriacetoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropylmethyldi-n-propyloxysilane, 3-glycidoxypropylmethyldi-i-propyloxysilane, 3-glycidoxypropylmethyldiacetoxysilane, 3-glycidoxypropylethyldimethoxysilane, 3 -Glycidoxypropyl Tildiethoxysilane, 3-glycidoxypropylethyldi-n-propyloxysilane, 3-glycidoxypropylethyldi-i-propyloxysilane, 3-glycidoxypropylethyldiacetoxysilane, 3-glycid Xylpropylphenyldimethoxysilane, 3-glycidoxypropylphenyldiethoxysilane, 3-glycidoxypropylphenyldi-n-propyloxysilane, 3-glycidoxypropylphenyldi-i-propyloxysilane, 3-glycidyl Sidoxypropylphenyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) methyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) methyltriethoxysilane, 2- (3,4-epoxycyclohexyl) methyltri- n-propyloxy Lan, 2- (3,4-epoxycyclohexyl) methyltriacetoxysilane, 2- (3,4-epoxycyclohexyl) methylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methylmethyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) methylmethyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) methylethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) methylethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methylethyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) methylethyldiacetoxysilane, 2- ( 3,4-epoxy Cyclohexyl) methylphenyldimethoxysilane, 2- (3,4-epoxycyclohexyl) methylphenyldiethoxysilane, 2- (3,4-epoxycyclohexyl) methylphenyldi-n-propyloxysilane, 2- (3,4- Epoxycyclohexyl) methylphenyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri -N-propyloxysilane, 2- (3,4-epoxycyclohexyl) ethyltriacetoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldie G Sisilane, 2- (3,4-epoxycyclohexyl) ethylmethyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) ethylmethyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) ethylethyldimethoxysilane 2- (3,4-epoxycyclohexyl) ethylethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylethyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) ethylethyldiacetoxysilane 2- (3,4-epoxycyclohexyl) ethylphenyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethylphenyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethylphenyldi-n-propyloxy Syrah 2- (3,4-epoxycyclohexyl) ethylphenyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) propyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) propyltriethoxysilane, 2- ( 3,4-epoxycyclohexyl) propyltri-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) propyltriacetoxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) propylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) propylmethyldiacetoxysilane, 2- (3,4-epoxy Cycyclohexyl) propylethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) propylethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) propylethyldi-n-propyloxysilane, 2- (3,4 -Epoxycyclohexyl) propylethyldiacetoxysilane, 2- (3,4-epoxycyclohexyl) propylphenyldimethoxysilane, 2- (3,4-epoxycyclohexyl) propylphenyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ) Propylphenyldi-n-propyloxysilane, 2- (3,4-epoxycyclohexyl) propylphenyldiacetoxysilane and the like;

  Specific examples of the compound (1) containing an episulfide group include 2,3-epithiopropyloxymethyltrimethoxysilane, 2,3-epithiopropyloxymethyltriethoxysilane, and 2,3-epithiopropyloxymethyl. Tri-n-propyloxysilane, 2,3-epithiopropyloxymethyltri-i-propyloxysilane, 2,3-epithiopropyloxymethyltriacetoxysilane, 2,3-epithiopropyloxymethylmethyldimethoxysilane 2,3-epithiopropyloxymethylmethyldiethoxysilane, 2,3-epithiopropyloxymethylmethyldi-n-propyloxysilane, 2,3-epithiopropyloxymethylmethyldi-i-propyloxysilane 2,3-epithiopropyloxymethyl methyl Diacetoxysilane, 2,3-epithiopropyloxymethylethyldimethoxysilane, 2,3-epithiopropyloxymethylethyldiethoxysilane, 2,3-epithiopropyloxymethylethyldi-n-propyloxysilane, 2, , 3-epithiopropyloxymethylethyldi-i-propyloxysilane, 2,3-epithiopropyloxymethylethyldiacetoxysilane, 2,3-epithiopropyloxymethylphenyldimethoxysilane, 2,3-epithio Propyloxymethylphenyldiethoxysilane, 2,3-epithiopropyloxymethylphenyldi-n-propyloxysilane, 2,3-epithiopropyloxymethylphenyldi-i-propyloxysilane, 2,3-epithio Propyloxymethylphenyl di Cetoxysilane, 2,3-epithiopropyloxyethyltrimethoxysilane, 2,3-epithiopropyloxyethyltriethoxysilane, 2,3-epithiopropyloxyethyltri-n-propyloxysilane, 2,3-epi Thiopropyloxyethyltri-i-propyloxysilane, 2,3-epithiopropyloxyethyltriacetoxysilane, 2,3-epithiopropyloxyethylmethyldimethoxysilane, 2,3-epithiopropyloxyethylmethyldiethoxy Silane, 2,3-epithiopropyloxyethylmethyldi-n-propyloxysilane, 2,3-epithiopropyloxyethylmethyldi-i-propyloxysilane, 2,3-epithiopropyloxyethylmethyldiacetoxy Silane, 2,3-epithiop Propyloxyethylethyldimethoxysilane, 2,3-epithiopropyloxyethylethyldiethoxysilane, 2,3-epithiopropyloxyethylethyl di-n-propyloxysilane, 2,3-epithiopropyloxyethylethyl Di-i-propyloxysilane, 2,3-epithiopropyloxyethylethyldiacetoxysilane, 2,3-epithiopropyloxyethylphenyldimethoxysilane, 2,3-epithiopropyloxyethylphenyldiethoxysilane, 2, , 3-epithiopropyloxyethylphenyldi-n-propyloxysilane, 2,3-epithiopropyloxyethylphenyldi-i-propyloxysilane, 2,3-epithiopropyloxyethylphenyldiacetoxysilane, 2, , 3-Epithiopropi Oxypropyltrimethoxysilane, 2,3-epithiopropyloxypropyltriethoxysilane, 2,3-epithiopropyloxypropyltri-n-propyloxysilane, 2,3-epithiopropyloxypropyltri-i-propyl Oxysilane, 2,3-epithiopropyloxypropyltriacetoxysilane, 2,3-epithiopropyloxypropylmethyldimethoxysilane, 2,3-epithiopropyloxypropylmethyldiethoxysilane, 2,3-epithiopropyl Oxypropylmethyldi-n-propyloxysilane, 2,3-epithiopropyloxypropylmethyldi-i-propyloxysilane, 2,3-epithiopropyloxypropylmethyldiacetoxysilane, 2,3-epithiopropyl Oxypropi Ethyldimethoxysilane, 2,3-epithiopropyloxypropylethyldiethoxysilane, 2,3-epithiopropyloxypropylethyldi-n-propyloxysilane, 2,3-epithiopropyloxypropylethyldi-i- Propyloxysilane, 2,3-epithiopropyloxypropylethyldiacetoxysilane, 2,3-epithiopropyloxypropylphenyldimethoxysilane, 2,3-epithiopropyloxypropylphenyldiethoxysilane, 2,3-epi Thiopropyloxypropylphenyldi-n-propyloxysilane, 2,3-epithiopropyloxypropylphenyldi-i-propyloxysilane, 2,3-epithiopropyloxypropylphenyldiacetoxysilane, and the like;

  Specific examples of the compound (1) containing an oxetanyl group include (oxetane-3-yl) methyltrimethoxysilane, (oxetane-3-yl) methyltriethoxysilane, and (oxetane-3-yl) methyltri-n-. Propyloxysilane, (oxetane-3-yl) methyltri-i-propyloxysilane, (oxetane-3-yl) methyltriacetoxysilane, (oxetane-3-yl) methylmethyldimethoxysilane, (oxetane-3-yl) Methylmethyldiethoxysilane, (oxetane-3-yl) methylmethyldi-n-propyloxysilane, (oxetane-3-yl) methylmethyldi-i-propyloxysilane, (oxetane-3-yl) methylmethyldiacetoxysilane, ( Oxetane-3-yl) methylethyldimethyl Xoxysilane, (oxetane-3-yl) methylethyldiethoxysilane, (oxetane-3-yl) methylethyldi-n-propyloxysilane, (oxetane-3-yl) methylethyldi-i-propyloxysilane, (oxetane-3- Yl) methylethyldiacetoxysilane, (oxetane-3-yl) methylphenyldimethoxysilane, (oxetane-3-yl) methylphenyldiethoxysilane, (oxetane-3-yl) methylphenyldi-n-propyloxysilane, (Oxetane-3-yl) methylphenyldi-i-propyloxysilane, (oxetane-3-yl) methylphenyldiacetoxysilane, (oxetane-3-yl) ethyltrimethoxysilane, (oxetane-3-yl) ethyl Triethoxysilane, (o Cetane-3-yl) ethyltri-n-propyloxysilane, (oxetane-3-yl) ethyltri-i-propyloxysilane, (oxetane-3-yl) ethyltriacetoxysilane, (oxetane-3-yl) ethylmethyl Dimethoxysilane, (oxetane-3-yl) ethylmethyldiethoxysilane, (oxetane-3-yl) ethylmethyldi-n-propyloxysilane, (oxetane-3-yl) ethylmethyldi-i-propyloxysilane, (oxetane-3 -Yl) ethylmethyldiacetoxysilane, (oxetane-3-yl) ethylethyldimethoxysilane, (oxetane-3-yl) ethylethyldiethoxysilane, (oxetane-3-yl) ethylethyldi-n-propyloxysilane, Oxetane-3-yl) Tylethyldi-i-propyloxysilane, (oxetane-3-yl) ethylethyldiacetoxysilane, (oxetane-3-yl) ethylphenyldimethoxysilane, (oxetane-3-yl) ethylphenyldiethoxysilane, (oxetane-3 -Yl) ethylphenyldi-n-propyloxysilane, (oxetane-3-yl) ethylphenyldi-i-propyloxysilane, (oxetane-3-yl) ethylphenyldiacetoxysilane, (oxetane-3-yl) Propyltrimethoxysilane, (oxetane-3-yl) propyltriethoxysilane, (oxetane-3-yl) propyltri-n-propyloxysilane, (oxetane-3-yl) propyltri-i-propyloxysilane, Oxetane-3-yl) propyl Riacetoxysilane, (oxetane-3-yl) propylmethyldimethoxysilane, (oxetane-3-yl) propylmethyldiethoxysilane, (oxetane-3-yl) propylmethyldi-n-propyloxysilane, (oxetane-3 -Yl) propylmethyldi-i-propyloxysilane, (oxetane-3-yl) propylmethyldiacetoxysilane, (oxetane-3-yl) propylethyldimethoxysilane, (oxetane-3-yl) propylethyldiethoxysilane (Oxetane-3-yl) propylethyldi-n-propyloxysilane, (oxetane-3-yl) propylethyldi-i-propyloxysilane, (oxetane-3-yl) propylethyldiacetoxysilane, (oxetane -3-yl) propyl Phenyldimethoxysilane, (oxetane-3-yl) propylphenyldiethoxysilane, (oxetane-3-yl) propylphenyldi-n-propyloxysilane, (oxetane-3-yl) propylphenyldi-i-propyloxysilane , (Oxetane-3-yl) propylphenyldiacetoxysilane, (3-methyloxetane-3-yl) methyltrimethoxysilane, (3-methyloxetane-3-yl) methyltriethoxysilane, (3-methyloxetane- 3-yl) methyltri-n-propyloxysilane, (3-methyloxetane-3-yl) methyltri-i-propyloxysilane, (3-methyloxetane-3-yl) methyltriacetoxysilane, (3-methyloxetane -3-yl) methylmethyldimethoxy Lan, (3-methyloxetane-3-yl) methylmethyldiethoxysilane, (3-methyloxetane-3-yl) methylmethyldi-n-propyloxysilane, (3-methyloxetane-3-yl) methylmethyldi-i- Propyloxysilane, (3-methyloxetane-3-yl) methylmethyldiacetoxysilane, (3-methyloxetane-3-yl) methylethyldimethoxysilane, (3-methyloxetane-3-yl) methylethyldiethoxysilane (3-methyloxetane-3-yl) methylethyldi-n-propyloxysilane, (3-methyloxetane-3-yl) methylethyldi-i-propyloxysilane, (3-methyloxetane-3-yl) methylethyldi Acetoxysilane, (3-methyloxetane-3-yl Methylphenyldimethoxysilane, (3-methyloxetane-3-yl) methylphenyldiethoxysilane, (3-methyloxetane-3-yl) methylphenyldi-n-propyloxysilane, (3-methyloxetane-3-yl) ) Methylphenyldi-i-propyloxysilane, (3-methyloxetane-3-yl) methylphenyldiacetoxysilane, (3-methyloxetane-3-yl) ethyltrimethoxysilane, (3-methyloxetane-3- Yl) ethyltriethoxysilane, (3-methyloxetane-3-yl) ethyltri-n-propyloxysilane, (3-methyloxetane-3-yl) ethyltri-i-propyloxysilane, (3-methyloxetane-3 -Yl) ethyltriacetoxysilane, (3-methyloxy) Tan-3-yl) ethylmethyldimethoxysilane, (3-methyloxetane-3-yl) ethylmethyldiethoxysilane, (3-methyloxetan-3-yl) ethylmethyldi-n-propyloxysilane, (3-methyloxetane -3-yl) ethylmethyldi-i-propyloxysilane, (3-methyloxetane-3-yl) ethylmethyldiacetoxysilane, (3-methyloxetane-3-yl) ethylethyldimethoxysilane, (3-methyloxetane- 3-yl) ethylethyldiethoxysilane, (3-methyloxetane-3-yl) ethylethyldi-n-propyloxysilane, (3-methyloxetane-3-yl) ethylethyldi-i-propyloxysilane, (3-methyl) Oxetane-3-yl) ethylethyldiacetoxy Silane, (3-methyloxetane-3-yl) ethylphenyldimethoxysilane, (3-methyloxetane-3-yl) ethylphenyldiethoxysilane, (3-methyloxetane-3-yl) ethylphenyldi-n-propyl Oxysilane, (3-methyloxetane-3-yl) ethylphenyldi-i-propyloxysilane, (3-methyloxetane-3-yl) ethylphenyldiacetoxysilane, (3-methyloxetane-3-yl) propyl Trimethoxysilane, (3-methyloxetane-3-yl) propyltriethoxysilane, (3-methyloxetane-3-yl) propyltri-n-propyloxysilane, (3-methyloxetane-3-yl) propyltri -I-propyloxysilane, (3-methyloxetane-3-i ) Propyltriacetoxysilane, (3-methyloxetane-3-yl) propylmethyldimethoxysilane, (3-methyloxetane-3-yl) propylmethyldiethoxysilane, (3-methyloxetane-3-yl) propylmethyldi -N-propyloxysilane, (3-methyloxetane-3-yl) propylmethyldi-i-propyloxysilane, (3-methyloxetane-3-yl) propylmethyldiacetoxysilane, (3-methyloxetane-3 -Yl) propylethyldimethoxysilane, (3-methyloxetane-3-yl) propylethyldiethoxysilane, (3-methyloxetane-3-yl) propylethyldi-n-propyloxysilane, (3-methyloxetane- 3-yl) propylethyldi-i-propylo Silane, (3-methyloxetane-3-yl) propylethyldiacetoxysilane, (3-methyloxetane-3-yl) propylphenyldimethoxysilane, (3-methyloxetane-3-yl) propylphenyldiethoxysilane, ( 3-methyloxetane-3-yl) propylphenyldi-n-propyloxysilane, (3-methyloxetane-3-yl) propylphenyldi-i-propyloxysilane, (3-methyloxetane-3-yl) propyl Phenyldiacetoxysilane,

(3-ethyloxetane-3-yl) methyltrimethoxysilane, (3-ethyloxetane-3-yl) methyltriethoxysilane, (3-ethyloxetane-3-yl) methyltri-n-propyloxysilane, (3 -Ethyloxetane-3-yl) methyltri-i-propyloxysilane, (3-ethyloxetane-3-yl) methyltriacetoxysilane, (3-ethyloxetane-3-yl) methylmethyldimethoxysilane, (3-ethyl Oxetane-3-yl) methylmethyldiethoxysilane, (3-ethyloxetane-3-yl) methylmethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) methylmethyldi-i-propyloxysilane, (3 -Ethyloxetane-3-yl) methylmethyldiacetoxy (3-ethyloxetane-3-yl) methylethyldimethoxysilane, (3-ethyloxetane-3-yl) methylethyldiethoxysilane, (3-ethyloxetane-3-yl) methylethyldi-n-propyloxysilane (3-ethyloxetane-3-yl) methylethyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) methylethyldiacetoxysilane, (3-ethyloxetane-3-yl) methylphenyldimethoxysilane, (3-ethyloxetane-3-yl) methylphenyldiethoxysilane, (3-ethyloxetane-3-yl) methylphenyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) methylphenyldi- i-propyloxysilane, (3-ethyloxetane-3 Yl) methylphenyldiacetoxysilane, (3-ethyloxetane-3-yl) ethyltrimethoxysilane, (3-ethyloxetane-3-yl) ethyltriethoxysilane, (3-ethyloxetane-3-yl) ethyltri- n-propyloxysilane, (3-ethyloxetane-3-yl) ethyltri-i-propyloxysilane, (3-ethyloxetane-3-yl) ethyltriacetoxysilane, (3-ethyloxetane-3-yl) ethyl Methyldimethoxysilane, (3-ethyloxetane-3-yl) ethylmethyldiethoxysilane, (3-ethyloxetane-3-yl) ethylmethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) ethylmethyldi- i-propyloxysilane, (3-ethyloxeta N-yl) ethylmethyldiacetoxysilane, (3-ethyloxetane-3-yl) ethylethyldimethoxysilane, (3-ethyloxetane-3-yl) ethylethyldiethoxysilane, (3-ethyloxetane-3 -Yl) ethylethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) ethylethyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) ethylethyldiacetoxysilane, (3-ethyloxetane -3-yl) ethylphenyldimethoxysilane, (3-ethyloxetane-3-yl) ethylphenyldiethoxysilane, (3-ethyloxetane-3-yl) ethylphenyldi-n-propyloxysilane, (3-ethyl) Oxetane-3-yl) ethylphenyldi-i-propyl Xysilane, (3-ethyloxetane-3-yl) ethylphenyldiacetoxysilane, (3-ethyloxetane-3-yl) propyltrimethoxysilane, (3-ethyloxetane-3-yl) propyltriethoxysilane, (3 -Ethyloxetane-3-yl) propyltri-n-propyloxysilane, (3-ethyloxetane-3-yl) propyltri-i-propyloxysilane, (3-ethyloxetane-3-yl) propyltriacetoxysilane , (3-ethyloxetane-3-yl) propylmethyldimethoxysilane, (3-ethyloxetane-3-yl) propylmethyldiethoxysilane, (3-ethyloxetane-3-yl) propylmethyldi-n-propyloxy Silane, (3-ethyloxetane-3-yl) pro Rumethyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) propylmethyldiacetoxysilane, (3-ethyloxetane-3-yl) propylethyldimethoxysilane, (3-ethyloxetane-3-yl) propyl Ethyldiethoxysilane, (3-ethyloxetane-3-yl) propylethyldi-n-propyloxysilane, (3-ethyloxetane-3-yl) propylethyldi-i-propyloxysilane, (3-ethyloxetane -3-yl) propylethyldiacetoxysilane, (3-ethyloxetane-3-yl) propylphenyldimethoxysilane, (3-ethyloxetane-3-yl) propylphenyldiethoxysilane, (3-ethyloxetane-3- Yl) propylphenyldi-n-propylio Xylsilane, (3-ethyloxetane-3-yl) propylphenyldi-i-propyloxysilane, (3-ethyloxetane-3-yl) propylphenyldiacetoxysilane and the like;

Specific examples of the compound (1) containing a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri-n-propyloxysilane, vinyltri-i-propyloxysilane, vinyltriacetoxysilane, vinyltri (methoxyethoxy). ) Silane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinylmethyldi-n-propyloxysilane, vinylmethyldi-i-propyloxysilane, vinylmethyldiacetoxysilane, vinylethyldimethoxysilane, vinylethyldiethoxysilane, vinylethyldi-n -Propyloxysilane, Vinylethyldi-i-propyloxysilane, Vinylethyldiacetoxysilane, Vinylethyldi (methoxyethoxy) silane, Vinylphenyldimethoxysilane Vinylphenyl diethoxysilane, vinylphenyl di -n- propyl silane, vinyl phenyl di -i- propyl silane, vinyl phenyl diacetoxy silane, and vinyl phenyl di (methoxyethoxy) silane;
Specific examples of the compound (1) containing an allyl group include allyltrimethoxysilane, allyltriethoxysilane, allyltri-n-propyloxysilane, allyltri-i-propyloxysilane, allyltriacetoxysilane, allyltri (methoxyethoxy). ) Silane, allylmethyldimethoxysilane, allylmethyldiethoxysilane, allylmethyldi-n-propyloxysilane, allylmethyldi-i-propyloxysilane, allylmethyldiacetoxysilane, allylethyldimethoxysilane, allylethyldiethoxysilane, allylethyldi-n -Propyloxysilane, allylethyldi-i-propyloxysilane, allylethyldiacetoxysilane, allylethyldi (methoxyethoxy) silane, allylphenyldimethoxysilane Allyl phenyl diethoxy silane, allyl phenyl di -n- propyl silane, allyl phenyl di -i- propyl silane, allyl phenyl diacetoxy silane, and allyl phenyl di (methoxyethoxy) silane;

  Specific examples of the compound (1) containing a (meth) acryloyl group include 3- (meth) acryloxymethyltrimethoxysilane, 3- (meth) acryloxymethyltriethoxysilane, and 3- (meth) acryloxymethyl. Tri-n-propyloxysilane, 3- (meth) acryloxymethyltri-i-propyloxysilane, 3- (meth) acryloxymethyltriacetoxysilane, 3- (meth) acryloxymethylmethyldimethoxysilane, 3- (Meth) acryloxymethylmethyldiethoxysilane, 3- (meth) acryloxymethylmethyldi-n-propyloxysilane, 3- (meth) acryloxymethylmethyldi-i-propyloxysilane, 3- (meth) Acryloxymethylmethyldiacetoxysilane, 3- (meth) acryloxymethyl ester Rudimethoxysilane, 3- (meth) acryloxymethylethyldiethoxysilane, 3- (meth) acryloxymethylethyldi-n-propyloxysilane, 3- (meth) acryloxymethylethyldi-i-propyloxysilane 3- (meth) acryloxymethylethyldiacetoxysilane, 3- (meth) acryloxymethylphenyldimethoxysilane, 3- (meth) acryloxymethylphenyldiethoxysilane, 3- (meth) acryloxymethylphenyldi- n-propyloxysilane, 3- (meth) acryloxymethylphenyldi-i-propyloxysilane, 3- (meth) acryloxymethylphenyldiacetoxysilane, 3- (meth) acryloxyethyltrimethoxysilane, 3- (Meth) acryloxyethyl triethoxysila 3- (meth) acryloxyethyltri-n-propyloxysilane, 3- (meth) acryloxyethyltri-i-propyloxysilane, 3- (meth) acryloxyethyltriacetoxysilane, 3- (meth) Acryloxyethylmethyldimethoxysilane, 3- (meth) acryloxyethylmethyldiethoxysilane, 3- (meth) acryloxyethylmethyldi-n-propyloxysilane, 3- (meth) acryloxyethylmethyldi-i- Propyloxysilane, 3- (meth) acryloxyethylmethyldiacetoxysilane, 3- (meth) acryloxyethylethyldimethoxysilane, 3- (meth) acryloxyethylethyldiethoxysilane, 3- (meth) acryloxyethyl Ethyldi-n-propyloxysilane, 3- (meth) acryl Loxyethylethyldi-i-propyloxysilane, 3- (meth) acryloxyethylethyldiacetoxysilane, 3- (meth) acryloxyethylphenyldimethoxysilane, 3- (meth) acryloxyethylphenyldiethoxysilane, 3 -(Meth) acryloxyethylphenyldi-n-propyloxysilane, 3- (meth) acryloxyethylphenyldi-i-propyloxysilane, 3- (meth) acryloxyethylphenyldiacetoxysilane, 3- (meth) ) Acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxypropyltri-n-propyloxysilane, 3- (meth) acryloxypropyltri-i-propyloxy Silane, 3- (meth) acryloxy Propyltriacetoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropylmethyldi-n-propyloxysilane, 3- (Meth) acryloxypropylmethyldi-i-propyloxysilane, 3- (meth) acryloxypropylmethyldiacetoxysilane, 3- (meth) acryloxypropylethyldimethoxysilane, 3- (meth) acryloxypropylethyldi Ethoxysilane, 3- (meth) acryloxypropylethyl di-n-propyloxysilane, 3- (meth) acryloxypropylethyldi-i-propyloxysilane, 3- (meth) acryloxypropylethyldiacetoxysilane, 3- (Meth) acryloxy Propylphenyldimethoxysilane, 3- (meth) acryloxypropylphenyldiethoxysilane, 3- (meth) acryloxypropylphenyldi-n-propyloxysilane, 3- (meth) acryloxypropylphenyldi-i-propyl Oxysilane, 3- (meth) acryloxypropylphenyldiacetoxysilane, etc .;

  Specific examples of the compound (1) containing a carboxyl group include carboxymethyltrimethoxysilane, carboxymethyltriethoxysilane, carboxymethyltri-n-propyloxysilane, carboxymethyltri-i-propyloxysilane, carboxymethyltrimethoxysilane. Acetoxysilane, carboxymethyltri (methoxyethoxy) silane, carboxymethylmethyldimethoxysilane, carboxymethylmethyldiethoxysilane, carboxymethylmethyldi-n-propyloxysilane, carboxymethylmethyldi-i-propyloxysilane, carboxymethylmethyl Diacetoxysilane, carboxymethylethyldimethoxysilane, carboxymethylethyldiethoxysilane, carboxymethylethyldi-n-propyloxysilane, Ruboxymethylethyldi-i-propyloxysilane, carboxymethylethyldiacetoxysilane, carboxymethylethyldi (methoxyethoxy) silane, carboxymethylphenyldimethoxysilane, carboxymethylphenyldiethoxysilane, carboxymethylphenyldi-n-propyl Oxysilane, carboxymethylphenyldi-i-propyloxysilane, carboxymethylphenyldiacetoxysilane, carboxymethylphenyldi (methoxyethoxy) silane, 2-carboxyethyltrimethoxysilane, 2-carboxyethyltriethoxysilane, 2-carboxy Ethyltri-n-propyloxysilane, 2-carboxyethyltri-i-propyloxysilane, 2-carboxyethyltriacetoxysilane, 2- Ruboxyethyltri (methoxyethoxy) silane, 2-carboxyethylmethyldimethoxysilane, 2-carboxyethylmethyldiethoxysilane, 2-carboxyethylmethyldi-n-propyloxysilane, 2-carboxyethylmethyldi-i-propyl Oxysilane, 2-carboxyethylmethyldiacetoxysilane, 2-carboxyethylethyldimethoxysilane, 2-carboxyethylethyldiethoxysilane, 2-carboxyethylethyldi-n-propyloxysilane, 2-carboxyethylethyldi-i -Propyloxysilane, 2-carboxyethylethyldiacetoxysilane, 2-carboxyethylethyldi (methoxyethoxy) silane, 2-carboxyethylphenyldimethoxysilane, 2-carboxyethylpheny Rudiethoxysilane, 2-carboxyethylphenyldi-n-propyloxysilane, 2-carboxyethylphenyldi-i-propyloxysilane, 2-carboxyethylphenyldiacetoxysilane, 2-carboxyethylphenyldi (methoxyethoxy) silane Such;

  Specific examples of the compound (1) containing a hydroxyl group include hydroxymethyltrimethoxysilane, hydroxymethyltriethoxysilane, hydroxymethyltri-n-propyloxysilane, hydroxymethyltri-i-propyloxysilane, hydroxymethyltrimethoxysilane. Acetoxysilane, hydroxymethyltri (methoxyethoxy) silane, hydroxymethylmethyldimethoxysilane, hydroxymethylmethyldiethoxysilane, hydroxymethylmethyldi-n-propyloxysilane, hydroxymethylmethyldi-i-propyloxysilane, hydroxymethylmethyl Diacetoxysilane, hydroxymethylethyldimethoxysilane, hydroxymethylethyldiethoxysilane, hydroxymethylethyldi-n-propyloxysilane, Droxymethylethyldi-i-propyloxysilane, hydroxymethylethyldiacetoxysilane, hydroxymethylethyldi (methoxyethoxy) silane, hydroxymethylphenyldimethoxysilane, hydroxymethylphenyldiethoxysilane, hydroxymethylphenyldi-n-propyl Oxysilane, hydroxymethylphenyldi-i-propyloxysilane, hydroxymethylphenyldiacetoxysilane, hydroxymethylphenyldi (methoxyethoxy) silane, 2-hydroxyethyltrimethoxysilane, 2-hydroxyethyltriethoxysilane, 2-hydroxy Ethyltri-n-propyloxysilane, 2-hydroxyethyltri-i-propyloxysilane, 2-hydroxyethyltriacetoxysilane, 2- Droxyethyltri (methoxyethoxy) silane, 2-hydroxyethylmethyldimethoxysilane, 2-hydroxyethylmethyldiethoxysilane, 2-hydroxyethylmethyldi-n-propyloxysilane, 2-hydroxyethylmethyldi-i-propyl Oxysilane, 2-hydroxyethylmethyldiacetoxysilane, 2-hydroxyethylethyldimethoxysilane, 2-hydroxyethylethyldiethoxysilane, 2-hydroxyethylethyldi-n-propyloxysilane, 2-hydroxyethylethyldi-i -Propyloxysilane, 2-hydroxyethylethyldiacetoxysilane, 2-hydroxyethylethyldi (methoxyethoxy) silane, 2-hydroxyethylphenyldimethoxysilane, 2-hydroxyethylpheny Rudiethoxysilane, 2-hydroxyethylphenyldi-n-propyloxysilane, 2-hydroxyethylphenyldi-i-propyloxysilane, 2-hydroxyethylphenyldiacetoxysilane, 2-hydroxyethylphenyldi (methoxyethoxy) silane 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltriethoxysilane, 3-hydroxypropyltri-n-propyloxysilane, 3-hydroxypropyltri-i-propyloxysilane, 3-hydroxypropyltriacetoxysilane, 3 -Hydroxypropyltri (methoxyethoxy) silane, 3-hydroxypropylmethyldimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropylmethyldi-n-propiyl Oxysilane, 3-hydroxypropylmethyldi-i-propyloxysilane, 3-hydroxypropylmethyldiacetoxysilane, 3-hydroxypropylethyldimethoxysilane, 3-hydroxypropylethyldiethoxysilane, 3-hydroxypropylethyldi-n- Propyloxysilane, 3-hydroxypropylethyldi-i-propyloxysilane, 3-hydroxypropylethyldiacetoxysilane, 3-hydroxypropylethyldi (methoxyethoxy) silane, 3-hydroxypropylphenyldimethoxysilane, 3-hydroxypropyl Phenyldiethoxysilane, 3-hydroxypropylphenyldi-n-propyloxysilane, 3-hydroxypropylphenyldi-i-propyloxysilane, 3-hydroxy Propylphenyldiacetoxysilane, 3-hydroxypropylphenyldi (methoxyethoxy) silane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyltrimethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyltri Ethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyltri-n-propyloxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyltri-i-propyloxysilane, 4-hydroxy- (p- Hydroxyphenylcarbonyloxy) benzyltriacetoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyltri (methoxyethoxy) silane, 4-hydroxy- ( p-hydroxyphenylcarbonyloxy) benzylmethyldimethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylmethyldiethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylmethyldi-n-propyloxy Silane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylmethyldi-i-propyloxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylmethyldiacetoxysilane, 4-hydroxy- (p-hydroxy) Phenylcarbonyloxy) benzylethyldimethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylethyldiethoxysilane, 4-hydroxy- (p-hydro) Ciphenylcarbonyloxy) benzylethyldi-n-propyloxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylethyldi-i-propyloxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzyl Ethyldiacetoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylethyldi (methoxyethoxy) silane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylphenyldimethoxysilane, 4-hydroxy- (p- Hydroxyphenylcarbonyloxy) benzylphenyldiethoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylphenyldi-n-propyloxysilane, 4-hydride Xy- (p-hydroxyphenylcarbonyloxy) benzylphenyldi-i-propyloxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) benzylphenyldiacetoxysilane, 4-hydroxy- (p-hydroxyphenylcarbonyloxy) Benzylphenyldi (methoxyethoxy) silane and the like;

Specific examples of the compound (1) containing a mercapto group include mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltri-n-propyloxysilane, mercaptomethyltri-i-propyloxysilane, mercaptomethyltri Acetoxysilane, mercaptomethyltri (methoxyethoxy) silane, mercaptomethylmethyldimethoxysilane, mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldi-n-propyloxysilane, mercaptomethylmethyldi-i-propyloxysilane, mercaptomethylmethyl Diacetoxysilane, mercaptomethylethyldimethoxysilane, mercaptomethylethyldiethoxysilane, mercaptomethylethyldi-n-propyloxysilane, Captomethylethyldi-i-propyloxysilane, mercaptomethylethyldiacetoxysilane, mercaptomethylethyldi (methoxyethoxy) silane, mercaptomethylphenyldimethoxysilane, mercaptomethylphenyldiethoxysilane, mercaptomethylphenyldi-n-propyloxy Silane, mercaptomethylphenyldi-i-propyloxysilane, mercaptomethylphenyldiacetoxysilane, mercaptomethylphenyldi (methoxyethoxy) silane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 2-mercaptoethyl Tri-n-propyloxysilane, 2-mercaptoethyltri-i-propyloxysilane, 2-mercaptoethyltriacetoxysilane, 2-me Captoethyltri (methoxyethoxy) silane, 2-mercaptoethylmethyldimethoxysilane, 2-mercaptoethylmethyldiethoxysilane, 2-mercaptoethylmethyldi-n-propyloxysilane, 2-mercaptoethylmethyldi-i-propyloxy Silane, 2-mercaptoethylmethyldiacetoxysilane, 2-mercaptoethylethyldimethoxysilane, 2-mercaptoethylethyldiethoxysilane, 2-mercaptoethylethyldi-n-propyloxysilane, 2-mercaptoethylethyldi-i- Propyloxysilane, 2-mercaptoethylethyldiacetoxysilane, 2-mercaptoethylethyldi (methoxyethoxy) silane, 2-mercaptoethylphenyldimethoxysilane, 2-mercaptoethylphenyl Diethoxysilane, 2-mercaptoethylphenyldi-n-propyloxysilane, 2-mercaptoethylphenyldi-i-propyloxysilane, 2-mercaptoethylphenyldiacetoxysilane, 2-mercaptoethylphenyldi (methoxyethoxy) silane 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltri-n-propyloxysilane, 3-mercaptopropyltri-i-propyloxysilane, 3-mercaptopropyltriacetoxysilane, 3 -Mercaptopropyltri (methoxyethoxy) silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldi-n-propyl Xysilane, 3-mercaptopropylmethyldi-i-propyloxysilane, 3-mercaptopropylmethyldiacetoxysilane, 3-mercaptopropylethyldimethoxysilane, 3-mercaptopropylethyldiethoxysilane, 3-mercaptopropylethyldi-n- Propyloxysilane, 3-mercaptopropylethyldi-i-propyloxysilane, 3-mercaptopropylethyldiacetoxysilane, 3-mercaptopropylethyldi (methoxyethoxy) silane, 3-mercaptopropylphenyldimethoxysilane, 3-mercaptopropyl Phenyldiethoxysilane, 3-mercaptopropylphenyldi-n-propyloxysilane, 3-mercaptopropylphenyldi-i-propyloxysilane, 3-mercaptop Pills phenyl diacetoxy silane, 3-mercaptopropyl phenyl di (methoxyethoxy) silane, and the like;
Specific examples of the compound (1) containing an isocyanate group include isocyanate methyltrimethoxysilane, isocyanatemethyltriethoxysilane, isocyanatemethyltri-n-propyloxysilane, isocyanatemethyltri-i-propyloxysilane, isocyanatemethyltri Acetoxysilane, isocyanatemethyltri (methoxyethoxy) silane, isocyanatemethylmethyldimethoxysilane, isocyanatemethylmethyldiethoxysilane, isocyanatemethylmethyldi-n-propyloxysilane, isocyanatemethylmethyldi-i-propyloxysilane, isocyanatemethylmethyl Diacetoxysilane, Isocyanatomethylethyldimethoxysilane, Isocyanatomethylethyldiethoxysilane Isocyanatomethylethyldi-n-propyloxysilane, Isocyanatomethylethyldi-i-propyloxysilane, Isocyanatomethylethyldiacetoxysilane, Isocyanatomethylethyldi (methoxyethoxy) silane, Isocyanatomethylphenyldimethoxysilane, Isocyanatomethylphenyldiethoxy Silane, isocyanate methylphenyldi-n-propyloxysilane, isocyanatemethylphenyldi-i-propyloxysilane, isocyanatemethylphenyldiacetoxysilane, isocyanatemethylphenyldi (methoxyethoxy) silane, 2-isocyanatoethyltrimethoxysilane, 2 -Isocyanatoethyltriethoxysilane, 2-isocyanatoethyltri-n-propyloxy Lan, 2-isocyanatoethyltri-i-propyloxysilane, 2-isocyanateethyltriacetoxysilane, 2-isocyanateethyltri (methoxyethoxy) silane, 2-isocyanateethylmethyldimethoxysilane, 2-isocyanateethylmethyldiethoxysilane, 2-isocyanatoethylmethyldi-n-propyloxysilane, 2-isocyanateethylmethyldi-i-propyloxysilane, 2-isocyanateethylmethyldiacetoxysilane, 2-isocyanateethylethyldimethoxysilane, 2-isocyanateethylethyldiethoxy Silane, 2-isocyanatoethylethyl di-n-propyloxysilane, 2-isocyanatoethylethyldi-i-propyloxysilane, 2-isocyanate Tylethyldiacetoxysilane, 2-isocyanateethylethyldi (methoxyethoxy) silane, 2-isocyanateethylphenyldimethoxysilane, 2-isocyanateethylphenyldiethoxysilane, 2-isocyanateethylphenyldi-n-propyloxysilane, 2- Isocyanatoethylphenyldi-i-propyloxysilane, 2-isocyanatoethylphenyldiacetoxysilane, 2-isocyanatoethylphenyldi (methoxyethoxy) silane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3- Isocyanatopropyltri-n-propyloxysilane, 3-isocyanatopropyltri-i-propyloxysilane, 3-isocyanatopropyltri Cetoxysilane, 3-isocyanatopropyltri (methoxyethoxy) silane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropylmethyldi-n-propyloxysilane, 3-isocyanatepropylmethyldi- i-propyloxysilane, 3-isocyanatepropylmethyldiacetoxysilane, 3-isocyanatepropylethyldimethoxysilane, 3-isocyanatepropylethyldiethoxysilane, 3-isocyanatepropylethyldi-n-propyloxysilane, 3-isocyanatepropylethyl Di-i-propyloxysilane, 3-isocyanatopropylethyldiacetoxysilane, 3-isocyanatopropylethyldi (me Xyethoxy) silane, 3-isocyanatopropylphenyldimethoxysilane, 3-isocyanatopropylphenyldiethoxysilane, 3-isocyanatepropylphenyldi-n-propyloxysilane, 3-isocyanatopropylphenyldi-i-propyloxysilane, 3-isocyanate Propylphenyldiacetoxysilane, 3-isocyanatopropylphenyldi (methoxyethoxy) silane, etc .;

  Specific examples of the compound (1) containing an amino group include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, aminomethyltri-n-propyloxysilane, aminomethyltri-i-propyloxysilane, aminomethyltrimethoxysilane. Acetoxysilane, aminomethyltri (methoxyethoxy) silane, aminomethylmethyldimethoxysilane, aminomethylmethyldiethoxysilane, aminomethylmethyldi-n-propyloxysilane, aminomethylmethyldi-i-propyloxysilane, aminomethylmethyl Diacetoxysilane, aminomethylethyldimethoxysilane, aminomethylethyldiethoxysilane, aminomethylethyldi-n-propyloxysilane, aminomethylethyldi-i-propyloxysilane, aminomethylethyl Rudiacetoxysilane, aminomethylethyldi (methoxyethoxy) silane, aminomethylphenyldimethoxysilane, aminomethylphenyldiethoxysilane, aminomethylphenyldi-n-propyloxysilane, aminomethylphenyldi-i-propyloxysilane, amino Methylphenyldiacetoxysilane, aminomethylphenyldi (methoxyethoxy) silane, 2-aminoethyltrimethoxysilane, 2-aminoethyltriethoxysilane, 2-aminoethyltri-n-propyloxysilane, 2-aminoethyltri- i-propyloxysilane, 2-aminoethyltriacetoxysilane, 2-aminoethyltri (methoxyethoxy) silane, 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane 2-aminoethylmethyldi-n-propyloxysilane, 2-aminoethylmethyldi-i-propyloxysilane, 2-aminoethylmethyldiacetoxysilane, 2-aminoethylethyldimethoxysilane, 2-aminoethylethyl Diethoxysilane, 2-aminoethylethyldi-n-propyloxysilane, 2-aminoethylethyldi-i-propyloxysilane, 2-aminoethylethyldiacetoxysilane, 2-aminoethylethyldi (methoxyethoxy) silane 2-aminoethylphenyldimethoxysilane, 2-aminoethylphenyldiethoxysilane, 2-aminoethylphenyldi-n-propyloxysilane, 2-aminoethylphenyldi-i-propyloxysilane, 2-aminoethylphenyldi Acetoxysilane, 2 -Aminoethylphenyldi (methoxyethoxy) silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltri-n-propyloxysilane, 3-aminopropyltri-i-propyloxysilane 3-aminopropyltriacetoxysilane, 3-aminopropyltri (methoxyethoxy) silane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldi-n-propyloxysilane, 3-aminopropylmethyldi-i-propyloxysilane, 3-aminopropylmethyldiacetoxysilane, 3-aminopropylethyldimethoxysilane, 3-aminopropylethyldiethoxysilane, 3-aminopropylethyldi- -Propyloxysilane, 3-aminopropylethyldi-i-propyloxysilane, 3-aminopropylethyldiacetoxysilane, 3-aminopropylethyldi (methoxyethoxy) silane, 3-aminopropylphenyldimethoxysilane, 3-amino Propylphenyldiethoxysilane, 3-aminopropylphenyldi-n-propyloxysilane, 3-aminopropylphenyldi-i-propyloxysilane, 3-aminopropylphenyldiacetoxysilane, 3-aminopropylphenyldi (methoxyethoxy) ) Silane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyl Tri-n-Pro Ruoxysilane, N-2- (aminoethyl) -3-aminopropyltri-i-propyloxysilane, N-2- (aminoethyl) -3-aminopropyltriacetoxysilane, N-2- (aminoethyl) -3 -Aminopropyltri (methoxyethoxy) silane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- ( Aminoethyl) -3-aminopropylmethyldi-n-propyloxysilane, N-2- (aminoethyl) -3-aminopropylmethyldi-i-propyloxysilane, N-2- (aminoethyl) -3- Aminopropylmethyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylethyldimethoxysilane N-2- (aminoethyl) -3-aminopropylethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropylethyldi-n-propyloxysilane, N-2- (aminoethyl)- 3-aminopropylethyldi-i-propyloxysilane, N-2- (aminoethyl) -3-aminopropylethyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylethyldi (methoxyethoxy) Silane, N-2- (aminoethyl) -3-aminopropylphenyldimethoxysilane, N-2- (aminoethyl) -3-aminopropylphenyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyl Phenyldi-n-propyloxysilane, N-2- (aminoethyl) -3-aminopropylphenyldi-i-pro Ruoxysilane, N-2- (aminoethyl) -3-aminopropylphenyldiacetoxysilane, N-2- (aminoethyl) -3-aminopropylphenyldi (methoxyethoxy) silane, aminomethyltrimethoxysilane, aminomethyltri Ethoxysilane, aminomethyltri-n-propyloxysilane, aminomethyltri-i-propyloxysilane, aminomethyltriacetoxysilane, aminomethyltri (methoxyethoxy) silane, aminomethylmethyldimethoxysilane, aminomethylmethyldiethoxysilane Aminomethylmethyldi-n-propyloxysilane, aminomethylmethyldi-i-propyloxysilane, aminomethylmethyldiacetoxysilane, aminomethylethyldimethoxysilane, aminomethylethyldie Xysilane, aminomethylethyldi-n-propyloxysilane, aminomethylethyldi-i-propyloxysilane, aminomethylethyldiacetoxysilane, aminomethylethyldi (methoxyethoxy) silane, aminomethylphenyldimethoxysilane, aminomethylphenyl Diethoxysilane, aminomethylphenyldi-n-propyloxysilane, aminomethylphenyldi-i-propyloxysilane, aminomethylphenyldiacetoxysilane, aminomethylphenyldi (methoxyethoxy) silane, 2-aminoethyltrimethoxysilane 2-aminoethyltriethoxysilane, 2-aminoethyltri-n-propyloxysilane, 2-aminoethyltri-i-propyloxysilane, 2-aminoethyltriacetoxysilane, 2-aminoethyltri (methoxyethoxy) silane, 2-aminoethylmethyldimethoxysilane, 2-aminoethylmethyldiethoxysilane, 2-aminoethylmethyldi-n-propyloxysilane, 2-aminoethylmethyldi-i- Propyloxysilane, 2-aminoethylmethyldiacetoxysilane, 2-aminoethylethyldimethoxysilane, 2-aminoethylethyldiethoxysilane, 2-aminoethylethyldi-n-propyloxysilane, 2-aminoethylethyldi- i-propyloxysilane, 2-aminoethylethyldiacetoxysilane, 2-aminoethylethyldi (methoxyethoxy) silane, 2-aminoethylphenyldimethoxysilane, 2-aminoethylphenyldiethoxysilane, 2-aminoethylphenyldi -N Propyloxysilane, 2-aminoethylphenyldi-i-propyloxysilane, 2-aminoethylphenyldiacetoxysilane, 2-aminoethylphenyldi (methoxyethoxy) silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltri-n-propyloxysilane, N-phenyl-3-aminopropyltri-i-propyloxysilane, N-phenyl-3- Aminopropyltriacetoxysilane, N-phenyl-3-aminopropyltri (methoxyethoxy) silane, N-phenyl-3-aminopropylmethyldimethoxysilane, N-phenyl-3-aminopropylmethyldiethoxysilane, N-phenyl- 3-aminopro Rumethyldi-n-propyloxysilane, N-phenyl-3-aminopropylmethyldi-i-propyloxysilane, N-phenyl-3-aminopropylmethyldiacetoxysilane, N-phenyl-3-aminopropylethyldimethoxysilane, N-phenyl-3-aminopropylethyldiethoxysilane, N-phenyl-3-aminopropylethyldi-n-propyloxysilane, N-phenyl-3-aminopropylethyldi-i-propyloxysilane, N-phenyl -3-aminopropylethyldiacetoxysilane, N-phenyl-3-aminopropylethyldi (methoxyethoxy) silane, N-phenyl-3-aminopropylphenyldimethoxysilane, N-phenyl-3-aminopropylphenyldiethoxysilane N-phenyl -3-aminopropylphenyldi-n-propyloxysilane, N-phenyl-3-aminopropylphenyldi-i-propyloxysilane, N-phenyl-3-aminopropylphenyldiacetoxysilane, N-phenyl-3- Aminopropylphenyldi (methoxyethoxy) silane, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, 3-tri-n-propyloxysilyl-N- (1,3-dimethyl-butylidene) propylamine and the like;

  Specific examples of the compound (1) containing a ureido group include isocyanate methyltrimethoxysilane, ureidomethyltriethoxysilane, ureidomethyltri-n-propyloxysilane, ureidomethyltri-i-propyloxysilane, ureidomethyltri Acetoxysilane, ureidomethyltri (methoxyethoxy) silane, ureidomethylmethyldimethoxysilane, ureidomethylmethyldiethoxysilane, ureidomethylmethyldi-n-propyloxysilane, ureidomethylmethyldi-i-propyloxysilane, ureidomethylmethyl Diacetoxysilane, ureidomethylethyldimethoxysilane, ureidomethylethyldiethoxysilane, ureidomethylethyldi-n-propyloxysilane, ureidomethylethyldi-i Propyloxysilane, ureidomethylethyldiacetoxysilane, ureidomethylethyldi (methoxyethoxy) silane, ureidomethylphenyldimethoxysilane, ureidomethylphenyldiethoxysilane, ureidomethylphenyldi-n-propyloxysilane, ureidomethylphenyldi- i-propyloxysilane, ureidomethylphenyldiacetoxysilane, ureidomethylphenyldi (methoxyethoxy) silane, 2-ureidoethyltrimethoxysilane, 2-ureidoethyltriethoxysilane, 2-ureidoethyltri-n-propyloxysilane 2-ureidoethyltri-i-propyloxysilane, 2-ureidoethyltriacetoxysilane, 2-ureidoethyltri (methoxyethoxy) silane, 2-uree Doethylmethyldimethoxysilane, 2-ureidoethylmethyldiethoxysilane, 2-ureidoethylmethyldi-n-propyloxysilane, 2-ureidoethylmethyldi-i-propyloxysilane, 2-ureidoethylmethyldiacetoxysilane, 2-ureidoethylethyldimethoxysilane, 2-ureidoethylethyldiethoxysilane, 2-ureidoethylethyldi-n-propyloxysilane, 2-ureidoethylethyldi-i-propyloxysilane, 2-ureidoethylethyldiacetoxy Silane, 2-ureidoethylethyldi (methoxyethoxy) silane, 2-ureidoethylphenyldimethoxysilane, 2-ureidoethylphenyldiethoxysilane, 2-ureidoethylphenyldi-n-propyloxysilane, 2-urea Raidethylphenyldi-i-propyloxysilane, 2-ureidoethylphenyldiacetoxysilane, 2-ureidoethylphenyldi (methoxyethoxy) silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3- Ureidopropyltri-n-propyloxysilane, 3-ureidopropyltri-i-propyloxysilane, 3-ureidopropyltriacetoxysilane, 3-ureidopropyltri (methoxyethoxy) silane, 3-ureidopropylmethyldimethoxysilane, 3 -Ureidopropylmethyldiethoxysilane, 3-ureidopropylmethyldi-n-propyloxysilane, 3-ureidopropylmethyldi-i-propyloxysilane, 3-ureidopropylmethyldiacetoxy Silane, 3-ureidopropylethyldimethoxysilane, 3-ureidopropylethyldiethoxysilane, 3-ureidopropylethyldi-n-propyloxysilane, 3-ureidopropylethyldi-i-propyloxysilane, 3-ureidopropylethyl Diacetoxysilane, 3-ureidopropylethyldi (methoxyethoxy) silane, 3-ureidopropylphenyldimethoxysilane, 3-ureidopropylphenyldiethoxysilane, 3-ureidopropylphenyldi-n-propyloxysilane, 3-ureidopropyl Phenyldi-i-propyloxysilane, 3-ureidopropylphenyldiacetoxysilane, 3-ureidopropylphenyldi (methoxyethoxy) silane and the like;

Specific examples of the compound (1) containing a styryl group include styryltrimethoxysilane, styryltriethoxysilane, styryltri-n-propyloxysilane, styryltri-i-propyloxysilane, styryltriacetoxysilane, styryltri (methoxyethoxy). ) Silane, styrylmethyldimethoxysilane, styrylmethyldiethoxysilane, styrylmethyldi-n-propyloxysilane, styrylmethyldi-i-propyloxysilane, styrylmethyldiacetoxysilane, styrylethyldimethoxysilane, styrylethyldiethoxysilane Styrylethyldi-n-propyloxysilane, styrylethyldi-i-propyloxysilane, styrylethyldiacetoxysilane, styrylethyldi (methoxyethoxy) silane Emissions, styryl phenyl dimethoxy silane, styryl phenyl diethoxy silane, styryl phenyl di -n- propyl silane, styryl phenyl di -i- propyl silane, styryl phenyl diacetoxy silane, styryl phenyl di (methoxyethoxy) silane, and the like;
Can be mentioned.

  Of these, the compound (1) containing an oxiranyl group, an oxetanyl group, a hydroxyl group, and a mercapto group is preferably used, particularly 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3- Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ( 3-ethyloxetane-3-yl) propyltrimethoxysilane, (3-ethyloxetane-3-yl) propyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane and [A] component Reactivity and Especially from the viewpoint of storage stability.

  Specific examples of the compound (2) include tetramethoxysilane, tetraethoxysilane (commonly referred to as TEOS), tetraalkoxysilane such as tetra-n-propyloxysilane, tetraisopropyloxysilane, tetra-n-butoxysilane; methyltrimethoxy Monoalkyltrialkoxysilanes such as silane, methyltriethoxysilane, methyltri-n-propyloxysilane, ethyltriethoxysilane, cyclohexyltriethoxysilane; phenyltriethoxysilane, naphthyltriethoxysilane, 4-chlorophenyltriethoxysilane, 4 -Cyanophenyltriethoxysilane, 4-aminophenyltriethoxysilane, 4-nitrophenyltriethoxysilane, 4-methylphenyltriethoxysilane, 4-hydroxyphenyl Monoaryltrialkoxysilanes such as triethoxysilane; phenoxytriethoxysilane, naphthyloxytriethoxysilane, 4-chlorophenyloxytriethoxysilane, 4-cyanophenyltrioxyethoxysilane, 4-aminophenyloxytriethoxysilane, 4- Monoaryloxytrialkoxysilanes such as nitrophenyloxytriethoxysilane, 4-methylphenyloxytriethoxysilane, 4-hydroxyphenyloxytriethoxysilane; monohydroxytrimethoxysilane, monohydroxytriethoxysilane, monohydroxytri-n Monohydroxytrialkoxysilanes such as propyloxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldi-n-propyl Dialkyl dialkoxysilanes such as xylsilane, methyl (ethyl) diethoxysilane, methyl (cyclohexyl) diethoxysilane; monoalkylmonoaryl dialkoxysilanes such as methyl (phenyl) diethoxysilane; diaryl dialkoxy such as diphenyldiethoxysilane Silanes; diaryloxy dialkoxy silanes such as diphenoxydiethoxy silane; monoalkyl monoaryloxy dialkoxy silanes such as methyl (phenoxy) diethoxy silane; monoaryl monoaryloxy dialkoxy silanes such as phenyl (phenoxy) diethoxy silane Dihydroxydialkoxysilanes such as dihydroxydimethoxysilane, dihydroxydiethoxysilane, dihydroxydi-n-propyloxysilane; Monoalkyl monohydroxy dialkoxysilanes such as ru (hydroxy) dimethoxysilane; monoaryl monohydroxy dialkoxysilanes such as phenyl (hydroxy) dimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, trimethyl-n-propyloxysilane, dimethyl ( Trialkylmonoalkoxysilanes such as ethyl) ethoxysilane, dimethyl (cyclohexyl) ethoxysilane; dialkylmonoarylmonoalkoxysilanes such as dimethyl (phenyl) ethoxysilane; monoalkyldiarylmonoalkoxysilanes such as methyl (diphenyl) ethoxysilane; Triaryloxy monoalkoxysilanes such as phenoxyethoxysilane; mono such as methyl (diphenoxy) ethoxysilane Alkyl diaryloxy monoalkoxysilanes; monoaryl diaryloxy monoalkoxy silanes such as phenyl (diphenoxy) ethoxysilane; dialkyl monoaryloxy monoalkoxy silanes such as dimethyl (phenoxy) ethoxysilane; diaryl monoaryls such as diphenyl (phenoxy) ethoxysilane Oxymonoalkoxysilanes; monoalkylmonoarylmonoaryloxymonoalkoxysilanes such as methyl (phenyl) (phenoxy) ethoxysilane; trihydroxymonosilanes such as trihydroxymethoxysilane, trihydroxyethoxysilane, trihydroxy-n-propyloxysilane Mention may be made of alkoxysilanes.

Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane It is preferable in terms of reactivity and adhesion to the substrate.
Any number of these compounds may be used in combination with any composition.
The above compound can be used as a component [D] used in the present invention by subjecting it to a cohydrolysis reaction.

  The hydrolysis reaction is preferably performed in a suitable solvent. Examples of such solvents include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, t-butyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, Examples thereof include water-soluble solvents such as tetrahydrofuran, dioxane and acetonitrile, and aqueous solutions thereof.

  Since these water-soluble solvents are removed in a later step, those having a relatively low boiling point such as methanol, ethanol, n-propanol, isopropyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, and tetrahydrofuran are suitable, and the raw material is dissolved. From the viewpoint of properties, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are more preferable, and methyl isobutyl ketone is most preferable.

  The hydrolysis reaction for synthesizing the component [D] is preferably an acid catalyst (for example, hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, acidic ion exchange resin, various Lewis acids, etc.) or base catalysts (eg, ammonia, primary amines, secondary amines, tertiary amines, nitrogen-containing aromatic compounds such as pyridine, basic ion exchange resins, hydroxides such as sodium hydroxide) , Carbonates such as potassium carbonate, carboxylates such as sodium acetate, and various Lewis bases). The amount of water used, the reaction temperature, and the reaction time are appropriately set. For example, the following conditions can be adopted.

The amount of water used is preferably 1.5 mol or less, more preferably 1 mol per mol of the total amount of alkoxyl groups in the compound represented by the above formula (1) and the compound represented by the above formula (2). The amount is not more than mol, more preferably not more than 0.9 mol.
The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C.
The reaction time is preferably 30 minutes to 24 hours, more preferably 1 to 12 hours.
The weight average molecular weight in terms of polystyrene (hereinafter sometimes referred to as “Mw”) by gel permeation chromatography (GPC) of the component [D] is preferably 500 to 10,000, more preferably 1,000 to 3,000. It is. If Mw is less than 500, it is difficult to exhibit sufficient adhesion and the effect of suppressing contaminants generated during spacer formation. On the other hand, if Mw exceeds 10,000, applicability may be deteriorated.

In the radiation sensitive resin composition of the present invention, the amount of the component [D] used is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the [A] copolymer. Part. When the amount of the component [D] used is less than 0.5 parts by weight, it is difficult to develop sufficient adhesion and peeling solution resistance. On the other hand, when it exceeds 50 parts by weight, the radiation-sensitive resin composition remains undeveloped. It tends to be easier.
In addition, the compounds represented by the above formulas (1) and (2), which are monomers of the siloxane oligomer, can be used in combination with the siloxane oligomer, if necessary. The amount to be used is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the [A] copolymer. If the amount used is less than 0.5 parts by weight, it is difficult to develop sufficient adhesion and peeling solution resistance, while if it exceeds 20 parts by weight, the storage stability of the radiation-sensitive resin composition tends to decrease. .

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

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

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

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

Furthermore, as surfactants other than the above, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene Polyoxyethylene aryl ethers such as n-nonyl phenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
The surfactants can be used alone or in admixture of two or more.
The blending amount of the surfactant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less with respect to 100 parts by weight of the polymer [A]. When the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening tends to occur during coating.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenyl. Examples include hydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.
The blending amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 to 0.5 parts by weight, with respect to 100 parts by weight of the [A] polymer. When the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity may be lowered and the pattern shape may be impaired.
Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.

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

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′. , N ″, N ″ -hexa (ethoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N , N ′, N ′, N ″, N ″ -hexa (t-butoxymethyl) melamine and the like.
Among these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is particularly preferable. For example, Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like can be mentioned.

The heat resistance improvers can be used alone or in admixture of two or more.
The blending amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the [A] polymer. When the blending amount of the heat resistance improver exceeds 30 parts by weight, the storage stability of the radiation sensitive resin composition tends to be lowered.
The radiation-sensitive resin composition of the present invention is preferably used as a composition solution dissolved in an appropriate solvent.

As the solvent, each component constituting the radiation-sensitive resin composition is uniformly dissolved, does not react with each component, and has a suitable volatility, but the solubility of each component, each component and Alcohols, ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether acetate, dipropylene glycol alkyl ether, alkoxypropionic acid Alkyl, acetate ester and the like are preferable, and in particular, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ester. Ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol dimethyl ether, 3-methoxybutyl acetate, 2-methoxyethyl acetate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

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

These high boiling point solvents can be used alone or in admixture of two or more.
Further, the composition solution prepared as described above can be filtered for use, preferably using a Millipore filter having a pore size of about 0.5 μm.
Especially the radiation sensitive resin composition of this invention can be used very suitably for formation of the spacer for liquid crystal display elements.

Method of forming spacers Next, a method of forming a spacer of the present invention will be described with reference to radiation-sensitive resin composition of the present invention.

The method for forming the spacer of the present invention includes at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition of the present invention on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.

  Hereinafter, each of these steps will be described sequentially.

-(I) Process-
A transparent conductive film is formed on one surface of a transparent substrate, and a radiation-sensitive resin composition is applied onto the transparent conductive film, preferably as a composition solution, and then the coated surface is heated (prebaked) to form a coating film. Form.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, a glass substrate such as soda lime glass and alkali-free glass; polyethylene terephthalate, polybutylene terephthalate, Examples thereof include a resin substrate made of a plastic such as polyethersulfone, polycarbonate, and polyimide.
Examples of the transparent conductive film provided on one surface of the transparent substrate include a NESA film (registered trademark of US PPG) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used.

As a method for applying the composition solution, for example, (1) a coating method and (2) a dry film method can be used as a method for forming a film of the photosensitive resin composition of the present invention.
As a coating method of the composition solution, for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an ink jet coating method can be employed. In particular, a spin coating method and a slit die coating method are preferable.

Further, when the film of the photosensitive resin composition of the present invention is formed, (2) when the dry film method is adopted, the dry film is formed on the base film, preferably a flexible base film. And a photosensitive layer made of the photosensitive resin composition (hereinafter referred to as “photosensitive dry film”).
The photosensitive dry film can be formed by laminating a photosensitive layer on the base film by applying the photosensitive resin composition of the present invention, preferably as a liquid composition, and then drying. As a base film of the photosensitive dry film, for example, a synthetic resin film such as polyethylene terephthalate (PET), polyethylene, polypropylene, polycarbonate, polyvinyl chloride, or the like can be used. The thickness of the base film is suitably in the range of 15 to 125 μm. The thickness of the obtained photosensitive layer is preferably about 1 to 30 μm.

Moreover, the photosensitive dry film can also be preserve | saved by laminating | stacking a cover film on the photosensitive layer at the time of unused. This cover film needs to have an appropriate releasability so that it does not peel off when not in use and can be easily peeled off when in use. As a cover film satisfying such conditions, for example, a film based on a silicone-based release agent or a baking film can be used on the surface of a synthetic resin film such as a PET film, a polypropylene film, a polyethylene film, or a polyvinyl chloride film. . A thickness of about 25 μm is usually sufficient for the cover film.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., Preferably it is about 1 to 15 minutes at 70-120 degreeC.

-(B) Process-
Next, at least a part of the formed film is exposed. In this case, when exposing a part of the film, for example, the exposure is 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 dose is preferably 100 to 10,000 J / m ² , more preferably 1 as a value measured with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of the radiation to be exposed. 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; Examples include aqueous solutions of alkaline compounds such as alkanolamines such as methylamine, methyldiethanolamine and triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the aqueous solution of the alkaline compound.
As a developing method, any of a liquid filling method, a dipping method, a shower method and the like may be used, and the developing time is usually about 10 to 180 seconds.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

-(2) Process-
Next, the obtained pattern is heated at a predetermined temperature, for example, 100 to 230 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, for 30 to 180 minutes in the oven, by a heating device such as a hot plate or an oven. A predetermined spacer can be obtained by heating (post-baking).
The conventional radiation-sensitive resin composition used for the formation of the spacer cannot obtain sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 ° C. or higher. In the radiation-sensitive resin composition, the heating temperature can be made lower than before, and as a result, without causing yellowing or deformation of the resin substrate, compressive strength, rubbing resistance during liquid crystal alignment, adhesion to the transparent substrate It is possible to form a spacer excellent in various properties such as properties.

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

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

Polymer synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 4.0 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 245 parts by weight of diethylene glycol methyl ethyl ether, followed by 18 parts by weight of methacrylic acid, While charging 38 parts by weight of glycidyl methacrylate, 5 parts by weight of styrene, and 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and substituting with nitrogen, 5 parts by weight of 1,3-butadiene was added, the temperature of the resulting solution was raised to 70 ° C., and this temperature was maintained for 4 hours for polymerization to obtain a resin solution containing [A] copolymer. . The solid content concentration of this resin solution is 29.3% by weight, and Mw is obtained using GPC (gel permeation chromatography) GPC-101 (trade name, manufactured by Showa Denko KK) for the obtained copolymer. The measured value was 20,000.
This copolymer is referred to as [A-1].

Polymer synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 4.0 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 245 parts by weight of diethylene glycol methyl ethyl ether, followed by 18 parts by weight of methacrylic acid, After charging with 38 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate, 5 parts by weight of styrene, and 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and after substituting with nitrogen, gently While stirring, 5 parts by weight of 1,3-butadiene was added, and the temperature of the resulting solution was raised to 70 ° C., and this temperature was maintained for 4.2 hours for polymerization. A resin solution containing a polymer was obtained. The resin solution had a solid content concentration of 29.3% by weight. For the obtained copolymer [A-2], Mw was changed to GPC (gel permeation chromatography) GPC-101 (trade name, Showa Denko K.K. ), And 18,000 were measured.

Polymer synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 7 parts by weight of 2,2′-azobisisobutyronitrile and 245 parts by weight of diethylene glycol methyl ethyl ether, followed by 18 parts by weight of methacrylic acid, 38 parts by weight of benzyl methacrylate, After 5 parts by weight of styrene and 34 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate were charged and purged with nitrogen, 5 of 1,3-butadiene was added while gently stirring. Part by weight was added, and the temperature of the resulting solution was raised to 70 ° C., and this temperature was maintained for 4.2 hours for polymerization to obtain a resin solution containing the [A-3] copolymer. The solid content concentration of this resin solution was 29.3% by weight. For the obtained copolymer [A-3], Mw was changed to GPC (gel permeation chromatography) GPC-101 (trade name, Showa Denko K.K. ) And 18,000, and it was 18,000.

Synthesis example 1 of siloxane oligomer [D]
In a 500 mL three-necked flask, 30.4 g of tetramethoxysilane and 47.2 g of 3-glycidoxypropyltrimethoxysilane are added and dissolved by adding 100 g of propylene glycol methyl ether, and the resulting mixed solution is mixed with a magnetic stirrer. Warm to 60 ° C. with stirring. To this, 8.6 g of ion-exchanged water containing 1% by weight of oxalic acid was continuously added over 1 hour. And after making it react at 60 degreeC for 4 hours, the obtained reaction liquid was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of this polymer [D-1] was 1,400.

Synthesis example 2 of siloxane oligomer [D]
In a 500 mL three-necked flask, 48.8 g of diphenyldimethoxysilane and 49.2 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are added, and 100 g of propylene glycol methyl ether acetate is added and dissolved, and the resulting mixture is mixed. The solution was heated to 60 ° C. while stirring with a magnetic stirrer. To this, 8.6 g of ion-exchanged water containing 1% by weight of oxalic acid was continuously added over 1 hour. And after making it react at 60 degreeC for 4 hours, the obtained reaction liquid was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of this polymer [D-2] was 2,000.

Synthesis example 3 of siloxane oligomer [D]
In a 500 mL three-necked flask, 39.6 g of phenyltrimethoxysilane and 64.0 g of (3-ethyloxetane-3-yl) propyltriethoxysilane are taken and dissolved by adding 100 g of methyl isobutyl ketone, and the resulting mixed solution Was heated to 60 ° C. while stirring with a magnetic stirrer. To this, 8.6 g of ion-exchanged water containing 1% by weight of oxalic acid was continuously added over 1 hour. And after making it react at 60 degreeC for 4 hours, the obtained reaction liquid was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of this polymer [D-3] was 1,600.

Synthesis example 4 of siloxane oligomer [D]
In a 500 mL three-necked flask, take 27.2 g of methyltrimethoxysilane and 39.2 g of 3-mercaptopropyltrimethoxysilane, add 100 g of propylene glycol methyl ether to dissolve, and stir the resulting mixed solution with a magnetic stirrer. While warming to 60 ° C. To this, 8.6 g of ion-exchanged water containing 1% by weight of oxalic acid was continuously added over 1 hour. And after making it react at 60 degreeC for 4 hours, the obtained reaction liquid was cooled to room temperature. Thereafter, the alcohol as a reaction by-product was distilled off from the reaction solution under reduced pressure. The weight average molecular weight of this polymer [D-4] was 1,900.

In the following, Examples 1 to 3 and 5 to 14 are reference examples.
Example 1
Preparation of Composition Solution As component [A], 100 parts of polymer solution (A-1) obtained in Synthesis Example 1 as polymer (A-1) and dipentaerystol hexaacrylate (product) as component [B] Name KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd. 60 parts and a commercial product containing a polyfunctional urethane acrylate compound (trade name KAYARAD DPHA-40H) 60 parts, [C] component as 1- [9-ethyl- 6- (2-Methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals), 2,2'-bis (2-chlorophenyl) -4,4 5 parts of ', 5,5'-tetraphenyl-1,2'-biimidazole, 2.5 parts of 2-mercaptobenzothiazole, 5 parts of polymer [D-1] as [D] component, surfactant FTX-218 (trade name, manufactured by Neos Co., Ltd.) 0.2 part, as a storage stabilizer, 0.5 part of 4-methoxyphenol was mixed, and propylene glycol monomethyl was mixed so that the solid content concentration was 33%. After dissolving in a mixed solvent of ether acetate and diethylene glycol ethyl methyl ether, it is filtered through a membrane filter with a pore size of 0.2 μm to prepare a composition solution. .
In Table 1, each component other than the polymer is as follows.

[B] Component B-1: Dipentaerystol hexaacrylate (trade name KAYARAD DPHA)
B-2: Commercial product containing a polyfunctional urethane acrylate compound (trade name KAYARAD DPHA-40H)
B-3: ω-carboxypolycaprolactone monoacrylate (trade name Aronix M-5300 (manufactured by Toa Gosei Co., Ltd.)
B-4: ω-carboxypolycaprolactone monoacrylate (trade name Aronix M-5300 (manufactured by Toa Gosei Co., Ltd.)
B-5: 1,9-nonane diacrylate (trade name: Light acrylate 1,9-NDA (manufactured by Kyoeisha)

[C] component C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name IRGACURE OX02, manufactured by Ciba Specialty Chemicals)
C-2: 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate C-3: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name Irgacure 907, Ciba Specialty Chemicals)
C-4: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)
C-5: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole C-6: 4,4′-bis (diethylamino) benzophenone C-7: 2-mercaptobenzothiazole

[E] Component E-1: Polyfunctional novolak type epoxy resin (trade name, manufactured by Japan Epoxy Resin Co., Ltd., Epicoat 152)

[F] Component F-1: γ-glycidoxypropyltrimethoxysilane In Examples 2 to 12 and Comparative Examples 1 to 3, a composition solution was prepared in the same manner as in Example 1. The results are shown in Table 1.

Formation of Spacer In Examples 1 to 13 and Comparative Examples 1 to 3, the spacers were formed by applying to a substrate using a spinner. The details are shown below.
The composition solution was applied on a non-alkali glass substrate using a spinner, and then pre-baked on a hot plate at 90 ° C. for 90 seconds to form a film having a thickness of 3.0 μm.
Next, the obtained coating film was exposed through a photomask having a remaining pattern of 8 to 30 μm. Thereafter, development was performed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by washing with pure water for 1 minute and further heating in an oven at 220 ° C. for 30 minutes to form a spacer.
In Example 14 and Comparative Example 4, spacers were formed by the dry film method. Details are shown below.

Example 14
A patterned thin film was formed and evaluated in the same manner as in Examples 1 to 13, except that a coating film was prepared from the liquid composition (S-14) of the radiation sensitive resin composition by the dry film method. Each component is shown in Table 1. The base film was peeled and removed before the exposure process. The evaluation results are shown in Table 2. Table 2 also shows the evaluation results of the following transferability.
Dry film preparation and transfer were performed as follows.
On a polyethylene terephthalate (PET) film having a thickness of 38 μm, a liquid composition (S-14) of a radiation sensitive resin composition was applied using an applicator, the coating film was heated at 100 ° C. for 5 minutes, and a thickness of 4 μm. A radiation-sensitive dry film (J-1) was prepared. Next, the radiation-sensitive transfer dry film is superposed on the surface of the glass substrate so that the surface of the radiation-sensitive transfer layer is in contact with the glass substrate, and the radiation-sensitive dry film (J-1) is laminated on the glass substrate by thermocompression bonding. Transcribed to.

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

Comparative Example 4
In Example 14, it replaces with the liquid composition (S-14) of a radiation sensitive resin composition, and uses the liquid composition (s-4) of a radiation sensitive resin composition, It is the same as that of Example 14. After producing a radiation-sensitive dry film (J-2), a patterned thin film was formed and evaluated. Each component is shown in Table 1. The evaluation results are shown in Table 2. Table 2 also shows the evaluation results of transferability.

  Next, various evaluations were performed in the following manner. The evaluation results are shown in Table 2.

(1) Sensitivity evaluation When the spacer is formed in the same manner as the formation of the spacer, the exposure amount at which the residual film ratio after post-baking (film thickness after post-baking × 100 / film thickness after exposure) is 90% or more. Was the sensitivity. When this exposure amount is 1,500 J / m ² or less, it can be said that the sensitivity is good.
(2) Evaluation of adhesion The film was formed as described above except that a film was formed on the substrate in the same manner as the formation of the spacer and was not exposed through a mask. After the film-formed substrate was subjected to a pressure cooker test (120 ° C., humidity 100%, 4 hours), the protective film adhesion (SiO 2) was measured according to JIS K-5400-1990 8.5.3 adhesive cross-cut tape method. ₂ ). Table 2 shows the number of remaining grids out of 100 grids. It can be said that the adhesiveness is good when the number is 90 or more.
(3) Evaluation based on haze value of presence / absence of contaminants (sublimates) After applying the above composition on a SiO ₂ dip glass substrate so as to have a post-baking film thickness of 2.0 μm using a spinner, pre-baking A glass wafer was set on 1 to 2 cm of the substrate to be sublimated, and the sublimate was adhered on the glass wafer by prebaking on a hot plate at 80 ° C. for 5 minutes. Then, the presence or absence of the sublimate was evaluated by measuring the haze value of the substrate on which the sublimate was adhered using a haze meter. When the amount of sublimation is large (the amount of outgas is large), the haze value is high (haze value> 1), and when there is no sublimation (there is no outgas), the haze value is close to zero.
(4) Evaluation of stripping solution resistance The substrate on which the spacer was formed was immersed in an alignment layer stripping solution (product name: TS-204, manufactured by Sanyo Chemical Co., Ltd.) at 50 ° C. for 30 minutes, and further heated at 210 ° C. for 15 minutes. The thickness change was measured. Evaluation was carried out by film thickness after heating × 100 / initial film thickness. If the change in the film thickness is 95% or more before and after immersion in the alignment film peeling solution, it can be said that the alignment film peeling liquid resistance is good. The results are shown in Table 2.

It is a schematic diagram of an example for demonstrating the structure of a liquid crystal display element. It is a schematic diagram of the other example for demonstrating the structure of a liquid crystal display element.

Claims (6)

[A ] ( a1) a copolymer of an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride and (a2) another unsaturated compound,
[B] polymerizable unsaturated compound,
[C] a photopolymerization initiator, and [D] Ca carboxyl group, you siloxane oligomer containing at least one functional group hydroxyl group, a mercapto group, an isocyanate group, selected from the group consisting of amino groups and ureido groups a radiation-sensitive resin composition,
The (a2) other unsaturated compound contains an unsaturated compound (a2-1) that can undergo a crosslinking reaction with the component [D],
The said composition (a2-1) is as follows according to the kind of functional group which [D] component has;
When the functional group of the [D] component is a carboxyl group, a hydroxyl group, a ureido group or an amino group, the compound (a2-1) is a (meth) acrylic acid epoxy (cyclo) alkyl ester, an α-alkylacrylic acid epoxy (cyclo ) Selected from alkyl esters and vinylbenzyl glycidyl ethers:
When the functional group of the component [D] is a mercapto group, the compound (a2-1) is allyl (meth) acrylate, (meth) acrylic acid epoxy (cyclo) alkyl ester, α-alkyl acrylic acid epoxy (cyclo) alkyl ester And vinylbenzyl glycidyl ether: and
When the functional group of the component [D] is an isocyanate group, the compound (a2-1) is a (meth) acrylic acid hydroxyalkyl ester, a (meth) acrylic acid hydroxyalkyl ester having an alicyclic structure, and (meth) acrylic acid. Selected from dihydroxyalkyl esters .
The radiation sensitive resin composition according to claim 1, wherein the component [D] is a siloxane oligomer obtained by cohydrolyzing an alkoxysilane represented by each of the following formula (1) and the following formula (2). object.
Si (R ¹ ) _l (R ² ) _m (OR ³ ) _n (1)
(Wherein R ¹ is Ca carboxyl group, a hydroxyl group, a mercapto group, an isocyanate group, a substituent containing an amino group or a ureido group, R ^2, R ³ may be the same or different, monovalent, respectively An organic group, l and n are each an integer of 1 to 3, and m is an integer of 0 to 2. However, l + m + n = 4.
Si (R ⁴ ) _x (OR ⁵ ) _4-x (2)
(Here, R ⁴ and R ⁵ may be the same or different, and each is a hydrogen atom or a monovalent organic group, and x is an integer of 0 to 3.)
The radiation sensitive resin composition of Claim 1 or 2 used for formation of the spacer for liquid crystal display elements. The spacer for liquid crystal display elements formed from the radiation sensitive resin composition of Claim 1 or 2. A method for forming a spacer for a liquid crystal display element, comprising at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition according to claim 1 on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development. A liquid crystal display device comprising the spacer according to claim 4.

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