JP2007102070A - Radiation-sensitive resin composition for spacer, spacer and method for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition having high sensitivity and high resolution, capable of easily forming a patterned thin film that is superior in various performances such as pattern profile, compressive strength, rubbing resistance and adhesion to a transparent substrate, and capable of suppressing generation of a sublimate in baking, spacers formed from the composition, and to provide a method for forming the spacers. <P>SOLUTION: The radiation-sensitive resin composition contains (A) a polymer having carboxyl and epoxy groups, wherein the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the polymer (expressed in terms of polystyrene) to the number average molecular weight (Mn) (expressed in terms of polystyrene) measured by gel permeation chromatography is ≤1.7, (B) a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator. A living radical polymerization for producing the polymer (A) is a polymerization that uses a specific thiocarbonyl thio(disulfide) compound as a molecular weight control agent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, a spacer, and a method for forming the same.

Conventionally, liquid crystal display elements have been used spacer particles such as glass beads and plastic beads having a predetermined particle diameter in order to keep the distance between two transparent substrates constant. Since spacer particles are randomly scattered on a transparent substrate such as a glass substrate, if spacer particles are present in the pixel formation region, the phenomenon of spacer particle reflection will occur, or incident light will be scattered, reducing the contrast of the liquid crystal display element. There was a problem.
In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form dot-shaped or stripe-shaped spacers. Since the spacer can be formed only at a predetermined position, the above-described problem is basically solved.

By the way, radiation from a mercury lamp used as a light source in photolithography is usually around 436 nm (g line), around 404 nm (h line), around 365 nm (i line), around 335 nm, around 315 nm (j line), In order to show a strong spectrum around 303 nm, etc., the radiation-sensitive polymerization initiator that is a component of the radiation-sensitive resin composition is selected to have a maximum absorption wavelength in the wavelength region of these strong spectra. Usually, from the viewpoint of transparency, a radiation-sensitive polymerization initiator having a maximum absorption wavelength in the region of the i-line or less is used (Patent Document 1: JP-A-2001-2001). No. 261,761). When a radiation-sensitive polymerization initiator having a maximum absorption wavelength near the g-line and h-line whose wavelength is longer than the i-line is used, the radiation-sensitive polymerization initiator has absorption in a wavelength region close to visible light. The contained radiation sensitive resin composition is colored, and the transparency of the formed film is lowered. When the transparency of the film is low, the curing reaction proceeds on the film surface during exposure, and the curing reaction in the depth direction of the film becomes insufficient. As a result, the spacer shape obtained after development has a reverse taper (as a cross-sectional shape) The side of the film surface has an inverted triangular shape that is longer than the side of the substrate side), which causes the spacer to peel off during the subsequent rubbing treatment of the alignment film.
However, in conventional radiation-sensitive resin compositions, including those of Patent Document 1 (Japanese Patent Laid-Open No. 2001-261661), sublimates generated during firing to form spacers may contaminate process lines and devices. There is a concern, and a radiation-sensitive resin composition in which generated sublimates are reduced has been desired.
JP 2001-261761 A

  The present invention has been made based on the above situation. Therefore, an object of the present invention is to easily form a patterned thin film having high sensitivity, high resolution, and excellent performance such as pattern shape, compressive strength, rubbing resistance, and adhesion to a transparent substrate. Another object of the present invention is to provide a radiation-sensitive resin composition for forming a spacer in which generation of sublimates during firing is suppressed, a spacer formed therefrom, and a method for forming the same.

The above object of the present invention is, firstly,
(A) It has a carboxyl group and an epoxy group, and the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is 1.7 or less. A radiation-sensitive resin composition containing (B) a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator, wherein (A) the living radical polymerization for producing the polymer is represented by the following formula: It is achieved by a radiation-sensitive resin composition for spacer formation, which is polymerization using a thiocarbonylthio compound represented by (1) or formula (2) as a molecular weight control agent.

[In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. Monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (═O) N (R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , or a monovalent group having a polymer chain, wherein each R is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of carbon atoms and hetero atoms 1 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent heterocyclic group having 3 to 20 atoms in total. And R may be each substituted, ^{R 1,} when the p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, 6 carbon atoms 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or polymer chain Each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or carbon. 1 represents a monovalent heterocyclic group having 3 to 18 total atoms of atoms and hetero atoms, and when p ≧ 2, a p-valent group derived from an alkane having 1 to 20 carbon atoms, 6 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon, a p-valent group derived from a heterocyclic compound having a total of 3 to 20 carbon atoms and hetero atoms. Represents a p-valent group having a polymer chain, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic group having 6 to 20 carbon atoms. Hydrocarbon group, monovalent heterocyclic group having 3 to 20 atoms in total, R, p-valent group derived from alkane having 1 to 20 carbon atoms, p derived from aromatic hydrocarbon having 6 to 20 carbon atoms The valent group and the p-valent group derived from the heterocyclic compound having a total of 3 to 20 atoms may each be substituted. ]

[In the formula (2), Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and a hetero atom. M-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain, m-valent group derived from an alkane having 1 to 20 carbon atoms, carbon number The m-valent group derived from an aromatic hydrocarbon having 6 to 20 and the m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted, and R ² may have 1 to 1 carbon atoms. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms A monovalent heterocyclic group, —OR, —SR, —N (R) ₂ or a monovalent group having a polymer chain, wherein each R is a phase Independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of 3 atoms of carbon atoms and hetero atoms 18 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic carbon group having 6 to 20 carbon atoms. The hydrogen group, monovalent heterocyclic group having 3 to 20 atoms in total and R may each be substituted. ]
Here, the polymer (A) has a group represented by the following formula (i) or a group represented by the following formula (ii) at at least one terminal of each polymer chain constituting the polymer.

[In Formula (i), Z ¹ is the same as Formula (1), and in Formula (ii), Z ² and m are the same as in Formula (2). ]
Here, the “radiation” as used in the present invention means those including ultraviolet rays, far ultraviolet rays, X-rays, electron beams, molecular beams, γ rays, synchrotron radiation, proton beam rays, and the like.
The above object of the present invention is secondly,
This is achieved by a spacer forming method characterized in that at least the following steps (1) to (4) are carried out in the order described below.
(1) A step of forming a coating of the above-mentioned radiation-sensitive resin composition for forming a spacer on a substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the film after exposure.
(4) A step of heating the film after development.
Thirdly, the above object of the present invention is achieved by the spacer formed by the above method.

  The radiation-sensitive resin composition for spacer formation of the present invention is a highly sensitive, high resolution, and easily patterned thin film with excellent performance such as pattern shape, compressive strength, rubbing resistance, and adhesion to a transparent substrate. The generation of sublimates during firing can be suppressed.

Radiation sensitive resin composition Hereinafter, each component of the radiation sensitive resin composition of this invention is explained in full detail.
(A) Polymer The (A) polymer in the radiation-sensitive resin composition of the present invention is preferably (a1) an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (hereinafter referred to as “compound ( a1) "), (a2) an epoxy group-containing unsaturated compound (hereinafter referred to as" compound (a2) ") and (a3) another unsaturated compound (hereinafter referred to as" compound (a3) "). It can be obtained by living radical polymerization of the polymerizable mixture.
For example, the polymer (A) can be produced by subjecting a polymerizable mixture containing the compound (a1), the compound (a2) and the compound (a3) to living radical polymerization in a solvent in the presence of a polymerization initiator. it can. The carboxyl group and epoxy group of the polymer (A) thus obtained are derived from the compound (a1) and the compound (a2), respectively.

Next, (A) Living radical polymerization for producing a polymer will be described.
The polymerizable unsaturated compound can be produced by living radical polymerization, preferably together with another copolymerizable unsaturated compound, in a solvent in the presence of a radical polymerization initiator system that generates a living radical.

  In living radical polymerization, when using a compound having a functional group that may deactivate an active radical such as a carboxyl group as a polymerizable unsaturated compound, in order to prevent the growth terminal from being deactivated, (A) A polymer can also be obtained by polymerizing the functional group in the polymerizable unsaturated compound by protecting it by, for example, esterification and then deprotecting it.

  Various radical polymerization initiator systems for living radical polymerization of polymerizable unsaturated compounds have been proposed. For example, a TEMPO system proposed by Georges et al. (See, for example, Non-Patent Document 1), and proposed by Matyjazewski et al. A system composed of a combination of copper bromide and a bromine-containing ester compound (for example, see Non-Patent Document 2), a system composed of a combination of carbon tetrachloride and a ruthenium (II) complex proposed by Hamasaki et al. Non-patent document 3) or a system comprising a combination of a thiocarbonyl compound having a chain transfer constant greater than 0.1 and a radical initiator, as disclosed in Patent Document 2, Patent Document 3 and Patent Document 4. And so on.

M.K.Georges, R.P.N.Veregin, P.M.Kazmaier, G.K.Hamer, Macromolecules, 1993, Vol.26, p.2987 Matyjaszewski, K. Coca, S. Gaynor, G. wei, M. Woodworth, B.E. Macromolecules, 1997, Vol. 30, p. 7348 Hamasaki, S.Kamigaito, M.Sawamoto, M. Macromolecules, 2002, Vol.35, p.2934 Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181) Special Table 2002-2002 JP-T-2004-518773

As a suitable radical polymerization initiator system used for living radical polymerization, a system in which the active radical at the growth end is not deactivated is appropriately selected depending on the type of the polymerizable unsaturated compound used. In consideration of efficiency and metal-free system, a combination of a thiocarbonylthio compound that is a molecular weight control agent and a radical initiator is preferable.
The combination of the thiocarbonylthio compound and the radical initiator is described in detail in Patent Documents 5 to 9 in addition to Patent Document 2, Patent Document 3 and Patent Document 4.

Special table 2002-508409 gazette Japanese translation of PCT publication No. 2002-512653 Special table 2003-527458 gazette Patent 3634843 (Japanese Patent Publication No. 2003-536105) JP-T-2005-503452

  As described in Patent Documents 2 to 5, a random copolymer or block copolymer having a narrow molecular weight distribution is obtained by living radical polymerization of an unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator. Coalescence can be obtained. Moreover, since a functional group can be introduced into the obtained random copolymer and block copolymer, the copolymer is converted into an aqueous gel (see Patent Document 6), a photoresist (see Patent Document 7), and a surface activity. It has been clarified that it can also be used for applications such as an agent (see Patent Document 8).

  Preferred examples of the thiocarbonylthio compound in the present invention include compounds represented by the above formula (1) or the above formula (2).

In the above formula (1), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec -Butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3- A dimethylbutyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of Z ¹ include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 9-anthracenyl group, a benzyl group, An α-methylbenzyl group, an α, α-dimethylbenzyl group, a phenethyl group, and the like can be given.

Examples of the monovalent heterocyclic group having 3 to 20 total atoms of the carbon atom and the hetero atom of Z ¹ include oxiranyl group, aziridinyl group, 2-furanyl group, 3-furanyl group, 2- Tetrahydrofuranyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3-pyrazole group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-thianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, etc. be able to.

Z ¹ —OR, —SR, —N (R) ₂ , —OC (═O) R, —C (═O) OR, —C (═O) N (R) ₂ , —P (= O) (OR) ₂ and —P (═O) (R) ₂ , an alkyl group having 1 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a carbon atom and a hetero atom. As the monovalent heterocyclic group having 3 to 18 atoms in total, for example, an alkyl group having 1 to 20 carbon atoms exemplified for Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or Among the monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, there can be mentioned groups having 18 or less carbon atoms in total.

  Examples of the alkenyl group having 2 to 18 carbon atoms of the same R include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, and 1-pentenyl group. 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.

For the above alkyl group having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, and R Examples of the substituent include, for example, hydroxyl group, carboxyl group, carboxylate group, sulfonate group, sulfonate group, isocyanate group, cyano group, vinyl group, epoxy group, silyl group, halogen atom, and Z ¹ . -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (= O) N (R) ₂ , -P (= O) (OR) ₂ or -P (= O) (R) ₂ ; an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms exemplified for R, or Same as monovalent heterocyclic group having 3 to 18 total atoms of carbon atom and hetero atom Can be appropriately selected from these substituents may be present one or more types in substituted derivatives. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the monovalent group having a polymer chain of Z ¹ include α-olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl fluoride, vinyl chloride, and chloride. Vinyl halides such as vinylidene; unsaturated alcohols such as vinyl alcohol and allyl alcohol; esters of unsaturated alcohols such as vinyl acetate and allyl acetate; unsaturated carboxylic acids such as (meth) acrylic acid and p-vinylbenzoic acid Acids: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t- (meth) acrylic acid (Meth) acrylic acid esters such as butyl, n-hexyl (meth) acrylate, and cyclohexyl (meth) acrylate (Meth) acrylamides, (meth) acrylamides such as N, N-dimethyl (meth) acramide; unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; conjugated dienes such as butadiene and isoprene In addition to a monovalent group having an addition polymerization polymer chain formed from one or more unsaturated compounds, polyoxyethylene whose terminal may be etherified, polyoxyethylene whose terminal may be etherified A monovalent group having a polyether such as propylene, a polyaddition polymer chain such as polyester, polyamide or polyimide, a polycondensation polymer chain, or the like can be given. In the monovalent group having these polymer chains, even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (1), for example, —CH ₂ —COO—, —C (CH _{3) (CN) CH 2 CH} 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (1) via a connecting hands like.
In the formula (1), a plurality of Z ¹ may be the same as or different from each other.

In Formula (1), when p = 1, R ¹ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent group having 6 to 20 carbon atoms. A monovalent heterocyclic group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or a monovalent polymer chain Indicates a group.

The alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, -OR, -SR, -N (R As the monovalent group having ₂ or a polymer chain or a substituted derivative thereof, for example, the same groups as those exemplified for the respective corresponding groups of Z ¹ can be mentioned. In a monovalent group having a polymer chain of R ¹ (p = 1), even when the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, -C (CH _{3) (CN)} may be through a linking hand, such _CH 2 CH 2 -COO- attached to the sulfur atom in the formula (1).

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, and a cyclohexenyl group.
Examples of the substituent for the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms in Z ^{1 and} a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. Group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, and a group similar to those exemplified for the substituent for R can be appropriately selected from these substituents. May be present in the substituted derivative one or more or one or more. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Further, when p ≧ 2, R ¹ is a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, or a carbon atom different from R ^1. A p-valent group or a p-valent group having a polymer chain derived from a heterocyclic compound having 3 to 20 atoms in total with the atom is shown.

  Examples of the alkane having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, n-octane, and n. -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane and the like can be mentioned.

  Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include benzene and 1,4-dimethylbenzene (for example, the carbon atom of each methyl group at the 1,4-position is a sulfur atom in the formula (1)). ), 1,2,4,5-tetramethylbenzene (for example, the carbon atom of each methyl group at the 1,2,4,5-position binds to the sulfur atom in formula (1).) 1,2,3,4,5,6-hexamethylbenzene (for example, the carbon atom of each methyl group at the 1,2,3,4,5,6-position binds to the sulfur atom in formula (1)) 1,4-di-i-propylbenzene (for example, the carbon atom at the 2-position of each i-propyl group at the 1,4-position is bonded to the sulfur atom in the formula (1)). Naphthalene, anthracene group and the like can be mentioned.

  Examples of the heterocyclic compound having 3 to 20 atoms in total include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thiane, pyridine, piperidine and morpholine.

P-valent group derived from the alkane having 1 to 20 carbon atoms, p-valent group derived from aromatic hydrocarbon having 6 to 20 carbon atoms and p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the above group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total number of 3 atoms of carbon atoms and hetero atoms. -20 monovalent heterocyclic groups and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are present in one or more or one or more kinds in the substituted derivative. be able to. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives the p-valent group of R ¹ include addition polymerization polymer chains, polyaddition polymer chains, and polycondensation systems exemplified for the monovalent group having the polymer chain of Z ^1. The thing similar to a polymer chain can be mentioned. In the p-valent group having the polymer chain of R ¹ , even when the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (1).

Next, in the formula (2), examples of the alkane having 1 to 20 carbon atoms that gives an m-valent group of Z ² include, for example, alkanes having 1 to 20 carbon atoms that give a p-valent group of the above R ¹ The same compounds as those described above can be mentioned.

In addition, examples of the aromatic hydrocarbon having 6 to 20 carbon atoms that give an m-valent group of Z ² include, for example, compounds exemplified for the aromatic hydrocarbon having 6 to 20 carbon atoms that give a p-valent group of R ¹ above. The same thing can be mentioned.

In addition, examples of the heterocyclic compound having a total of 3 to 20 carbon atoms and a hetero atom of a carbon atom that gives an m-valent group of Z ² include, for example, the carbon atom and the hetero ring that give a p-valent group of R ¹ above. The thing similar to the compound illustrated about the heterocyclic compound of 3-20 total atoms with an atom can be mentioned.

Derived from an m-valent group derived from an alkane having 1 to 20 carbon atoms of Z ² , an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total Examples of the substituent for the m-valent group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total atom of carbon atoms and hetero atoms. The monovalent heterocyclic group of 3 to 20 and the same groups as those exemplified for the substituent for R can be selected as appropriate, and these substituents are one or more or one or more in the substituted derivatives. Can exist. However, it is preferable that the total number of carbon atoms or the total number of atoms in the substituted derivative does not exceed 20.

Examples of the polymer chain that gives an m-valent group of Z ² include, for example, an addition polymerization polymer chain, a polyaddition polymer chain, a heavy chain exemplified for the monovalent group having a polymer chain of Z ¹ above. The thing similar to a condensation type polymer chain can be mentioned. In the m-valent group having a polymer chain of Z ² , even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (2), for example, —CH ₂ —COO—, —C ( _{CH 3) (CN) CH 2} CH 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (2) via a connecting hands like.

In the formula (2), a C 1-20 alkyl group of R ₂ , a C 6-20 monovalent aromatic hydrocarbon group, a monovalent C 3-20 monovalent carbon atom and a hetero atom. As the monovalent group having a heterocyclic group, —OR, —SR, —N (R) ₂ and a polymer chain, or a substituted derivative thereof, for example, groups exemplified for the corresponding groups of Z ¹ above The same thing can be mentioned. In the monovalent group having the polymer chain of R ² , even when the polymer chain is directly bonded to the sulfur atom in the formula (2), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (2).

Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ² and substituted derivatives thereof include, for example, the monovalent alicyclic ring having 3 to 20 carbon atoms of the above R ¹ , p = 1). Examples thereof are the same as those exemplified for the aromatic hydrocarbon group and substituted derivatives thereof.
In the formula (2), a plurality of R ² may be the same as or different from each other.

In Formula (2), when the connecting part between Z ² and —C (═S) —S—R ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ² is —C (═S ) When bonded to —S—R ² and the linking moiety is an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to —C (═S) —S—R ^2, and When the moiety is a sulfur atom, the sulfur atom in —SR representing Z ² is bonded to —C (═S) —S—R ² .

Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (3) to (22).

These thiocarbonylthio compounds can be used alone or in admixture of two or more.
In the present invention, at the time of living radical polymerization, other molecular weight control agents such as α-methylstyrene dimer and t-dodecyl mercaptan can be used in combination with the thiocarbonylthio compound.

The radical initiator used in the living radical polymerization is not particularly limited, and those generally known as radical polymerization initiators can be used, for example, 2,2′-azobisisobutyrate. Azo compounds such as rhonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, 1 , 1'-bis (t-butylperoxy) cyclohexane, organic peroxides such as t-butylperoxypivalate; hydrogen peroxide; redox initiators composed of these peroxides and reducing agents. it can.
These radical initiators can be used alone or in admixture of two or more.

The solvent used in the living radical polymerization is not particularly limited as long as the active radical is not deactivated.
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, etc. Poly) alkylene glycol alkyl ether acetates;
(Poly) alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether;
Other ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as Le;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility and coating properties of each component when used as a radiation sensitive resin composition, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, i-butylacetate , Formic acid n- pentyl acetate, i- pentyl, n- butyl propionate, ethyl butyrate, i- propyl butyrate n- butyl, ethyl pyruvate are preferred.
The said solvent can be used individually or in mixture of 2 or more types.

In the living radical polymerization, the amount of the thiocarbonylthio compound used is usually 0.1 to 50 parts by weight, preferably 0.2 to 16 parts by weight, based on 100 parts by weight of the total unsaturated compounds. The usage-amount of an initiator is 0.1-50 weight part normally with respect to 100 weight part of all the unsaturated compounds, Preferably it is 0.1-20 weight part.
The polymerization temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and the polymerization time is usually 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

On the other hand, among the polymerizable unsaturated compounds, the compound (a1) is an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride having radical polymerizability, such as monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride. , Mono [(meth) acryloyloxyalkyl] esters of polycarboxylic acids, mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, polycyclic compounds having carboxyl groups and anhydrides thereof Things can be mentioned.
Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
Examples of dicarboxylic acid anhydrides include, for example, acid anhydrides of the above compounds exemplified as the dicarboxylic acid;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples of mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at each of both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate;
Examples of the polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene. Ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6- Methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] And hept-2-ene anhydride.
Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability. . These may be used alone or in combination.

  The protecting group for protecting the carboxyl group of the compound (a1) is not particularly limited, and a known protecting group for the carboxyl group can be used. Examples thereof include a trialkylsilyl group, a 1-alkoxyalkyl group, and a cyclic 1-alkoxyalkyl group. More specifically, for example, trimethylsilyl, dimethylbutylsilyl, 1-ethoxyethyl, 1-propoxyethyl, tetrahydrofuranyl, tetrahydropyranyl, triphenylmethyl and the like can be mentioned.

  In the polymer (A), the content of the structural unit derived from the compound (a1) is preferably 5 to 5 based on the total of the structural units derived from the compounds (a1), (a2) and (a3). 50% by weight, particularly preferably 10 to 40% by weight. In this case, if the content of the structural unit is less than 5% by weight, the compressive strength, heat resistance and chemical resistance of the resulting spacer tend to decrease, while if it exceeds 50% by weight, the radiation sensitive resin The storage stability of the composition may be reduced.

Examples of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4-acrylic acid. Epoxy butyl, 3,4-epoxy butyl methacrylate, 3,4-epoxy butyl α-ethyl acrylate, 6,7-epoxy heptyl acrylate, 6,7-epoxy heptyl methacrylate, α-ethyl acrylate 6,7 -Epoxyheptyl, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, β-ethylglycidyl acrylate, β-ethylglycidyl methacrylate, β-n-propyl glycidyl acrylate, β-n-propyl glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate And carboxylic acid esters such as 3,4-epoxycyclohexyl methacrylate; ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.
Among these compounds (a2), glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, β-methylglycidyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl Ether, p-vinylbenzyl glycidyl ether and the like are preferable from the viewpoint of increasing the copolymerization reactivity and the strength of the resulting spacer.
The said compound (a2) can be used individually or in mixture of 2 or more types.

  The polymer (A) used in the present invention preferably has a structural unit derived from the compound (a2) based on the total of structural units derived from the compounds (a1), (a2) and (a3). It contains 10 to 70% by weight, particularly preferably 20 to 60% by weight. When this structural unit is less than 10% by weight, the heat resistance and surface hardness of the obtained interlayer insulating film and microlens tend to be reduced. On the other hand, when the amount of this structural unit exceeds 70% by weight, a radiation sensitive resin is used. The storage stability of the composition tends to decrease.

Furthermore, examples of the compound (a3) include acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate. Alkyl ester; methacrylic acid alkyl ester such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; cyclohexyl acrylate, 2- methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl acrylate (hereinafter, "tricyclo [5.2. .0 ^2,6] decan-8-yl "is called" dicyclopentanyl ".), 2-dicyclopentanyl oxyethyl acrylate, isobornyl acrylate, alicyclic esters of acrylic acid such as tetrahydrofuryl acrylate Alicyclic esters of methacrylic acid such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate; phenyl acrylate, benzyl acrylate, etc. Acrylic acid aryl esters; methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; diethyl maleate, diethyl fumarate, itaconate Dicarboxylic acid diesters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate and other acrylic acid hydroxyalkyl esters; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and other methacrylic acid hydroxyalkyl esters; styrene, α-methyl Aromatic vinyl compounds such as styrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3- Mention may be made of maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.
Of these compounds (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate, dicyclopentanyl methacrylate, styrene, p-methoxystyrene, 1,3-butadiene and the like are preferable from the viewpoint of copolymerization reactivity.
The said compound (a3) can be used individually or in mixture of 2 or more types.

  In the polymer (A), the content of the structural unit derived from the compound (a3) is preferably 10 to 10 based on the total of the structural units derived from the compounds (a1), (a2) and (a3). 80% by weight, particularly preferably 20 to 60% by weight. In this case, if the content of the structural unit is less than 10% by weight, the storage stability of the radiation-sensitive resin composition may be lowered, whereas if it exceeds 80% by weight, the developability may be lowered. is there.

  The polymer (A) used in the radiation-sensitive resin composition of the present invention can be obtained by living radical polymerization of an unsaturated compound as described above. In this case, the above formula (1) or the above formula is used. The thiocarbonylthio compound represented by (2) is used as a molecular weight control agent. For this reason, the polymer (A) is a group represented by the above formula (i) derived from the compound of the above formula (1) at at least one end of the polymer chain, or the above formula derived from the above formula (2). It has a group represented by the formula (ii).

The polymer (A) used in the present invention is a ratio of polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) and polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography ( Mw / Mn) is 1.7 or less, preferably 1.5 or less. When Mw / Mn exceeds 1.7, the pattern shape of the obtained spacer may be inferior. Further, Mw is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . If Mw is less than 2 × 10 ³ , the development margin may not be sufficient, and the remaining film ratio of the resulting coating may decrease, or the pattern shape and heat resistance of the resulting spacer may be inferior. . On the other hand, if Mw exceeds 1 × 10 ⁵ , the sensitivity may decrease or the pattern shape may be inferior. Further, Mn is preferably 1.2 × 10 ³ to 1 × 10 ⁵ , and more preferably 2.9 × 10 ^{3 to} 5 × 10 ⁴ . The radiation-sensitive resin composition containing the polymer (A) can easily form a predetermined pattern shape without causing development residue during development.

Further, the residual monomer amount measured by gel permeation chromatography of the (A) polymer used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, and particularly preferably 2.0%. Is less than. By using a polymer having such a residual monomer content, a coating film in which sublimates during firing are reduced can be obtained.
In the present invention, the (A) polymer can be used alone or in admixture of two or more.

(B) Polymerizable unsaturated compound (B) The polymerizable unsaturated compound in the radiation-sensitive resin composition of the present invention is preferably a bifunctional or higher functional acrylate and methacrylate (hereinafter referred to as “(meth) acrylate”). .
Examples of the bifunctional (meth) acrylate include ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9. -Nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, and the like.
Moreover, as a commercial item of bifunctional (meth) acrylate, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, R-604, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (above, Nippon Kayaku Manufactured by Co., Ltd.), Viscoat 260, 312 and 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

Examples of the tri- or more functional (meth) acrylates include 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, (Meth) acrylate has a linear alkylene group and an alicyclic structure, and two or more Urethane acrylate obtained by reacting a compound having an isocyanate group with a compound having one or more hydroxyl groups in the molecule and having 3, 4, or 5 acryloyloxy groups and / or methacryloyloxy groups And the like.
Examples of commercially available tri- or higher functional (meth) acrylates include, for example, Aronix M-309, -400, -402, -405, -450, -1310, -1600, -1960, -7100, -8030, -8060, -8100, -8100, -8530, -8560, -9050, Aronix TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA -20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) or as a urethane acrylate compound, New Frontier R-1150 (Daiichi Kogyo) Co., Ltd.), KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), and the like.
In this invention, a polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.

(C) Radiation-sensitive polymerization initiator (C) The radiation-sensitive polymerization initiator is a component that generates an active species that can initiate polymerization of (B) a polymerizable unsaturated compound in response to radiation.
As such a radiation sensitive polymerization initiator (C), for example, a radiation sensitive radical polymerization initiator is preferable.
Examples of the radiation sensitive radical polymerization initiator include α-diketones such as benzyl and diacetyl; acyloins such as benzoin; acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether; thioxanthone and 2,4-diethyl. Benzophenones such as thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone; acetophenone, p-dimethylaminoacetophenone, 4- (α , Α′-dimethoxyacetoxy) benzophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophene) Nyl) -1-propanone, acetophenones such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; quinones such as anthraquinone and 1,4-naphthoquinone; phenacyl chloride , Halogen compounds such as tribromomethylphenylsulfone and tris (trichloromethyl) -s-triazine; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl Examples thereof include acyl phosphine oxides such as pentyl phosphine oxide and bis (2,4,6-trimethylbenzoyl) phenyl phosphine oxide; peroxides such as di-t-butyl peroxide.

Examples of commercially available (C) radiation-sensitive radical polymerization initiators include IRGACURE-124, 149, 184, 369, -500, 651, -819, and 907. -1000, -1700, -1800, -1850, -1959, Darocur-1116, -1173, -1664, -2959, -4093 (above, manufactured by Ciba Specialty Chemicals) ), KAYACURE-DETX, -MBP, -DMBI, -EPA, -OA (above, manufactured by Nippon Kayaku Co., Ltd.), LUCIRIN TPO (made by BASF), VICURE-10, -55 (above , STAFFFER), TRIGONALP1 (manufactured by AKZO), SANDORAY 1000 (manufactured by SANDOZ), DEAP APJOHN Co., Ltd.), QUANTACURE-PDO, the -ITX, same -EPD (manufactured by WARD BLEKINSOP Co., Ltd.) and the like.
These radiation-sensitive radical polymerization initiators can be used alone or in admixture of two or more.

A highly sensitive radiation-sensitive resin composition that is less deactivated by oxygen in the air by using one or more (D) radiation sensitizers together with the (C) radiation-sensitive radical polymerization initiator. It is also possible to obtain
Examples of the (D) radiation sensitizer include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, Examples include i-amyl p-dimethylaminobenzoate, 2,4-diethylthioxanthone, and thioxanthone-4-sulfonic acid. Of these sensitizers, 4,4′-bis (diethylamino) benzophenone, 2,4-diethylthioxanthone and the like are preferable.
Two or more of these (D) radiation sensitizers may be used at the same time.
The proportion of the (D) radiation sensitizer used is preferably 40 parts by weight or less, more preferably 20 parts by weight or less, with respect to 100 parts by weight of the (C) radiation sensitive radical polymerization initiator. In this case, when the use ratio of the above-mentioned (D) radiation sensitizer exceeds 40 parts by weight, there is a tendency that undeveloped development tends to occur.

The amount of each component used in the radiation-sensitive resin composition of the present invention is such that (B) the polymerizable unsaturated compound is preferably 10 to 150 parts by weight, more preferably 100 parts by weight of the (A) polymer. 20 to 120 parts by weight, and (C) the radiation-sensitive polymerization initiator is preferably 1 to 40 parts by weight, more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the polymer (A).
(B) If the amount of the polymerizable unsaturated compound used is less than 10 parts by weight, it tends to be difficult to form a coating film having a uniform film thickness. Tends to decrease. In addition, when the amount of the (C) radiation sensitive polymerization initiator used is less than 1 part by weight, the heat resistance, surface hardness and chemical resistance tend to decrease, whereas when it exceeds 40 parts by weight, the transparency decreases. Tend.

Optional additives In the radiation-sensitive resin composition of the present invention, if necessary, optional additives other than those described above within a range not impairing the effects of the present invention, for example, adhesion assistants, surfactants, storage stabilizers, A heat resistance improver can be blended.
The adhesion assistant is a component used for improving the adhesion between the formed spacer and the substrate.
As such an adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group is preferable, and examples thereof include trimethoxysilylbenzoic acid. , Γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl And trimethoxysilane.
These adhesion assistants can be used alone or in admixture of two or more.
The compounding amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the polymer (A). In this case, when the compounding amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue is likely to occur.

Moreover, the said surfactant is a component used in order to improve applicability | paintability.
As such a surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant and the like are preferable.
The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain, and examples thereof include 1,1,2,2 -Tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, hexaethylene glycol di (1, 1,2,2,3,3-hexafluoro-n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2, 2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n- Til) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10 -Decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoro Examples thereof include alkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (manufactured by BM CHEMIE), MegaFack F142D, F172, F173, F183, F178, F191, F191, F471, F476 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M), Surflon S-112 -113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, Asahi Glass ( Co., Ltd.), Ftop EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), Footent FT-100, -110, -140A The -150, the -250, the -251, the -300, the -310, the same -400S, Ftergent FTX-218, the -251 (or more, (Ltd.) NEOS), and the like.

  Examples of the silicone-based surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF -8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (The above-mentioned, GE Toshiba Silicone Co., Ltd. product) etc. can be mentioned what is marketed.

Moreover, as surfactants other than the above, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n -Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured), (meth) acrylic acid copolymer polyflow No. 57, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.

  The compounding amount of the surfactant is preferably 1.0 part by weight or less, more preferably 0.5 part by weight or less, with respect to 100 parts by weight of the polymer (A). In this case, when the compounding amount of the surfactant exceeds 1.0 part by weight, film unevenness tends to occur.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-. Examples include phenylhydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.
The blending amount of the storage stabilizer is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the polymer (A). In this case, when the amount of the storage stabilizer exceeds 3.0 parts by weight, the sensitivity may be lowered and the pattern shape may be deteriorated.

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, and compounds having two or more epoxy groups.
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.
Of these N- (alkoxymethyl) glycoluril compounds, N, N, N, N-tetra (methoxymethyl) glycoluril is 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, Examples thereof include N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.
Of these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N-hexa (methoxymethyl) melamine is preferred, and examples of commercially available products thereof include Nicalac N-2702 and MW- 30M (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene glycol diglycidyl. Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl List ethers, bisphenol A diglycidyl ether, etc. It can be.
Examples of commercially available compounds having two or more epoxy groups include Epolite 40E, 100E, 200E, 70P, 200P, 400P, 1500NP, 80MF, 100MF, 1600, 3002 and 4000 (manufactured by Kyoeisha Chemical Co., Ltd.).
These heat resistance improvers can be used alone or in admixture of two or more.

Preparation of Radiation Sensitive Resin Composition The radiation sensitive resin composition of the present invention uniformly comprises the above-mentioned (A) polymer, (B) component and (C) component, and other components optionally added as described above. It is prepared by mixing. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, preparing a radiation-sensitive resin composition in a solution state by mixing the polymer (A), the component (B) and the component (C), and other components optionally added at a predetermined ratio. Can do.

As a solvent used for preparation of the radiation sensitive resin composition of the present invention, (A) the polymer, (B) component, (C) component and other components optionally blended are uniformly dissolved. And what does not react with each component is used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the polymer (A) mentioned above can be mentioned.

  Of these solvents, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used from the viewpoints of solubility of each component, reactivity with each component, and ease of film formation. It is done. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether Propylene glycol monomethyl ether acetate, methyl methoxypropionate, and ethyl ethoxypropionate can be particularly preferably used.

  Furthermore, in order to improve the in-plane uniformity of the film thickness together with the above solvent, a high boiling point solvent can be used in combination. Examples of the high boiling point solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

  When a high boiling point solvent is used in combination as the solvent of the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30%, based on the total amount of the solvent. It can be made into weight% or less. When the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may be reduced.

When preparing the radiation sensitive resin composition of the present invention in a solution state, components other than the solvent in the solution, that is, (A) polymer, (B) component and (C) component and other optionally added The ratio of the total amount of the components can be arbitrarily set according to the purpose of use and the value of the desired film thickness, for example, 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore size of about 0.5 μm.

Method of forming spacers Next, a method of forming a spacer of the present invention will be described with reference to radiation-sensitive resin composition of the present invention.
The spacer forming method of the present invention is characterized in that the following steps are performed in the order described below.
(1) A step of forming a coating of the above-mentioned radiation-sensitive resin composition for forming a spacer on a substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the film after exposure.
(4) A step of heating the film after development.
Hereinafter, each of these steps will be described sequentially.

(1) Step of forming a film of the radiation sensitive resin composition of the present invention on a substrate A transparent conductive film is formed on one surface of a transparent substrate, and the radiation sensitive resin composition of the present invention is formed on the transparent conductive film. After coating the composition solution, the coating surface is heated (prebaked) to form a coating.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, Examples thereof include a resin substrate made of a plastic such as polyethersulfone, polycarbonate, and polyimide.
As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) And so on.
The method for applying the composition solution is not particularly limited. For example, an appropriate method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating, or ink jet coating may be used. In particular, a spin coating method and a slit die coating method are preferable.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., it is normally about 1 to 15 minutes at 70-120 degreeC.
The film thickness after pre-baking of the coating is not particularly limited, but is usually about 0.5 to 10 μm, preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least a part of the coating film Next, the radiation is exposed to at least a part of the formed coating film. In this case, when exposing a part of the film, the exposure is performed through a photomask having a predetermined pattern.
Visible light, ultraviolet light, deep ultraviolet light, or the like can be used as radiation used for exposure. Radiation having a wavelength in the range of 190 to 450 nm is preferable, and radiation containing ultraviolet light of 365 nm is particularly preferable.
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. 500-3,000 J / m ² .

(3) Development Step Next, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; aliphatic primary amines such as ethylamine and n-propylamine. Aliphatic secondary amines such as diethylamine and di-n-propylamine; aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1, Aliphatic tertiary amines such as 8-diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene; fragrances such as pyridine, collidine, lutidine and quinoline Group tertiary amine; dimethylethanolamine, methyl It can be used an aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide; ethanolamine, alkanolamines such as triethanolamine.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can be added to the aqueous solution of the alkaline compound.
As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is usually about 10 to 180 seconds at room temperature.
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.

(4) Heating step Next, the obtained pattern (coating film) is heated at a predetermined temperature, for example, 100 to 160 ° C. for a predetermined time, for example, 5 to 30 minutes on the hot plate, for example, by a heating device such as a hot plate or oven. A predetermined spacer can be obtained by heating (post-baking) for 30 to 180 minutes in an oven.
The conventional radiation-sensitive resin composition used for the formation of the spacer cannot exhibit sufficient performance unless the heat treatment is performed at a temperature of about 180 to 200 ° C. or higher. The radiation sensitive resin composition can be heated at a lower temperature than before, and as a result, without causing yellowing or deformation of the resin substrate, compressive strength, rubbing resistance during liquid crystal alignment, A spacer having excellent performance such as adhesion can be provided.

Liquid crystal display element The liquid crystal display element of this invention is produced with the following method. First, two substrates on which a protective film having a liquid crystal alignment ability is formed are prepared, and the two substrates are placed through a gap (cell gap) so that the liquid crystal alignment directions in the respective protective films are orthogonal or antiparallel. The peripheral portions of the two substrates are bonded together via the spacer of the present invention, the liquid crystal is filled in the cell gap defined by the surface of the substrate and the spacer, the filling hole is sealed, and the liquid crystal cell is Constitute. Then, on the outer surface of the liquid crystal cell, that is, on the other surface side of each substrate constituting the liquid crystal cell, a polarizing plate is aligned or orthogonal to the liquid crystal alignment direction of the protective film formed on one surface of the substrate. Thus, the liquid crystal display element of the present invention is obtained.

  Examples of the liquid crystal include a nematic liquid crystal and a smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal, etc. are used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

  In addition, the polarizing plate used outside the liquid crystal cell is composed of a polarizing plate in which a polarizing film called an H film that has absorbed iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
<Measurement of molecular weight of copolymer by gel permeation chromatography>
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid

(A) Polymer Synthesis Examples Synthesis Examples 1-20
In a flask equipped with a condenser and a stirrer, 2 parts by weight of 2,2′-azobisisobutyronitrile and compounds represented by the above formulas (3) to (22) as molecular weight control agents are shown in Table 1. The amount shown and 200 parts by weight of diethylene glycol dimethyl ether were charged, followed by 20 parts by weight of styrene, 17 parts by weight of methacrylic acid, 18 parts by weight of dicyclopentanyl methacrylate, and 45 parts by weight of glycidyl methacrylate. Then, the temperature of the reaction solution was raised to 80 ° C., and polymerization was performed for 6 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 1 part by weight of 2,2′-azobisisobutyronitrile was added, and polymerization was further continued for 1 hour, whereby the polymers (A- Each solution of 1) to polymer (A-20) was obtained. The solid content, Mw, and Mw / Mn values of the obtained polymers were measured and found to be as shown in Table 1.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of styrene and 17 parts by weight of methacrylic acid. Part, 18 parts by weight of dicyclopentanyl methacrylate and 45 parts by weight of glycidyl methacrylate, and after purging with nitrogen, the temperature of the reaction solution was raised to 70 ° C. while gently stirring, and this temperature was maintained for 4 hours. By polymerizing, a polymer solution containing the polymer (a-1) was obtained. Mw of polymer (a-1) was 13,000, and molecular weight distribution (Mw / Mn) was 2.4. The solid content concentration of the polymer solution was 29.5% by weight.

Examples 1 to 20 and Comparative Example 1
(I) Preparation of Radiation Sensitive Resin Composition (A) Polymer of Synthesis Example above, Component (B) below and Component (C) below, and γ-glycidoxypropyltrimethoxysilane 5 wt. Part, 0.5 parts by weight of FTX-218 (trade name, manufactured by Neos Co., Ltd.) as a surfactant and 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer are mixed to a solid content concentration of 30% by weight. After being dissolved in propylene glycol monomethyl ether acetate, it was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a composition solution. The amount of each component is shown in Table 2.

(B) Component B-1: Dipentaerythritol hexaacrylate (C) Component C-1: 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole C -2: 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole C-3: 2-methyl [4- (methylthio) phenyl] -2-morpholino-1 -Propanone C-4: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
(Radiosensitizer)
D-1: 4,4′-bis (dimethylamino) benzophenone D-2: 2-mercaptobenzothiazole D-3: pentaerythritol tetra (mercaptoacetate)

Evaluation The composition prepared as described above was evaluated as follows. The evaluation results are shown in Table 3.

(II) Formation of Spacer The above composition solution was applied on an alkali-free glass substrate using a spinner and then pre-baked on a hot plate at 90 ° C. for 3 minutes to form a film having a thickness of 6.0 μm.
Next, the obtained coating film was exposed to ultraviolet rays having an intensity of 365 W / m ² at 365 nm for 10 seconds through a photomask having a 10 μm square remaining pattern. 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. Then, the spacer of the predetermined pattern was formed by post-baking for 120 minutes at 150 degreeC in oven.

(III) Evaluation of Resolution When the pattern was formed in the above (II), the case where the remaining pattern was resolved was evaluated as good (◯), and the case where the pattern was not resolved was evaluated as defective (×). The evaluation results are shown in Table 3.

(IV) Evaluation of sensitivity When the pattern obtained in the above (II) has a residual film ratio after development (film thickness after development × 100 / initial film thickness) of 90% or more (◯), less than 90% The case of was evaluated as defective (×). The evaluation results are shown in Table 3.

(V) Evaluation of pattern shape The cross-sectional shape of the pattern obtained in the above (II) was observed with a scanning electron microscope and evaluated according to which of A to D shown in FIG. At this time, when the pattern edge is forward tapered or vertical like A or B, it can be said that the pattern shape as a spacer is good. On the other hand, as shown in C, when the sensitivity is insufficient, the remaining film rate is low, the cross-sectional dimension is smaller than A and B, and the bottom surface of the cross-sectional shape is a flat semi-convex lens shape, The pattern shape as a spacer is poor, and as shown in D, the pattern shape as a spacer is very high because there is a great risk that the pattern will be peeled off during the subsequent rubbing process. Defective. The evaluation results are shown in Table 3.

(VI) Evaluation of compressive strength When using a micro compression tester (MCTM-200, manufactured by Shimadzu Corporation) for the pattern obtained in (II) above, a load of 10 mN was applied by a flat indenter with a diameter of 50 μm. The amount of deformation of was measured at a measurement temperature of 23 ° C. When this value is 0.5 or less, it can be said that the compressive strength is good. The evaluation results are shown in Table 3.

(VII) Evaluation of rubbing resistance After applying AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent to the substrate on which the pattern obtained in the above (II) was formed, using a printer for applying a liquid crystal aligning film. And dried at 180 ° C. for 1 hour to form a coating film of an orientation agent having a dry film thickness of 0.05 μm. Thereafter, a rubbing machine having a roll around which a polyamide cloth was wound was applied to this coating film, and the rubbing treatment was performed at a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern shaving or peeling was evaluated. The evaluation results are shown in Table 3.

(VIII) Evaluation of adhesion A cured film was formed in the same manner as in (II) above except that the mask of the remaining pattern was not used. Thereafter, the adhesive test of JIS K-5400 (1900) 8.5 was evaluated by the 8.5 / 2 cross-cut tape method. At this time, the number of remaining grids out of 100 grids is shown in Table 3.

(IX) Evaluation of Sublimation Product After applying the above composition solution on a silicon substrate using a spinner, it was pre-baked on a hot plate at 90 ° C. for 2 minutes to form a coating film having a thickness of 3.0 μm. . The obtained coating film was exposed with a PLA-501F exposure machine (extra-high pressure mercury lamp) manufactured by Canon Co., Ltd. so that the integrated irradiation amount was 3,000 J / m ^2, and this silicon substrate was placed in a clean oven. A cured film was obtained by heating at 220 ° C. for 1 hour. A bare silicon wafer for cooling was mounted at an interval of 1 cm above the obtained cured film, and a heating process was performed at 230 ° C. for 1 hour on a hot plate. Without replacing the bare silicon wafer for cooling, 20 silicon substrates on which the cured film was separately formed were processed in succession, and then the presence or absence of sublimated material adhering to the bare silicon was verified visually. When the sublimate is not confirmed, the sublimate evaluation is good.

It is a schematic diagram which illustrates the cross-sectional shape of a spacer.

Claims (7)

(A) It has a carboxyl group and an epoxy group, and the ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography is 1.7 or less. A radiation-sensitive resin composition containing (B) a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator, wherein (A) the living radical polymerization for producing the polymer is represented by the following formula: A radiation-sensitive resin composition for forming a spacer, which is polymerization using a thiocarbonylthio compound represented by formula (1) or formula (2) as a molecular weight control agent.

[In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. Monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OR, -SR, -N (R) ₂ , -OC (= O) R, -C (= O) OR, -C (═O) N (R) ₂ , —P (═O) (OR) ₂ , —P (═O) (R) ₂ , or a monovalent group having a polymer chain, wherein each R is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of carbon atoms and hetero atoms 1 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent heterocyclic group having 3 to 20 atoms in total. And R may be each substituted, ^{R 1,} when the p = 1, an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, 6 carbon atoms 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 total atoms of carbon atoms and hetero atoms, -OR, -SR, -N (R) ₂ or polymer chain Each R independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or carbon. 1 represents a monovalent heterocyclic group having 3 to 18 total atoms of atoms and hetero atoms, and when p ≧ 2, a p-valent group derived from an alkane having 1 to 20 carbon atoms, 6 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon, a p-valent group derived from a heterocyclic compound having a total of 3 to 20 carbon atoms and hetero atoms. Represents a p-valent group having a polymer chain, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic group having 6 to 20 carbon atoms. Hydrocarbon group, monovalent heterocyclic group having 3 to 20 atoms in total, R, p-valent group derived from alkane having 1 to 20 carbon atoms, p derived from aromatic hydrocarbon having 6 to 20 carbon atoms The valent group and the p-valent group derived from the heterocyclic compound having a total of 3 to 20 atoms may each be substituted. ]

[In the formula (2), Z ² represents an m-valent group derived from an alkane having 1 to 20 carbon atoms, an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a carbon atom and a hetero atom. M-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain, m-valent group derived from an alkane having 1 to 20 carbon atoms, carbon number The m-valent group derived from an aromatic hydrocarbon having 6 to 20 and the m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted, and R ² may have 1 to 1 carbon atoms. 20 alkyl groups, monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms, monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms, and 3 to 20 total atoms of carbon atoms and hetero atoms A monovalent heterocyclic group, —OR, —SR, —N (R) ₂ or a monovalent group having a polymer chain, wherein each R is a phase Independently of each other, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of 3 atoms of carbon atoms and hetero atoms 18 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent aromatic carbon group having 6 to 20 carbon atoms. The hydrogen group, monovalent heterocyclic group having 3 to 20 atoms in total and R may each be substituted. ] The polymer (A) has a group represented by the following formula (i) or a group represented by the following formula (ii) at at least one terminal of each polymer chain constituting the polymer. A radiation-sensitive resin composition for forming a spacer.

[In Formula (i), Z ¹ is the same as Formula (1), and in Formula (ii), Z ² and m are the same as in Formula (2). ]   The radiation-sensitive resin composition for forming a spacer according to claim 1 or 2, wherein (B) the polymerizable unsaturated compound is a bifunctional or higher functional (meth) acrylate.   The radiation-sensitive resin composition for spacer formation according to any one of claims 1 to 3, wherein (C) the radiation-sensitive polymerization initiator is a radiation-sensitive radical polymerization initiator.   The spacer formed from the radiation sensitive resin composition for spacer formation in any one of Claims 1-4. A method for forming a spacer, wherein at least the following steps (1) to (4) are carried out in the order described below.
(1) The process of forming the film of the radiation sensitive resin composition for spacer formation in any one of Claims 1-5 on a board | substrate.
(2) A step of exposing radiation to at least a part of the coating.
(3) A step of developing the film after exposure.
(4) A step of heating the film after development. A liquid crystal display device comprising the spacer according to claim 5.

Images