JP2008250273A - Radiation-sensitive resin composition, spacer and method for forming the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation sensitive resin composition for forming a spacer, the composition having high sensitivity and high resolution with which a patterned thin film having excellent performances such as a pattern profile, compression characteristics, rubbing durability and adhesiveness to a transparent substrate can be easily formed and image persistence in a LCD can be suppressed, to provide a spacer and a method for forming the spacer from the above resin composition, and to provide a photosensitive resin composition for forming a spacer, the composition capable of reducing failure in an unfilled region depending on a drop amount of a liquid crystal, preventing damages by pressure on a color filter and eliminating uneven thickness occurring in a production process. <P>SOLUTION: The radiation sensitive resin composition contains (A) a block copolymer, (B) a polymerizable unsaturated compound and (C) a radiation sensitive polymerization initiator, wherein the (A) block copolymer has two or more block segments and at least one of the block segments contains an alkali-soluble moiety. <P>COPYRIGHT: (C)2009,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 size in order to keep the distance between two transparent substrates constant. Since it is randomly distributed on a transparent substrate such as a glass substrate, if there are spacer particles in the pixel formation region, the reflection phenomenon of the spacer particles occurs or the incident light is scattered and the contrast of the liquid crystal display element is lowered. 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 from those having 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 i-line or less is used (see Patent Document 1). However, in a conventionally known radiation-sensitive resin composition for forming a spacer, depending on the selection of the radiation-sensitive polymerization initiator, the cross-sectional shape of the spacer formed is inversely tapered (the length of the side of the film surface is the substrate). In the case of an inverted trapezoidal shape that is longer than the length of the side edge), which causes the spacer to peel off during the subsequent rubbing treatment of the alignment film.
Furthermore, there is a problem of “burn-in” of the LCD display, which is presumed to be caused by impurities eluted from the in-cell permanent film formed from the radiation-sensitive resin composition. Therefore, there has been a demand for a radiation-sensitive resin composition that can form an LCD panel with a high product yield.

On the other hand, if too much emphasis is placed on the high restoring force that recovers the original cell gap after deformation due to compressive strength and external force, the external force cannot be absorbed and the TFT and CF may be damaged or destroyed. was there.
In addition, in order to shorten the filling process time for injecting liquid crystal in a vacuum after bonding the TFT plate and the CF plate, there is a new process for dropping the liquid crystal at a time and bonding the TFT plate and the CF plate. It has been developed. However, the conventional spacer has a problem that the amount of deformation is not sufficient, the margin for the liquid crystal dropping process is insufficient, and a defect occurs.

By the way, in the manufacture of a liquid crystal display panel, the substrate size has been increased from the viewpoint of improving productivity and adapting to a large screen. Substrate size is 300mm × 400mm first generation, 370mm × 470mm second generation, 620mm × 750mm third generation, 960mm × 1,100mm fourth generation, then 1,100mm × 1,300mm fifth Generations are now mainstream. Further, the sixth generation of 1,500 mm × 1,850 mm, the seventh generation of 1,850 mm × 2,100 mm, and the eighth generation of 2,200 mm × 2,600 mm will be further increased in the future.
When the substrate size is small, for example, 370 mm × 470 mm or less, the photosensitive resin composition is dropped onto the substrate in the center and applied by a spin coating method. This method has a drawback that a large amount of the photosensitive resin composition solution is required for coating, and it cannot be applied to a large substrate.
When the substrate size is 960 mm × 1,100 mm or less, the coating is performed by the slit & spin method for the purpose of saving the photosensitive resin composition solution. In this method, a photosensitive resin composition solution is applied to a substrate surface from a slit nozzle, and then the substrate is rotated to form a uniform coating film. This method is effective for saving liquid, but it is difficult to cope with the substrate size of the fifth generation and later.

From such a background, as the substrate size increases, coating by a slit die coater has been performed. However, in the case of a slit die coater, streaky unevenness, haze unevenness, substrate transport arms and pins, suction pad marks (pin marks), and unevenness of the film thickness at the substrate end are likely to occur.
For these reasons, in the slit die coater method, a photosensitive resin composition solution for forming a spacer having a uniform film thickness and no unevenness has been strongly desired.
JP 2001-261761 A Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181) Special Table 2002-2002 JP-T-2004-518773 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 MKGeorges, RPNVeregin, PMKazmaier, GKHamer, Macromolecules, 1993, Vol.26, p.2987 Matyjaszewski, K. Coca, S. Gaynor, G. wei, M. Woodworth, BE Macromolecules, 1997, Vol. 30, p. 7348 Hamasaki, S.Kamigaito, M.Sawamoto, M. Macromolecules, 2002, Vol.35, p.2934

  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, compression characteristics, 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 image sticking in an LCD display is suppressed, a spacer formed therefrom, and a method for forming the same.

  Another object of the present invention is to reduce defects in the unfilled area due to the liquid crystal dripping amount, to prevent damage due to pressure on the color filter, and to overcome the thickness deviation generated in the process. Is to provide a photosensitive resin composition for spacers suitable for the slit die coater method with a uniform film thickness and no unevenness.

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

The above objects and advantages of the present invention are as follows.
It is achieved by a radiation-sensitive resin composition for forming a spacer, comprising (A) a block copolymer, (B) a polymerizable unsaturated compound, and (C) a radiation-sensitive polymerization initiator.

  Secondly, the above objects and advantages of the present invention are preferably achieved by a radiation sensitive resin composition further containing (D) an epoxy group-containing compound in addition to the above components (A), (B) and (C). .

  Thirdly, the object and advantage of the present invention are as follows. (A) The block copolymer has two or more block segments, and at least one of the block segments contains an alkali-soluble site. This is preferably achieved by the radiation sensitive resin composition.

  Fourthly, the above objects and advantages of the present invention are preferably achieved by the radiation sensitive resin composition containing a carboxyl group as the alkali soluble site.

  Fifth, the object and advantage of the present invention are as follows. (A) The block copolymer comprises (a1) an unsaturated carboxylic acid having a radical polymerizability, an unsaturated carboxylic acid anhydride, and a protected product of these carboxylic acids. The radiation sensitive composition comprising at least one selected from the group and a first block segment composed of a radical polymerizable compound other than (a2) and (a1) and a second block segment composed only of (a1) or (a2). This is preferably achieved by the resin composition.

  Sixth, the above objects and advantages of the present invention are preferably achieved by the above radiation sensitive resin composition using the block copolymer (A) obtained by living radical polymerization.

  Seventhly, the above object and advantage of the present invention are that the (A) block copolymer is polymerizable using a thiocarbonylthio compound represented by the following formula (1), (2) or (3) as a molecular weight control agent. It is preferably achieved by the radiation sensitive resin composition which is a resin produced by polymerizing an unsaturated compound.

[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, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted. ]

[In Formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic carbon atom having 6 to 20 carbon atoms. A hydrogen group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms,
^{-OR 1, -SR 1, -OC (} = O) R 1, -N (R 1) (R 2), - C (= O) OR 1,
—C (═O) N (R ¹ ) (R ² ), —P (═O) (OR ¹ ) ₂ , —P (═O) (R ¹ ) ₂ or a monovalent group having a polymer chain. R ¹ and R ² are 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 carbon atom. A monovalent heterocyclic group having 3 to 18 atoms in total with the atom, the alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom and a different group The monovalent heterocyclic group having 3 to 20 atoms in total, R ¹ and R ² may be substituted. ]

  Eighth, the above objects and advantages of the present invention are as follows. The ratio (Mw) of polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer (A). / Mn) is preferably achieved by the radiation sensitive resin composition having a value of 2.5 or less.

  Ninth, the above objects and advantages of the present invention are achieved by a spacer formed from the above radiation sensitive resin composition.

The above objects and advantages of the present invention are achieved by a spacer forming method characterized by including the following steps (a) to (d).
(A) forming a film of the radiation sensitive resin composition on a substrate;
(B) exposing at least a part of the film to radiation such as visible light, ultraviolet light, or far ultraviolet light;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development.

  The above object and eleventh aspect of the present invention are achieved, eleventhly, by a liquid crystal display device comprising the above spacer.

  The radiation-sensitive resin composition of the present invention easily forms a patterned thin film having high sensitivity and high resolution and excellent performance such as pattern shape, compressive strength, rubbing resistance, and adhesion to a transparent substrate. And image sticking in the LCD display can be suppressed. The amount of deformation of the spacer becomes sufficient, the TFT and CF are not damaged or destroyed by an external force, and a margin for the liquid crystal dropping process can be expected to be improved.

The following radiation-sensitive resin composition will be described in detail for each component in the radiation-sensitive resin composition of the present invention.

(A) Block copolymer The (A) block copolymer in the radiation sensitive resin composition of the present invention is a copolymer containing at least two block segments composed of polymerizable unsaturated compounds having different chemical structures. It shall mean coalescence. The block segment can consist of a single polymer or a plurality of polymers of polymerizable unsaturated compounds. At this time, the block segment may be a random copolymer. (A) The block copolymer may contain two block segments each consisting of a random copolymer. It has two or more segments of a first block segment produced by primary polymerization and a second block segment given to the first block segment by secondary polymerization, and at least one of them contains an alkali-soluble site. It is preferable. For example, the block copolymer (A) includes the compound (a1) an unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability, or a protected product of these carboxylic acids, and the compounds (a2) (a1). A polymerizable mixture containing a radically polymerizable compound other than the above is subjected to living radical polymerization in a solvent in the presence of a polymerization initiator, and further containing the compound (a2) or the compound (a1) and the compound (a2). Can be added to continue the polymerization. If necessary, a block segment can be added by further adding a polymerizable mixture. The alkali-soluble part of the thus obtained (A) block copolymer is derived from the compound (a1).

Next, (A) Living radical polymerization for producing a block copolymer will be described.
A first block segment is produced by living radical polymerization of the above polymerizable unsaturated compound, preferably together with other copolymerizable unsaturated compounds, in a solvent in the presence of a radical polymerization initiator system that generates a living radical. Further, the block copolymer (A) can be produced by adding the polymerizable unsaturated compound a plurality of times as necessary.
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, The functional group in the polymerizable unsaturated compound can be protected by, for example, esterification and then polymerized, and then deprotected to obtain (A) a block copolymer.

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 (see Non-patent Document 2), a system composed of a combination of carbon tetrachloride and a ruthenium (II) complex proposed by Hamasaki et al. (See Non-patent Document 3) And 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. .
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 8 in addition to Patent Document 2, Patent Document 3 and Patent Document 4.

  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), the above formula (2), or the above formula (3).
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 carbon atoms and hetero atoms 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 to 18 carbon atoms in total.
Examples of the alkenyl group having 2 to 18 carbon atoms of the same R include, for example, 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.

The above-mentioned 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 It can be appropriately selected from groups wherein the substituents can 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 vinylidene chloride. 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; ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth ) (Meth) acrylic acid esters such as n-hexyl acrylate and cyclohexyl (meth) acrylate; 1) One or more of unsaturated compounds such as (meth) acrylamides such as acrylamide and N, N-dimethyl (meth) acrylamide; 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 polyoxyethylene whose terminal may be etherified, polyether such as polyoxypropylene whose terminal may be etherified, Examples thereof include monovalent groups having polyaddition polymer chains such as polyester, polyamide, and polyimide, and polycondensation polymer chains. 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 in 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.
In addition, 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, morpholine, and the like.

P-valent group derived from the alkane having 1 to 20 carbon atoms, p-valent group derived from an 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). P in the formula (1) is preferably an integer of 1 to 6.

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 including a m ² valent group of Z ² include, for example, a carbon atom and a hetero atom that provide the 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), R ₂ is an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent atom having 3 to 20 total atoms of carbon atoms and hetero atoms. 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, monovalent fatty acids having 3 to 20 carbon atoms of the above R ¹ (p = 1). The thing similar to the group illustrated about the cyclic hydrocarbon group and its substituted derivative can be mentioned.

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 . M in Formula (2) is preferably an integer of 2 to 6.

In Formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. A monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom,
^{-OR 1, -SR 1, -OC (} = O) R 1, -N (R 1) (R 2), - C (= O) OR 1,
—C (═O) N (R ¹ ) (R ² ), —P (═O) (OR ¹ ) ₂ , —P (═O) (R ¹ ) ₂ or a monovalent group having a polymer chain. R ¹ and R ² are 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 carbon atom. A monovalent heterocyclic group having 3 to 18 atoms in total with the atom, the alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom and a different group The monovalent heterocyclic group having 3 to 20 atoms in total, R ¹ and R ² may be substituted.

As Z ³ and Z ⁴ , those exemplified above as Z ¹ in the above formula (1) can be exemplified.
As Z ³ and Z ⁴ , in addition to the alkyl group having 1 to 20 carbon atoms, in view of reactivity with the polymerizable unsaturated compound, in particular, the thiocarbonyl group (C═S) in the formula (1) A group in which a carbon atom and a hetero atom such as a nitrogen atom or an oxygen atom in Z ³ and Z ⁴ are covalently bonded, more specifically, the total number of atoms of the carbon atom and the hetero atom is 3 to 20 Are preferably a monovalent heterocyclic group, —OR ¹ , —N (R ¹ ) (R ² ) and the like, and in particular, a methyl group, an ethyl group, a 1-pyrrole group, a 1-pyrazole group, a methoxy group, and an ethoxy group. , A dimethylamino group, a diethylamino group and the like are preferable.
Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (4) to (28).

  Next, the polymerization method for producing the (A) block copolymer will be described. (A) The block copolymer is compound (a1) other than unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability, or a protected product of these carboxylic acids, and compounds (a2) (a1) A polymerizable mixture containing a radical polymerizable compound is subjected to living radical polymerization in a solvent in the presence of a polymerization initiator and a thiocarbonylthio compound, and further contains compound (a2) or compound (a1) and compound (a2). It can be produced by adding a polymerizable mixture and continuing the polymerization. If necessary, a block segment can be added by further adding a polymerizable mixture.

When the polymerization takes the form of living radical polymerization, when using a compound having a functional group that may deactivate an active radical such as a carboxyl group as the polymerizable unsaturated compound, in order to prevent the growth terminal from being deactivated. If necessary, the copolymer (A) having a narrower molecular weight distribution can be obtained by deprotecting the functional group in the unsaturated compound after protecting the functional group by, for example, esterification. .
The radical polymerization initiator is appropriately selected depending on the type of the polymerizable unsaturated compound to be used, and those generally known as radical polymerization initiators can be used. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. An azo compound; an organic peroxide such as benzoyl peroxide, lauroyl peroxide, 1,1′-bis (t-butylperoxy) cyclohexane, t-butylperoxypivalate; hydrogen peroxide; The redox type | system | group initiator which consists of etc. can be mentioned.

Among these radical polymerization initiators, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) are particularly preferable from the viewpoint that side reactions due to oxygen or the like are unlikely to occur. Azo compounds such as) are preferred. The radical polymerization initiators can be used alone or in admixture of two or more kinds. In the polymerization, other molecular weight control agents such as α-methylstyrene dimer, t-dodecyl mercaptan and the like 1 More than one species can be used in combination with the disulfide compound (1).

The solvent used for the polymerization is not particularly limited. For example,
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and propylene glycol monoethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether (Poly) alkylene glycol monoalkyl ether acetates such as acetate;
(Poly) alkylene glycol diethers 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-methylhexan-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 ethoxy acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 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, active radicals are not deactivated during living radical polymerization, and from the viewpoints 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, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2 -Heptanone, 3-heptanone, 3-methoxypro Ethyl onate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate N-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

In the said polymerization, the usage-amount of a radical polymerization initiator becomes like this. Preferably it is 0.1-50 weight part with respect to 100 weight part of all the unsaturated compounds, More preferably, it is 0.1-20 weight part.
The amount of the thiocarbonylthio compound used is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 16 parts by weight, particularly preferably 0.4 to 100 parts by weight based on 100 parts by weight of the total unsaturated compounds. 8 parts by weight. When the amount of the thiocarbonylthio compound used is less than 0.1 parts by weight, the regulation effect of the molecular weight and the molecular weight distribution tends to be reduced. There is.

The amount of the other molecular weight control agent used is preferably 80 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the total molecular weight control agent. When the usage-amount of another molecular weight control agent exceeds 80 weight part, there exists a possibility that the desired effect of this invention may be impaired.
Moreover, the amount of the solvent used is preferably 50 to 1,000 parts by weight, more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the total unsaturated compounds.
The polymerization temperature is preferably 0 to 150 ° C., more preferably 50 to 120 ° C., and the polymerization time is preferably 10 minutes to 20 hours, more 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 unsaturated carboxylic acid anhydride having radical polymerizability, or a protected product of these carboxylic acids.
Examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability include, for example, monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, polycarboxylic acid mono [(meth) acryloyloxy Alkyl] ester, mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, and anhydrides thereof.

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.

Examples of the compound (a2) 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 esters; methacrylic acid alkyl esters 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 [5.2.1 . 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 ester; Methacrylic acid aryl ester such as phenyl methacrylate, benzyl methacrylate; Diethyl maleate, Diethyl fumarate, Diethyl 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-methylstyrene , M-methylstyrene, p-methylstyrene, p-methoxystyrene and other aromatic vinyl compounds, 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-ma Examples include reimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide. .

Of these compounds (a2), 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 (a2) can be used individually or in mixture of 2 or more types.
In the block copolymer (A) used in the present invention, as the first block segment, for example, a block segment composed of polymerization units derived from two compounds (a1) and (a2) is preferable.
In this case, the content of the polymerized units derived from the compound (a1) in the block segment is preferably 5 to 50% by weight based on the total of polymerized units derived from the compounds (a1) and (a2). Preferably it is 10 to 40% by weight. When the content of the polymerized unit derived from the compound (a1) is less than 5% by weight, the compression strength, heat resistance and chemical resistance of the resulting spacer tend to decrease, while when it exceeds 50% by weight, There is a possibility that the storage stability of the radiation resin composition is lowered.

Further, the content of the polymerized units derived from the compound (a2) in the block segment is preferably 50 to 95 weight based on the total of polymerized units derived from the compounds (a1), (a2) and (a3). %, More preferably 60 to 90% by weight. If the content of the polymerized unit derived from the compound (a2) is less than 50% by weight, the storage stability of the radiation-sensitive resin composition may be lowered. On the other hand, if it exceeds 95% by weight, the developability is lowered. There is a risk.
(A) The second block segment in the block copolymer is a block segment composed of polymerized units derived from the compound (a1), a block segment composed of polymerized units derived from the compound (a2), or the compounds (a1) and (a2). ) In the block segment composed of polymerized units derived from the two. However, the polymerization units constituting the first block segment and the second block segment are not the same combination.

In the present invention, the second block segment is preferably a block segment consisting only of the compound (a1) or a block segment consisting only of the compound (a2). In this case, when the block copolymer (A) has a second block segment composed only of the compound (a2) not involved in crosslinking, a spacer having a smaller hardness, excellent compatibility at the time of spacer formation, and a uniform surface state is obtained. Can be obtained.
The block copolymer (A) can further control the hardness and shape of the spacer by further having a third block segment as necessary. Examples of the third block segment include those similar to the second block segment, but the polymerization units constituting the second block segment and the third block segment are not the same combination. Moreover, it is preferable that a 3rd block segment is added to a 2nd block segment in the tertiary polymerization performed subsequent to the secondary polymerization which synthesize | combines a 2nd block segment.

As the (A) block copolymer of the present invention, for example,
A block copolymer comprising at least a first block segment composed of polymerized units derived from two of compounds (a1) and (a2) and a second block segment composed only of compound (a1);
A block copolymer comprising at least a first block segment composed of polymerized units derived from two of the compounds (a1) and (a2) and a second block segment composed only of the compound (a2);
Etc. are preferred.
The ratio of (A) the first block segment in the block copolymer ((weight of first block segment / (A) block copolymer weight) × 100) is preferably 30 to 95% by weight, particularly preferably 50 -90% by weight. When it is lower than 30% by weight, Mw / Mn may exceed 2.5, and electrical characteristics may be deteriorated. On the other hand, if it is larger than 90% by weight, the amount of residual monomer is increased, and there is a concern that volatile components increase during baking, which is not preferable.

The (A) block copolymer used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) and a polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography. The ratio (Mw / Mn) is 2.5 or less, preferably 2.0 or less. When Mw / Mn exceeds 2.5, 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 the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, and the remaining film ratio of the resulting film may decrease, or the pattern shape of the resulting spacer, heat resistance, etc. 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 copolymer (A) can easily form a predetermined pattern shape without causing a 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 the (A) polymer having such Mw, preferably further having the specific Mw / Mn, and having the residual monomer content described above, at the time of exposure or baking of the photosensitive composition The generation of sublimates is low, the possibility of contamination of an apparatus used when manufacturing an LCD panel is low, and “burn-in” of the LCD panel can be more effectively prevented.
Said (A) polymer can be used individually or in mixture of 2 or more types.
Moreover, in this invention, 1 or more types of other alkali-soluble resin can also be used together with (A) polymer.

(B) Polymerizable unsaturated compound (B) The polymerizable unsaturated compound in the radiation-sensitive resin composition of the present invention is a monofunctional, bifunctional or higher acrylate and methacrylate (hereinafter referred to as “(meth) acrylate”). Is preferred.

  Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, and 3-methoxybutyl. Examples include acrylate, 3-methoxybutyl methacrylate, 2-acryloyloxyethyl-2-hydroxypropyl phthalate, 2-methacryloyloxyethyl-2-hydroxypropyl phthalate, and ω-carboxypolycaprolactone monoacrylate. For example, Aronix M-101, M-111, M-114, M-5300 (manufactured by Toa Gosei Co., Ltd.); KAYA AD TC-110S, the TC-120S (manufactured by Nippon Kayaku Co.); Viscoat 158, the 2311 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

  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 higher functional (meth) acrylate include, 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, (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) Medicine), 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.
The proportion of the (B) polymerizable unsaturated compound used in the radiation-sensitive resin composition of the present invention is preferably 40 to 250 parts by weight, more preferably 60 parts per 100 parts by weight of the (A) block copolymer. -180 parts by weight.

(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.
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- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -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, 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 1,500 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 methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one. The 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-methylbenzyl) -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.
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 decrease. 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 addition amount of the thiol compound 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.

Further, as the radiation-sensitive cationic polymerization initiator, onium salts such as phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trifluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium- p-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazoniumtri Fluoroacetate, 4-methoxyphenyl Azonium-p-toluenesulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarsenate, 4-ter-butylphenyldiazonium trifluoro Diazonium salts such as romethanesulfonate, 4-ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium Hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, trif Nylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxy Phenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate 4-phenylthiophenyl diphenyl hex Sulfonium salts such as safluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfonate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate;
Examples include iodonium salts such as bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate and (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate.

Examples of the metallocene compound include (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-).
Commercially available products of these radiation-sensitive cationic polymerization initiators include, for example, Adeka Ultra Set PP-33 (made by Asahi Denka Kogyo Co., Ltd.) which is a diazonium salt, OPTOMER SP-150 and 170 (both Asahi Denka) which are sulfonium salts. Kogyo Co., Ltd.) and Irgacure 261 (Ciba Specialty Chemicals Co., Ltd.), which is a metallocene compound.
Said radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types.
In the radiation sensitive resin composition of the present invention, the use ratio of (C) the radiation sensitive polymerization initiator is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the (A) block copolymer. Preferably it is 3-40 weight part.

(D) Epoxy group-containing compound Examples of the (D) epoxy group-containing compound in the present invention include (d1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (d2) epoxy group-containing unsaturated compound, (d3 ) Copolymers (D-1) of other olefinic unsaturated compounds or copolymers (D-2) of (d2) and (d3). (D-1) can be produced by radical polymerization of compound (d1), compound (d2) and compound (d3) in the presence of a polymerization initiator in a solvent, and (D-2) is a compound. (D2) and compound (d3) can be produced by radical polymerization in a solvent in the presence of a polymerization initiator.
Examples of the (d1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride include monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, and poly [carboxylic acid] mono [(meth) acryloyloxyalkyl] ester. And mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, and anhydrides thereof.

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.

  Examples of the (d2) epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, acrylic acid- 3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid Examples include 3,4-epoxycyclohexylmethyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether. Among these, glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, methacrylic acid-3,4-epoxycyclohexyl, methacrylic acid-3,4-epoxycyclohexylmethyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl Glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferably used from the viewpoint of increasing the copolymerization reactivity and the strength of the resulting spacer. These may be used alone or in combination.

Examples of (d3) other olefinically unsaturated compounds include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, and t-butyl. Acrylic acid alkyl esters such as acrylates; Methacrylic acid alkyl esters 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 [5.2.1.0 ^2,6] decan-8-yl "is called" dicyclopentanyl ".), 2-dicyclopentanyl oxyethyl acrylate, isobornyl acrylate, such as tetrahydrofuryl acrylate Alicyclic esters of acrylic acid; alicyclic esters of methacrylic acid such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; aryl methacrylates such as phenyl methacrylate and benzyl methacrylate; diethyl maleate and difumarate Dicarboxylic diesters such as chill and diethyl itaconate; acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; styrene , Α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and other aromatic vinyl compounds, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N- Succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide be able to.

Of these compounds (d3), 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 (d3) can be used individually or in mixture of 2 or more types.
As the radical polymerization initiator, the same ones described in paragraphs (0076) to (0077) can be used.
As the solvent that can be used for the radical polymerization, the same solvents as those described in paragraphs (0078) to (0079) can be used.

As the (D) epoxy group-containing compound in the present invention, in addition to the above (D-1) and (D-2), a compound (D-3) having two or more epoxy groups in one molecule can be used. . By adding this, the heat resistance and chemical resistance of the spacer may be improved.
Examples of the compound (D-3) 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, 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, water Bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, etc. It can gel.

Moreover, as a commercial item of the compound which has two or more epoxy groups, for example, Epolite 40E, 100E, 200E, 70P, 200P, 400P, 1500NP, 80MF, 100MF, 1600, 3002, 4000 (manufactured by Kyoeisha Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (manufactured by Japan Epoxy Resin Co., Ltd.), and the like. These can be used individually or in mixture of 2 or more types.
The said epoxy group containing compound (D-1), (D-2), (D-3) can be used individually or in mixture.

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). (D) The epoxy group-containing compound is preferably 0 to 150 parts by weight.
(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. Moreover, when the (D) epoxy group-containing compound exceeds 150 parts by weight, developability may be deteriorated, which is not preferable.

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, for example, 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. Examples thereof include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β -(3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
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). When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that 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.

  As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. 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-butyl) ether, perfluoro-n Sodium dodecanesulfonate 1,1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10- Cafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other fluoroalkyls Examples thereof include polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F183, F178, F191, F471, F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, Sumitomo 3M Limited), 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.

Further, as surfactants other than the above, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene- polyoxyethylene aryl ethers such as n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; and organosiloxane polymers KP341 (Shin-Etsu Chemical Co., Ltd.) )), (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). When the 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 co (A) polymer. 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 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 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 Examples include ', N', N ″, N ″ -hexa (t-butoxymethyl) melamine.
Of these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred. -2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Preparation of Radiation Sensitive Resin Composition The radiation sensitive resin composition of the present invention is optionally added with the above-mentioned (A) polymer, (B) component, (C) component and (D) component and the above. It is prepared by mixing other ingredients uniformly. 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, the (A) polymer, the (B) component, the (C) component, the (D) component, and other components that are optionally added are mixed in a predetermined ratio to provide a radiation-sensitive resin composition in a solution state. Product can be prepared.
As a solvent used for the preparation of the radiation sensitive resin composition of the present invention, (A) polymer, (B) component, (C) component and (D) component and other components optionally blended Those that dissolve the components uniformly and do not react with each component are used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the above-mentioned (A) polymer 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, the (A) polymer, the (B) component, the (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 diameter 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) The process of forming the coating film of the said radiation sensitive resin composition 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.
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, A resin substrate made of a plastic such as polyethersulfone, polycarbonate, or polyimide can be used.

As a transparent conductive film provided on one surface of the transparent substrate, an 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 coating method of the composition solution is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coater method, a bar coating method, an ink jet coating method or the like can be used. In particular, a spin coating method and a slit die coater method are preferable.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., Preferably it is about 1 to 15 minutes at 70-120 degreeC.
In addition, the film thickness after the pre-baking of the film is not particularly limited, but is preferably about 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least a part of the coating film Next, at least a part of the formed coating film is exposed to radiation. In this case, when exposing a part of the film, the exposure is performed through a photomask having a predetermined pattern, for example.
Visible light, ultraviolet light, far 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 amount is preferably 100 to 10,000 J / m ² , more preferably 1, as a value obtained by measuring the intensity of the radiation to be exposed at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). 500 to 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.
The developing method may be any of a liquid piling method, a dipping method, a shower method, and the like, and the developing time is preferably 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 can be produced, for example with the following method (a) or (b).

  (A) First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates. A spacer is formed according to the method described above. Subsequently, an alignment film having a liquid crystal alignment brain is formed on the transparent conductive film and spacers of these substrates. These substrates are arranged to face each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to constitute a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Can be obtained.

  (B) First, a pair of transparent substrates on which a transparent conductive film, a spacer and an alignment film are formed are prepared in the same manner as in the first method. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both substrates are sealed by irradiating the above-mentioned sealant part with ultraviolet rays using a high-pressure mercury lamp. Finally, the liquid crystal display element of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

  Examples of the liquid crystal 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. Further, 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 (manufactured by Showa Denko KK),
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are bound,
Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.
The following synthesis examples 1 to 10 are synthesis examples of the block copolymer (A), and synthesis examples 11 and 12 are synthesis examples of the epoxy group-containing compound (D).

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid and 10 parts by weight of styrene. Parts, 40 parts by weight of n-butyl methacrylate, and 30 parts by weight of benzyl methacrylate were substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and polymerization was carried out while maintaining this temperature for 5 hours, whereby a solid content concentration of 32.5% [S] A living copolymer solution was obtained. This is designated as [S-1] polymer. For the obtained [S-1] polymer, Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (manufactured by Showa Denko KK) and found to be 6,290, and Mw / Mn = 1.5.

  100 parts by weight of this [S-1] polymer, 40 parts by weight of benzyl methacrylate, and 40 parts by weight of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer as described above, purged with nitrogen, and then gently stirred. However, after raising the temperature of the solution to 80 ° C., 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and this temperature was maintained for 4 hours for polymerization. A (A) block copolymer solution having a solid content concentration of 36.8% was obtained. This is referred to as [A-1] polymer. For the obtained [A-1] polymer, Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (manufactured by Showa Denko KK) and found to be 7,290, and Mw / Mn = 1.6.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of n-butyl and 30 parts by weight of benzyl methacrylate and purging with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and polymerization was carried out while maintaining this temperature for 5 hours, whereby a solid content concentration of 32.5% [S] A living copolymer solution was obtained. This is designated as [S-2] polymer.

  100 parts by weight of this [S-2] polymer, 40 parts by weight of benzyl methacrylate, and 40 parts by weight of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer in the same manner as described above, after substituting with nitrogen, and then gently stirred. However, after raising the temperature of the solution to 80 ° C., 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and this temperature was maintained for 4 hours for polymerization. A (A) block copolymer solution having a solid content concentration of 36.8% was obtained. This is referred to as [A-2] polymer. For the obtained [A-2] polymer, Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (manufactured by Showa Denko KK). = 1.6.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of acrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of methyl and 30 parts by weight of tetrahydrofurfuryl methacrylate and replacing with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 30 parts by weight of n-butyl methacrylate was added. By holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 35.5% was obtained. This is referred to as [A-3] polymer. For the obtained [A-3] polymer, Mw was measured using GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko KK). = 1.7.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl and 30 parts by weight of benzyl acrylate and purging with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. Raise. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 20 parts by weight of n-butyl methacrylate was added. After holding for 20 hours, 20 parts by weight of benzyl methacrylate was further added and held for 2 hours to obtain a (A) block copolymer solution having a solid content concentration of 35.1%. This is designated as [A-4] polymer. About the obtained [A-4] polymer, when Mw was measured using GPC (gel permeation chromatography) GPC-101 (made by Showa Denko KK), it was 5,500 and Mw / Mn = 1.6.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of methacrylic acid, 18 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of cyclohexyl and 22 parts by weight of cyclohexylmaleimide and replacing with nitrogen, 5 parts by weight of 1,3-butadiene is further charged, and the temperature of the solution is raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, tricyclomethacrylate [5.2.1.0 ^{2, 6} ] 30 parts by weight of decan-8-yl was added, and the mixture was further held for 3 hours to obtain a block copolymer solution (A) having a solid content concentration of 35.7%. This is referred to as [A-5] polymer. With respect to the obtained [A-5] polymer, Mw was measured using GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko KK), and was 6,300, and Mw / Mn = 2.3.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol dimethyl ether, followed by 25 parts by weight of 2-methacryloyloxyethyl hexahydrophthalic acid and 5 parts of styrene. Part by weight, 30 parts by weight of 2-ethylhexyl methacrylate, and 35 parts by weight of benzyl acrylate were charged, and after nitrogen substitution, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was adjusted to 80 with gentle stirring. Raise to ℃. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 20 parts by weight of n-lauryl methacrylate was added. By holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 35.0% was obtained. This is designated as [A-6] polymer. About the obtained [A-6] polymer, when Mw was measured using GPC (gel permeation chromatography) GPC-101 (made by Showa Denko KK), it was 5,820 and Mw / Mn = 2.1.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of bis-3,5-dimethylpyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 10 parts by weight of methacrylic acid and styrene. 5 parts by weight, 30 parts by weight of 2-ethylhexyl methacrylate and 35 parts by weight of benzyl acrylate were substituted with nitrogen, and then the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 10 parts by weight of 2-methacryloyloxyethyl hexahydrophthalic acid was added. By adding and maintaining for 3 hours, a (A) block copolymer solution having a solid content concentration of 34.1% was obtained. This is designated as [A-7] polymer. For the obtained [A-7] polymer, Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (manufactured by Showa Denko KK), and was 8,100, and Mw / Mn = 1.9.

Synthesis example 8
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 10 parts by weight of methacrylic acid, 4 parts by weight of acrylic acid and styrene. After 5 parts by weight, 40 parts by weight of n-ethyl methacrylate and 41 parts by weight of benzyl methacrylate were charged and purged with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 18 parts by weight of styrene and 22 parts by weight of cyclohexylmaleimide were added. Further, by holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 36.7% was obtained. This is designated as [A-8] polymer. With respect to the obtained [A-8] polymer, Mw was measured using GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko KK), and was 7,400, and Mw / Mn = 1.7.

Synthesis Example 9
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bismorpholinothiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 18 parts by weight of methacrylic acid, 5 parts by weight of styrene, and isobornyl acrylate 20 After adding parts by weight, 27 parts by weight of butyl acrylate, and 30 parts by weight of benzyl acrylate and replacing with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 15 parts by weight of butyl methacrylate and 15 parts by weight of benzyl methacrylate Was added and held for 3 hours to obtain a block copolymer solution (A) having a solid content concentration of 35.2%. This is designated as [A-9] polymer. For the obtained [A-9] polymer, Mw was measured using GPC (Gel Permeation Chromatography) GPC-101 (manufactured by Showa Denko KK), and was 9,100, and Mw / Mn = 2.2.

Synthesis Example 10
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of 2-cyanoprop-2-yl-1-pyrrolecarbodithioate and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 25-acryloyloxyethylphthalic acid 25 After 5 parts by weight, 5 parts by weight of styrene, 20 parts by weight of n-stearyl acrylate, 20 parts by weight of butyl acrylate, and 30 parts by weight of benzyl acrylate were purged with nitrogen, the temperature of the solution was adjusted while gently stirring. Raise to 80 ° C. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 20 parts by weight of tetrahydrofurfuryl acrylate was added. By holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 34.5% was obtained. This is designated as [A-10] polymer. With respect to the obtained [A-10] polymer, Mw was measured using GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko KK). = 2.3.

Synthesis Example 11
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid and 5 parts by weight of styrene. , Tricyclomethacrylate [5.2.1.0 ^2,6 ] decan-8-yl 25 parts, glycidyl methacrylate 25 parts, tetrahydrofurfuryl methacrylate 20 parts, and after nitrogen substitution, 1,3- [D] copolymer having a solid content concentration of 28.2 wt% is prepared by charging 5 parts of butadiene and raising the temperature of the solution to 70 ° C. while gently stirring and polymerizing while maintaining this temperature for 5 hours. A solution was obtained. This is designated as [D-1] polymer.
With respect to the obtained [D-1] polymer, Mw was measured by GPC to be 8,900.

Synthesis Example 12
A flask equipped with a condenser and a stirrer is charged with 4 parts of 2,2′-azobis (isobutyronitrile) and 220 parts of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of styrene and 80 parts of glycidyl methacrylate. After replacing with nitrogen, the temperature of the solution was raised to 95 ° C. while gently stirring, and polymerization was carried out while maintaining this temperature for 4 hours. A coalesced solution was obtained. This is designated as [D-2] polymer.
With respect to the obtained [D-2] polymer, Mw was measured by GPC to be 9,200.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (isobutyronitrile) and 220 parts of propylene glycol monomethyl ether acetate, followed by 5 parts of styrene, 10 parts of methacrylic acid and 5 parts of acrylic acid. Parts, benzyl methacrylate 40 parts, butyl methacrylate 40 parts, and after nitrogen substitution, the temperature of the solution was raised to 80 ° C. while gently stirring, and this temperature was maintained for 4 hours to polymerize, A (a) copolymer solution having a solid concentration of 30.2% was obtained. This is referred to as [a-1] polymer.
About the obtained [a-1] polymer, it was 15,000 and Mw / Mn = 2.3 when it measured using Mw by GPC.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 4 parts of 2,2′-azobis (isobutyronitrile) and 220 parts of diethylene glycol methyl ethyl ether, followed by 5 parts of styrene, 10 parts of methacrylic acid, and 5 parts of acrylic acid. Then, after adding 40 parts of benzyl methacrylate and 35 parts of butyl methacrylate and replacing with nitrogen, 5 parts by weight of 1,3-butadiene was further added and the temperature of the solution was raised to 80 ° C. while gently stirring. By polymerizing while maintaining the temperature for 4 hours, a copolymer solution (a) having a solid content concentration of 30.1% was obtained. This is referred to as [a-2] polymer.
About the obtained [a-2] polymer, it was 9,500 and Mw / Mn = 2.1 when Mw was measured using GPC.

Example 1-20 and Comparative Example 1-6
(I) Preparation of radiation-sensitive resin composition Example 1-10 and Comparative Example 1-3
The block copolymer (A) component and (B), (C), (D) components obtained in the above synthesis examples were used in the proportions shown in Table 1, and γ-glycidoxypropyl was used as an adhesion assistant. 5 parts by weight of trimethoxysilane, 0.5 part by weight of FTX-218 (trade name, manufactured by Neos Co., Ltd.) as a surfactant, 0.5 part by weight of 4-methoxyphenol as a storage stabilizer are mixed, and the solid content concentration Was dissolved in propylene glycol monomethyl ether acetate so as to be 30% by weight, and then 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 1.

Examples 11-20 and Comparative Example 4-6
The block copolymer (A) component obtained in the above synthesis example and the components (B), (C) and (D) and the surfactant (E) component were used in the proportions shown in Table 2, and further adhesion aids were used. 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as an agent and 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer were mixed and dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 23% by weight. Then, it filtered with the Millipore filter with the hole diameter of 0.2 micrometer, and prepared the composition solution. The amount of each component is shown in Table 2.

The components (B), (C), (D) and (E) in Table 1 and Table 2 are as follows.

(B) component B-1: dipentaerythritol hexaacrylate,
B-2: 1,9-nonanediol diacrylate,
B-3: ω-carboxypolycaprolactone monoacrylate (trade name Aronix M-5300 (manufactured by Toa Gosei Co., Ltd.),

(C) Component C-1: 1- [9-Ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name Irgacure OXE02, manufactured by Ciba Specialty Chemicals),
C-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals) ,
C-3: 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
C-4: Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) (NADE19 manufactured by ADEKA),

(D) Component D-1: Epoxy-containing resin composition shown in Synthesis Example 11 D-2: Epoxy-containing resin composition shown in Synthesis Example 12 D-3: Novolac-type epoxy resin (trade name: Epicoat 152 Japan Epoxy Resin Co., Ltd. Made)

(E) Component E-1: MegaFuck F178 (Dainippon Ink Chemical Co., Ltd.),
E-2: Torre Silicone SH28PA (manufactured by Toray Dow Corning Silicone Co., Ltd.),
E-3: TSF-4460 (manufactured by GE Toshiba Silicone),
E-4: Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

Evaluation The composition prepared as described above was evaluated as follows. The evaluation results are shown in Tables 3 and 4.

(II) Formation of Spacer After applying the composition solution on an alkali-free glass substrate, it was pre-baked on a hot plate at 80 ° C. for 3 minutes to form a film having a thickness of 4.0 μm.
Next, the obtained 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 15 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 20 minutes at 230 degreeC in oven.

(III) Evaluation of developability When the development time is shortened to 40 seconds during development in (II), the pattern is formed as good (◯) and the residue is evaluated as bad (Δ). did. The evaluation results are shown in Table 3.

(IV) Evaluation of resolution When the pattern was formed in (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 (x). The evaluation results are shown in Table 3.

(V) Evaluation of spacer shape The cross-sectional shape of the pattern obtained in (II) above was observed with a scanning electron microscope, and was evaluated according to which of A and B shown in FIG. At this time, if the spacer shape is round type as in A, the upper part of the spacer is easily deformed, and it has a sufficient amount of deformation when the TFT plate and the CF plate are bonded together, and the margin for the liquid crystal dropping process is improved. To do. On the other hand, if the pattern shape is close to a trapezoidal shape as shown in B, the spacer is hardly deformed and the margin of the liquid crystal dropping process is insufficient. The evaluation results are shown in Table 3.

(VI) Observation of spacer surface condition The cross-sectional shape of the pattern obtained in (II) above is observed with a scanning electron microscope. If the spacer surface is uniform, it is good (○), and phase separation and aggregates are observed. The case was evaluated as defective (Δ). The evaluation results are shown in Table 2.

(VII) Evaluation of Compression Displacement A load of 50 mN was applied to the pattern obtained in (II) above using a micro compression tester (DUH-201, manufactured by Shimadzu Corporation) with a flat indenter having a diameter of 50 μm. The amount of deformation was measured at a measurement temperature of 23 ° C. When this value is 0.5 or more, it can be said that the amount of compressive displacement is good. The evaluation results are shown in Table 3.

(VIII) Evaluation of heat resistance About the pattern obtained in (II) above, after leaving for 20 minutes at 230 ° C. in an oven, if the change in the height of the spacer is less than 4%, it is good (◯), 4% or more Then, it evaluated as a defect (x). The evaluation results are shown in Table 3.

(IX) Evaluation of rubbing resistance After applying AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent to a substrate on which the pattern obtained in (II) is formed, using a printing machine for applying a liquid crystal alignment 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 scraping or peeling was evaluated. The evaluation results are shown in Table 3.

(X) Evaluation of Adhesiveness A cured film was formed in the same manner as in (II) 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.

(XI) Evaluation of voltage holding ratio A prepared soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on a liquid composition, and an ITO (indium-tin oxide alloy) electrode is deposited in a predetermined shape. After spin coating, pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 200 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. And the coating film was cured to form a permanent cured film.

Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 (trade name) is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured with a liquid crystal voltage holding ratio measuring system VHR-1A (trade name) manufactured by Toyo Technica. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 60 Hz. Here, the voltage holding ratio is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds). The results are shown in Table 3. When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of burning.

(XII) Evaluation of applicability (muscle unevenness, haze unevenness, pin mark) The prepared composition solution was applied on a 550 × 650 mm chromium-deposited glass using a slit die coater. After drying under reduced pressure to 0.5 Torr, pre-baking on a hot plate at 100 ° C. for 2 minutes to form a coating film, and further exposing at an exposure amount of 2000 J / m ² , A film having a thickness of 4 μm was formed.
The surface of the film was illuminated with a sodium lamp, and the coated film surface was visually confirmed. Straight lines (single or multiple straight lines that can be applied in the direction of application or crossing it), haze (cloud-like unevenness), pin marks (dots on the substrate support pins) are clearly confirmed When it was possible, it was evaluated as “X”, when it was slightly confirmed, “△”, when it could hardly be confirmed, “◯”, when it was not able to confirm any streaks, haze, and pin marks, “◎”. The results are shown in Table 4.

(XIII) Evaluation of applicability (uniformity) The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact type measuring device (AS200 manufactured by KLA Tencor).
The uniformity was calculated from the film thickness at nine measurement points. The nine measurement points are X (mm) and Y (mm) when the short axis direction of the substrate is X and the long axis direction is Y (275, 20), (275, 30), (275, 60), (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).
The uniformity calculation formula is expressed by the following formula (3). In the following formula (3), FT (X, Y) max is the maximum value in the film thickness at nine measurement points, FT (X, Y) min is the minimum value in the film thickness at nine measurement points, and FT (X, Y Y) avg is an average value in the film thickness at nine measurement points. When the uniformity is less than 2%, ◎, when 2-3%, ◯, when 3-5%, △, when 5% or more, ×.
Uniformity (%) = {FT (X, Y) max−FT (X, Y) min} × 100 / {2 × FT (X, Y) avg} (3)
The results are shown in Table 4.

(XIV) Measurement of viscosity It measured at 25 degreeC using the E-type viscosity meter (The Toki Sangyo Co., Ltd. product VISCONIC ELD.R). The results are shown in Table 4.

The schematic diagram of the cross-sectional shape of a spacer.

Claims (11)

A radiation-sensitive resin composition for forming a spacer, comprising (A) a block copolymer (B) a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator. Furthermore, the radiation sensitive resin composition of Claim 1 containing the epoxy group containing compound (D). The radiation sensitive resin composition according to claim 1 or 2, wherein the block copolymer (A) has two or more block segments, and an alkali-soluble site is contained in at least one block segment. The radiation sensitive resin composition of Claim 3 which contains the carboxyl group as an alkali-soluble site | part. (A) The block copolymer is at least one selected from the group consisting of (a1) an unsaturated carboxylic acid having radical polymerizability, an unsaturated carboxylic acid anhydride, and a protected product of these carboxylic acids, and (a2) (a1 The radiation sensitive resin composition according to any one of claims 1 to 4, comprising at least a first block segment comprising a radically polymerizable compound other than (a) and a second block segment comprising only (a1) or (a2). . (A) The radiation sensitive resin composition according to any one of claims 1 to 5, wherein the block copolymer is obtained by living radical polymerization. The block copolymer (A) is produced by polymerizing a polymerizable unsaturated compound using a thiocarbonylthio compound represented by the following formula (1), (2) or (3) as a molecular weight control agent. A radiation-sensitive resin composition according to any one of claims 1 to 6.

[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, the monovalent heterocyclic group having 3 to 20 atoms in total, and R may each be substituted. ]

[In Formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic carbon atom having 6 to 20 carbon atoms. A hydrogen group, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms,
^{-OR 1, -SR 1, -OC (} = O) R 1, -N (R 1) (R 2), - C (= O) OR 1,
—C (═O) N (R ¹ ) (R ² ), —P (═O) (OR ¹ ) ₂ , —P (═O) (R ¹ ) ₂ or a monovalent group having a polymer chain. R ¹ and R ² are 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 carbon atom. A monovalent heterocyclic group having 3 to 18 atoms in total with the atom, the alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a carbon atom and a different group The monovalent heterocyclic group having 3 to 20 atoms in total, R ¹ and R ² may be substituted. ] The ratio (Mw / Mn) of polystyrene-converted weight average molecular weight (Mw) and polystyrene-converted number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer (A) is 2.5 or less. The radiation sensitive resin composition in any one of -7. The spacer formed from the radiation sensitive resin composition in any one of Claims 1-8. A method for forming a spacer, comprising the following steps (a) to (d):
(A) forming a film of the radiation sensitive resin composition according to any one of claims 1 to 8 on a substrate;
(B) a step of exposing radiation to at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development. A liquid crystal display device comprising the spacer according to claim 9.

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