KR20080034792A - Radiation sensitive resin composition for forming spacer, spacer and its forming method - Google Patents

Abstract

A radiation-sensitive resin composition for forming a spacer is provided to easily form a pattern type thin film having high sensitivity, high resolution, and excellent performances such as pattern profile, compressive characteristics, rubbing resistance, and heat resistance. A radiation-sensitive resin composition for forming a spacer includes (A) a copolymer comprising at least one polymerization unit derived from a compound having at least two polymerizable unsaturated groups in the molecule, (B) a polymerizable unsaturated compound, and (C) a radiation-sensitive polymerization initiator. A patterning method of a spacer includes the steps of: forming a coating layer of the radiation-sensitive resin composition on a substrate; exposing at least a part of the coating layer to a light; developing the coating layer after the exposure; and heating the coating layer after the development.

Description

Radiation-sensitive resin composition for spacer formation, spacer and formation method thereof {RADIATION SENSITIVE RESIN COMPOSITION FOR FORMING SPACER, SPACER AND ITS FORMING METHOD}

This invention relates to the radiation sensitive resin composition for spacer formation, a spacer, and its formation method.

In the liquid crystal display device, spacer particles such as glass beads and plastic beads having a predetermined particle diameter are conventionally used to maintain a constant gap between two transparent substrates. These spacer particles are randomly formed on a transparent substrate such as a glass substrate. Since the particles are dispersed in the pixel forming region, the phenomenon of projection of the spacer particles occurs, or incident light is scattered and the contrast of the liquid crystal display element is lowered.

In order to solve these problems, the method of forming a spacer by photolithography is mainstream at present. In this method, the radiation-sensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form a dot- or stripe-shaped spacer. The spacer is formed only at a predetermined place other than the pixel formation region. Since the problem can be formed, the problem as described above 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), near 404 nm (h line), around 365 nm (i line), around 335 nm, and around 315 nm. Since the intensity | strength strong spectrum (j-ray), 303 nm vicinity, etc. are shown, as a radiation sensitive polymerization initiator which is a structural component of a radiation sensitive resin composition, what has the largest absorption wavelength in the wavelength range of these strong intensity spectrum is selected. It is common to use it, and in most cases, the radiation sensitive polymerization initiator which has a maximum absorption wavelength in the area | region whose wavelength is i line or less from a transparency point is used (refer Unexamined-Japanese-Patent No. 2001-261761). However, in the conventionally known radiation-sensitive resin composition for forming a spacer, the cross-sectional shape of the spacer to be formed is inverse tapered depending on the selection of the radiation-sensitive polymerization initiator (the inverse trapezoid has a length longer than the length of the substrate side). Shape), which causes the spacer to peel off during the subsequent rubbing treatment of the alignment film.

In addition, "baking" such as an afterimage in an LCD display, which is presumed to be caused by impurities eluted from an intracellular permanent film formed from a radiation-sensitive resin composition, becomes a problem, thereby forming an intracellular permanent film in which "baking" does not occur. There has been a desire for a radiation sensitive resin composition which enables production of LCD panels with high product yields.

Moreover, in the conventional radiation sensitive resin composition including the radiation sensitive resin composition of Unexamined-Japanese-Patent No. 2001-261761, the sublimation which arises at the time of baking for forming a spacer contaminates a process line or a device. There has been a concern, and there has been a demand for a radiation sensitive resin composition having reduced sublimation generated.

On the other hand, if the high resilience to be restored to the original cell interval after deformation due to compressive strength and external force is too important, the external force cannot be absorbed and the thin film transistor TFT and the color filter CF may be damaged or destroyed. There was.

In addition, conventionally, in order to shorten the charging process time for injecting the liquid crystal by vacuum after bonding the TFT plate and the CF plate, a new process of dropping the liquid crystal at once and bonding the TFT plate and the CF plate has been developed. However, the conventional spacers are not sufficiently deformed and have insufficient margin for the liquid crystal dropping process, and thus problems such as foaming problems due to shrinkage of the liquid crystal under low temperature and so-called "gravity nonuniformity" due to liquid crystal expansion at high temperature occur. There was a problem. In recent years, in view of these phenomena, spacer materials that are easily deformed with respect to loads have been developed, but these have problems such as plastic deformation and inferior heat resistance compared to conventional spacers.

In addition, with the recent increase in the size of LCD mother glass, the tendency of reusing and reusing defective substrates generated in each step is increasing. In particular, when defects occur in the alignment film forming step, the alignment film is peeled off with a chemical solution, and again. The case where the alignment film process is performed is common. Therefore, sufficient resistance to the alignment film release liquid is also required for the spacer.

The present invention has been made in view of the above circumstances. Therefore, it is an object of the present invention to easily form a patterned thin film having high sensitivity and high resolution, and excellent in various performances such as pattern shape, compression characteristics, rubbing resistance, heat resistance, and the like. It is an object of the present invention to provide a radiation-sensitive resin composition for forming a spacer which is prevented from burning in LCD displays, hardly causes plastic deformation with respect to a load load, and has sufficient resistance to chemical liquids such as an alignment film peeling liquid.

Another object of the present invention is to reduce the foaming problem at low temperature or the gravity unevenness at high temperature due to the amount of liquid crystal dropping, and to prevent damage caused by pressure on the color filter and to overcome the thickness variation occurring in the process. It is providing the radiation sensitive resin composition for formation.

Another object of the present invention is to provide a spacer formed from the radiation-sensitive resin composition for spacer formation and a method of forming the same.

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 firstly,

(A) a copolymer comprising at least one polymerized unit derived from a compound containing two or more polymerizable unsaturated bonds in the molecule (a1),

(B) a polymerizable unsaturated compound, and

(C) radiation sensitive polymerization initiator

It is achieved by the radiation sensitive resin composition for spacer formation containing a.

The above objects and advantages of the present invention are second,

The said (A) copolymer is preferably achieved by the radiation sensitive resin composition for spacer formation containing the polymerization unit derived from (a2) alkali-soluble polymerizable unsaturated compound.

Thirdly, the object and advantages of the present invention are:

The said (A) copolymer is preferably achieved by the radiation sensitive resin composition for spacer formation containing the polymer unit derived from (a3) another polymerizable unsaturated compound different from (a1) and (a2).

Fourth, the above object and advantages of the present invention,

The (A) copolymer is preferably attained by the radiation-sensitive resin composition for forming a spacer obtained by living radical polymerization.

Fifth object and advantage of the present invention,

The (A) copolymer is preferably achieved by the radiation-sensitive resin composition for forming a spacer, wherein the copolymer is produced by polymerization using a thiocarbonylthio compound represented by the following formula (1), (2) or (3) as a molecular weight control agent.

In Chemical Formula 1, Z ¹ represents a hydrogen atom, a chlorine atom, a hydroxyl group, 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, a total atom number of carbon atoms and binary atoms 3-20 monovalent heterocyclic group, -OX, -SX, -N (X) ₂ , -OC (= 0) X, -C (= 0) OX, -C (= 0) N (X) ₂ , -P (= 0) (OX) ₂ , -P (= 0) (X) ₂ or a monovalent group having a polymer chain, each X independently of one another is an alkyl group having 1 to 18 carbon atoms, An alkenyl group, a C6-C18 monovalent aromatic hydrocarbon group, or a C3-C18 monovalent heterocyclic group of carbon atoms and a binomial atom in total is represented, The said C1-C20 alkyl group, C6-C20 1 The aromatic aromatic hydrocarbon group, the monovalent heterocyclic group having 3 to 20 atoms in total, and X may each be substituted, p is an integer of 1 or more, and when X ¹ is p = 1, a hydrogen atom, Anano group, an alkyl group of 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a monovalent compound having 3 to 20 monovalent atoms in total with a carbon atom and a binary atom Monocyclic groups having a monocyclic group, —OX, —SX, —N (X) ₂ or a polymer chain, the definition of each X being as defined above and derived from alkane having 1 to 20 carbon atoms when p ≧ 2; p-valent group, p-valent group derived from C6-C20 aromatic hydrocarbon, p-valent group derived from a heterocyclic compound of 3 to 20 carbon atoms in total, and a pvalent group having a polymer chain , The alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, X, and 1 to 1 carbon atoms. P derived from 20 alkanes In the group, a p-valent group derived from a heterocyclic compound of a p-valent group and a total of 3 to 20 atoms derived from an aromatic hydrocarbon having 6 to 20 carbon atoms may be each substituted;

In Formula 2, m is an integer greater than or equal to 2, Z <^2> is a m-valent group derived from C1-C20 alkanes, a m-valent group derived from C6-C20 aromatic hydrocarbons, and a carbon atom and a binary atom. Derived from m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain and derived from m-valent group derived from alkane having 1 to 20 carbon atoms and aromatic hydrocarbon having 6 to 20 carbon atoms. The m-valent group and the m-valent group derived from the heterocyclic compound having 3 to 20 carbon atoms in total may be substituted, and X ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. A monovalent aromatic hydrocarbon group having from 20 to 20, a monovalent heterocyclic group having from 3 to 20 carbon atoms, and a monovalent group having -OX, -SX, -N (X) ₂ or a polymer chain; , Each X is 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 monovalent heterocyclic ring having 3 to 18 carbon atoms in total; Representing a table, wherein the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 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, and X are Each may be substituted]

In Formula 3, Z ³ and Z ⁴ are independently of each other 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, a carbon atom and a binary atom, Monovalent heterocyclic group having 3 to 20 atoms in total, -OR ¹ , -SR ¹ , -OC (= O) R ¹ , -N (R ¹ ) (R ² ), -C (= O) OR ¹ , -C (= 0) N (R ¹ ) (R ² ), -P (= 0) (OR ¹ ) ₂ , -P (= 0) (R ¹ ) ₂ or a monovalent group having a polymer chain, R ¹ and R ² are each 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 carbon atoms and a binary atom; It represents a valent heterocyclic group, the said C1-C20 alkyl group, the C6-C20 monovalent aromatic hydrocarbon group, the C1-C20 monovalent heterocyclic group with a total of 3 to 20 carbon atoms, R <^1> and R ² May each be substituted;

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

The above objects and advantages of the present invention are seventh achieved by a method of forming a spacer, which comprises at least the steps (1) to (4) below.

(1) forming a film of the radiation sensitive resin composition for spacer formation on a substrate;

(2) exposing to at least a portion of the film;

(3) developing the film after exposure, and

(4) The process of heating the film after image development.

Eighth, the above objects and advantages of the present invention are achieved by a liquid crystal display device comprising the spacer.

Spacer  Forming Radiation  Resin composition

Hereinafter, each component of the radiation sensitive resin composition for spacer formation of this invention (henceforth simply a "radiation sensitive resin composition") is explained in full detail.

(A) copolymer

The (A) copolymer in the radiation sensitive resin composition of the present invention is preferably a compound having two or more polymerizable unsaturated bonds in the molecule (a1) (hereinafter sometimes referred to as "compound (a1)"). (a2) alkali-soluble polymerizable unsaturated compounds (hereinafter sometimes referred to as "compound (a2)"), and (a3) other polymerizable unsaturated compounds different from (a1) and (a2) (hereinafter "compound ( a3) ", which may be referred to as"), is a copolymer obtained by radical polymerization. The compounds (a1), (a2) and (a3) may each be used as a single species or in plural kinds. Conventionally, when radical polymerization is carried out using a compound having two or more polymerizable unsaturated bonds in a molecule, complex three-dimensional crosslinking is formed by the formation of a bond by polymerization, and as a result, gelation by insolubilization in a polymerization solvent. It was generally believed that there occurred. However, the present inventors have succeeded in proceeding well without gelling the reaction by using a living radical polymerization method. The copolymer (A) may be formed by mixing and polymerizing the compounds (a1), (a2) and (a3) together, and further adding the compounds (a1), (a2) and (a3) in multiple stages in order. It can also form using what is called a living block polymerization superposed | polymerized. Living block polymerization preferably comprises a combination of compounds (a1) and (a2) and (a3) in the first step or a combination of compounds (a2) and (a3) in the first step, followed by compound (a1) 1 or more types of (a2) and (a3) is added, and it superpose | polymerizes. However, it is necessary to use compound (a1) in either step. Although this manufacturing order is not specifically limited, The method of obtaining a branched structure by adding the polymerizable unsaturated compound containing a compound (a1) in the last stage of living block polymerization is more preferable from the viewpoint of the compressibility and toughness of a spacer. Further, more robust resin can be obtained by using a polymerizable unsaturated compound containing an epoxy group and / or an oxetanyl group in at least a part of the compound (a3).

For example, the (A) copolymer is a compound having two or more polymerizable unsaturated bonds in the molecule (a1), (a2) an alkali soluble polymerizable unsaturated compound, and (a3) other than (a1) and (a2) Among the polymerizable unsaturated compounds, first, a polymerizable mixture containing at least compound (a2) and (a3) is subjected to living radical polymerization in the presence of a polymerization initiator in a solvent, followed by compounds (a1), (a2) and (a3). It can be manufactured by further adding a polymerizable mixture containing at least one of the polymers and continuing the polymerization. In addition, if desired, further polymerizable mixtures may be further added to add block segments. However, in order to obtain the (A) copolymer, the compound (a1) needs to be used in any one polymerization step.

Next, living radical polymerization which manufactures (A) copolymer is demonstrated.

A copolymer or (A) copolymer is synthesized by living radical polymerization of the polymerizable unsaturated compound with a copolymerizable unsaturated compound, preferably in the presence of a radical polymerization initiator that generates living radicals in a solvent, and furthermore, the polymerization. (A) copolymer can be manufactured by adding a sex unsaturated compound in multiple times as needed.

In living radical polymerization, when using the compound which has functional groups, such as a carboxyl group which may inactivate active radical as a polymerizable unsaturated compound, in order to prevent a growth terminal from deactivating, the said functional group in a polymerizable unsaturated compound is needed as needed. For example, (A) copolymer can also be obtained by protecting by esterification etc., superposing | polymerizing, and then deprotecting.

Various radical polymerization initiators for living radical polymerization of polymerizable unsaturated compounds have been proposed in various ways, for example, TEMPO system proposed by George et al. (MKGeorges, RPNVeregin, PMKazmaier, GKHamer, Macromolecules, 1993). , Vol. 26, p. 2987), a combination of copper bromide and bromine containing ester compounds proposed by Matyjaszewski et al. (Matyjaszewski, K. Coca, S. Gaynor, G.wei, M. Woodworth, BE Macromolecules, 1997, Vol. 30, p.7348), a combination of carbon tetrachloride and ruthenium (II) complexes proposed by Hamasaki et al. (Hamasaki, S.Kamigaito, M. Sawamoto, M. Macromolecules, 2002, Vol. 35, p. 2934), Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181), Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004- Having a chain transfer constant greater than 0.1, as disclosed in 518773 There may be mentioned combinations of Oka Viterbo carbonyl compound and a radical initiator.

As a preferable radical polymerization initiator used for living radical polymerization, the type | system | group in which the active radical which is a growth terminal is inactivated is selected suitably according to the kind of polymerizable unsaturated compound used, but considering the polymerization efficiency, a metal-free system, etc., it is thio which is a molecular weight control agent. Combinations of carbonylthio compounds and radical initiators are preferred.

As for the combination of the thiocarbonylthio compound and the radical initiator, Japanese Patent Publication No. 3639859 (Japanese Patent Publication No. 2000-515181), Japanese Patent Publication No. 2002-500251 and Japanese Patent Publication No. 2004-518773 In addition, Japanese Patent Publication No. 2002-508409, Japanese Patent Publication No. 2002-512653, Japanese Patent Publication No. 2003-527458, Japanese Patent No. 3634843 (Japanese Patent Publication No. 2003-536105), and It is described in detail in Unexamined-Japanese-Patent No. 2005-503452.

Thiocarbonyl, as described in Japanese Patent Publication No. 2002-500251, Japanese Patent Publication No. 2004-518773, Japanese Patent Publication No. 2002-508409 and Japanese Patent Publication No. 2002-512653. By living radical polymerization of an unsaturated compound in the presence of a thio compound and a radical initiator, a random copolymer or a block copolymer having a narrow molecular weight distribution can be obtained. In view of this feature, the present invention takes advantage of the fact that even if a compound having two or more polymerizable unsaturated bonds in the molecule (a1) is used for radical polymerization, the polymerization is completed without gelation. Moreover, since a functional group can be introduce | transduced into the random copolymer and block copolymer obtained by living radical polymerization, the said copolymer is used as an aqueous gel (refer Japanese Unexamined-Japanese-Patent No. 2003-527458), a photoresist (Japanese Patent No. 3634843). It has been found that it can also be used in applications such as Japanese Patent Application Laid-Open No. 2003-536105 and surfactant (see Japanese Patent Laid-Open No. 2005-503452).

As said preferable thiocarbonylthio compound in this invention, the compound represented by the said General formula (1), the said Formula (2), or the said Formula (3) (hereinafter, "thiocarbonyl compound (1)", "thiocarbonyl compound, respectively) (2) "or" thiocarbonyl compound (3) ") and the like.

In the above formula (1), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include, for example, 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-dimethylbutyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. are mentioned.

Further, as the first phase-valent aromatic hydrocarbon group having 6 to 20 Z ^1, for example, phenyl, 1-naphthyl, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, benzyl group, methyl α- A benzyl group, the (alpha), (alpha)-dimethyl benzyl group, a phenethyl group etc. are mentioned.

As the monovalent heterocyclic group having 3 to 20 carbon atoms in total between Z ¹ carbon atoms and binomial atoms, for example, an oxiranyl group, an aziridinyl group, 2-furanyl group, 3-furanyl group, and 2-tetra Hydrofuranyl group, 3-tetrahydrofuranyl group, pyrrole-1-yl group, pyrrole-2-yl group, pyrrole-3-yl group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, Pyrazol-1-yl group, pyrazol-2-yl group, pyrazol-3-yl group, imidazol-2-yl group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2 -Thianyl group, 3-tianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-pipe A lidinyl group, a 2-morpholinyl group, a 3-morpholinyl group, etc. are mentioned.

Further, Z ¹ -OX, -SX, -N (X) ₂ , -OC (= 0) X, -C (= 0) OX, -C (= 0) N (X) ₂ , -P (= O) (OX) ₂ and -P (= O) (X) ₂ The alkyl group of 1 to 18 carbon atoms of X, the monovalent aromatic hydrocarbon group of 6 to 18 carbon atoms, or the total number of atoms of carbon atoms and binary atoms 3 As a monovalent heterocyclic group of 18 to 18, for example, an alkyl group having 1 to 20 carbon atoms as illustrated for Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a total of 3 to 20 atoms of a carbon atom and a binomial atom Examples of monovalent heterocyclic groups include groups having 18 or less carbon atoms or total atoms.

Moreover, as a C2-C18 alkenyl group of the said X, For example, a vinyl group, a 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 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, etc. are mentioned.

Examples of the alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, and a substituent to X include a hydroxyl group, -OX, -SX, -N (X) ₂ exemplified for Z ¹ in addition to a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group, an isocyanate group, a cyano group, a vinyl group, an epoxy group, a silyl group, and a halogen atom -OC (= 0) X, -C (= 0) OX, -C (= 0) N (X) ₂ , -P (= 0) (OX) ₂ or -P (= 0) (X) 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, or a monovalent heterocyclic group having 3 to 18 atoms in total between carbon atoms and binary atoms It can select suitably from the same group as. One or more of these substituents may be present in the molecule. However, it is preferable that the sum total carbon number or sum total atom number of a substituent in a molecule | numerator does not exceed 20.

Moreover, as monovalent group which has a polymer chain of Z <^1> , For example, alpha-olefins, such as ethylene and propylene; Aromatic vinyl compounds such as styrene and α-methylstyrene; Vinyl halides such as 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 (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n- (meth) acrylate (Meth) acrylic acid esters, such as hexyl and cyclohexyl (meth) acrylate; (Meth) acrylamide; (Meth) acrylamides such as N, N-dimethyl (meth) acrylamide; Unsaturated nitriles such as (meth) acrylonitrile and vinylidene cyanide; In addition to monovalent groups having an addition polymerized polymer chain formed from one or more of unsaturated compounds such as conjugated dienes such as butadiene and isoprene, polyoxyethylene which can be etherified at the terminal, polyoxy which can be etherified at the terminal Monovalent groups which have polyethers, such as propylene, and polyaddition polymer chains, such as polyester, polyamide, and polyimide, a polycondensation system chain, etc. are mentioned. In monovalent groups having these polymer chains, the polymer chains may be directly bonded to the carbon atom of the thiocarbonyl group of the formula (1), for example, -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ CH It may be bonded to the carbon atom of the thiocarbonyl group represented by the general formula (1) via a linking water such as ₂ -COO-.

로 표시되는 기 등을 들 수 있다. Specific examples of Z ¹ in formula (I), for example, a hydrogen atom, a chlorine atom, a cyano group, a hydroxyl group, a carboxyl group, an octadecyl group, a phenyl group, a butoxy group, a dodecyloxy group, a phenoxy group, butoxycarbonyl group, dimethylamino group, A group or formula represented by a diethylamino group, an imidazol-2-yl group, a pyrazol-1-yl group, and the formula -P (= 0) R ₂ (wherein R is a methyl group, a phenyl group, an ethoxy group or a phenoxy group)

The group etc. which are represented by are mentioned.

In Formula 1, a plurality of Z ¹ present may be the same or different from each other.

In the formula 1, X ¹ is p = 1, the C 1 -C 20 alkyl group, a C3 to a monovalent alicyclic hydrocarbon group of 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms group, carbon atoms and the binary atoms and Monovalent heterocyclic group having 3 to 20 atoms in total, -OX, -SX, -N (X) ₂ or a monovalent group having a polymer chain.

The alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, -OX, -SX, -N (X) ₂ or 1 having a polymer chain Examples of the valent group and substituted derivatives thereof include the same groups as those exemplified for the corresponding groups of Z ¹ . In a monovalent group having a polymer chain of X ¹ (p = 1), the polymer chain may be directly bonded to a sulfur atom in the formula (1), for example -CH ₂ -COO-, -C (CH ₃ ) It may be bonded to the sulfur atom in the formula (1) through a linking water such as (CN) CH ₂ CH ₂ -COO-.

As said C3-C20 monovalent alicyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, a cyclohexenyl group etc. are mentioned, for example.

Examples of substituents for groups monovalent alicyclic of the C 3 -C 20 hydrocarbons, e.g., total atoms with the Z ¹ groups of the monovalent aromatic hydrocarbon group having 1 to 20 carbon atoms, having a carbon number of 6 to 20 carbon atoms and the binary atoms It can select suitably from the same thing as the group illustrated about the monovalent heterocyclic group of the number 3-20, and the substituent with respect to X. One or more of these substituents may be present in the molecule. However, it is preferable that total carbon number or total atom number in the substituent in a molecule | numerator does not exceed 20.

In addition, X ¹ is p≥2 one time, the total number of atoms of a carbon number of 1 p valent group, with the carbon atom and the binary atoms derived from aromatic hydrocarbons, p valent group, having 6 to 20 carbon atoms derived from an alkane of 3 to 20 to Pvalent group which has pvalent group or polymer chain | strand derived from the heterocyclic compound of 20 is shown.

Examples of the alkanes 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, n -Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eichoic acid, etc. are mentioned.

Moreover, as said C6-C20 aromatic hydrocarbon, For example, benzene, 1, 4- dimethyl benzene (For example, the carbon atom of each methyl group of a 1, 4-position is couple | bonded with the sulfur atom in Formula 1), 1 , 2,4,5-tetramethylbenzene (eg, carbon atoms of two methyl groups in 1,2,4,5-position are bonded to sulfur atoms in formula 1), 1,2,3,4,5 , 6-hexamethylbenzene (eg, carbon atoms of two methyl groups in 1,2,3,4,5,6-position are bonded to sulfur atoms in formula 1), 1,4-di-i-propyl Benzene (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.

Examples of the heterocyclic compound having 3 to 20 total atoms include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, imidazole, tetrahydropyran, thian, pyridine, Piperidine, morpholine, and the like.

As a substituent for the p-valent group derived from the said C1-C20 alkane, the p-valent group derived from a C6-C20 aromatic hydrocarbon, and the p-valent group derived from the heterocyclic compound of 3 to 20 atoms in total, Examples thereof include an alkyl group having 1 to 20 carbon atoms of Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms, and a substituent for X. It can select suitably from the same thing as one group. One or more of these substituents may be present in the substituted derivatives. However, it is preferable that the sum total carbon number or sum total atom number of a substituent in a molecule | numerator does not exceed 20.

Moreover, as a polymer chain which provides the p-valent group of X <^1> , the same thing as the addition polymerization type polymer chain, polyaddition type polymer chain, and polycondensation type polymer chain which were illustrated about the monovalent group which has the said polymer chain of Z <^1> is mentioned. In a pvalent group having a polymer chain of X ¹ , the polymer chain may be directly bonded to the sulfur atom in formula (I), for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ CH ₂ It may be bonded to the sulfur atom of the formula (1) via a linking water such as -COO-.

As p in General formula (1), it is preferable that it is an integer of 1-6, and it is more preferable that it is 2.

로 표시되는 기 등을 각각 들 수 있다. Specific examples of X ¹ in the formula (1), when p = 1 day, for example, a hydrogen atom, a cyano group, a benzyl group, a 2-hydroxyethyl group, a silanol group-octanoic, 2-cyano ethyl group, 2- (2-hydroxy Oxy) propyl group, 2- (2-cyano) propyl group, 2- (2-carboxy) propyl group or 2- (2-ethoxycarbonyl) propyl group; When p = 2, for example, a chemical formula

The group etc. which are represented by these are mentioned, respectively.

Next, in the formula (2), examples of the alkanes having 1 to 20 carbon atoms that provide the m-valent group of Z ² are the same as those of the compounds exemplified for the alkenes having 1 to 20 carbon atoms that provide the p-valent group of X ¹ . Can be mentioned.

Further, as the aromatic hydrocarbon having 6 to 20 carbon atoms to provide an m-valent of Z ^2, such may be mentioned example is the same as illustrated with respect to the aromatic hydrocarbon group having 6 to 20 carbon atoms compound to provide an p-valent of the X ^1.

Also, as the total of the heterocyclic compounds of the atom number of 3 to 20 of the carbon atom and the binary atoms to provide an m-valent of Z ^2, for example, the total atoms of the carbon atom and the binary atoms to provide an p-valent of the X ¹ The same thing as the compound illustrated about the heterocyclic compound of the number 3-20 is mentioned.

Examples of substituents for groups m monovalent derived from the heterocyclic compounds of the m-valent group, and a total atom number of from 3 to 20 that is derived from an aromatic hydrocarbon of the m-valent group, having 6 to 20 carbon atoms is derived from alkanes having a carbon number of 1 to 20, Z ^2, For example, the alkyl group of 1 to 20 carbon atoms of Z ¹ , a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms and a hetero atom, and a substituent to X It can select suitably from the same thing as the group illustrated about, and these substituents may exist in 1 or more types or 1 or more types in a molecule | numerator. However, it is preferable that the sum total carbon number or sum total atom number of a substituent in a molecule | numerator does not exceed 20.

Further, as the polymer chain to provide an m-valent of Z ^2, for example, the Z include ¹ to the same as the addition polymerization-based polymer chain, heavy household polymer swaena polycondensation polymer chain illustrated for groups monovalent having a polymer chain have. In m-valent groups having a polymer chain of Z ² , the polymer chain may be directly bonded to a carbon atom of a thiocarbonyl group of the formula (2), for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH It may be bonded to the carbon atom of the thiocarbonyl group in the formula (2) via a linking water such as ₂ CH ₂ -COO-.

In the formula (2), an alkyl group having 1 to 20 carbon atoms of X ² , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 carbon atoms and a total atom of a carbon atom and a binary atom, -OX,- As a monovalent group which has SX, -N (X) _2, and a polymer chain, and these substituted derivatives, the same thing as the group illustrated about the corresponding group of said Z <^1> is mentioned, for example. In monovalent groups with a polymer chain of X ² the polymer chain may be directly bonded to the sulfur atom in formula (2), for example -CH ₂ -COO-, -C (CH ₃ ) (CN) CH ₂ CH ₂ It may be bonded to the sulfur atom of the formula (2) through a linking water such as -COO-.

In addition, as a C3-C20 monovalent alicyclic hydrocarbon group of X <^2> and its substituted derivatives, it is mentioned to the C1-C20 monovalent alicyclic hydrocarbon group of X <^1> (p = 1), and its substituted derivatives, for example. The same thing as the group illustrated about is mentioned.

As a specific example of X <^2> in General formula (2), a 2- (2-cyano) propyl group etc. are mentioned, for example.

In Formula 2, a plurality of X ² present may be the same or different from each other.

In the formula 2, and Z ^2, and -C (= S) -SX ² is combined with the case that is connected to an aliphatic carbon atom of Z ^2, Z ² aliphatic carbon atoms are -C (= S) -SX ² in, When connected with an aromatic carbon atom, the aromatic carbon atom in Z ^{2 is} bonded with -C (= S) -SX ^2, and when connected with a sulfur atom, the sulfur atom in -SX representing Z ² is -C (= S) -SX ² is combined.

M in the formula (2) is preferably an integer of 2 to 6, more preferably 2.

Specific examples of Z ² in Formula (2), and the like, for example, 1,4-phenylene group when m = 2.

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, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom and a binary atom Monovalent heterocyclic group having 3 to 20 atoms in total, -OR ¹ , -SR ¹ , -OC (= 0) R ¹ , -N (R ¹ ) (R ² ), -C (= 0) OR ¹ , -C (= O) N (R ¹ ) (R ² ), -P (= 0) (OR ¹ ) ₂ , -P (= 0) (R ¹ ) ₂ or a monovalent group having a polymer chain, R ¹ and R ² are each 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 monovalent having 3 to 18 monovalent atoms in total between a carbon atom and a binary atom. It denotes a heterocyclic group, the C 1 -C 20 alkyl group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms group, a monovalent heterocyclic ring of 3 total circle of the carbon atoms and the binary atoms atoms to 20 dishes, R ¹ and R ² Each may be substituted.

As Z ³ and Z ⁴ it can be similarly exemplified above as Z ¹ in the formula (1).

Z ³ and Z ⁴ are each a carbon atom of a thiocarbonyl group (C = S) and Z ³ and Z ^{4 in} terms of reactivity with a polymerizable unsaturated compound, in addition to an alkyl group having 1 to 20 carbon atoms, respectively. Groups in which a binary atom such as a nitrogen atom or an oxygen atom in the group is covalently bonded, more specifically, a monovalent heterocyclic group having 3 to 20 carbon atoms in total with a carbon atom and a binary atom, -OR ¹ , -N (R ¹ (R ² ) and the like are preferable, and in particular, methyl group, ethyl group, pyrrole-1-yl group, pyrazol-1-yl group, 3,5-dimethylpyrazol-1-yl group, morpholino group, methoxy group, ethoxy group, Dimethylamino group, diethylamino group, etc. are preferable.

As a specific example of the especially preferable thiocarbonylthio compound in this invention, it corresponds to a thiocarbonylthio compound (1), For example, following General formula (1-1)-(1-20)

Compounds represented by;

Corresponding to thiocarbonylthio compound (2), for example, the following general formula (2-1)

Compounds represented by such as;

Corresponding to thiocarbonylthio compound (3), for example, the following formulas (3-1) to (3-5)

The compound etc. which are represented by these are mentioned, respectively.

These thiocarbonylthio compounds can be used individually or in mixture of 2 or more types.

Next, the preferable polymerization method of manufacturing (A) copolymer is demonstrated. (A) The copolymer is preferably (a1) a compound having two or more polymerizable unsaturated bonds in the molecule, (a2) an alkali-soluble polymerizable unsaturated compound, and (a3) other than (a1) and (a2) Among the polymerizable unsaturated compounds, the polymerizable mixture containing at least the compounds (a2) and (a3) is a living radical in a solvent in the presence of a polymerization initiator and at least one of the above-described thiocarbonylthio compounds (1) to (3). It can superpose | polymerize and can manufacture by further adding the polymeric mixture containing 1 or more types of compound (a1), (a2), and (a3) as needed, and continuing superposition | polymerization. At this time, further, if necessary, a polymerizable mixture may be further added to further add components. However, in order to obtain the (A) copolymer, it is necessary to use the compound (a1) in any one of the polymerization steps.

When the said polymerization takes the form of living radical polymerization, when using a compound which has functional groups, such as a carboxyl group which may inactivate active radicals as a polymerizable unsaturated compound, in order to prevent a growth terminal from deactivating, the said unsaturated is necessary as needed. The (A) copolymer can be satisfactorily obtained by protecting the functional group in the compound, for example, by esterification or the like, and then deprotecting it.

As said radical polymerization initiator, although it selects suitably according to the kind of polymerizable unsaturated compound used, what is generally known as a radical polymerization initiator can be used, For example, 2,2'- azobisisobutyronitrile, 2 Azo compounds such as 2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); Organic peroxides such as benzoyl peroxide, lauroyl peroxide, 1,1'-bis (t-butylperoxy) cyclohexane and t-butylperoxy pivalate; Hydrogen peroxide; And redox initiators containing these peroxides and reducing agents.

Among these radical polymerization initiators, azo, such as 2,2'-azobisisobutyronitrile and 2,2'-azobis (2,4-dimethylvaleronitrile), is particularly preferable in view of the side reactions caused by oxygen and the like. Compound is preferred. The said radical polymerization initiator can be used individually or in mixture of 2 or more types.

Moreover, in the said superposition | polymerization, 1 or more types, such as another molecular weight control agent, for example, (alpha) -methylstyrene dimer, t-dodecyl mercaptan, can also be used together with a disulfide compound (1).

Although it does not specifically limit as a solvent used for the said superposition | polymerization, For example, propylene glycol monoalkyl ether, 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 (Poly) alkylene glycol monoalkyl ether acetates such as acetate, dipropylene glycol monoethyl ether acetate and cyclohexanol 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, and dipropylene glycol diethyl ether;

Other ethers such as tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

Ketoalcohols such as diacetone alcohol (ie, 4-hydroxy-4-methylpentan-2-one) and 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 Ethyl ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n acetate -Butyl, i-butyl acetate, 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-pyruvate Other esters such as propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Among these solvents, propylene glycol monomethyl ether and ethylene glycol monomethyl ether acetate are not deactivated at the time of living radical polymerization and in terms of solubility and coating property of each component when the radiation-sensitive resin composition is used. , 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, cyclohexanol acetate, diethylene glycol dimethyl ether , Diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3 Methyl-3-methoxybutylpropionate, n-butyl acetate, acetic acid i -Butyl, 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 polymerization, the amount of the radical polymerization initiator used is preferably 0.1 to 50 parts by weight, more preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total unsaturated compound.

Further, the amount of the thiocarbonylthio compound (1) to (3) 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 of the total unsaturated compound. To 8 parts by weight. If the amount of the thiocarbonylthio compound (1) to (3) is less than 0.1 part by weight, the regulatory effect of molecular weight and molecular weight distribution tends to decrease, while if it exceeds 50 parts by weight, a low molecular weight component is preferentially produced. I might throw it away.

Moreover, the usage-amount of another molecular weight control agent is preferably 80 weight part or less, More preferably, it is 40 weight part or less with respect to 100 weight part of total molecular weight control agents. 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.

The amount of the solvent used is preferably 50 to 1,000 parts by weight, more preferably 100 to 500 parts by weight based on 100 parts by weight of the total unsaturated compound.

In addition, 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, the compound having two or more polymerizable unsaturated bonds in the above (a1) molecule is not particularly limited, but an aliphatic chain, an alicyclic ring, an aromatic ring, an ether group, an ester group, between two or more polymerizable unsaturated bonds, A carbonate group, a urethane group, an amide group, a siloxy group, a heterocyclic ring, etc. may be included, and also the hydroxyl group and carboxyl group may take the form of pendant between two or more polymerizable unsaturated bonds. From the polymerizable point of view, the number of polymerizable unsaturated bonds is preferably 2 to 6, more preferably 2 to 3. In the case of having six or more polymerizable unsaturated bonds, there is a fear of thickening or gelation during polymerization.

As a compound which has two or more polymerizable unsaturated bonds in a molecule | numerator (a1), it is bifunctional, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 6- hexanediol diacrylate, 1 , 6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol di Acrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxy ethanol fluorene dimethacrylate, etc. are mentioned. As a commercial item of the bifunctional (meth) acrylate, for example, Aronix M-210, M-215, M-220, M-240, M-260, M-270, M-1200 , M-1600, M-6200 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, HX-620, R-526, R-167, R-604, R R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (above, manufactured by Nippon Kayaku Co., Ltd.), Atresin UN-9000PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN-6060P (above, manufactured by Nagami Kogyo Co., Ltd.), SH-500B, Biscot 260, East 215, East 312, East 335HP (above, manufactured by Osaka Yuki Chemical Co., Ltd.) ), Light acrylate BEPG-A, copper HPP-A, light ester G-201P, epoxy ester 40EM, copper 70PA, copper 80MFA, copper 3002M, copper 3002A (above, manufactured by Kyoeisha Chemical Co., Ltd.), dena Colacrylate DA-721, copper DA-722, DM-201 (or more, Nagase Chemtex Co., Ltd. make, BMI-70, BMI-80 (above, KAI Kasei Co., Ltd. make), etc. are mentioned.

Moreover, as (meth) acrylate more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylic acid, for example. Laterate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, or linear alkylene group and alicyclic ring 3- to 6-functional urethane acrylate compounds obtained by reacting a compound having an isocyanate group with a formula structure with a compound having an acryloyloxy group and / or methacryloyloxy group while having at least one hydroxyl group in the molecule Can be mentioned.

As a commercial item of (meth) acrylate more than trifunctional, for example, Aronix M-309, copper M-315, copper M-350, copper M-400, copper M-408, copper M-450, copper M-1960 M-7100, M-8030, M-8060, M-8100, M-8530, M-8560, M-9050, ARONICS TO-1450 (above, manufactured by Toa Kosei Co., Ltd.) ), KAYARAD TMPTA, copper GPO-303, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120, copper MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.) As coat 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (above, Osaka Yuki Chemical Co., Ltd.) and a urethane acrylate compound, New frontier R-1302, copper R-1303, Copper R-1304, Copper R-1305, Copper R-1306, Copper R-1308 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARAD UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), Atresin UN-9000H (Negami Kogyo Co., Ltd. product) etc. are mentioned.

Of these compounds (a1), ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, UX-0937, atresin UN-9200A , Epoxy ester 3002A, BMI-80, etc. are preferable at the point of polymerizability.

The alkali-soluble polymerizable unsaturated compound of the compound (a2) is preferably an unsaturated carboxylic acid, unsaturated carboxylic anhydride or unsaturated carboxylic acid having a radical polymerizability protected. As unsaturated carboxylic acid and / or unsaturated carboxylic anhydride which has radical polymerizability, for example, monocarboxylic acid, dicarboxylic acid, anhydride of dicarboxylic acid, mono [(meth) acryl of polyhydric carboxylic acid, for example. Royloxyalkyl] ester, the mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in each of both terminal, the polycyclic compound which has a carboxyl group, its anhydride, etc. are mentioned.

As these specific examples, As monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As anhydride of dicarboxylic acid, For example, acid anhydride of the said compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, For example, monosuccinate mono [2- (meth) acryloyloxyethyl], mono phthalate [2- (meth) acryloyloxyethyl ] Etc;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in each of both terminal, For example, (omega) -carboxypolycaprolactone mono (meth) acrylate etc .;

As the polycyclic compound having a carboxyl group and anhydrides thereof, for example, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-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] hept-2-ene anhydride, and the like. Each can be mentioned.

Among them, anhydrides of monocarboxylic acid and dicarboxylic acid are preferably used, and acrylic acid, methacrylic acid and maleic anhydride are particularly preferably used in view of copolymerization reactivity, solubility in an aqueous alkali solution and availability. These are used alone or in combination.

It does not specifically limit as a protecting group which protects the carboxyl group of the unsaturated carboxylic acid of a compound (a2), A well-known thing can be used as a protecting group of a carboxyl group. For example, a trialkyl silyl group, a 1-alkoxyalkyl group, a cyclic 1-alkoxyalkyl group, etc. are mentioned. More specifically, trimethylsilyl, dimethylbutyl silyl, 1-ethoxyethyl, 1-propoxyethyl, tetrahydrofuranyl, tetrahydropyranyl, triphenylmethyl, etc. are mentioned, for example.

Compound (a2) can be used individually or in combination of 2 or more types. It is to be understood that the compound (a2) includes unsaturated carboxylic acids which are themselves alkali-soluble as described above, and unsaturated carboxylic acids which are hydrolyzed to alkali-soluble or unsaturated carboxylic acids in which the carboxyl group is protected.

As the compound (a3), for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, t Acrylic acid alkyl esters such as butyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate Methacrylic acid alkyl esters, such as a rate; Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate (hereinafter “tricyclo [5.2.1.0 ^2,6 ] decane-8-yl” Alicyclic esters of acrylic acid such as dicyclopentanyl), 2-dicyclopentanyloxyethyl acrylate, isoboroyl acrylate and tetrahydrofuryl acrylate; Meta, such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentanyl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate Cycloaliphatic esters of krylic acid; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate 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; Aromatic vinyl compounds, such as styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, and p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, and methacryl Amide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl- 3-maleimidebenzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- ( 9-acridinyl) maleimide etc. are mentioned.

Among these compounds (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate, dicyclopentanyl methacrylate, styrene, p-methoxy styrene, 1,3-butadiene and the like are preferable in terms of copolymerization reactivity. .

Moreover, an epoxy group containing polymerizable unsaturated compound and / or an oxetanyl group containing unsaturated compound can be used further as a compound (a3). Specific examples of the epoxy group-containing polymerizable unsaturated compound include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, and 3,4-epoxycyclohexyl acrylate. Acrylic acid epoxy alkyl esters such as acrylic acid-3,4-epoxycyclohexylmethyl; Glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methacrylic acid Methacrylic acid epoxy alkyl esters such as acid-3,4-epoxycyclohexylmethyl; α-alkylacrylic acid epoxy alkyl esters such as α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl and α-ethyl acrylate 6,7-epoxyheptyl; and glycidyl ethers such as o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether.

As a specific example of the said oxetanyl group containing polymerizable unsaturated compound, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl oxetane, 3- (meth), for example Chryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyl Oxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl ) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (methacryloyloxyethyl) jade Cetane, 3- (methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2- Trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyl Cetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (meth Chryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3 -(Acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyl Oxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) -2 , 2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- ( Acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (Acryloyloxyethyl) -2 -Pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyl Oxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetrafluorooxetane, 2- (methacryloyloxymethyl) Oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- (methacryloyloxymethyl ) Oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacrylo) Iloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -3-pentafluoro Ethyloxetane, 2- (methacryloyloxymethyl) -4-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacrylo Yloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (methacryloyloxymethyl) oxetane, 2 , 4-difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2 -(Methacryloyloxymethyl) oxetane, 4,4-difluoro-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -3,3,4- Trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,3,4,4-tetrafluoro Rooxetane, 2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethylmethacrylate, 2- (2- (3-methyloxetanyl)) Ethyl methacrylate, 2- (methacryloyloxyethyl) -2-methyloxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (methacryloyloxyethyl)- 2-trifluoromethyloxetane, 2- (methacryloyloxye ) -3-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -2-pentafluoroethyloxetane , 2- (methacryloyloxyethyl) -3-pentafluoroethyl oxetane, 2- (methacryloyloxyethyl) -4-pentafluoroethyl oxetane, 2- (methacryloyloxyethyl ) -2-phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro- 2- (methacryloyloxyethyl) oxetane, 2,4-difluoro-2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxy Ethyl) oxetane, 3,4-difluoro-2- (methacryloyloxyethyl) oxetane, 4,4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- ( Methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (methacryloyl Oxyethyl) -3,3,4,4- Trifluorooxetane, 2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoro Methyl oxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (acryloyloxymethyl ) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxetane, 2- (acrylic Royloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxymethyl) oxetane, 2, 4-difluoro-2- (acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro- 2- (acryloyloxymethyl) oxetane, 4,4-difluoro-2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -3,3,4-trifluoro Looxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3,4,4-tetrafluorooxetane, 2- (acryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane , 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (acryloyloxyethyl) -4-trifluoromethyloxetane, 2- (acryloyloxyethyl) -2 -Pentafluoroethyl oxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxyethyl) -4-pentafluoroethyl oxetane, 2- (acrylic Royle Oxyethyl) -2-phenyloxetane, 2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro- 2- (acryloyloxyethyl) oxetane, 2,4-difluoro-2- (acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) Oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane, 4,4-difluoro-2- (acryloyloxyethyl) oxetane, 2- (acryloyloxy Ethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,3 (Meth) acrylic acid ester, such as 4, 4- tetrafluoro oxetane, is mentioned.

Among them, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl Spacer obtained by wide process margin of photosensitive resin composition from which oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. are obtained It is used preferably at the point which improves chemical-resistance.

The said compound (a3) can be used individually or in mixture of 2 or more types.

The content rate of the polymer unit derived from the compound (a1) in the (A) copolymer is preferably a bifunctional compound based on the sum of the polymer units derived from the compound (a1), (a2) and (a3). Preferably from 3 to 50% by weight, particularly preferably from 5 to 30% by weight. If the content of the polymerized unit of the bifunctional compound is less than 3% by weight, the compressive strength, heat resistance and chemical resistance of the spacer to be obtained tends to decrease, while if it exceeds 50% by weight, there is a fear of thickening of the polymer and gelation. If it is a trifunctional or more compound, Preferably it is 2-30 weight%, Especially preferably, it is 3-20 weight%. If the content of the polymerized unit of the trifunctional or higher compound is less than 2% by weight, the compressive strength, heat resistance and chemical resistance of the spacer to be obtained tends to decrease, while if it exceeds 30% by weight, there is a fear of thickening and gelling of the polymer. .

When using a bifunctional compound and a trifunctional or more compound together, the content rate of the sum total of the polymer unit derived from these compounds becomes like this. Preferably it is 2-50 weight%, Especially preferably, it is 3-30 weight%. In this case, it is preferable that the content rate of the polymer unit derived from each of a bifunctional compound and a trifunctional or more than trifunctional compound exists in the range of the preferable content rate at the time of using independently, respectively.

The content rate of the polymer unit derived from the compound (a2) in the (A) copolymer is preferably 5 to 50 weight based on the total of the polymer units derived from the compound (a1), (a2) and (a3). %, Especially preferably, it is 10-40 weight%. When the content rate of these polymerized units is less than 5 weight%, there exists a tendency for the developability and compressive strength of the spacer obtained to fall, and when it exceeds 50 weight%, the storage stability of a radiation sensitive resin composition will fall, or by image development Peeling may occur.

The content of the polymer unit derived from the compound (a3) in the (A) copolymer is preferably 20 to 90 weight based on the total of the polymer units derived from the compound (a1), (a2) and (a3). %, Especially preferably, it is 30 to 85 weight%. In this case, when the content rate of these polymerized units is less than 20 weight%, there exists a possibility that the storage stability of a radiation sensitive resin composition may fall, and when it exceeds 90 weight%, developability may fall. When the epoxy group-containing unsaturated compound and / or oxetanyl group-containing unsaturated compound are used as the compound (a3), their content rate is based on the total amount of the polymerized units derived from the compound (a3). It is preferably 5 to 75% by weight, particularly preferably 20 to 60% by weight. In this case, when the content rate of these polymerized units is less than 5 weight%, the compressive strength of the spacer obtained tends to fall, and when it exceeds 75 weight%, there exists a possibility that the storage stability of a radiation sensitive resin composition may fall.

When the (A) copolymer is prepared by multistage polymerization, the proportion ((first copolymer weight / (A) copolymer weight) × 100) of the first copolymer prepared in the first step is preferably 30. To 95% by weight, particularly preferably 50 to 90% by weight. When it is lower than 30 weight%, a polymerization reaction may not fully advance, an electrical property may fall, developability, and toughness may fall, and it is unpreferable. Moreover, when larger than 95%, the effect of the component added further cannot fully be exhibited, and it is unpreferable.

The copolymer (A) used in the present invention preferably has a polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography, preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ³ to 5 × 10 ⁴ . When Mw is less than 2x10 <^3> , developing margin may become inadequate, the residual film ratio etc. of a film obtained may fall, or the pattern shape of a spacer obtained, heat resistance, etc. may fall. On the other hand, when Mw exceeds 1 * 10 < ⁵ >, a sensitivity may fall or a pattern shape may fall.

The radiation sensitive resin composition containing the above-mentioned (A) copolymer can form a predetermined pattern shape easily, without developing developing residue, when developing.

In addition, the residual monomer amount measured by gel permeation chromatography of the copolymer (A) used in the present invention is preferably less than 5.0%, more preferably less than 3.0%, particularly preferably less than 2.0%.

By using the (A) copolymer of the above-mentioned residual monomer content which has such Mw, there is little generation | occurrence | production of the sublimation at the time of exposure and baking of a radiation sensitive resin composition, and it is used at the time of manufacture of a liquid crystal display panel (LCD panel). The possibility of contamination of the device being lowered can be reduced, and the "baking" of the LCD panel can be prevented more effectively.

The said (A) copolymer can be used individually or in mixture of 2 or more types.

In addition, in this invention, another alkali-soluble resin different from (A) copolymer can also be used together with 1 or more types (A) copolymer.

(B) Polymerizable  Unsaturated compounds

As the (B) polymerizable unsaturated compound in the radiation-sensitive resin composition of the present invention, bifunctional or higher acrylates and methacrylates (hereinafter referred to as "(meth) acrylates") are preferable.

As a bifunctional (meth) acrylate, for example, ethylene glycol acrylate, ethylene glycol methacrylate, 1, 6- hexanediol diacrylate, 1, 6- hexanediol dimethacrylate, 1, 9- furnace Nandiol diacrylate, 1,9-nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxy Ethanol flu ore diacrylate, bisphenoxyethanol fluorene dimethacrylate, and the like.

Moreover, as a commercial item of a bifunctional (meth) acrylate, for example, an aronix M-210, copper M-215, copper M-220, copper M-240, copper M-260, copper M-270, copper M -1200, East M-1600, East M-6200 (above, manufactured by Toa Kosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, East HX-620, East R-526, East R-167, East R-604 , R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX- 0937, MU-2100, MU-4001 (above, manufactured by Nippon Kayaku Co., Ltd.), atresin UN-9000PEP, east UN-9200A, east UN-7600, east UN-333, east UN-1003, east UN- 1255, East UN-6060PTM, East UN-6060P (above, manufactured by Nagami Kogyo Co., Ltd.), East SH-500B, Biscot 260, East 215, East 312, East 335HP (above, Osaka Yuki Kagaku High School, Ltd. ) Manufacture), light acrylate BEPG-A, copper HPP-A, light ester G-201P, epoxy ester 40EM, copper 70PA, copper 80MFA, copper 3002M, copper 3002A (above, manufactured by Kyoeisha Chemical Co., Ltd.) , Denacol acrylate DA-721, copper DA-722, DM- 201 (above, manufactured by Nagase Chemtex Co., Ltd.), BMI-70, BMI-80 (above, manufactured by KAI Kasei Co., Ltd.), and the like.

Moreover, as (meth) acrylate more than trifunctional, for example, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylic acid, for example. Late, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acrylo) Monooxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, or a compound having two or more isocyanate groups having a linear alkylene group and an alicyclic structure as a (meth) acrylate having 9 or more functional groups, and a molecule 3, 4 or 5 acryloyloxy groups and / or meta having at least one hydroxyl group in the By reacting a compound having a reel-yloxy group and the like can be obtained urethane acrylate compound.

As a commercial item of the (meth) acrylate more than trifunctional, for example, Aronix M-309, Copper M-315, Copper M-350, Copper M-400, Copper M-402, Copper M-405, Copper M-408 , M-450, M-1310, M-1600, M-1960, M-7100, M-8030, M-8060, M-8100, M-8530, M-8560 , Copper M-9050, aronix TO-1450 (above, Toagosei Co., Ltd.), KAYARAD TMPTA, copper GPO-303, copper DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA -120, East MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscot 295, East 300, East 360, East GPT, East 3PA, East 400 (above, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.) B, New frontier R-1150, copper R-1303, copper R-1304, copper R-1305, copper R-1306, copper R-1308 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) And KAYARAD DPHA-40H, UX-5000 (manufactured by Nippon Kayaku Co., Ltd.), UN-9000H (manufactured by Negami Kogyo 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 polymerizable unsaturated compound (B) is preferably used in an amount of 40 to 250 parts by weight, more preferably 60 to 180 parts by weight based on 100 parts by weight of the (A) copolymer.

(C) Radiation  polymerization Initiator

The radiation sensitive polymerization initiator (C) is a component that generates active species capable of initiating polymerization of the polymerizable unsaturated compound (B) in response to radiation.

As such a (C) radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, a benzoin compound, a benzophenone compound, the (alpha)-diketone compound, a polynuclear quinone compound, a xanthone compound, for example , Phosphine compounds, triazine compounds and the like.

As the O-acyl oxime compound, a 9.H.-carbazole-based O-acyl oxime type polymerization initiator is preferable. 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] -nonan-1,2-nonan-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-onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-benzoate , 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime-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-onoxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9 .H.- Rbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-diox Solanyl) methoxybenzoyl] -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime), and the like.

Among these O-acyl oxime compounds, in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate, eta Non, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9.H.-carbazol-3-yl] -, 1- (O-acetyl oxime) is preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof. In the present invention, by using an O-acyl oxime compound, it is possible to obtain a spacer having sufficient sensitivity and adhesion even at an exposure amount of 1,500 J / m ² or less.

As said acetophenone compound, the (alpha)-hydroxy ketone compound, the (alpha)-amino ketone compound, etc. are mentioned, for example.

As said α-hydroxy ketone compound, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like. Moreover, as said (alpha)-amino ketone compound, 2-methyl-1- (4-methylthio phenyl) -2-morpholino propane- 1-one, 2-benzyl-2- dimethylamino-1- ( 4-morpholinophenyl) -butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one, etc. are mentioned. have. As compounds other than these, 2, 2- dimethoxy acetophenone, 2, 2- diethoxy acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, etc. are mentioned, for example.

Among these acetophenone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholino propane-1-one or 2- (4-methylbenzyl) -2- (dimethylamino) -1- Preference is given to (4-morpholinophenyl) -butan-1-one.

In this invention, by using an acetophenone compound together, it becomes possible to further improve a sensitivity, a spacer shape, and compressive strength.

Moreover, as said biimidazole compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2 is, for example. '-Biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6 -Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are 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 preferred, in particular 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred.

In this invention, it becomes possible to further improve a sensitivity, a resolution, and adhesiveness by using a biimidazole compound together.

In addition, when using a biimidazole compound together, in order to sensitize it, the aliphatic type or aromatic type compound which has a dialkylamino group (henceforth "amino sensitizer") can be added.

As an amino sensitizer, N-methyl diethanolamine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, ethyl p-dimethylamino benzoate, p, for example -Dimethylaminobenzoic acid i-amyl etc. are mentioned.

Among these amino sensitizers, 4,4'-bis (diethylamino) benzophenone is particularly preferable.

The said amino sensitizer can be used individually or in mixture of 2 or more types.

In addition, when using a biimidazole compound and an amino sensitizer together, a thiol compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino-based sensitizer to generate imidazole radicals, but the high polymerization initiation capacity is not expressed as it is, so that the spacer obtained may have an undesirable shape such as an inverse taper shape. many. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, as a result of donating a hydrogen radical from a thiol compound to an imidazole radical, the imidazole radical is converted into a neutral imidazole and the polymerization initiation ability is improved. A component having high sulfur radicals is generated, whereby the shape of the spacer can be made more preferable forward tapered.

Examples of the thiol compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-5-methoxybenzothiazole, and 2-mercapto-. Aromatic compounds such as 5-methoxybenzoimidazole; Aliphatic monothiols such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, and octyl 3-mercaptopropionate; And bifunctional or higher functional aliphatic thiols such as 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), and pentaerythritol tetra (3-mercaptopropionate).

Among these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.

In addition, when using a biimidazole compound and an amino sensitizer together, the addition amount of an amino sensitizer becomes like this. Preferably it is 0.1-50 weight part, More preferably, it is 1-20 weight part with respect to 100 weight part of biimidazole compounds. . When the amount of the amino sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, resolution, and adhesion tends to decrease, while when the amount of the amino sensitizer exceeds 50 parts by weight, the shape of the spacer to be obtained tends to be damaged.

In addition, when using a biimidazole compound and an amino sensitizer together, the addition amount of a thiol compound becomes like this. Preferably it is 0.1-50 weight part, More preferably, it is 1-20 weight part with respect to 100 weight part of biimidazole compounds. When the amount of the thiol compound added is less than 0.1 part by weight, the effect of improving the shape of the spacer tends to be lowered or film reduction tends to occur. On the other hand, when the amount of the thiol compound exceeds 50 parts by weight, the shape of the obtained spacer tends to be damaged.

Moreover, as a radiation sensitive cationic polymerization initiator, it is an onium salt, for example, phenyldiazonium tetrafluoro borate, phenyldiazonium hexafluoro phosphonate, phenyldiazonium hexafluoro arsenate, phenyl diazonium trifluoromethane. Sulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium-p-toluenesulfonate, 4-methoxy phenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxy Methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazonium trifluoroacetate, 4-methoxyphenyldiazonium-p-toluenesulfonate , 4-tert-butylphenyldiazonium tetrafluoroborate, 4-tert-butylphenyldiazonium hexafluorophosphonate, 4-tert-butylphenyldiazonium hexafluoro Diazo such as loarsenate, 4-tert-butylphenyldiazonium trifluoromethanesulfonate, 4-tert-butylphenyldiazonium trifluoroacetate, 4-tert-butylphenyldiazonium-p-toluenesulfonate Nium salts; Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate , Triphenylsulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsul Phosphorous hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p- Toluenesulfonate, 4-phenylthiophenyldiphenyl tetrafluoroborate, 4-phenylthiophenyldiphenyl hexafluorophosphonate, 4-phenylthiophenyldiphenyl hexafluoroarsenate, 4-phenylthiophenyl Phenyl trifluoromethanesulfonate, 4-thiophenyl-diphenyl-trifluoroacetate, 4-thiophenyl-diphenyl -p- toluenesulfonate salts such as sulfonate;

Iodonium salts such as bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate and (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate Can be.

Moreover, (1-6- (eta)-cumene) ((eta) -cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1-) etc. are mentioned as a metallocene compound.

As a commercial item of these radiation-sensitive cationic polymerization initiators, For example, Adeka Ultraset PP-33 (made by Adeka Co., Ltd.) which is a diazonium salt, Optomer SP-150 which is a sulfonium salt, and Copper-170 (Co., Ltd.) Deca), and Irgacure 261 (made by Ciba Specialty Chemicals Co., Ltd.) which are metallocene compounds, etc. are mentioned.

In the radiation-sensitive resin composition, the use ratio of the radiation-sensitive cationic polymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, particularly preferably 60 parts by weight of 100 parts by weight of the total radiation-sensitive polymerization initiator. It is below a weight part. When the use ratio of the radiation sensitive cationic polymerization initiator exceeds 100 parts by weight, the desired effect of the present invention may be impaired.

Said (C) radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types.

(C) The radiation sensitive polymerization initiator is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight based on 100 parts by weight of the (B) polymerizable unsaturated compound.

Arbitrary additives

The radiation sensitive resin composition of this invention can mix | blend arbitrary additives other than the above, for example, an adhesion | attachment adjuvant, an surfactant, a storage stabilizer, a heat resistance improver, etc. in the range which does not impair the effect of this invention as needed.

The said adhesion | attachment adjuvant is a component used in order to improve the adhesiveness of the formed spacer and a board | substrate.

As such an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an epoxy group, is preferable. Examples thereof include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, and γ-glycidoxypropyltrimethoxy Silane, (beta)-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. are mentioned.

These adhesion aids can be used individually or in mixture of 2 or more types.

The compounding quantity of an adhesion | attachment adjuvant becomes like this. Preferably it is 20 weight part or less, More preferably, it is 15 weight part or less with respect to 100 weight part of (A) copolymers. When the compounding quantity of an adhesion | attachment adjuvant exceeds 20 weight part, there exists a tendency for image development residue to occur easily.

In addition, the said surfactant is a component used in order to improve applicability | paintability.

As such surfactant, a fluorine surfactant, a silicone surfactant, etc. are preferable, for example.

As said fluorosurfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least one site | part of a terminal, a main chain, and a side chain is preferable, As an example, 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, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,3,3,9,9,10,10-decafluoro-n Dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkyl phosphate, sodium fluoroalkyl carboxylate, diglycerin tetraki (Fluoroalkyl polyoxyethylene ether), fluoroalkyl ammonium iodide, fluoroalkyl betaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carbon Acid fluoroalkyl ester etc. are mentioned.

Moreover, as a commercial item of a fluorine-type surfactant, BM-1000, BM-1100 (above, BM CHEMIE company make), Megapack F142D, copper F172, copper F173, copper F183, copper F178, copper F191 , F471, F476 (above, Dai Nippon Ink Chemical Co., Ltd.), Florade FC-170C, copper-171, copper-430, copper-431 (above, Sumitomo 3M Co., Ltd.), Supron S-112, East-113, East-131, East-141, East-145, East-382, Surflon SC-101, East-102, East-103, East-104, East-105, East- 106 (above, Asahi Glass Co., Ltd.), F-Top EF301, east 303, east 352 (above, Shin Akita Kasei Co., Ltd.), plantgent FT-100, copper -110, copper -140A, copper- 150, copper-250, copper-251, copper-300, copper-310, copper-400S, aftergent FTX-218, copper-251 (above, manufactured by Neos), etc. are mentioned.

As said silicone surfactant, Toray silicon DC3PA, copper DC7PA, copper SH11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH-190, copper SH-193, copper SZ-6032, copper SF-8428 , DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicon Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 (more, Momen And commercially available products such as T Performance Materials Japan Co., Ltd.).

Moreover, as surfactant other than the above, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene aryl ethers such as polyoxyethylene-n-octylphenyl ether and polyoxyethylene-n-nonylphenyl ether; Nonionic surfactants, such as polyoxyethylene dialkyl ester, such as polyoxyethylene dilaurate and polyoxyethylene distearate, and organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), (meth) Acrylic acid copolymer polyflow No. 57, copper No. 95 (above, Kyoeisha Chemical Co., Ltd. product) etc. are mentioned.

These surfactant can be used individually or in mixture of 2 or more types.

The compounding quantity of surfactant is 1.0 weight part or less with respect to 100 weight part of (A) copolymers, More preferably, it is 0.5 weight part or less. When the compounding quantity of surfactant exceeds 1.0 weight part, there exists a tendency for film nonuniformity to arise easily.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and the like. More specifically, 4-methoxyphenol and N-nitroso-N-phenyl Hydroxylamine aluminum etc. are mentioned.

These storage stabilizers can be used individually or in mixture of 2 or more types.

The compounding quantity of a storage stabilizer is 3.0 weight part or less with respect to 100 weight part of (A) copolymers, More preferably, it is 0.5 weight part or less. When the compounding quantity of a storage stabilizer exceeds 3.0 weight part, there exists a possibility that a sensitivity may fall and a pattern shape may deteriorate.

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, compounds having two or more epoxy groups, and the like.

For example, an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, etc. are mentioned.

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.

Among these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril is preferable.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ', N', N '', N ''-hexa (methoxymethyl) melamine, N, N, N ', N', N '', N ''-hexa (ethoxymethyl) melamine, N, N, N ', N', N '', N ''-hexa (n-propoxymethyl) melamine, N, N, N ' , N ', N' ', N' '-hexa (i-propoxymethyl) melamine, N, N, N', N ', N' ', N' '-hexa (n-butoxymethyl) melamine, N, N, N ', N', N ", N" -hexa (t-butoxymethyl) melamine, etc. are mentioned.

Of these N- (alkoxymethyl) melamine compounds, N, N, N ', N', N '', N ''-hexa (methoxymethyl) melamine is preferable, and as the commercially available product thereof, for example, Nikalac N -2702, copper MW-30M (above, Sanwa Chemical Co., Ltd.), etc. are mentioned.

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene. Glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanedioldi Glycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like.

Moreover, as a commercial item of the compound which has two or more epoxy groups, for example, epolite 40E, copper 100E, copper 200E, copper 70P, copper 200P, copper 400P, copper 1500NP, copper 80MF, copper 100MF, copper 1600, copper 3002, Copper 4000 (above, manufactured by Kyoeisha Chemical Co., Ltd.), epicoat 152, epicoat 154 (above, manufactured by Japan Epoxy Resin Co., Ltd.), and the like. These can be used individually or in mixture of 2 or more types.

Radiation  Preparation of Resin Composition

The radiation sensitive resin composition of this invention is manufactured by uniformly mixing the said (A) copolymer, (B) component, (C) component, and the other components which can be added arbitrarily as mentioned above. The radiation-sensitive resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the radiation sensitive resin composition of a solution state can be manufactured by mixing (A) copolymer, (B) component, (C) component, and the other component added arbitrarily at predetermined ratio.

As a solvent used for manufacture of the radiation sensitive resin composition of this invention, each component of (A) copolymer, (B) component, (C) component, and the other component arbitrarily mix | blended is melt | dissolved uniformly, and each component What does not react with is used.

As such a solvent, the same thing as what was illustrated as a solvent which can be used for manufacturing the above-mentioned (A) copolymer is mentioned.

Among these solvents, for example, alcohols, glycol ethers, ethylene glycol alkyl ether acetates, esters and diethylene glycol are preferably used in view of solubility of each component, reactivity with each component, ease of coating film formation, and the like. Among these, for example, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, cyclohexanol acetate, diethylene glycol diethyl ether, Diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxy propionate and ethyl ethoxy propionate can be particularly preferably used.

In addition, a high boiling point solvent may be used in combination with the solvent in order to increase in-plane uniformity of the film thickness. As a high boiling point solvent which can be used together, it is N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpi, for example. Rollidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate And diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.

When using a high boiling point solvent together as a solvent of the radiation-sensitive resin composition of this invention, the usage-amount is 50 weight% or less with respect to solvent whole quantity, More preferably, it is 40 weight% or less, More preferably, 30 weight% It can be set as follows. When the usage-amount of a high boiling point solvent exceeds this usage-amount, the film thickness uniformity, a sensitivity, and a residual film ratio of a coating film may fall.

In the case where the radiation-sensitive resin composition of the present invention is prepared in a solution state, the components other than the solvent occupied in the solution, that is, (A) copolymer, (B) component and (C) component and other components optionally added The ratio (solid content concentration) of the total amount can be arbitrarily set according to the purpose of use, the value of the desired film thickness, the film formation method, and the like. For example, when the dry film method is employed as the film formation method, it is preferably 30 to 70% by weight. , More preferably, it is 40-65 weight%, and when employing the other film formation method, Preferably it is 5-50 weight%, More preferably, it is 7-40 weight%, More preferably, it is 10-35 weight %to be.

The composition solution thus prepared can be used for use after being filtered using a Millipore filter having a pore size of about 0.5 μm.

Spacer  Formation method

Next, the method of forming the spacer of this invention using the radiation sensitive resin composition of this invention is demonstrated.

The formation method of the spacer of this invention includes the following process (1)-(4) at least. The following steps (1) to (4) are carried out in the order described below.

(1) forming a film of the radiation-sensitive resin composition on a substrate;

(2) exposing to at least a portion of the film;

(3) developing the film after exposure, and

(4) The process of heating the film after image development.

Hereinafter, each of these steps will be described in order.

(1) of the present invention Radiation  The film of the resin composition On a substrate  Forming process

A transparent conductive film is formed on one surface of a transparent substrate, and after apply | coating the composition solution of the radiation sensitive resin composition of this invention on the said transparent conductive film, a film is formed by heating (prebaking) an application surface.

As a transparent substrate used for formation of a spacer, a glass substrate, a resin substrate, etc. are mentioned, for example, More specifically, Glass substrates, such as soda-lime glass and an alkali free glass; And resin substrates containing plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and polyimide.

Examples of the transparent conductive film provided on one surface of the transparent substrate include an NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA) and an ITO film containing indium tin oxide (In ₂ O ₃ -SnO ₂ ). Etc. can be mentioned.

The coating method of the composition solution is not particularly limited, and for example, spraying, roll coating, rotary coating (spin coating), slit die coating (spinless), bar coating, inkjet coating, or the like is appropriate. The method can be employed, and in particular, the spin coating method and the slit die coating method are preferable.

In addition, although prebaking conditions differ also with kinds, compounding ratio, etc. of each component, Preferably it is about 1 to 15 minutes at 70-120 degreeC.

On the other hand, the film thickness after prebaking of a film is not specifically limited, Preferably it is 0.5-10 micrometers, More preferably, it is about 1.0-7.0 micrometers.

The dry film method is mentioned further as a method of forming the film of the radiation sensitive resin composition of this invention.

As a coating method of the composition solution, for example, a spraying method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an inkjet coating method, or the like can be adopted, and in particular, spin coating. Method, the slit die coating method is preferred.

Moreover, when forming the film of the radiation sensitive resin composition of this invention, when employing the dry film method, as said dry film, the radiation sensitive resin composition of this invention on a base film, Preferably a flexible base film What consists of laminating | stacking the radiation sensitive layer containing this (hereinafter called a "radiation sensitive dry film") is used.

The radiation-sensitive dry film can be formed by laminating a radiation-sensitive layer by applying the radiation-sensitive resin composition of the present invention as a liquid composition, preferably on a base film and then drying. As a base film of a radiation sensitive dry film, the film of synthetic resins, such as polyethylene terephthalate (PET), polyethylene, a polypropylene, polycarbonate, polyvinyl chloride, can be used, for example. The thickness of the base film is suitably in the range of 15 to 125 μm. As for the thickness of the radiation sensitive layer obtained, about 1-30 micrometers is preferable.

Moreover, when a radiation sensitive dry film is not in use, a cover film can also be laminated | stacked and preserve | saved further on the radiation sensitive layer. This cover film does not peel at the time of non-use, but needs to have appropriate mold release property so that it may peel easily at the time of use. As a cover film which satisfies these conditions, the film which apply | coated or baked the silicone type release agent to the surface of synthetic resin films, such as a PET film, a polypropylene film, a polyethylene film, a polyvinyl chloride film, and a polyurethane film, can be used, for example. . As for the thickness of a cover film, about 5-30 micrometers is preferable.

These cover films can laminate | stack two or three layers of cover films as needed.

(2) irradiating radiation to at least a portion of the film

Subsequently, at least part of the formed film is exposed to radiation. In this case, when exposing to a part of film, it exposes through the photomask which has a predetermined pattern.

As radiation used for exposure, visible light, an ultraviolet-ray, an ultraviolet-ray, etc. can be used, for example. Preference is given to radiation in which the wavelength is in the range from 190 to 450 nm, in particular radiation comprising an ultraviolet of 365 nm.

The exposure amount is a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) of the intensity at a wavelength of 365 nm of the radiation to be exposed, preferably 100 to 10,000 J / m 2, more preferably 1,500 to 3,000 J / m 2.

(3) developing process

Next, by developing the film after exposure, an unnecessary part is removed and a predetermined pattern is formed.

As a developing solution used for image development, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, 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, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] Alicyclic tertiary amines such as -5-nonene; Aromatic tertiary amines such as pyridine, collidine, lutidine and quinoline; Alkanolamines such as dimethylethanolamine, methyldiethanolamine and triethanolamine; An aqueous solution of alkaline compounds, such as quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, can be used.

In addition, a suitable amount of water-soluble organic solvents and / or surfactants such as methanol and ethanol may be added to the aqueous solution of the alkaline compound.

The developing method may be any one of a puddle method, an immersion method, a shower method, and the like, and the developing time is preferably about 10 to 180 seconds at room temperature.

After the development, for example, washing with running water for 30 to 90 seconds, and then drying with, for example, compressed air or compressed nitrogen, a desired pattern is formed.

(4) heating process

Subsequently, the obtained pattern (film) is, for example, a heating device such as a hot plate or an oven at a predetermined temperature, for example, 180 to 240 ° C., for a predetermined time, for example, for 5 to 30 minutes on a hot plate, in the oven. In the above, a predetermined spacer can be obtained by heating (postbaking) for 15 to 180 minutes.

Liquid crystal display element

The liquid crystal display element of this invention can be manufactured by the following method (a) or (b), for example.

(a) First, a pair (two pieces) of transparent substrates which have a transparent conductive film (electrode) on one side are prepared, and the radiation sensitive resin composition of this invention is used on the transparent conductive film of one board | substrate among them, The spacer is formed according to the method described above. Subsequently, an alignment film having liquid crystal alignment capability is formed on the transparent conductive film and the spacer of these substrates. These substrates are placed facing each other with a predetermined gap (cell spacing) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on the side where the alignment film is formed on the inside, and placed on the surface (alignment film) and the spacer of the substrate. The liquid crystal is filled in the cell gap partitioned by the cell, and the filling hole is sealed to form a liquid crystal cell. And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell so that the polarization direction may coincide with or perpendicular to the liquid crystal aligning direction of the alignment film formed in the one surface of the said board | substrate.

(b) First, a pair of transparent substrates on which a transparent conductive film, a spacer, and an alignment film are formed in the same manner as in the first method is prepared. Then, the ultraviolet curable sealing agent is apply | coated using the dispenser along the edge part of one board | substrate, a liquid crystal is dripped in the shape of a micro droplet using a liquid crystal dispenser, and both board | substrates are bonded under vacuum. Then, the above-mentioned sealant is irradiated with ultraviolet rays using a high pressure mercury lamp to seal both substrates. Finally, the liquid crystal display element of this invention can be obtained by bonding a polarizing plate to both outer surfaces of a liquid crystal cell.

As said liquid crystal, a nematic liquid crystal and a smectic liquid crystal are mentioned, for example. Especially, a nematic type liquid crystal is preferable, for example, a Schiff base type liquid crystal, a subfamily clock liquid crystal, a biphenyl type liquid crystal, a phenylcyclohexane type liquid crystal, an ester type liquid crystal, a terphenyl type liquid crystal, a biphenyl cyclohexane type liquid crystal, a pyrimi Din type liquid crystals, dioxane type liquid crystals, bicyclooctane type liquid crystals, Kuban type liquid crystals, etc. are used. Moreover, it is sold to these liquid crystals as cholesteric liquid crystals, such as a cholesteryl chloride, a cholesteryl nonaate, a cholesteryl carbonate, and brand names "C-15", "CB-15" (made by Merck), for example. It is also possible to add and use a chiral agent. Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.

Moreover, as a polarizing plate used on the outer side of a liquid crystal cell, the polarizing plate etc. which included the polarizing film called "H film | membrane" which absorbed iodine while extending-orienting polyvinyl alcohol between the cellulose acetate protective film, or the H film itself are mentioned. Can be.

As described above, the radiation-sensitive resin composition of the present invention can easily form a patterned thin film having high sensitivity and high resolution, and excellent in various performances such as pattern shape, compressive strength, rubbing resistance, heat resistance, and the like. It can suppress generation | occurrence | production, can suppress the burnout, such as an afterimage in a liquid crystal display, and it becomes difficult to produce plastic deformation with respect to a load load. Moreover, it becomes possible to improve resistance to chemical liquids, such as an alignment film peeling liquid. In addition, the amount of deformation of the spacer formed therefrom becomes sufficient, and the TFT and CF are not damaged or destroyed against external force, and further improvement in margin for the liquid crystal dropping step can be expected.

<Example>

Although a synthesis example and an Example are shown to the following and this invention is demonstrated to it further more concretely, this invention is not limited to a following example.

<Measurement of Molecular Weight of Copolymer by Gel Permeation Chromatography>

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803, and GPC-KF-804

Mobile phase: tetrahydrofuran containing 0.5 wt% phosphoric acid

Synthesis Examples 1 to 10 and Comparative Synthesis Examples 1 to 3 of (A) Copolymer

Synthesis Example 1

4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester (compound represented by the formula (1-20)) and diethylene glycol methylethyl ether in a flask equipped with a cooling tube and a stirrer. 200 parts by weight, followed by 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, 30 parts by weight of benzyl methacrylate, and 1 10 parts by weight of, 9-nonanediol diacrylate was added and replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. 2 weight part of 2,2'- azobis (isobutyronitrile) was added at the stage which reached 80 degreeC, and it superposed | polymerized holding this temperature for 5 hours, and obtained the copolymer solution of 32.5 weight% of solid content concentration. This copolymer was used as the [A-1] copolymer. About the obtained [A-1] copolymer, Mw was 7,200 when measured using GPC (gel permeation chromatography).

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester and 200 parts by weight of diethylene glycol methylethyl ether were added, followed by 20 parts by weight of methacrylic acid. , 10 parts by weight of styrene, 35 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl and 35 parts by weight of benzyl methacrylate, and nitrogen-substituting, followed by stirring gently to obtain a solution temperature of 80 It was raised to ℃. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added in a step of reaching 80 ° C, and the polymerization was carried out while maintaining this temperature for 3 hours, followed by further addition of 1,9-nonanedioldiacrylate 10 The copolymer solution of 34.0 weight% of solid content concentration was obtained by adding a weight part and holding for 3 hours. This copolymer was used as the [A-2] copolymer. About the obtained [A-2] copolymer, Mw was 6,800 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide (compound represented by the formula (3-2)) and 200 parts by weight of diethylene glycol methylethyl ether, 15 parts by weight of acrylic acid, 10 parts by weight of styrene, 35 parts by weight of n-butyl methacrylate, 30 parts by weight of tetrahydrofurfuryl methacrylate and 10 parts by weight of UX-0937 (manufactured by Nippon Kayaku Co., Ltd.) After nitrogen substitution, the temperature of the solution was raised to 80 ° C. with gentle stirring. 2 weight part of 2,2'- azobis (isobutyronitrile) was added at the stage which reached 80 degreeC, and this copolymerization was hold | maintained for 5 hours, and the copolymer solution of 33.0 weight% of solid content concentration was obtained. This copolymer was used as the [A-3] copolymer. About the obtained [A-3] copolymer, Mw was 8,400 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methylethyl ether were added, followed by 15 parts by weight of acrylic acid, 10 parts by weight of styrene, and meta 40 parts by weight of n-butyl methacrylate and 35 parts by weight of tetrahydrofurfuryl methacrylate were added and replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added at the step of reaching 80 ° C, and the polymerization was carried out while maintaining this temperature for 3 hours, followed by UX-0937 (manufactured by Nippon Kayaku Co., Ltd.) 10 weight part was added and it hold | maintained for 2 hours, and the copolymer solution of 35.0 weight% of solid content concentration was obtained. This copolymer was used as the [A-4] copolymer. About the obtained [A-4] copolymer, Mw was 7,900 when measured using GPC (gel permeation chromatography).

Synthesis Example 5

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methylethyl ether were added, followed by 15 parts by weight of acrylic acid, 10 parts by weight of styrene, and meta 35 parts by weight of n-butyl methacrylate, 30 parts by weight of tetrahydrofurfuryl methacrylate, and 10 parts by weight of UX-0937 (manufactured by Nippon Kayaku Co., Ltd.) were added thereto, followed by nitrogen replacement. It was raised to ℃. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added in a step of reaching 80 ° C, and polymerization was carried out while maintaining this temperature for 3 hours, and then 20 parts by weight of benzyl methacrylate was added, and 3 hours The copolymer solution of 36.1 weight% of solid content concentration was obtained by holding. This copolymer was used as the [A-5] copolymer. About the obtained [A-5] copolymer, Mw was 8,600 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 6

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol dimethyl ether were added, followed by 2-methacryloyloxyethyl hexahydrophthalic acid 25 Parts by weight, 5 parts by weight of styrene, 35 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl and 30 parts by weight of glycidyl methacrylate, and after nitrogen replacement, further added 1, 5 parts by weight of 3-butadiene was added and the temperature of the solution was raised to 70 ° C. with gentle stirring. 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added at the step of reaching 70 ° C, and the polymerization was carried out while maintaining this temperature for 2 hours, followed by M-220 (Doagosei Co., Ltd.). ) 20 parts by weight was added, and the copolymer solution having a solid content concentration of 36.2% by weight was obtained by holding for 3 hours. This copolymer was used as the [A-6] copolymer. About the obtained [A-6] copolymer, Mw was 8,020 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 7

6 parts by weight of bis-3,5-dimethylpyrazol-1-ylthiocarbonyl disulfide (compound represented by the above formula (3-3)) and diethylene glycol methylethyl in a flask equipped with a cooling tube and a stirrer. 200 parts by weight of ether was added, followed by 20 parts by weight of methacrylic acid, 5 parts by weight of styrene, 35 parts by weight of 2-ethylhexyl methacrylic acid, and 30 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane. And 10 parts by weight of epoxy ester 3002A (manufactured by Kyoeisha Chemical Co., Ltd.), and after nitrogen substitution, the temperature of the solution was raised to 70 ° C. with gentle stirring. 2 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) was added in a step of reaching 70 ° C, and the polymerization solution was maintained at this temperature for 5 hours to give a solid solution concentration of 32.9% by weight. Got. This copolymer was used as the [A-7] copolymer. About the obtained [A-7] copolymer, Mw was 8,400 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 8

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of dipropylene glycol dimethyl ether were added, followed by 10 parts by weight of methacrylic acid and 5 parts by weight of acrylic acid, 5 parts by weight of styrene, 35 parts by weight of tetrahydrofurfuryl methacrylate, 35 parts by weight of benzyl methacrylate, and 10 parts by weight of atresin UN-9200A (manufactured by Negami Kogyo Co., Ltd.), followed by nitrogen substitution, followed by gentle stirring While raising the temperature of the solution to 80 ℃. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added in a step of reaching 80 ° C, and the polymerization was carried out while maintaining this temperature for 3 hours, followed by Atresin UN-9000PEP (Negami Kogyo Co., Ltd.) Preparation) 10 weight part was added, and it hold | maintained for 3 hours, and the copolymer solution of 34.9 weight% of solid content concentration was obtained. This copolymer was used as the [A-8] copolymer. About the obtained [A-8] copolymer, Mw was 9,100 when Mw was measured using GPC (gel permeation chromatography).

Synthesis Example 9

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate were added, followed by 20 parts by weight of methacrylic acid and 5 parts by weight of styrene. 20 parts by weight of isoboroyl acrylate, 25 parts by weight of n-butyl methacrylate and 30 parts by weight of benzyl methacrylate were added and replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added at the step of reaching 80 ° C, and the polymerization was carried out while maintaining this temperature for 2 hours, and then Aronix M-315 manufactured by Toagosei Co., Ltd. 10 parts by weight of the solution was added and maintained for 3 hours to obtain a copolymer solution having a solid content concentration of 34.7% by weight. This copolymer was used as an [A-9] copolymer. About the obtained [A-9] copolymer, Mw was 9,300 as a result of measuring using GPC (gel permeation chromatography).

Synthesis Example 10

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate were added, followed by 25 parts by weight of 2-acryloyloxyethylphthalic acid. , 5 parts by weight of styrene, 20 parts by weight of n-lauryl acrylate, 20 parts by weight of tetrahydrofurfuryl methacrylate, and 30 parts by weight of benzyl acrylate were added and replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. . 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added at the step of reaching 80 ° C, and the polymerization was carried out while maintaining this temperature for 2 hours, and then Aronix M-450 (Toago Kosei Co., Ltd.) was manufactured. ) 5 parts by weight was added and the mixture was kept for 2 hours to obtain a copolymer solution having a solid content concentration of 33.0% by weight. This copolymer was used as the [A-10] copolymer. About the obtained [A-10] copolymer, Mw was 8,100 when Mw was measured using GPC (gel permeation chromatography).

Comparative Synthesis Example 1

In a flask equipped with a cooling tube and a stirrer, 4 parts of 2,2'-azobis (isobutyronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added, followed by 10 parts by weight of methacrylic acid and 5 parts by weight of acrylic acid. , 5 parts by weight of styrene, 40 parts by weight of n-butyl methacrylate and 35 parts by weight of benzyl methacrylate, and nitrogen replacement, and then 5 parts by weight of 1,3-butadiene were added, and the temperature of the solution was gradually changed to 80 ° C. The copolymer solution was raised to 3 ° C. and maintained at this temperature for 5 hours to polymerize with a solid content concentration of 30.4 wt%. This copolymer was used as the [a-1] copolymer.

Mw was measured by GPC with respect to the obtained [a-1] copolymer, and it was 7,800.

Comparative Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 4 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by weight of diethylene glycol methylethyl ether were added, followed by 20 parts by weight of methacrylic acid. 5 parts by weight of styrene, 25 parts by weight of tricyclo methacrylate [5.2.1.0 ^2,6 ] decane-8-yl, 25 parts by weight of glycidyl methacrylate and 20 parts by weight of tetrahydrofurfuryl methacrylate After nitrogen substitution, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was raised to 70 ° C. with gentle stirring, and the polymerization was carried out while maintaining this temperature for 5 hours to thereby obtain a 30.6% by weight copolymer solution. Got it. This copolymer was used as the [a-2] copolymer.

It was 9,800 when Mw was measured by GPC with respect to the obtained [a-2] copolymer.

Comparative Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methylethyl ether were added, followed by 15 parts by weight of acrylic acid and 10 parts by weight of styrene, 40 parts by weight of methyl methacrylate and 30 parts by weight of tetrahydrofurfuryl methacrylate were added and replaced with nitrogen, and then the temperature of the solution was raised to 80 ° C. with gentle stirring. 2 parts by weight of 2,2'-azobis (isobutyronitrile) was added in a step of reaching 80 ° C, and polymerization was carried out while maintaining this temperature for 2 hours, and then 30 parts by weight of n-butyl methacrylate was added, The block copolymer solution of 35.5 weight% of solid content concentration was obtained by holding for 3 hours. This copolymer was used as the [a-3] copolymer. About the obtained [a-3] copolymer, Mw was 6,300 when Mw was measured using GPC (gel permeation chromatography).

Examples 1 to 12 and Comparative Examples 1 to 3

(I) Preparation of a radiation sensitive resin composition

The copolymer obtained in the synthesis example shown in Table 1 below, component (C) and component (C), 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion aid, FTX-218 as a surfactant 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration is 30% by weight, and then millipore having a pore diameter of 0.5 µm. Filtration with a filter produced a composition solution.

In addition, in Example 11, 20 weight part of novolak-type epoxy resins (brand name "Epicoat 152", Japan Epoxy Resin Co., Ltd. product) was used further besides each said component.

Table 1 shows the types and amounts of each component.

(II) Formation of spacer

After apply | coating the said composition solution using a spinner on the alkali free glass substrate, it prebaked for 3 minutes on the 80 degreeC hotplate, and formed the film of 4.0 micrometers in film thicknesses.

Subsequently, the obtained film was exposed to the ultraviolet-ray whose intensity | strength at 365 nm is 250 W / m <^2> for 10 second through the photomask which has a residual pattern of 15 micrometers in length and width. Then, after developing for 60 second at 25 degreeC with the 0.05 weight% aqueous solution of potassium hydroxide, it wash | cleaned with pure water for 1 minute. Thereafter, by post-baking at 230 ° C. for 20 minutes in an oven, a spacer of a predetermined pattern was formed.

(III) developability evaluation

In the above (II), when the development time was shortened to 40 seconds at the time of development, the case where the pattern was formed was evaluated as good (○) and the case where a residue occurred as defective (×). The evaluation results are shown in Table 2.

(IV) resolution evaluation

When forming a pattern in said (II), the case where the residual pattern could be resolved was evaluated as good ((circle)) and the case where it was not able to resolve as defect (x). The evaluation results are shown in Table 2.

(V) Evaluation of Spacer Shape

The cross-sectional shape of the pattern obtained by said (II) was observed with the scanning electron microscope, and it evaluated according to which of A and B shown in FIG. At this time, when the spacer shape is round as in A, the upper portion of the spacer tends to be deformed, which has a sufficient deformation amount when the TFT and CF plates are bonded together, and the margin for the liquid crystal dropping step is improved. On the other hand, if the pattern shape is a trapezoidal shape like B, the deformation of the spacer is less likely to occur, and the margin of the liquid crystal dropping step is likely to occur. The evaluation results are shown in Table 2.

(VI) Compression displacement evaluation

About the pattern obtained by said (II), the deformation amount at the time of applying 50 mN load by 50 micrometer diameter planar indenter using a micro compression tester (DUH-201, the Shimadzu Corporation make) It measured at the temperature of 23 degreeC. When this value is 0.5 micrometer or more, it can be said that a compression displacement amount is favorable. The evaluation results are shown in Table 2.

(VII) toughness assessment

For the pattern obtained in the above (II), the height change of the spacer after applying a load of 200 mN by a flat indenter having a diameter of 50 µm using a micro compression tester (DUH-201, manufactured by Shimadzu Corporation) Was 6% or less, it evaluated as good ((circle)) and 6% or more as defect (x). The evaluation results are shown in Table 2.

(VIII) heat resistance evaluation

About the pattern obtained by said (II), after leaving for 20 minutes at 230 degreeC in oven, it evaluated as a good ((circle)), and a bad (x) when the height change of a spacer is less than 4%, and 4% or more. The evaluation results are shown in Table 2.

(IX) chemical resistance evaluation

The pattern obtained in the above (II) was immersed in an alignment film peeling solution Chemiclean TS-204 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) heated at 60 ° C. for 15 minutes, washed with water, and then washed at 120 ° C. for 15 minutes in an oven. After drying, if the height change of the spacer was less than 4%, it was good (○), and if it was 4% or more, it was evaluated as defective (×). The evaluation results are shown in Table 2.

(X) Evaluation of the amount of sublimation

Each radiation sensitive resin composition was apply | coated on the board | substrate so that it might become a predetermined | prescribed film thickness, and the thin film was formed. Head space sampler JHS-100A (manufactured by Nihon Bunsei Kogyo Co., Ltd.) and gas chromatography / mass spectrometer JEOL JMS-AX505W (Nihon Denshi Co., Ltd.) The amount of the sublimate which generate | occur | produced by the head space gas chromatography / mass spectrometry on the conditions of the analysis temperature range 25-230 degreeC and the temperature increase rate 100 degreeC / 10min was manufactured. Octane (specific gravity: 0.701, injection amount: 0.02 µL) was used as a standard substance for quantification of the sublimation amount, and the sublimation amount per unit area was calculated as a value of octane conversion by the following equation 1 based on the peak area.

Sublimation amount (μg / cm ² ) = (peak area of sublime per 1 cm ² / peak area of octane) x 0.02 x 0.701

When this amount of volatile components was less than 2 micrograms, when sublimation was few ((circle)) and when it was 2 micrograms or more, it evaluated as many sublimation (x). The evaluation results are shown in Table 2.

(XI) rubbing tolerance assessment

After apply | coating AL3046 (brand name, JSR Corporation make) to the board | substrate with which the pattern obtained by said (II) was formed using the printing machine for liquid crystal aligning film coating as a liquid crystal aligning agent, it dried at 180 degreeC for 1 hour, and dried film The coating film of the orientation agent of thickness 0.05micrometer was formed.

Then, the rubbing process was performed to this coating film using the rubbing machine which has the roll wound the polyamide cloth at the rotation speed of 500 rpm and the stage movement speed of 1 cm / sec. At this time, the pattern was scraped or peeled off. The evaluation results are shown in Table 2.

(XII) Voltage Retention Rate Evaluation

The prepared liquid composition was formed with a SiO ₂ film on the surface to prevent elution of sodium ions, and was spin coated onto a soda glass substrate on which an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, followed by 90 ° C. It prebaked for 10 minutes in the clean oven of and formed the coating film with a film thickness of 2.0 micrometers.

Subsequently, the high pressure mercury lamp was used to expose the radiation containing the respective wavelengths of 365 nm, 405 nm and 436 nm to the coating film at an exposure amount of 200 J / m ² without passing through the photomask. Then, this board | substrate is immersed for 1 minute in the developing solution containing 23 degreeC 0.04 weight% potassium hydroxide aqueous solution, and after developing, it is wash | cleaned with ultrapure water, air-dried, and post-baking is carried out at 230 degreeC for 30 minutes further, hardening a coating film The permanent cured film was formed.

Subsequently, after bonding the board | substrate which formed this pixel and the board | substrate which only deposited the ITO electrode to a predetermined shape with the sealing agent which mixed 0.8 mm glass beads, the liquid crystal cell made by Merck Corporation was injected, and the liquid crystal cell was injected. Prepared.

Subsequently, the liquid crystal cell was put into the 60 degreeC thermostat, and the voltage retention of the liquid crystal cell was measured by the liquid crystal voltage retention measurement system VHR-1A type (brand name) by Toyo Technica. The applied voltage at this time was a 5.5 V square wave, and the measurement frequency was 60 Hz. Here, voltage retention is a value of (the voltage applied by the liquid crystal cell potential difference / 0 millisecond after 16.7 millisecond). If the voltage retention of the liquid crystal cell is 90% or less, the liquid crystal cell cannot maintain the applied voltage at a predetermined level for a time of 16.7 milliseconds, which means that the liquid crystal cannot be oriented sufficiently, and there is a fear of causing "burning" such as an afterimage. high.

Examples 13 and 14

(I) Preparation of a radiation sensitive resin composition

The kind and amount of each component contained in the composition were as shown in Table 1, respectively, except that the amount of propylene glycol monomethyl ether acetate was adjusted to 50% by weight of solid content, The radioactive resin composition was prepared.

(II) Evaluation of the Composition

Instead of coating using a spinner, a patterned thin film was formed and evaluated in the same manner as in Examples 1 to 12 except that the liquid film of each radiation-sensitive resin composition was formed by a dry film method. Here, peeling removal of the base film was performed before the exposure process. The evaluation results are shown in Table 2.

In addition, manufacture and transfer of a dry film were performed as follows.

On the 38-micrometer-thick polyethylene terephthalate (PET) film, the liquid composition of a radiation sensitive resin composition is apply | coated using an applicator, a coating film is heated at 100 degreeC for 5 minutes, and the radiation-sensitive dry film of 4 micrometers thick is Prepared. Next, the radiation sensitive transfer dry film was superimposed on the surface of a glass substrate so that the surface of a radiation sensitive transfer layer might contact, and the radiation sensitive dry film was transferred to the glass substrate by the thermocompression bonding method.

(A) component

We describe in synthesis example

(B) component

B-1: dipentaerythritol hexaacrylate

B-2: KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.)

B-3: 1,9-nonanediol diacrylate

(C) component

C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name Irgacure OXE 02 Manufactured by Ciba Specialty Chemicals Co., Ltd.)

C-2: 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)

Arbitrary additives

D-1: novolak-type epoxy resin (brand name: Epicoat 152, Japan epoxy resin Co., Ltd. product)

1 is a schematic diagram illustrating a cross-sectional shape of a spacer.

Claims (8)

(A) a copolymer comprising at least one polymerized unit derived from a compound containing at least two polymerizable unsaturated groups in the molecule (a1), (B) a polymerizable unsaturated compound, and (C) radiation sensitive polymerization initiator A radiation sensitive resin composition for spacer formation, comprising a. The radiation sensitive resin composition for spacer formation of Claim 1 in which (A) copolymer contains the polymer unit derived from (a2) alkali-soluble polymerizable unsaturated compound. The radiation sensitive resin composition for spacer formation of Claim 2 in which (A) copolymer contains the polymer unit derived from the other polymerizable unsaturated compound different from (a3) (a1) and (a2). The radiation sensitive resin composition for spacer formation of any one of Claims 1-3 whose (A) copolymer is obtained by living radical polymerization. The spacer formation according to any one of claims 1 to 3, wherein the (A) copolymer is prepared by polymerization using a thiocarbonylthio compound represented by the following general formula (1), (2) or (3) as a molecular weight control agent. Radiation-sensitive resin composition for. <Formula 1>

In Chemical Formula 1, Z ¹ represents a hydrogen atom, a chlorine atom, a hydroxyl group, 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, a total atom number of carbon atoms and binary atoms 3-20 monovalent heterocyclic group, -OX, -SX, -N (X) ₂ , -OC (= 0) X, -C (= 0) OX, -C (= 0) N (X) ₂ , -P (= 0) (OX) ₂ , -P (= 0) (X) ₂ or a monovalent group having a polymer chain, each X independently of one another is an alkyl group having 1 to 18 carbon atoms, An alkenyl group, a C6-C18 monovalent aromatic hydrocarbon group, or a C3-C18 monovalent heterocyclic group of carbon atoms and a binomial atom in total is represented, The said C1-C20 alkyl group, C6-C20 1 The aromatic aromatic hydrocarbon group, the monovalent heterocyclic group having 3 to 20 atoms in total, and X may each be substituted, p is an integer of 1 or more, and when X ¹ is p = 1, a hydrogen atom, Anano group, an alkyl group of 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group of 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group of 6 to 20 carbon atoms, a monovalent compound having 3 to 20 monovalent atoms in total with a carbon atom and a binary atom Monocyclic groups having a monocyclic group, —OX, —SX, —N (X) ₂ or a polymer chain, the definition of each X being as defined above and derived from alkane having 1 to 20 carbon atoms when p ≧ 2; p-valent group, p-valent group derived from a C6-C20 aromatic hydrocarbon, p-valent group derived from a heterocyclic compound having 3 to 20 carbon atoms in total, and a bivalent group having a polymer chain , The alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, X, and 1 to 1 carbon atoms. P derived from 20 alkanes In the group, a p-valent group derived from a heterocyclic compound of a p-valent group and a total of 3 to 20 atoms derived from an aromatic hydrocarbon having 6 to 20 carbon atoms may be each substituted; <Formula 2>

In Formula 2, m is an integer greater than or equal to 2, Z <^2> is a m-valent group derived from C1-C20 alkanes, a m-valent group derived from C6-C20 aromatic hydrocarbons, and a carbon atom and a binary atom. Derived from m-valent group derived from a heterocyclic compound having 3 to 20 atoms in total or m-valent group having a polymer chain and derived from m-valent group derived from alkane having 1 to 20 carbon atoms and aromatic hydrocarbon having 6 to 20 carbon atoms. The m-valent group and the m-valent group derived from the heterocyclic compound having 3 to 20 carbon atoms in total may be substituted, and X ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 carbon atoms. A monovalent aromatic hydrocarbon group having from 20 to 20, a monovalent heterocyclic group having from 3 to 20 carbon atoms, and a monovalent group having -OX, -SX, -N (X) ₂ or a polymer chain; Each X 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 a monovalent compound having 3 to 18 monovalent atoms in total between a carbon atom and a binary atom A monocyclic group, said alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, and X May each be substituted] <Formula 3>

In Formula 3, Z ³ and Z ⁴ are independently of each other 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, a carbon atom and a binary atom, Monovalent heterocyclic group having 3 to 20 atoms in total, -OR ¹ , -SR ¹ , -OC (= O) R ¹ , -N (R ¹ ) (R ² ), -C (= O) OR ¹ , -C (= 0) N (R ¹ ) (R ² ), -P (= 0) (OR ¹ ) ₂ , -P (= 0) (R ¹ ) ₂ or a monovalent group having a polymer chain, R ¹ and R ² are each 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 carbon atoms and a binary atom; It represents a valent heterocyclic group, the said C1-C20 alkyl group, the C6-C20 monovalent aromatic hydrocarbon group, the C1-C20 monovalent heterocyclic group with a total of 3 to 20 carbon atoms, R <^1> and R ² May each be substituted; The spacer formed from the radiation sensitive resin composition for spacer formation in any one of Claims 1-3. A method of forming a spacer, comprising at least the steps (1) to (4) below. (1) Process of forming the film of the radiation sensitive resin composition for spacer formation in any one of Claims 1-3 on a board | substrate, (2) exposing to at least a portion of the film; (3) developing the film after exposure, and (4) The process of heating the film after image development. The liquid crystal display element provided with the spacer of Claim 6.

Images