TWI412848B - Sensitive radiation linear resin compositions, spacers and methods for their formation - Google Patents

Abstract

The present invention provides a sensible radiation linear resin combination, the characteristic in that the combination contains (A) block copolymer, (B) polymerization non saturation compound, (C) sensible radiation linear polymerization initiator, thereinto, the block copolymer has more than two block chain segments, and at least one of the block chain segments has alkali soluble position. A pattern film which has high sensitivity and high resolution forms easily, the film has excellent performance of pattern shape, compression characteristics, tolerance friction, good contact with transparent substrate, so as to restrain the spacer which burns screen within LCD display from forming sensible radiation linear resin combination, and the spacer composed of the combination and its forming method. In addition, the present invention reduces fault of non filling area caused by decreasing liquid crystal drop amount, prevents the damage due to press on the filter and the spacer with different deepness generated during working procedure from forming sensible radiation linear resin combination.

Description

Sensitive radiation linear resin composition, spacer and method of forming same

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

In the conventional liquid crystal display device, spacer particles such as glass beads or plastic beads having a predetermined particle size are used in order to keep the interval between the two transparent substrates constant. However, these spacer particles are randomly dispersed in a transparent glass substrate or the like. On the substrate, when the spacer particles are present in the pixel formation region, the phenomenon of the spacer particles or the scattering of the incident light is caused, and the contrast of the liquid crystal display element is lowered.

Therefore, in order to solve such problems, a method of forming a spacer by a lithography method is employed. In this method, the sensitive radiation linear resin composition is applied onto a substrate, and is exposed to ultraviolet light after being exposed through a predetermined mask to form a dot-like or stripe-shaped spacer, which is determined only in the field of pixel formation. The space can form a spacer, which basically solves the aforementioned problems.

However, the radiation of the mercury lamp used as the light source of the photolithography is usually displayed in the vicinity of 436 nm (g line), near 404 nm (h line), around 365 nm (i line), near 335 nm, near 315 nm (j line), near 303 nm, and the like. A stronger intensity spectrum, and therefore a sensitive radiation linear polymerization initiator which is a constituent of the sensitive radiation linear resin composition is generally selected to have a maximum absorption wavelength in the spectral wavelength region where the intensity is strong, and in most cases, transparent From the viewpoint of the use, a sensitive radiation linear polymerization initiator having a maximum absorption wavelength in a wavelength range below the i-line is used (refer to Japanese Laid-Open Patent Publication No. 2001-261761). However, in the conventionally known spacer-forming radiation sensitive linear resin composition, the linear radiation polymerization initiator is selected, and the cross-sectional shape of the spacer may be inverted conical (the side of the film surface is longer than the side of the substrate side). In the case of the rubbing treatment of the subsequent alignment film, the spacer causes the peeling.

It is presumed that the scorching of the LCD caused by the impurities eluted by the permanent film in the cell formed by the sensitive radiation linear resin composition becomes a problem, and therefore it is expected to form a permanent intracellular film which does not cause "burning". And high product yield, the sensitive radiation linear resin composition of the LCD panel can be manufactured.

In addition, when the compressive strength and deformation due to an external force are excessively emphasized, when the high restoring force of the original cell gap is restored, there is a problem that the external force cannot be absorbed and the TFT and CF are damaged or destroyed.

In the past, after bonding a TFT board and a CF board, in order to shorten the filling process time of injecting liquid crystal under vacuum, a new process of bonding a TFT board and a CF board after dropping a liquid crystal was developed. However, in the prior art, the amount of deformation of the spacer is insufficient, and the tolerance of the liquid crystal dropping process is insufficient, which causes a problem.

However, in the manufacture of a liquid crystal display panel, the substrate size is increasing in size from the viewpoint of improving productivity and being suitable for a large screen. The substrate size is the first generation of 300mm × 400mm, the second generation of 370mm × 470mm, the third generation of 620mm × 750mm, the fourth generation of 960mm × 1,100mm, and the fifth generation of 1,100mm × 1,300mm is now mainstream . Further, the substrate size will be a sixth generation of 1,500 mm × 1,850 mm, a seventh generation of 1,850 mm × 2,100 mm, and an eighth generation of 2,200 mm × 2,600 mm in the future.

When the substrate size is small, for example, 370 mm × 470 mm or less, the photosensitive resin composition is dropped on the center of the substrate and applied by spin coating. This method must coat a large amount of the photosensitive resin composition solution, and has a drawback that it cannot be adapted to a large substrate.

When the substrate size is 960 mm × 1,100 mm or less, in order to save the solution of the photosensitive resin composition, a slit type and a spin and spin method are used. In this method, a solution of a photosensitive resin composition is applied to a substrate surface by a slit nozzle, and then a uniform coating film is formed by rotating the substrate. Although this method has the effect of saving a solution, it is difficult to fit the substrate size after the fifth generation.

Therefore, with the background, as the size of the substrate is increased, coating is performed using a slit die coater. However, when a slit die coater is used, unevenness of the stripe shape, unevenness of the mist, unevenness of the substrate transfer arm or the needle, the adsorption pad (needle mark), and film thickness at the end portion of the substrate are likely to occur.

For this reason, in the die coater method, a solution of a photosensitive resin composition for forming a spacer having a uniform film thickness is strongly desired.

The present invention has been accomplished in light of the above problems. Therefore, an object of the present invention is to provide a pattern-like film which can easily form high sensitivity, high resolution, and various characteristics such as pattern shape, compression characteristics, abrasion resistance, and adhesion to a transparent substrate, and can suppress burning during LCD display. The spacer of the coke forms a linear composition of the sensitive radiation, a spacer formed therefrom, and a method of forming the same.

Another object of the present invention is to provide a method for reducing the unfilled area caused by the amount of liquid crystal dropping, preventing damage caused by pressure on a color filter, and overcoming the thickness deviation caused by the production, and uniform film thickness during coating. It does not cause unevenness, and is suitable for a photosensitive resin composition for forming a spacer for a slit die coater method.

Other objects and advantages of the present invention are as described below.

The object and the advantages of the present invention are the first to form a sensitive radiation linear resin composition by a spacer, which is characterized by: (A) a block copolymer (B) a polymerizable unsaturated compound and (C) a linear radiation spectrum. A polymerization initiator is achieved.

The object and the advantages of the present invention are achieved by the fact that (D) a radiation-sensitive linear resin composition containing an epoxy group is contained in addition to the above components (A), (B) and (C).

The object and the advantages of the present invention are achieved by the above (A) block copolymer having two or more block segments, wherein at least one block segment has an alkali-soluble portion of the above-mentioned radiation-sensitive linear resin composition. .

The object and the advantage of the present invention are attained by the above-mentioned radiation-sensitive linear resin composition containing a carboxyl group as an alkali-soluble portion.

The object and the advantage of the present invention is that the (A) block copolymer contains at least (a1) a protective compound selected from the group consisting of a radically polymerizable unsaturated carboxylic acid, an unsaturated carboxylic anhydride, and a carboxylic acid thereof. At least one of the group and (a2) the first block segment composed of the radical polymerizable compound other than (a1) and the second block segment composed only of the (a1) or (a2) Sensitive radiation linear resin composition is achieved.

The object and advantage of the present invention are attained by the above-mentioned radiation-sensitive linear resin composition of the (A) block copolymer obtained by living radical polymerization.

The object and the advantage of the present invention is that the (A) block copolymer is a thiocarbonylsulfide compound represented by the following formula (1), (2) or (3) as a molecular weight controlling agent, and the polymerizable property is unsaturated. The radiation-sensitive linear resin composition according to any one of claims 1 to 6, wherein the (A) block copolymer is the following formula (1), (2) or (3) The thiocarbonylthio compound represented by the above-mentioned radiation-sensitive linear resin composition of a resin produced by polymerizing a polymerizable unsaturated compound is used as a molecular weight controlling agent.

[In the formula (1), Z ¹ represents 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, and a total of carbon atoms and hetero atoms. A monovalent heterocyclic group of 3 to 20 atoms, -OR, -SR, -N(R) ₂ , -OC(=O)R, -C(=O)OR, -C(=O)N(R ₂ , -P(=O)(OR) ₂ , -P(=O)(R) ₂ , or a monovalent group having a polymer chain, and each R group 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 heterocyclic group having 3 to 18 carbon atoms in total of a carbon atom and a hetero atom, and an 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 total atoms, and R may be substituted, and R ¹ is an alkyl group having 1 to 20 carbon atoms when p=1. An alicyclic hydrocarbon group having a carbon number of 3 to 20, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a total of 3 to 20 monovalent heterocyclic groups having a carbon atom and a hetero atom, -OR, - SR, -N(R) ₂ or a monovalent group having a polymer chain, and each R group independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a valence of 6 to 18 carbon atoms. Aromatic hydrocarbon group or carbon atom and hetero atom a monovalent heterocyclic group having 3 to 18 atomic numbers, and a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a p-valent group derived from a carbon atom and a hetero atom having a total of 3 to 20 atomic number of a heterocyclic compound or a group having a p-valent group of a polymer chain, an alkyl group having 1 to 20 carbon atoms, and a carbon number of 3 to 20 a alicyclic hydrocarbon group having a valence, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 atoms in total, R, a p-valent group derived from an alkane having 1 to 20 carbon atoms, The p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and the p-valent group derived from a total of 3 to 20 ring atoms of a carbon atom and a hetero atom may be substituted, respectively. [In the formula (2), Z ² represents a m-valent group derived from an alkane having 1 to 20 carbon atoms, a m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a total of carbon atoms and hetero atoms. a m-valent group of a heterocyclic compound having 3 to 20 atoms or a group having a m-valent group of a polymer chain, the above-mentioned alkyl group derived from a carbon number of 1 to 20, and an aromatic hydrocarbon derived from a carbon number of 6 to 20. The m-valent group and the m-valent group of the heterocyclic compound having a total of 3 to 20 atoms may be substituted, and R ² is derived from an alkyl group having 1 to 20 carbon atoms and a monovalent alicyclic group having 3 to 20 carbon atoms. a hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a total of 3 to 20 monovalent heterocyclic groups of carbon atoms and hetero atoms, -OR, -SR, -N(R) ₂ or having a polymer The monovalent group of the chain, each R independently of each other 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 total atom of a carbon atom and a hetero atom. The monovalent heterocyclic group of 3 to 18, the alkyl group having 1 to 20 carbon atoms, the alicyclic hydrocarbon group having a carbon number of 3 to 20, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the total atom The number of 3 to 20 monovalent heterocyclic groups and R can be substituted respectively] [In the formula (3), Z ³ and Z ⁴ each independently represent a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. a monovalent heterocyclic group having 3 to 20 atoms in total with a hetero atom, -OR ³ , -SR ³ , -OC(=O)R ³ , -N(R ³ )(R ⁴ ), -C(=O )OR ³ , -C(=O)N(R ³ )(R ⁴ ), -P(=O)(OR ³ ) ₂ , -P(=O)(R ³ ) ₂ or having a polymer chain The valence group, R ³ and R ⁴ are each independently represent 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 atom of a carbon atom and a hetero atom. a monovalent heterocyclic group of 3 to 18, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having a carbon number of 6 to 20, a total of 3 to 20 carbon atoms and a hetero atom of a hetero atom The ring group, R ³ and R ⁴ systems can be substituted respectively].

The object and the advantages of the present invention are the ratio of the polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of the (A) block copolymer to the arithmetic mean molecular weight (Mn) in terms of polystyrene ( Mw/Mn) is achieved by a radiation sensitive linear resin composition of 2.5 or less.

The object and advantage of the present invention are attained by the formation of a spacer formed by the above-mentioned radiation-sensitive linear resin composition.

The object and the advantages of the present invention are the 10th method for forming a spacer, which comprises the following steps (A) to (D), and (a) forming a patent application range of 1 to 8 on the substrate. a step of sensitizing a film of a linear resin composition, (b) a step of exposing at least a portion of the film, (c) a step of developing a film after exposure, and a film of the film after development The step of heating is carried out.

OBJECT AND ADVANTAGES OF THE INVENTION The tenth aspect of the present invention is achieved by a liquid crystal display element having the features of the ninth application of the patent application.

Best form for implementing the invention Sensitive radiation linear resin composition

The components of the sensitive radiation linear resin composition of the present invention are detailed below.

(A) Block Copolymer The (A) block copolymer of the radiation sensitive linear resin composition of the present invention means a copolymer of a block segment composed of two or more polymerizable unsaturated compounds having different chemical structures. . The block segments may be composed of a single polymer or a plurality of polymers of a polymerizable unsaturated compound. At this time, the block segment may be a random copolymer. The (A) block copolymer may each contain two block segments composed of a random copolymer. The first block segment formed by primary polymerization and the block segment of 2 or more of the second block segment of the first block segment which is secondarily polymerized, wherein at least one of the block segments preferably contains Alkali soluble fraction. For example, the (A) block copolymer may have a compound (a1) having a radical polymerizable unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride or a protective compound of the carboxylic acid and the compound (a2) other than (a1). The polymerizable mixture of the radically polymerizable compound is subjected to living radical polymerization in the presence of a polymerization initiator in a solvent, and further a compound (a2) or a polymerizable mixture containing the compound (a1) and the compound (a2) is continuously polymerized. Got it. If necessary, a polymerizable mixture may be added, and then a block segment may be added. The alkali-soluble portion of the (A) block copolymer obtained as described above is derived from the compound (a1).

Next, the living radical polymerization for producing the (A) block copolymer will be described. Preferably, the first block segment is produced by living radical polymerization in the presence of a radical polymerization initiator which forms the living radical in the solvent and other copolymerizable unsaturated compound in a solvent. The (A) block copolymer can be produced by adding the above polymerizable unsaturated compound several times if necessary.

In the case of a living radical polymerization, when a compound having a functional group which may deactivate an active radical such as a carboxyl group as a polymerizable unsaturated compound is used, in order to prevent the growth terminal from being deactivated, if necessary, a polymerizable unsaturated compound is used. The functional group is, for example, protected by polymerization such as esterification, and then deprotected to produce (A) a block copolymer.

A radical polymerization initiator of various living radical polymerization polymerizable unsaturated compounds is proposed, for example, a TEMPO system proposed by Georges et al. (refer to MK Georges, RPN Veregin, PM Kazmaier, GK Hamer, Macromolecules, 1993, Vol. 26, p. 2987), a combination of copper bromide and bromine-containing ester compounds proposed by Matyjaszewski et al. (cf. 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. (cf. Hamasaki, S. Kamigaito, M. Sawamoto, M. Macromolecules, 2002, Vol. 35, p. 2934) or Japanese Patent No. 3,639,859 (Japanese Patent Application Publication No. 2000-515181), No. 2002-500251, and No. 2004-518773, having a chain shift constant greater than 0.1 A combination of a thiocarbonyl compound and a radical initiator.

The preferred radical polymerization initiator to be used in the living radical polymerization is a type in which the polymerizable unsaturated compound is used in combination, and a system which does not inactivate the living radical at the growth end is appropriately selected, but the polymerization efficiency and the inclusion are not considered. In the case of a metal or the like, a combination of a thiocarbonylthio compound of a molecular weight controlling agent and a radical initiator is preferred.

The combination of the above thiocarbonylthio compound and the radical initiator is described in detail in the following Japanese Patent No. 3,639,859 (Japanese Patent Application Publication No. 2000-515181), No. 2002-500251, and No. 2004-518773. JP-A-2002-508409, JP-A-2002512653, JP-A-2003-527458, and JP-A No. 3,634,484 (Special Publication No. 2003-536105).

As described in the specification of Japanese Patent No. 3,639,859 (Japanese Patent Application Publication No. 2000-515181), No. 2002-500251, No. 2004-518773, and No. 2002-508409, thiocarbonyl sulfur compounds and radical initiators In the presence of the unsaturated compound, living radical polymerization can obtain a random copolymer or a block copolymer having a narrow molecular weight distribution. Since the functional group can be introduced into the obtained random copolymer and the block copolymer, it is apparent that the copolymer can also be used for an aqueous gel (refer to Japanese Laid-Open Patent Publication No. 2002-512653), and the light resistance (refer to Japanese Patent Publication No. 2003-527458) The use of the surfactant (refer to the specification of No. 3,634,843 (Japanese Patent Application Publication No. 2003-536105)).

The above-mentioned thiocarbonylthio compound of the present invention is, for example, a compound represented by the above formula (1), the above formula (2) or the above formula (3).

In the above formula (1), the alkyl group having 1 to 20 carbon atoms of Z ^{1 may} , for example, be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a second butyl group or a third group. Butyl, n-pentyl, 1,1-dimethylpropyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 1,1-dimethyl-3,3-dimethyl-n-butyl , n-decyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-icosyl, and the like.

a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of Z ¹ , for example, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-fluorenyl group, a 9-fluorenyl group, a benzyl group, an α-methylbenzyl group, α,α-dimethylbenzyl, phenethyl and the like.

a monovalent heterocyclic group having 3 to 20 atoms in total of a carbon atom and a hetero atom of Z ¹ , and examples thereof include an oxiranyl group, an aziridine group, a 2-furyl group, a 3-furyl group, and a 2-tetrahydrofuranyl group. , 3-tetrahydrofuranyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 1-pyrazolyl, 2-pyrazolyl , 3-pyrazolyl, 2-tetrahydropyranyl, 3-tetrahydropyranyl, 4-tetrahydropyranyl, 2-thiol, 3-thiol, 4-thiol, 2 Pyridyl, 3-pyridyl, 4-pyridyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-morpholinyl, 3-morpholinyl and the like.

Z ¹ -OR, -SR, -N(R) ₂ , -OC(=O)R, -C(=O)OR, -C(=O)N(R) ₂ , -P(=O) (OR) ₂ and -P(=O)(R) ₂ , the carbon number of R of 1 to 18, the carbon number of 6 to 18, the monovalent aromatic hydrocarbon group or the total number of carbon atoms and hetero atoms 3~ The monovalent heterocyclic group of 18, for example, an alkyl group having 1 to 20 carbon atoms exemplified as Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total of 3 to 20 carbon atoms and a hetero atom. In the valent heterocyclic group, the number of carbon atoms or the total number of atoms is 18 or less.

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

The above-mentioned 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 of a carbon atom and a hetero atom, and a substituent having a hydroxyl group, for example, a hydroxyl group outer carboxyl, a carboxylate, a sulfonate group, an isocyanate group, a cyano group, a vinyl group, an epoxy group, A silicon group, a halogen atom, selected still the illustrated Z -OR ^1, -SR, - N(R) ₂ , -OC(=O)R, -C(=O)OR, -C(=O)N(R) ₂ , -P(=O)(OR) ₂ and -P(=O (R) ₂ ; an alkyl group having 1 to 18 carbon atoms, 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 atomic atoms of a carbon atom and a hetero atom The group having the same monovalent heterocyclic group of ~18 may contain one or more or more of the substituents. However, it is preferred that the total carbon number or the total number of atoms in the substituted derivative does not exceed 20.

Z ¹ has a valence group of a polymer chain, such as an α-olefin of ethylene or propylene; an aromatic vinyl compound such as styrene or α-methylstyrene; fluorinated ethylene, ethylene chloride, vinylidene chloride The halogenated ethylene; an unsaturated alcohol such as vinyl alcohol or allyl alcohol; an ester of an unsaturated alcohol such as vinyl acetate or allyl acetate; an unsaturated carboxylic acid such as (meth)acrylic acid or p-vinylbenzoic acid; Methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, third (meth)acrylate (Meth) acrylate such as butyl ester, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate; (meth) acrylamide, N, N-dimethyl (meth) acrylamide (meth)acrylamide; an unsaturated nitrile such as (meth)acrylonitrile or vinylidene cyanide; or one or more unsaturated compounds such as a conjugated diene such as butadiene or isoprene; A polyether having a valence group of an addition polymerization polymer chain, a polyether having a terminally etherified ether group, and a polyetherether having an etherizable terminal at the end Polyester, polyamide, polyimide and the like having an addition polymerized polymer chains and the polycondensation polymer chain one monovalent group. Among these having a valence group of a polymer chain, the polymer chain may be directly bonded to a carbon atom of the thiocarbonyl group in the formula (1), for example, via -CH ₂ -COO-, -C(CH ₃ ) (CN The bond of CH ₂ CH ₂ -COO- or the like is directly bonded to the carbon atom of the thiocarbonyl group in the formula (1).

The plurality of Z ¹ present in the formula (i) may be the same or different from each other.

In the formula (i), R ¹ system when p = 1, represents an alkyl group having 1 to 20 carbon atoms, and 3 to 20 carbon atoms of the monovalent alicyclic hydrocarbon group, having 6 to 20 carbon atoms of the monovalent aromatic The hydrocarbon group, the carbon atom and the hetero atom have a total of 3 to 20 monovalent heterocyclic groups, -OR, -SR, -N(R) ₂ or have a monovalent group of a polymer chain.

The alkyl group having 1 to 20 carbon atoms, the alicyclic hydrocarbon group having 3 to 20 carbon atoms, the aromatic hydrocarbon group having 1 to 20 carbon atoms, and the total number of atoms of carbon atoms and hetero atoms 3 to 20 The monovalent heterocyclic group, -OR, -SR, -N(R) ₂ or a monovalent group having a polymer chain or a substituted derivative thereof is, for example, the same as those exemplified for the group corresponding to the above Z ¹ . R ¹ (but p=1) has one of the polymer chain valencies, and the polymer chain can be directly bonded to the sulfur atom in the formula (1), for example, via -CH ₂ -COO-, -C(CH ₃ ) The bonding hand of (CN)CH ₂ CH ₂ -COO- or the like is directly bonded to the sulfur atom in the formula (1).

The alicyclic hydrocarbon group having a carbon number of 3 to 20 is, for example, a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group or a cyclohexenyl group.

The substituent of the above-mentioned alicyclic hydrocarbon group having 3 to 20 carbon atoms may be, for example, an alkyl group having 1 to 20 carbon atoms selected from the above Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a carbon atom and In the case where the number of the hetero atoms of the total number of the hetero atoms is 3 to 20, and the substituents exemplified for the substituent of R are the same, these substituents may be contained in the substituted derivative in an amount of one or more or more. However, it is preferred that the total carbon number or the total number of atoms in the substituted derivative does not exceed 20.

R ¹ is a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a total atom derived from a carbon atom and a hetero atom. The p-valent group of the heterocyclic compound of 3 to 20 or the p-valent group of the polymer chain.

The above-mentioned alkane having 1 to 20 carbon atoms is, for example, methane, ethane, propane, n-butane, isobutane, n-pentane, neopentane, n-hexane, n-heptane, n-octane, n-decane, and Decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-icosane, and the like.

The above aromatic hydrocarbon group having 6 to 20 carbon atoms is, for example, benzene or 1,4-dimethylbenzene (for example, a carbon atom of each methyl group at the 1,4-position is bonded to a sulfur atom in the formula (1)), 1 , 2,4,5-tetramethylbenzene (for example, a carbon atom of each methyl group at the 1, 2, 4, and 5 positions is bonded to a sulfur atom in the formula (1)), 1, 2, 3, 4, 5,6-hexamethylbenzene (for example, a carbon atom of each methyl group at the 1, 2, 3, 4, 5, 6-position is bonded to a sulfur atom in the formula (1)), 1,4-di-iso Propylbenzene (for example, a carbon atom at the 2-position of each isopropyl group at the 1,4-position is bonded to a sulfur atom in the formula (1)), a naphthalene group, a fluorenyl group or the like.

The above monovalent heterocyclic group having a total atomic number of 3 to 20 is, for example, ethylene oxide, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thiamine, pyridine, piperidine, Morpholine and the like.

a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound derived from a total of 3 to 20 carbon atoms and a hetero atom. the monovalent substituent group, for example, may be suitably selected from the above-described Z ¹ carbon number of alkyl group having 1 to 20 carbon atoms of 6 to 20 monovalent aromatic hydrocarbon group having 3 to 20 total carbon atoms and hetero atoms atom When the monovalent heterocyclic group and the group exemplified for the substituent of R are the same, these substituents may contain one or more or more than one in the substituted derivative. However, it is preferred that the total carbon number or the total number of atoms in the substituted derivative does not exceed 20.

The polymer chain which provides a p-valent group of R ¹ has, for example, an addition polymerization polymer chain, an addition polymerization polymer chain, and a polycondensation polymer which are exemplified by the above-mentioned Z ¹ having a valence group of a polymer chain. The same chain. In the p-valent group having a polymer chain of R ¹ , the polymer chain may be directly bonded to a sulfur atom in the formula (1), for example, via -CH ₂ -COO-, -C(CH ₃ )(CN) The bonding hand of CH ₂ CH ₂ -COO- or the like is directly bonded to the sulfur atom in the formula (1). The p of the formula (1) is preferably an integer of from 1 to 6.

In the formula (2), the alkane having 1 to 20 carbon atoms which provides the m-valent group of Z ^{2 is} , for example, the same as the compound exemplified as the alkane having 1 to 20 carbon atoms which provides a p-valent group of R ¹ described above.

The aromatic hydrocarbon having 6 to 20 carbon atoms which provides an m-valent group of Z ^{2 is} , for example, the same as the compound exemplified as the aromatic hydrocarbon having 6 to 20 carbon atoms which provides a p-valent group of R ¹ described above.

The heterocyclic compound having a total of 3 to 20 atoms of carbon atoms and a hetero atom which provides a m-valent group of Z ^{2 has} , for example, a total of 3 to 20 carbon atoms and a hetero atom of the above-mentioned R ¹ which provides a p-valent group. The compounds exemplified for the cyclic compounds are the same.

Z ² is a m-valent group derived from an alkane having 1 to 20 carbon atoms, a m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic ring having 3 to 20 total atoms from a carbon atom and a hetero atom. The substituent of the m-valent group of the compound can be appropriately selected, for example, from the alkyl group having 1 to 20 carbon atoms of the above Z ^{1 ,} the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the total number of atoms of the carbon atom and the hetero atom. The monovalent heterocyclic group of 3 to 20 and the group exemplified for the substituent of R may be one or more or more selected from the substituted derivatives. However, it is preferred that the total carbon number or the total number of atoms in the substituted derivative does not exceed 20.

The polymer chain which provides the m-valent group of Z ^{2 is} , for example, an addition polymerization polymer chain, an addition polymerization polymer chain, and a polycondensation polymer which are exemplified by the above-mentioned Z ¹ having a valence group of a polymer chain. The same chain. In the m valent group having a polymer chain of Z ² , the polymer chain may be directly bonded to a carbon atom of the thiocarbonyl group in the formula (2), for example, via -CH ₂ -COO-, -C(CH ₃ ) The bond of (CN) CH ₂ CH ₂ -COO- or the like is directly bonded to the carbon atom of the thiocarbonyl group in the formula (2).

In the formula (2), the alkyl group having 1 to 20 carbon atoms of R ² , the aromatic hydrocarbon group having a carbon number of 6 to 20, the monovalent heterocyclic group having 3 to 20 carbon atoms in total of a carbon atom and a hetero atom, -OR, -SR, -N(R) ₂ and a monovalent group having a polymer chain or a substituted derivative thereof are, for example, the same as those exemplified for the group corresponding to the above Z ¹ . R ² has a valence group of a polymer chain which can be directly bonded to a sulfur atom in formula (2), for example, via -CH ₂ -COO-, -C(CH ₃ )(CN)CH The linking hand of ₂ CH ₂ -COO- or the like is directly bonded to the sulfur atom in the formula (2).

The alicyclic hydrocarbon group having a carbon number of 3 to 20 in R ² or a derivative thereof, for example, the above alicyclic hydrocarbon group having 3 to 20 carbon atoms of R ¹ (but p=1) or a derivative thereof The examples are the same.

In the formula (2), most of the R ² present may be the same or different from each other.

In the formula (2), when the linking moiety between Z ² and -C(=S)-SR ² is an aliphatic carbon atom, the aliphatic carbon atom in Z ² is bonded to -C(=S)-SR ² When the linking moiety is an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to -C(=S)-SR ² , and when the linking moiety is a sulfur atom, it represents sulfur in the -SR of Z ² The atom is bonded to -C(=S)-SR ² . The m of the formula (2) is preferably an integer of 2 to 6.

In the formula (3), Z ³ and Z ⁴ each independently represent 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, and a carbon atom and A total of 3 to 20 monovalent heterocyclic groups of a hetero atom, -OR ³ , -SR ³ , -OC(=O)R ³ , -N(R ³ )(R ⁴ ), -C(=O) OR ³ , -C(=O)N(R ³ )(R ⁴ ), -P(=O)(OR ³ ) ₂ , -P(=O)(R ³ ) ₂ or have a valence of the polymer chain The R ³ and R ⁴ groups independently represent an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total number of atoms of a carbon atom and a hetero atom. a monovalent heterocyclic group of 3 to 18, the alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent heterocyclic ring having 3 to 20 carbon atoms in total of a carbon atom and a hetero atom. The groups, R ³ and R ⁴ , respectively, may be substituted.

Z ³ and Z ⁴ may be the same as those exemplified for Z ^{1 of} the above formula (1).

Z ³ and Z ⁴ each have, in addition to the alkyl group having 1 to 20 carbon atoms, from the viewpoint of reactivity with the polymerizable unsaturated compound, particularly the carbon atom and Z of the thiocarbonyl group (C=S) in the formula (1). heteroatom ³ and Z ⁴ are a nitrogen atom and the oxygen atom of covalently bonded, more specifically 3 to 20 of the monovalent heterocyclic group and the sum of the carbon atom of the hetero atom, -OR ^3, -N(R ³ )(R ⁴ ), etc., particularly preferably methyl, ethyl, 1-pyrrolyl, 1-pyrazolyl, methoxy, ethoxy, dimethylamino, diethylamine Base.

Specific examples of the particularly preferable thiocarbonylthio compound of the present invention include compounds represented by the following formulas (4) to (28).

Next, a polymerization method for producing the (A) block copolymer will be described. (A) The block copolymer contains a radical carboxylic acid-containing unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride or a protective compound of the carboxylic acid and the compound (a2) containing (a1) other than (a1) The polymerizable mixture of the radically polymerizable compound is subjected to living radical polymerization in the presence of a polymerization initiator or a thiocarbonylthio compound in a solvent, and further compound (a2) or a polymerization containing the compound (a1) and the compound (a2) The mixture is then continuously polymerized. If necessary, a polymerizable mixture may be added, and then a block segment may be added.

When the polymerization is in the form of living radical polymerization, when the polymerizable unsaturated compound is a compound having a functional group which may deactivate the active radical such as a carboxyl group, if necessary, the functional group in the unsaturated compound is, for example, esterified. After the protection and polymerization, the copolymer (A) having a narrower molecular weight distribution can be obtained by deprotection.

The radical polymerization initiator can be appropriately selected depending on the type of the polymerizable unsaturated compound to be used, and a general radical polymerization initiator can be used. For example 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy- Azo compound such as 2,4-dimethylvaleronitrile; benzoquinone peroxide, 1,1'-bis(t-butylperoxy)cyclohexane, tert-butylperoxytrimethylacetic acid An organic peroxide such as an ester; a redox initiator composed of such a peroxide and a reducing agent.

Among these radical polymerization initiators, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis (2, 2) are particularly preferable from the viewpoint that secondary substances such as oxygen are less likely to be generated. An azo compound such as 4-dimethylvaleronitrile. These radical polymerization initiators can be used alone or in combination of two or more.

In the above polymerization, one or more other molecular weight controlling agents such as α-methylstyrene dimer and thiricododecyl mercaptan are used in combination with the disulfide compound (1).

The solvent for the above polymerization is not particularly limited. For example, propylene glycol monomethyl ether, propylene glycol monoethyl ether and other propylene glycol monoalkyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate (poly) alkanediol monoalkyl ether acetate; (poly)alkylene glycol diethers such as glyme, diethylene glycol methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether, dipropylene glycol diethyl ether, etc.; other ethers such as tetrahydrofuran Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone; diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methyl- Keto alcohols such as hexan-2-one; alkyl lactate such as methyl lactate or ethyl lactate; ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, 2-hydroxy-3-methylbutyl Methyl ester, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate , 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate , isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , other esters such as n-propyl pyruvate, methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone, N, N - decylamine such as dimethylformamide or N,N-dimethylacetamide.

Among these solvents, active radicals do not lose activity when polymerized by living radicals, and propylene glycol monomethyl ether is preferred from the viewpoints of solubility, coating properties, and the like of each component when the radiation-sensitive linear resin composition is used. Ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl Ether acetate, diglyme, diethylene glycol methyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 3-methoxypropionate, 3 - methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, Isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

These solvents may be used singly or in combination of two or more.

In the above polymerization, the amount of the radical polymerization initiator used is 0.1 to 50 parts by weight, preferably 0.1 to 20 parts by weight, per 100 parts by weight of the wholly unsaturated compound.

The thiocarbonyl sulfide compound is used in an amount of 0.1 to 50 parts by weight, preferably 0.2 to 16 parts by weight, particularly preferably 0.4 to 8 parts by weight, per 100 parts by weight of the wholly unsaturated compound. When the amount of the thiocarbonylthio compound used is less than 0.1 part by weight, the control effect of the molecular weight and the molecular weight distribution tends to be lowered, and when it exceeds 50 parts by weight, the low molecular weight component may be preferentially produced.

When the total molecular weight controlling agent is 100 parts by weight, the other molecular weight controlling agent is used in an amount of 80 parts by weight or less, preferably 40 parts by weight or less. When the amount of the other molecular weight controlling agent used exceeds 80 parts by weight, the effects of the present invention may be affected.

The solvent is used in an amount of 50 to 1000 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by weight of the wholly unsaturated compound.

The polymerization temperature is 0 to 150 ° C, preferably 50 to 120 ° C, and the polymerization time is 10 minutes to 20 hours, preferably 30 minutes to 6 hours.

Among the above polymerizable unsaturated compounds, the compound (a1) is a radically polymerizable unsaturated carboxylic acid and/or an unsaturated carboxylic anhydride or a protective compound of these carboxylic acids.

The above-mentioned radically polymerizable unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, for example, mono[(methyl)acryloxyalkylene group of a monocarboxylic acid, a dicarboxylic acid, a dicarboxylic anhydride, and a polycarboxylic acid] An ester, a mono(meth)acrylate having a polymer of a carboxyl group and a hydroxyl group at both ends, a polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

Specific examples of these are monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like; and dicarboxylic acid anhydrides such as An acid anhydride or the like of the above-mentioned compound represented by the above dicarboxylic acid; a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid such as succinic acid mono [2-(methyl) propylene oxyl a mono-(meth) acrylate having a polymer of a carboxyl group and a hydroxyl group at both ends, for example, an ω-carboxy group Lactone mono(meth)acrylate or the like; a polycyclic compound having a carboxyl group and an anhydride thereof are, for example, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]g 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 - ankenic anhydride and the like.

Among them, acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and easy availability. These can be used alone or in combination.

The protecting group for protecting the carboxyl group of the compound (a1) is not particularly limited, and a protective group of a known carboxyl group can be used. Trialkylcarbenyl, 1-alkoxyalkyl, cyclic 1-alkoxyalkyl, and the like. Specific examples thereof include trimethylmethane alkyl, dimethylbutylcarbyl, 1-ethoxyethyl, 1-propoxyethyl, tetrahydrofuranyl, tetrahydropyranyl, triphenylmethyl and the like.

The compound (a2) is, for example, methacrylate, ethacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, second butyl acrylate, third butyl Alkyl acrylate such as acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate , alkyl methacrylate such as second butyl methacrylate, tert-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8- Acrylate (hereinafter referred to as "tricyclo[5.2.1.0 ^2.6 ]decane-8-yl" as "dicyclopentyl"), 2-dicyclopentyloxyethyl acrylate, isobornyl acrylate, tetrahydrofuran An alicyclic ester of acrylic acid such as acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentyl methacrylate, 2-dicyclopentyloxyethyl methacrylate Ester, isobornyl methacrylate, tetrahydrofuranylmethyl An alicyclic ester of methacrylic acid such as an enoate; an aryl acrylate such as a phenyl acrylate or a benzyl acrylate; or an aryl methacrylate such as a phenyl methacrylate or a benzyl methacrylate; a dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; a hydroxyalkyl acrylate such as 2-hydroxyethyl acrylate or 2-hydroxypropyl acrylate; a hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, An aromatic vinyl compound such as p-methoxystyrene or acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, Isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide N-Amber succinimide-3-maleimide benzoate maleic imine N-succinimide-4-maleimine butyrate, N-succinimide Base-6-maleimide Ester, N- succinimidyl-3- alkylene maleic acyl (PEI) propionate, N- (of 9- acridinyl) maleic acyl imine.

Among these compounds (a2), from the viewpoint of copolymerization reactivity, 2-methylcyclohexyl acrylate, tert-butyl methacrylate, dicyclopentyl methacrylate, styrene, and para Oxystyrene, 1,3-butadiene, and the like.

The above compound (a2) may be used alone or in combination of two or more.

In the (A) block copolymer used in the present invention, the first block segment is preferably a block segment composed of, for example, a polymerization unit derived from both of the compounds (a1) and (a2).

In this case, the content of the polymerization unit derived from the compound (a1) in the block copolymer is preferably from 5 to 50% by weight, based on the total of the polymerization units derived from the compounds (a1) and (a2), more preferably 10~40% by weight. When the content of the polymerization unit derived from the compound (a1) is less than 5% by weight, the compressive strength, heat resistance or chemical resistance of the obtained spacer tends to be lowered, and when it exceeds 50% by weight, the linear composition of the sensitive radiation is formed. The preservation stability of the substance may be reduced.

The content of the polymerization unit derived from the compound (a2) in the block copolymer is preferably from 50 to 95% by weight, based on the total of the polymerization units derived from the compounds (a1), (a2) and (a3), more preferably It is 60 to 90% by weight. When the content ratio of the polymerization unit derived from the compound (a2) is less than 50% by weight, the storage stability of the radiation sensitive linear resin composition may be lowered, and when it exceeds 95% by weight, the development property may be lowered.

The second block segment of the (A) block copolymer may be a segment composed of a polymerization unit derived from the compound (a1), a segment composed of a polymerization unit derived from the compound (a2), or a compound (a1). And two of (a2) The block segment formed by the polymerization unit. However, the polymerization unit constituting the first block segment and the second block segment is a different combination.

In the present invention, the second block segment is preferably a block segment composed only of the compound (a1) or a block segment composed only of the compound (a2). In this case, when the (A) block copolymer has a second block segment composed only of the compound (a2) which is not involved in crosslinking, the hardness is lower, and when the spacer is formed, the compatibility is excellent, and the surface state is excellent. Uniform spacers.

The (A) block copolymer may have a hardness and shape of the third block segment control spacer as necessary. The third block segment is, for example, the same as the second block segment described above, but the polymerization unit constituting the second block segment and the third block segment is different. When the third block segment is subjected to tertiary polymerization after the secondary polymerization of the second block segment, it is preferred to add to the second block segment.

The (A) block copolymer of the present invention preferably has, for example, a first block segment composed of at least a polymerization unit derived from both of the compounds (a1) and (a2) and a compound (a1) alone. a block copolymer of a second block segment, a first block segment composed of at least a polymerization unit derived from both of the compounds (a1) and (a2), and a second block composed only of the compound (a2) Block copolymers of block segments and the like.

(A) The proportion of the first block segment in the block copolymer (weight of the first block segment / weight of the (A) block copolymer) × 100) is preferably from 30 to 95% by weight, particularly preferably It is 50-90% by weight. When it is less than 30% by weight, Mw/Mn may exceed 2.5, and electrical properties may be lowered. When the amount is more than 95% by weight, the amount of residual monomers increases, and the volatile component may increase during baking, which is not preferable.

The (A) block copolymer used in the present invention is a polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") and a polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn" measured by gel permeation chromatography. The ratio (Mw/Mn) of ") is 2.5 or less, preferably 2.0 or less. When Mw/Mn exceeds 2.5, the pattern of the spacer formed is not good. Further, Mw is preferably 2 × 10 ³ to 1 × 10 ^{5 , more} preferably 5 × 10 ³ to 5 × 10 ⁴ . When the Mw is less than 2 × 10 ³ , the development safety margin may be insufficient, and the resulting spacer may have a poor pattern shape and heat resistance. When the Mw exceeds 1 × 10 ⁵ , the sensitivity may be lowered or the pattern shape may be poor. Mn is preferably from 1.2 × 10 ³ to 1 × 10 ⁵ , more preferably from 2.9 × 10 ³ to 5 × 10 ⁴ . The radiation sensitive linear resin composition containing the above copolymer (A) does not cause development residue upon development, and it is easy to form a predetermined pattern shape.

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

The Mw having the above-mentioned Mw, more preferably the above-mentioned specific Mw/Mn, by using the (A) block copolymer copolymer having a residual monomer content, the sublimate at the time of exposure or firing of the photosensitive composition is more Less, it can reduce the equipment used in the manufacture of contaminated LCD panels, and can effectively reduce the burn-in of the LCD panel.

The above (A) block copolymer may be used singly or in combination of two or more.

In the present invention, one or more other alkali-soluble resins may be used in combination with the (A) block copolymer.

(B) Polymerizable unsaturated compound (B) The polymerizable unsaturated compound of the radiation sensitive linear resin composition of the present invention is preferably a monofunctional or bifunctional acrylate or methacrylate (hereinafter referred to as "( Methyl) acrylate").

The aforementioned monofunctional (meth) acrylates are, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl acrylate, diethylene glycol monoethyl methacrylate, isobornyl acrylic acid. Ester, isobornyl methacrylate, 3-methoxybutyl acrylate, 3-methoxybutyl methacrylate (2-propenyloxyethyl-2-hydroxypropyl phthalate, 2-methylpropenyloxyethyl-2-hydroxypropyl phthalate, etc. Commercially available products such as trade names Aronix M-101, M-111, M-114, M-5300 (East Asian Synthetic )); KAYARAD TC-110S, TC-120S (manufactured by Nippon Kayaku Co., Ltd.); Viscoat 158, 2311 (Osaka Organic Chemical Industry Co., Ltd.).

The bifunctional (meth) acrylates are, 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 diacrylate, polypropylene glycol Methacrylate, diphenoxyethanol oxime diacrylate, diphenoxyethanol oxime dimethacrylate, and the like.

Commercial products of a bifunctional (meth) acrylate include, for example, Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, HX-220, and R-604. UX-2201, UX-2301, UX-3204, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, MU-2100, MU-4001 (the above are made by Nippon Chemical Co., Ltd.) , Viscoat 260, 312, and 335HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.).

The trifunctional or higher (meth) acrylate is, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol IV. Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tris(2-propenyloxyethyl) phosphate, tris(2) -Methyl propylene oxiranyl ethyl phosphate, or a hexa- or higher-functional (meth) acrylate having a linear alkyl group and an alicyclic structure, and having two or more isocyanate groups and having intramolecular A urethane acrylate-based compound obtained by reacting a compound having one or more hydroxyl groups and having three, four or five acryloxy groups and/or methacryloxy groups.

A commercially available product of a trifunctional or higher (meth) acrylate, such as Aronix M-309, homo-400, homo-402, homo-405, homo-450, same--1310, homo-1600, and the same. -1960, the same -7001, the same -8003, the same -8601, the same -8001, the same -8530, the same -86060, the same -9050, Aronix TO-1450 (manufactured by the East Asia Synthetic Company), KAYARAD TMPTA, the same DPHA, the same DPCA-20, same as DPCA-30, same DPCA-60, same DPCA-120, same as MAX-3150 (manufactured by Nippon Kayaku Co., Ltd.), Viscoat 295, same 300, same 360, same GPT, same 3PA, same 400 ( The above-mentioned urethane acrylate-based compound, for example, New Frontier R-1150 (manufactured by Daiichi Kogyo Co., Ltd.) and KAYARAD DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) Wait.

In the present invention, the polymerizable unsaturated compound may be used singly or in combination of two or more kinds.

The proportion of the (B) polymerizable unsaturated compound in the sensitive radiation linear resin composition of the present invention is 40 to 250 parts by weight, preferably 60 to 180 parts by weight, based on 100 parts by weight of the (A) block copolymer. Share.

(C) Sensitizing Radiation Linear Polymerization Initiator (C) The radiation-sensitive linear polymerization initiator is a component that induces radiation, and produces an active species which can initiate polymerization of (B) a polymerizable unsaturated compound.

The (C) radiation-sensitive linear polymerization initiator is, for example, an O-mercapto fluorene-based compound, an acetophenone-based compound, a biimidazole-based compound, a benzoin-based compound, a benzophenone-based compound, or an α-diketone. A compound, a polynuclear oxime compound, a xanthone compound, a phosphine compound, a triazine compound, or the like.

The O-mercapto fluorene-based compound is preferably a 9.H.-carbazole-based O-fluorenyl hydrazine type polymerization initiator. For example, 1-[9-ethyl-6-benzoquinone-9.H.-oxazol-3-yl]-decane-1,2-decane-2-indole-O-benzoate, 1 -[9-ethyl-6-benzoquinone-9.H.-oxazol-3-yl]-decane-1,2-decane-2-indole-O-acetate, 1-[9- Ethyl-6-benzoquinone-9.H.-oxazol-3-yl]-pentane-1,2-pentane-2-indole-O-acetate, 1-[9-ethyl-6 -phenylhydrazine-9.H.-oxazol-3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylphenylhydrazine)- 9.H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylphenylhydrazine)-9.H .-oxazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(1,3,5-trimethylphenylhydrazine)-9. H.-carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-butyl-6-(2-ethylphenylhydrazine)-9.H.- Oxazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydropyranyl methoxybenzene)醯)-9.H.-咔3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoquinone)-9. H.-carbazol-3-yl]-ethane-1-one oxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-(2,2) -Dimethyl-1,3-dioxolyl)methoxybenzoquinone-9.H.-carbazol-3-yl]-, 1-(ethylhydrazine) and the like.

Among these O-mercapto lanthanide compounds, 1-[9-ethyl-6-(2-methylphenylhydrazine)-9.H.-oxazol-3-yl]-ethane-1 is particularly preferred. -ketooxime-O-acetate, ethyl ketone, 1-[9-ethyl-6-(2-methyl-4-(2,2-dimethyl-1,3-dioxolane) (Methoxybenzoquinone)-9.H.-carbazol-3-yl]-, 1-(ethylhydrazine).

The above O-indenyl ruthenium compound may be used singly or in combination of two or more. Further, in the present invention, a spacer having sufficient sensitivity and adhesion can be obtained even when the O-indenyl ruthenium compound is exposed to an amount of 1,500 J/m ² or less.

Examples of the acetaminophen compound include an α-hydroxyketone compound and an α-aminoketone compound.

The aforementioned α-hydroxyketone compound is, for example, 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-ketone, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like. The aforementioned α-amino ketone compound is, for example, 2-methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one or 2-benzyl-2-dimethylamino group. 1-(4-morpholinylphenyl)-butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylbenzene Base)-butane-1-one and the like. Other compounds other than these are, for example, 2,2-dimethoxyacetamidine, 2,2-diethoxyethyl benzene, 2,2-dimethoxy-2-phenyl ethene benzene, and the like.

Among the above acetylbenzene compounds, particularly preferred are 2-methyl-1-(4-methylphenylthio)-2-morpholinylpropan-1-one and 2-(4-methylbenzyl)- 2-(Dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one.

In the present invention, the sensitivity, the shape of the spacer, and the compressive strength can be further improved by using the acetophenone compound in combination.

Further, the above biimidazole-based compound is, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2' -biimidazole, 2,2'-bis(2-bromophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichloro Phenyl)-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, and the like.

Among these bisimidazole compounds, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2, is preferred. 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, etc., particularly preferably 2,2'-bis(2,4-dichlorophenyl) -4,4',5,5'-tetraphenyl-1,2'-biimidazole.

In the present invention, the bisimidazole-based compound can be used in combination to further improve the sensitivity, the resolution, and the adhesion.

When a bisimidazole compound is used in combination, an aliphatic or aromatic compound having a dialkylamine group (hereinafter referred to as "amine sensitizer") may be added in order to increase the sensitivity.

Examples of the amine sensitizer include N-methyldiethanolamine, 4,4'-bis(dimethylamino)benzophenone, and 4,4'-bis(diethylamino)benzophenone. Ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like.

Among these amine sensitizers, 4,4'-bis(diethylamino)benzophenone is particularly preferred.

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

Further, when a bisimidazole-based compound and an amine-based sensitizer are used in combination, a thiol-based compound which supplies a hydrogen compound can be added. The biimidazole-based compound is cleavable by the above-mentioned amine-based sensitizer, and an imidazole radical is generated. However, in this state, a high polymerization initiation energy cannot be obtained, and most of the obtained spacer has a poor shape of an inverted tapered shape. However, when a thiol compound is added to a system containing a bisimidazole compound and an amine sensitizer, the thiol compound supplies a hydrogen radical to the imidazole radical, and the imidazole radical is converted into a neutral imidazole. A component having a sulfur radical having a higher polymerization initiating energy is produced, whereby the shape of the spacer can be formed into a preferred tapered shape.

The thiol-based compound is, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxy An aromatic compound such as benzoimidazole; an aliphatic monothiol such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate or octyl 3-mercaptopropionate; 3,6-di A difunctional or higher aliphatic thiol such as oxa-1,8-octanedithiol, pentaerythritol tetrakis(mercaptoacetate) or pentaerythritol tetrakis(3-mercaptopropionate).

Among these thiol-based compounds, 2-mercaptobenzothiazole is particularly preferred.

When the bisimidazole compound and the amine sensitizer are used in combination, the amount of the amine sensitizer added is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20% by weight based on 100 parts by weight of the biimidazole compound. Share. When the amount of the amine-based sensitizer added is less than 0.1 part by weight, the effect of improving the sensitivity, the resolution, and the adhesion tends to be lowered, and when it exceeds 50 parts by weight, the shape of the obtained spacer may be impaired.

When the bisimidazole compound and the thiol compound are used in combination, the amount of the thiol compound added is preferably from 0.1 to 50 parts by weight, more preferably from 1 to 20 parts by weight, per 100 parts by weight of the biimidazole compound. When the amount of the thiol-based compound added is less than 0.1 part by weight, the effect of improving the shape of the spacer is lowered, or the film tends to be reduced, and when it exceeds 50 parts by weight, the shape of the obtained spacer may be impaired. .

The radiation radiation cationic polymerization initiator is a phosphonium salt, for example, phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroarsenate, phenyldiazonium trichloride Fluoromethanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium p-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyl Nitrogen hexafluorophosphate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxyphenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyldiazonium Trifluoroacetate, 4-methoxyphenyldiazonium p-toluenesulfonate, 4-tert-butylphenyldiazonium tetrafluoroborate, 4-tert-butylphenyldiazonium hexafluorophosphate Phosphate, 4-t-butylphenyldiazonium hexafluoroarsenate, 4-t-butylphenyldiazonium trifluoromethanesulfonate, 4-tert-butylphenyldiazonium a diazonium salt such as fluoroacetate or 4-tert-butylphenyldiazonium p-toluenesulfonate; triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Fluor arsenate, triphenylsulfonium trifluoromethanesulfonate, three Base trifluoroacetate, triphenylsulfonium p-toluenesulfonate, 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphate, 4 -Methoxyphenyldiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium p-toluenesulfonate, 4-phenylthiophenyldiphenylphosphonium tetrafluoroborate, 4-phenylthiophenyldiphenylphosphonium hexafluorophosphate, 4 -phenylthiophenyldiphenylphosphonium hexafluoroarsenate, 4-phenylthiophenyldiphenylphosphonium trifluoromethanesulfonate, 4-phenylthiophenyldiphenylphosphonium trifluoroacetate, a sulfonium salt of 4-phenylthiophenyldiphenylphosphonium p-toluenesulfonate; bis(p-phenyl)iodonium, tetrakis(pentafluorophenyl)borate, (p-phenyl) (p-isopropyl) An iodonium salt such as phenyl)iodonium or tetrakis(pentafluorophenyl)borate.

The aromatic cycloolefin metal compound is, for example, (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphoric acid (1-) or the like.

Commercial products of these radiation radiation cationic polymerization initiators, for example, Adekaultra set PP-33 (made by Asahi Denki Kogyo Co., Ltd.), OPTOMER SP-150, and -170 (Asahi Chemical Industry Co., Ltd.) (manufactured by Ciba. Specialty. Chemicals Co., Ltd.) and the like.

The above-mentioned radiation radiation cationic polymerization initiator may be used singly or in combination of two or more.

In the sensitive radiation linear resin composition, the ratio of the (C) radiation-sensitive linear polymerization initiator is preferably from 1 to 50 parts by weight, more preferably from 3 to 40 parts by weight, based on 100 parts by weight of the (A) block copolymer. Share.

(D) epoxy group-containing compound (D) The epoxy group-containing compound of the present invention, for example, (d1) unsaturated carboxylic acid and/or unsaturated carboxylic anhydride, (d2) epoxy group-containing unsaturated compound (d3) a copolymer (D-1) of another olefin-based unsaturated compound or a copolymer (D-2) of (d2) or (d3). The copolymer (D-1) can be obtained by radical polymerization of the compound (d1), the compound (d2) and the compound (d3) in the presence of a polymerization initiator in a solvent, and the copolymer (D-2) can be obtained. The compound (d2) and the compound (d3) are obtained by radical polymerization in the presence of a polymerization initiator in a solvent.

The above (d1) unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride may, for example, be a monocarboxylic acid, a dicarboxylic acid, a dicarboxylic anhydride or a monocarboxylic acid mono[(meth)acryloxyalkylalkyl]ester, and both ends. A mono(meth)acrylate having a polymer of a carboxyl group and a hydroxyl group, a polycyclic compound having a carboxyl group, an anhydride thereof, and the like.

In these specific examples, the monocarboxylic acid is, for example, acrylic acid, methacrylic acid, crotonic acid or the like; the dicarboxylic acid is, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid or the like; and the dicarboxylic acid anhydride is, for example. An acid anhydride or the like of the above-exemplified compound exemplified above as the dicarboxylic acid; a mono[(meth)acryloxyalkylalkyl] ester of a polyvalent carboxylic acid such as succinic acid mono [2-(methyl) propylene methoxyethyl An ester, a mono [2-(methyl)propenyloxyethyl] phthalate or the like; a mono(meth) acrylate having a polymer of a carboxyl group and a hydroxyl group at both ends, for example, an ω-carboxy group Lactone mono(meth)acrylate or the like; a polycyclic compound having a carboxyl group and an anhydride thereof are, for example, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]g 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 - ankenic anhydride and the like.

Among them, acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in an aqueous alkali solution, and easy availability. These can be used alone or in combination.

The epoxy group-containing unsaturated compound of the compound (d2), for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl methacrylate, glycidyl α-n-propyl acrylate, α-positive Glycidyl butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate , 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinyl glycidyl ether , m-vinyl glycidyl ether, p-vinyl glycidyl ether, and the like. Among them, from the viewpoint of copolymerization reactivity and improvement of the strength of the obtained spacer, it is preferred to use glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxy ring of methacrylic acid. Hexyl ester, 3,4-epoxycyclohexylmethyl methacrylate, o-vinyl glycidyl ether, m-vinyl glycidyl ether, p-vinyl glycidyl ether, and the like.

The above (d3) other olefin-based unsaturated compound may, for example, be methacrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate or the second Alkyl acrylate such as acrylate, third butyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate Ethyl methacrylate such as ester, isobutyl methacrylate, second butyl methacrylate, tert-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclic [5.2.1.0 ^2.6 ] decane-8-yl acrylate (hereinafter referred to as "tricyclo[5.2.1.0 ^2.6 ]decane-8-yl" as "dicyclopentyl"), 2-dicyclopentyloxyethyl acrylate, An alicyclic ester of acrylic acid such as isobornyl acrylate or tetrahydrofuran acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentyl methacrylate, 2-dicyclopentane Oxyethyl methacrylate, isobornyl methyl propyl An alicyclic ester of methacrylic acid such as an acid ester or tetrahydrofuranyl methacrylate; an aryl acrylate such as a phenyl acrylate or a benzyl acrylate; a phenyl methacrylate or a benzyl methacrylate; Aryl methacrylate; dicarboxylic acid diester such as diethyl maleate, diethyl fumarate or diethyl itaconate; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, etc. a hydroxyalkyl acrylate; a hydroxyalkyl methacrylate such as 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate; styrene, α-methyl styrene, m-methyl styrene, An aromatic vinyl compound such as p-methylstyrene or p-methoxystyrene or acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1, 3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzyl Kamalyimide, N-succinimide-3-maleimide benzoate maleate imino N-amber quinone imine-4-醯iminobutyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9 - acridinyl) maleate and the like.

Among these compounds (d3), from the viewpoint of copolymerization reactivity, 2-methylcyclohexyl acrylate, tert-butyl methacrylate, dicyclopentyl methacrylate, styrene, and para Oxystyrene, 1,3-butadiene, and the like.

The above compound (d3) can be used singly or in combination of two or more.

The radical polymerization initiator may be the same as those described in the polymerization method for producing the (A) block copolymer.

The solvent used for the radical polymerization described above can also be used in the same manner as described in the polymerization method for producing the (A) block copolymer.

In the (D) epoxy group-containing compound of the present invention, a compound (D-3) having two or more epoxy groups in one molecule other than the above (D-1) and (D-2) can be used. The addition of this compound sometimes improves the heat resistance and chemical resistance of the spacer.

The above compound (D-3) having two or more epoxy groups, for example, ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether , propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin Diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether, and the like.

Commercial products having a compound having two or more epoxy groups, for example, Epolight 40E, 100E, 200E, 70P, 200P, 400P, 1500NP, 80MF, 100MF, 1600, 3002, 4000 (above is Gongrongshe Chemical Co., Ltd.) System), Epikote 152, Epikote 154 (made by Nippon Epoxy Co., Ltd.), etc. These can be used individually or in mixture of 2 or more types.

The amount of each component of the sensitive radiation linear resin composition of the present invention is (B) the polymerizable unsaturated compound is used in an amount of 10 to 150 parts by weight, more preferably 20 to 120, per 100 parts by weight of the (A) block copolymer. The component (C) radiation sensitive linear polymerization initiator is used in an amount of 1 to 40 parts by weight, more preferably 3 to 35 parts by weight, per 100 parts by weight of the (A) block copolymer.

The (D) epoxy group-containing compound is preferably 0 to 150 parts by weight.

(B) When the amount of the polymerizable unsaturated compound is less than 10 parts by weight, the coating film having a uniform film thickness tends not to be formed, and when it exceeds 150 parts by weight, the adhesion to the substrate tends to be lowered. Further, when the amount of the (C) radiation-sensitive linear polymerization initiator used is less than 1 part by weight, the heat resistance, the surface hardness, and the chemical resistance tend to be lowered, and when it exceeds 40 parts by weight, the transparency tends to be lowered. Further, when (D) the epoxy group-containing compound exceeds 150 parts by weight, the development property may be lowered, which is not preferable.

Any additive

In the sensitive radiation linear resin composition of the present invention, any additives other than the above may be added as necessary within the range which does not impair the effects of the present invention, for example, an auxiliary agent, a surfactant, a storage stabilizer, a heat resistance enhancer, and the like.

The above-mentioned adhesion aid is a component used to improve the adhesion to the formed spacer and the substrate.

Such a secondary auxiliary agent is, for example, a functional decane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group or an epoxy group. For example, there are trimethoxymethyl methacrylate, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, ethylene trimethoxy decane, γ-isocyanate propyl triethoxy. Decane, γ-glycidylpropyltrimethoxydecane, β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, and the like.

These adjunct agents may be used singly or in combination of two or more.

The amount of the auxiliary agent is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight of the (A) block copolymer. When the amount of the auxiliary agent exceeds 20 parts by weight, the development of the image tends to be likely to occur.

The above surfactant is a component used to improve coatability.

Such a surfactant is, for example, a fluorine-based surfactant or a polyoxyn-based surfactant.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and/or a fluorine alkyl group at at least any of a terminal, a main chain and a side chain. For example, there are 1,1,2,2-tetrafluoro-n-octyl (1,1,2,2-tetrafluoro-n-propyl)ether, 1,1,2,2-tetrafluoro-n-octyl (positive Ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octaethylene glycol bis(1,1,2,2-tetrafluoro-n-butyl Ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoro-n-pentyl)ether, octapropylene glycol bis(1,1,2,2-tetrafluoro-n-butyl)ether, Sodium perfluoro-n-dodecylsulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10 - decafluoro-n-dodecane and sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerol tetrakis(fluoroalkylpolyoxyethylene ether), fluoroalkyl iodide Ammonium, fluoroalkylbetaine, other fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethylene, perfluoroalkyl alkoxylate, fluoroalkyl carboxylate, and the like.

Commercial products of a fluorine-based surfactant include, for example, BM-1000, BM-1100 (above, BM Chemie), MEGAFAC F142D, F172, F173, F183, F178, F191, F471, and the same F476 (above is Dainippon Ink Chemical Industry Co., Ltd.), FULORAD FC-170C, FC-171, FC-430, FC-431 (above Sumitomo 3M (share) system), SURFLON S-112, and S- 113, with S-131, with S-141, with S-145, with S-382, Surflon SC-101, with -102, with -103, with -104, with -105, with -106 (above Asahi Glass ( Stock system), F-TOP EF301, same 303, same 352 (above, new Akita Chemicals Co., Ltd.), FTERGENT FT-100, same-110, same-140A, same-150, same-250, same- 251, the same -300, the same -310, the same -400S, FTERGENT FTX-218, the same -251 (above, (stock) NEOS company) and so on. The polyfluorene-based surfactants include, for example, Toray Polyoxygen DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, and SZ-6032. With SF-8428, the same DC-57, the same DC-190 (above is Toray.Dowcorning.Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF4452 (The above is a commercial product of the trade name of GE Toshiba Poly Oxide Co., Ltd.).

The surfactant other than the above is, for example, polyoxyethylene alkyl ether such as polyoxyethylene lauryl ether, polyethylene oxide stearyl ether or polyethylene oxide oleyl ether; polyoxyethylene-n-octylphenyl ether, polyethylene oxide- a nonionic surfactant such as a polyoxyethylene aryl ether such as n-nonylphenyl ether, a polyoxyethylene dilaurate such as polyoxyethylene dilaurate or polyoxyethylene distearate; and an organic polyfluorene; An oxyalkylene polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), a (meth)acrylic copolymer POLYFLOW No. 57, and a No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

These surfactants can be used singly or in combination of two or more.

When the amount of the surfactant is 100 parts by weight based on the (A) block copolymer, it is preferably used in an amount of 1.0 part by weight or less, more preferably 0.5 part by weight or less. At this time, the amount of the surfactant used exceeds 1.0 part by weight, and film unevenness tends to occur.

The above-mentioned preservation stabilizers are, for example, sulfur, hydrazines, hydroquinones, polyoxygen compounds, amines, nitronitroso compounds, and the like, and more specifically, for example, 4-methoxyphenol, N-nitroso-N -Phenylhydroxylamine aluminum or the like.

These preservation stabilizers may be used singly or in combination of two or more.

The amount of the stabilizer to be added is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less, based on 100 parts by weight of the (A) block copolymer. In this case, the amount of the stabilizer is more than 3.0 parts by weight. The sensitivity may be lowered and the shape of the pattern may be degraded.

The heat resistance improving agent is, for example, an N-(alkoxymethyl)glycolide compound or an N-(alkoxymethyl)melamine compound.

The above N-(alkoxymethyl) glycoluril compound is, for example, N,N,N',N'-tetrakis(methoxymethyl)glycoluril, N,N,N',N'-tetra(ethoxylate) Methyl urea), N, N, N', N'-tetrakis (n-propoxymethyl) glycoluril, N, N, N', N'-tetrakis(isopropoxymethyl) glycoluril , N, N, N', N'-tetrakis(n-butoxymethyl) glycoluril, N, N, N', N'-tetrakis(t-butoxymethyl) glycoluril, and the like.

Among these N-(alkoxymethyl)glycoluric compounds, N,N,N',N'-tetrakis(methoxymethyl)glycolil is preferred.

The above N-(alkoxymethyl)melamine compound, for example, 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(isopropoxymethyl)melamine, N,N,N',N'N",N"-hexa(n-butoxymethyl)melamine, N,N,N', N'N", N"-hexa(t-butoxymethyl) melamine, and the like.

Among these N-(alkoxymethyl)melamine compounds, preferred are N,N,N',N'N",N"-hexa(methoxymethyl)melamine, and commercially available products such as Niclac N - 2702, the same as MW-30M (above is Sanwa Chemical (share) system).

Modulation of sensitive radiation linear resin composition

The sensitive radiation linear resin composition of the present invention is prepared by uniformly mixing the above (A) block copolymer, the component (B), the component (C) and the component (D), and the other components added arbitrarily. The sensitive radiation linear resin composition of the present invention is preferably dissolved in a suitable solvent and used in a solution state. For example, the (A) block copolymer, the component (B), the component (C), and the component (D) and the other components added arbitrarily are mixed in a predetermined ratio to prepare a radiation sensitive linear resin composition in a solution state.

The solvent for modulating the linear radiation-sensitive resin composition of the present invention can be uniformly dissolved by using the components of the (A) block copolymer, the component (B), the component (C) and the component (D), and other components added arbitrarily. And a solvent that does not react with each component.

Such a solvent is used, for example, in the manufacture of the above (A) block copolymer. The solvent exemplified by the solvent is the same.

In such a solvent, from the viewpoints of solubility of each component, reactivity with each component, easiness of formation of a coating film, etc., it is preferred to use an alcohol, a glycol ether, an ethylene glycol alkyl ether acetate, or an ester. And diethylene glycol. Among them, for example, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, digan can be used. Alcohol ethyl methyl ether, diglyme, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl methoxypropionate, ethyl ethoxy propionate.

In order to increase the uniformity in the surface of the film thickness, the above solvent and a high boiling point solvent may be used in combination. High boiling solvents which can be used, for example, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethyl Ethyl amide, N-methylpyrrolidone, dimethyl hydrazine, benzyl ether, dihexyl ether, acetone acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, acetic acid Benzyl ester, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like. Among them, preferred are N-methylpyrrolidone, γ-butyrolactone, and N,N-dimethylacetamide.

When it is used as a high boiling point solvent for the solvent of the sensitive radiation linear resin composition of the present invention, it can be used in an amount of 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less based on the total amount of the solvent. . When the amount of the high boiling point solvent used exceeds the amount used, there is a case where the film thickness uniformity, the sensitivity, and the residual film ratio of the coating film are lowered.

When the sensitive radiation linear resin composition of the present invention is prepared in a solution state, components other than the solvent occupied by the solution, that is, (A) block copolymer, (B) component, and (C) component, and any other components added thereto The ratio of the total amount can be arbitrarily set depending on the purpose of use, the desired film thickness value, and the like, and can be, for example, 5 to 50% by weight, preferably 10 to 40% by weight, and more preferably 15 to 35% by weight.

The composition solution prepared as described above can be used after being filtered using a micropore filter having a pore diameter of about 0.5 μm.

Method for forming spacers

Next, a method of forming the spacer of the present invention using the radiation sensitive linear resin composition of the present invention will be described.

The method for forming the spacer of the present invention is carried out in the following order.

(1) A step of forming a film of the above-mentioned radiation-sensitive linear resin composition on a substrate.

(2) a step of exposing at least a portion of the film to radiation.

(3) A step of developing the film after exposure.

(4) A step of heating the film after development.

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

(1) a step of forming a film of the radiation sensitive linear resin composition of the present invention on a substrate; forming a transparent conductive film on one side of the transparent substrate, and coating the composition of the sensitive radiation linear resin composition of the present invention on the transparent conductive film After the solution, the coated surface is heated (prebaked) to form a film.

A transparent substrate for forming a spacer, for example, a glass substrate, a resin substrate, or the like, more specifically, for example, a glass substrate such as soda lime glass or alkali-free glass; polyethylene terephthalate or polybutylene terephthalate; A resin substrate composed of a plastic such as polyether oxime, polycarbonate, or polyimide.

A transparent conductive film provided on one surface of a transparent substrate, for example, a NESA film composed of tin oxide (SnO ₂ ) (registered trademark of PPG Corporation of the United States) and indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) ITO film, etc.

The coating method of the composition solution is not particularly limited, and examples thereof include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, and an inkjet coating method. The method is particularly preferably a spin coating method or a slit die coating method.

The prebaking conditions vary depending on the type of the components and the blending ratio, and are preferably 70 to 120 ° C for 1 to 15 minutes.

The film thickness after prebaking of the film is not particularly limited, but is preferably 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

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

Next, at least a portion of the formed film is exposed to radiation, and when a portion of the film is exposed, for example, exposure can be performed through a photomask having a predetermined pattern.

For the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, or the like can be used. It is preferably a radiation having a wavelength in the range of 190 to 450 nm, particularly a radiation containing ultraviolet rays of 365 nm.

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

(3) Developing Step Next, by exposing the film after exposure, unnecessary portions are removed to form a predetermined pattern.

For the developing liquid for imaging, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate or ammonia; an aliphatic primary amine such as ethylamine or n-propylamine; diethylamine can be used. An aliphatic secondary amine such as di-n-propylamine; an aliphatic tertiary amine such as trimethylamine, methyldiethylamine, dimethylethylamine or triethylamine; pyrrole, piperidine and N-methylpiperidine , N-methylpyrrolidine, 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-decene, etc. a cyclic tertiary amine; an aromatic tertiary amine such as pyridine, trimethylpyridine, lutidine or quinoline; an alkanolamine such as dimethylethanolamine, methyldiethanolamine or triethanolamine; tetramethylhydrogen An aqueous solution of a basic compound such as a quaternary ammonium salt such as ammonium oxide or tetraethylammonium hydroxide.

Further, an aqueous solution of the above basic compound may be added after adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and/or a surfactant.

The development method is, for example, a liquid-filling method, a dipping method, a spraying method, etc., and the development time is preferably about 10 to 180 seconds at normal temperature.

After the alkali image is washed, for example, by running water for 30 to 90 seconds, it is dried by, for example, compressed air or compressed nitrogen to form a desired pattern.

(4) Heating step Next, the obtained pattern (film) is heated by a heating means such as a hot plate or an oven at a specified temperature, for example, 100 to 160 ° C for a predetermined time, for example, 5 to 30 on a hot plate. In minutes, in an oven for 30 to 180 minutes, the spacers are obtained by heating (post-baking).

Further, the conventional sensitive radiation linear resin composition used for the spacer formation is not subjected to heat treatment at a temperature of about 180 to 200 ° C or higher, and the resulting spacer cannot exhibit sufficient performance, and the sensitive radiation linear resin of the present invention When the heating temperature of the composition is lower than the conventional temperature, the resin substrate is not yellowed or deformed, and excellent properties such as compressive strength, abrasion resistance during liquid crystal alignment, and adhesion to a transparent substrate can be obtained. Spacer.

Liquid crystal display element

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

(a) First, prepare a pair of (two) transparent substrates having a transparent conductive film (electrode) on one side, wherein the photosensitive conductive linear resin composition of the present invention is used on the transparent conductive film of one of the substrates, and the interval is formed according to the above method. Things. Next, an alignment film having a liquid crystal alignment energy is formed on the transparent conductive film and the spacer of these substrates. The inner side of the substrate is a surface on the side where the alignment film is formed, and the liquid crystal alignment directions of the respective alignment films are perpendicular or opposite to each other, and are arranged opposite to each other by a cell gap, and the liquid crystal is filled on the surface of the substrate (alignment film). And in the gap between the spacers, the liquid crystal cell is formed after the pores are sealed and filled. Then, the liquid crystal display elements of the present invention can be obtained by bonding the polarizing plates to the outer surfaces of the liquid crystal cell in such a manner that the polarizing direction thereof coincides with the liquid crystal alignment direction of the alignment film formed on one surface of the substrate or in a vertical state.

(b) First, a transparent substrate in which one pair of a transparent conductive film, a spacer, and an alignment film is formed is prepared in the same manner as the first method described above. Thereafter, the ultraviolet curable sealant was applied along the end portion of one of the substrates using a disperser, and then the liquid crystal was dropped in the form of fine droplets using a liquid crystal disperser, and the two substrates were bonded under vacuum. The above-mentioned sealant portion was then irradiated with high-pressure mercury to close the two substrates. Finally, the liquid crystal display element of the present invention can be obtained by bonding the outer surfaces of the liquid crystal cell to the polarizing plate.

The liquid crystal has, for example, a nematic liquid crystal or a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, Schiff base liquid crystal, azo alkoxy liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, or the like can be used. A triphenyl liquid crystal, a biphenyl cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cuba liquid crystal, or the like. Cholesteric liquid crystals such as cholestyl chloride, cholestyl phthalate, and cholestyl carbonate may be added to these liquid crystals, and sold under the trade names "C-15" and "CB-15" (manufactured by MELC). Use after the chiral agent, etc. A ferroelectric liquid crystal such as p-methoxybenzylidene-p-amino-2-methylbutylcinnamate may also be used.

a polarizing plate used outside the liquid crystal cell, for example, stretching a polyvinyl alcohol In the state of alignment, a polarizing film called absorbing iodine, a polarizing plate which is sandwiched by a cellulose acetate protective film, a polarizing plate made of an H film, or the like is simultaneously used.

As described above, the sensitive radiation linear resin composition of the present invention is high in sensitivity and high resolution, and is easy to form a pattern-like film having excellent pattern properties, compressive strength, abrasion resistance, and adhesion to a transparent substrate, and can be suppressed. The LCD shows burnt. The amount of deformation of the spacer is sufficient, and the TFT and the CF are not damaged or broken by the external force, and the tolerance of the liquid crystal dropping step can be improved.

Example

The present invention will be more specifically described below by way of Synthesis Examples and Examples, but the present invention is not limited to the following examples.

<Molecular weight determination of copolymers by gel permeation chromatography>

Device: GPC-101 (Showa Denko Electric Co., Ltd.)

Pipe column: combined with GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran containing 0.5% by weight of phosphoric acid

The synthesis examples of the following Synthesis Examples 1 to 10 are block copolymers (A), and Synthesis Examples 11 and 12 are synthesis examples of the epoxy group-containing compound (D).

Synthesis Example 1

4 parts by weight of pyrazol-1-dithiocarbamate (dimethyl)methyl ester and 200 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then 20 parts by weight of methacrylic acid was added. 10 parts by weight of styrene, 40 parts by weight of n-butyl methacrylate, and 30 parts by weight of benzyl methacrylate were substituted with nitrogen, and the reaction solution was slowly stirred to 80 ° C after stirring. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobisisobutyronitrile was added, and the temperature was maintained for 5 hours to carry out polymerization to obtain a [S] active copolymer solution having a solid concentration of 32.5%. This is the [S-1] polymer. The Mw of the obtained [S-1] polymer was measured by GPC (gel permeation chromatography) GPC-101 (manufactured by Showa Denko Co., Ltd.) to obtain 6,290, Mw/Mn = 1.5.

In the same manner as in the above, 100 parts by weight of the [S-1] polymer, 40 parts by weight of benzyl methacrylate, and 40 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then replaced with nitrogen. After slowly stirring the reaction solution to 80 ° C, 1 part by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the temperature was maintained for 4 hours to carry out polymerization to obtain a solid concentration of 36.8%. (A) Block copolymer solution. This is the [A-1] polymer. The Mw of the obtained [A-1] polymer was 7,290, Mw/Mn = 1.6 using GPC.

Synthesis Example 2

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then 20 parts by weight of methacrylic acid and 10 parts by weight of styrene were added. 40 parts by weight of n-butyl methacrylate and 30 parts by weight of benzyl methacrylate were substituted with nitrogen, and the solution was slowly stirred to raise the temperature to 80 °C. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 5 hours to carry out polymerization to obtain a [S] active copolymer solution having a solid concentration of 32.5%. This is the [S-2] polymer.

In the same manner as in the above, 100 parts by weight of the [S-2] polymer, 40 parts by weight of benzyl methacrylate, and 40 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then replaced with nitrogen. After slowly stirring the reaction solution to 80 ° C, 1 part by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the temperature was maintained for 4 hours to carry out polymerization to obtain a solid concentration of 36.8%. (A) Block copolymer solution. This is the [A-2] polymer. The Mw of the obtained [A-2] polymer was 7,180, Mw/Mn = 1.6 using GPC.

Synthesis Example 3

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 15 parts by weight of acrylic acid and 10 parts by weight of styrene. 40 parts by weight of methyl acrylate and 30 parts by weight of tetrahydrofurfuryl methacrylate were substituted with nitrogen, and the solution was slowly stirred to raise the temperature to 80 °C. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours to carry out polymerization. Then, 30 parts by weight of n-butyl methacrylate was added, and the mixture was further kept for 3 hours. A (A) block copolymer solution having a solid concentration of 35.5%. This is the [A-3] polymer. The Mw of the obtained [A-3] polymer was 6,300, and Mw/Mn = 1.7 as measured by GPC.

Synthesis Example 4

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, and then 20 parts by weight of methacrylic acid and 10 parts by weight of styrene were added. 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ]decane-8-ester of methacrylic acid and 30 parts by weight of benzyl acrylate were substituted with nitrogen, and the solution was slowly stirred to raise the temperature to 80 °C. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours. After polymerization, 20 parts by weight of n-butyl methacrylate was added, and then added for 2 hours. 20 parts by weight of benzyl acrylate was kept for 2 hours to obtain a (A) block copolymer solution having a solid concentration of 35.1%. This is the [A-4] polymer. The Mw of the obtained [A-4] polymer was measured by GPC to be 5,500, Mw/Mn = 1.6.

Synthesis Example 5

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 15 parts by weight of methacrylic acid and 18 parts by weight of styrene. 40 parts by weight of cyclohexyl methacrylate and 22 parts by weight of cyclohexylmaleimide were added with nitrogen, and then 5 parts by weight of 1,3-butadiene was added thereto, and the solution was slowly stirred to raise the temperature to 80 °C. To reach the stage of 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours to carry out polymerization, and then tricyclomethacrylate [5.2.1.0 ^2,6 ] decane was added. 30 parts by weight of the 8-ester, and further maintained for 3 hours to obtain a (A) block copolymer solution having a solid concentration of 35.7%. This is the [A-5] polymer. The Mw of the obtained [A-5] polymer was 6,300, and Mw/Mn = 2.3 as measured by GPC.

Synthesis Example 6

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of diglyme were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of 2-methylpropenyloxyethylhexahydrobenzene 25 parts by weight of diformate, 5 parts by weight of styrene, 30 parts by weight of 2-ethylhexyl methacrylate, and 35 parts by weight of benzyl acrylate. After being substituted with nitrogen, 5 weights of 1,3-butadiene are added. The mixture was slowly stirred to raise the temperature to 80 °C. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours. After polymerization, 20 parts by weight of n-lauryl methacrylate was added, and the temperature was maintained for 3 hours. The (A) block copolymer solution having a solid concentration of 35.0%. This is the [A-6] polymer. The Mw of the obtained [A-6] polymer was measured by GPC to be 5,820, Mw/Mn = 2.1.

Synthesis Example 7

6 parts by weight of bis-3,5-dimethylpyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by the addition of methacrylic acid. 10 parts by weight, 5 parts by weight of styrene, 30 parts by weight of 2-ethylhexyl methacrylate, and 35 parts by weight of benzyl acrylate, after being substituted with nitrogen, 5 parts by weight of 1,3-butadiene is added, and stirring is carried out slowly. The solution was allowed to warm to 80 °C. At a stage of reaching 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours to carry out polymerization, and then 2-methylpropenyloxyethyl hexahydrophthalate was added. 10 parts by weight, further maintained for 3 hours, gave a (A) block copolymer solution having a solid concentration of 34.1%. This is the [A-7] polymer. The Mw of the obtained [A-7] polymer was 8,100, Mw/Mn = 1.9 as measured by GPC.

Synthesis Example 8

5 parts by weight of bispyrazole-1-ylthiocarbonyl disulfide and 200 parts by weight of dipropylene glycol dimethyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 10 parts by weight of methacrylic acid, 4 parts by weight of acrylic acid, and benzene. 5 parts by weight of ethylene, 40 parts by weight of 2-ethyl methacrylate, and 41 parts by weight of benzyl methacrylate were substituted with nitrogen, and the solution was slowly stirred to raise the temperature to 80 °C. At a stage of reaching 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours. After polymerization, 18 parts by weight of styrene and 22 parts by weight of cyclohexylmaleimide were added. Further, for 3 hours, a (A) block copolymer solution having a solid concentration of 36.7% was obtained. This is the [A-8] polymer. The Mw of the obtained [A-8] polymer was 7,400, Mw/Mn = 1.7 using GPC.

Synthesis Example 9

5 parts by weight of bismorpholinylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 18 parts by weight of methacrylic acid, 5 parts by weight of styrene, and acrylic acid. 20 parts by weight of isobornyl ester, 27 parts by weight of butyl acrylate, and 30 parts by weight of benzyl acrylate were substituted with nitrogen, and the solution was slowly stirred to raise the temperature to 80 °C. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours. After polymerization, 15 parts by weight of butyl methacrylate and 15 parts by weight of benzyl methacrylate were added. The mixture was further kept for 3 hours to obtain a (A) block copolymer solution having a solid concentration of 35.2%. This is the [A-9] polymer. The Mw of the obtained [A-9] polymer was 9,100, and Mw/Mn was 2.2 using GPC.

Synthesis Example 10

4 parts by weight of 2-cyanopropyl-2-yl-1-pyrrole dithiocarboxylate and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by addition of 2-propene oxime 25 parts by weight of oxyethyl hexahydrophthalate, 5 parts by weight of styrene, 20 parts by weight of n-stearyl acrylate, 20 parts by weight of butyl acrylate, and 30 parts by weight of benzyl acrylate, after being replaced by nitrogen, slowly The solution was allowed to warm to 80 ° C with stirring. When the temperature reached 80 ° C, 2 parts by weight of 2,2'-azobis(isobutyronitrile) was added, and the temperature was maintained for 2 hours. After polymerization, 20 parts by weight of tetrahydrofurfuryl acrylate was added, and the solid content was further maintained for 3 hours. (A) a block copolymer solution having a concentration of 34.5%. This is the [A-10] polymer. The Mw of the obtained [A-10] polymer was 8,200, and Mw/Mn = 2.3 as measured by GPC.

Synthesis Example 11

7 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 250 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 20 weight of methacrylic acid. Parts, 5 parts by weight of styrene, 25 parts by weight of tricyclo [5.2.1.0 ^2,6 ]decane-8-ester, 25 parts by weight of glycidyl methacrylate, 20 parts by weight of tetrahydrofurfuryl methacrylate After replacing with nitrogen, 5 parts by weight of 1,3-butadiene was added, and the solution was slowly stirred to 70 ° C, and the temperature was maintained for 5 hours to carry out polymerization to obtain a (D) copolymer having a solid concentration of 28.2% by weight. Solution. This is the [D-1] polymer. The Mw of the obtained [D-1] polymer was 8,900 as measured by GPC.

Synthesis Example 12

4 parts by weight of 2,2'-azobis(2,4-dimethylvaleronitrile) and 220 parts by weight of propylene glycol monoether acetate were placed in a flask equipped with a cooling tube and a stirrer, and then 20 parts by weight of styrene was added. 80 parts by weight of glycidyl methacrylate, after replacing with nitrogen, 5 parts by weight of 1,3-butadiene was added, and the solution was slowly stirred to raise the temperature to 95 ° C. The temperature was maintained for 4 hours to carry out polymerization to obtain a solid concentration. 29.4% by weight of the (D) copolymer solution. This is the [D-2] polymer. The Mw of the obtained [D-2] polymer was 9,200 as measured by GPC.

Comparative Synthesis Example 1

5 parts by weight of 2,2'-azobis(isobutyronitrile) and 220 parts by weight of propylene glycol monoether acetate were placed in a flask equipped with a cooling tube and a stirrer, and then 5 parts by weight of styrene and 10 parts by weight of methacrylic acid were added. 5 parts by weight of acrylic acid, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of butyl methacrylate, and 40 parts by weight of butyl methacrylate, after being substituted with nitrogen, the solution was slowly stirred to raise the temperature to 80 ° C, and the temperature was maintained for 4 hours to carry out polymerization to obtain a solid form. (a) a copolymer solution having a concentration of 30.2%. This is the [a-1] polymer. The Mw of the obtained [a-1] polymer was measured by GPC to be 15,000, and Mw/Mn = 2.3.

Comparative Synthesis Example 2

4 parts by weight of 2,2'-azobis(isobutyronitrile) and 220 parts by weight of diethylene glycol methyl ether were placed in a flask equipped with a cooling tube and a stirrer, followed by adding 5 parts by weight of styrene and 10 parts by weight of methacrylic acid. 5 parts by weight of acrylic acid, 40 parts by weight of glycidyl methacrylate, 40 parts by weight of butyl methacrylate, and after replacing with nitrogen, 5 parts by weight of 1,3-butadiene is added, and the solution is slowly stirred until the temperature is raised to The polymerization was carried out at 80 ° C for 4 hours, to obtain a (a) copolymer solution having a solid concentration of 30.1%. This is the [a-2] polymer. The Mw of the obtained [a-2] polymer was 9,500, and Mw/Mn = 2.1 as measured by GPC.

(I) Modulation of sensitive radiation linear resin composition Examples 1 to 10 and Comparative Examples 1 to 3

The block copolymer (A) component and the components (B), (C), and (D) obtained in the above Synthesis Example were used in the proportions shown in Table 1, and then mixed as an γ-glycidoxypropyl group as an adhesion aid. 5 parts by weight of trimethoxy decane, 0.5 parts by weight of FTX-218 (trade name, manufactured by NEOS) as a surfactant, and 0.5 parts by weight of 4-methoxyphenol as a stabilizer, and then dissolved in propylene glycol After the solid content concentration was 30% by weight in methyl ether acetate, the composition solution was filtered by a micropore filter having a pore diameter of 0.5 μm. The amounts of the respective components are shown in Table 1.

Examples 11 to 20 and Comparative Examples 4 to 6

The block copolymer (A) component and the (B), (C), and (D) components and the surfactant (E) component obtained in the above Synthesis Example were used in the ratio of Table 2, and then mixed as an adhesion aid γ. 5 parts by weight of glycidoxypropyltrimethoxydecane, 0.5 parts by weight of 4-methoxyphenol as a stabilizer, and then dissolved in diethylene glycol ethyl methyl ether to have a solid concentration of 23% by weight Thereafter, the composition solution was filtered by filtration through a micropore filter having a pore size of 0.2 μm. The amounts of the respective components are shown in Table 2.

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

(B) component

B-1: dipentaerythritol hexaacrylate

B-2: 1,9-nonanediol diacrylate

B-3: ω-carboxypolypropane lactone monoacrylate (trade name: Alonix M-5300 (manufactured by Toagos Corporation)),

(C) component

C-1:1-[9-Ethyl-6-(2-methylmethylphenyl)-9.H.-oxazol-3-yl]-ethane-1-one oxime-O-acetate (trade name Irgacure OXE02, manufactured by Ciba.Speciality. Chemicals), C-2: 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinylphenyl)-butan-1-one (trade name Irgacure 379, Ciba. Speciality.Chemicals company), C-3: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, C-4: ethanol ketone, 1-[9-ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dicyclopentyl)methoxytolylhydrazyl ]-9.H.-carbazol-3-yl]-, 1-(O-ethylindenyl) (N-1919, manufactured by ADEKA),

(D) component

D-1: an epoxy group-containing resin composition shown in Synthesis Example 11

D-2: an epoxy group-containing resin composition shown in Synthesis Example 12.

D-3: Novolak type epoxy resin (trade name: Epikote 152, Japan Epoxy Resin Co., Ltd.)

E) ingredients

E-1: MEGAFAC F78 (made by Dainippon Ink Chemical Industry Co., Ltd.)

E-2: Toray. Dow Corning SH28PA (Toray. Dow Corning. Silicone Co., Ltd.), E-3: TSF-4460 (GE Toshiba Silicone Co., Ltd.), E-4: Organic Polyoxane Polymer KP341 (Shin-Etsu Chemical Industry Co., Ltd.).

The above-prepared composition was evaluated by the following method. The evaluation results are shown in Tables 3 and 4.

(II) Formation of spacers

The composition solution was applied onto an alkali-free glass substrate, and then prebaked on a hot plate at 80 ° C for 3 minutes to form a film having a film thickness of 4.0 μm.

Next, the obtained film was exposed to ultraviolet rays having a strength of 250 W/m ² at 365 nm for 10 seconds in a pattern mask having a square shape of 15 μm. Then, it was developed by a 0.05% by weight aqueous solution of potassium hydroxide at 25 ° C for 60 seconds, and then washed with pure water for 1 minute. The spacers of the defined pattern were then post-baked in an oven at 230 ° C for 60 minutes.

(III) Evaluation of resolution

In the case of developing the above (II), when the development time was shortened to 40 seconds, when the pattern was formed, it was evaluated as good (○), and when the residue was generated, it was evaluated as defective (×). The evaluation results are shown in Table 3.

(IV) Sensitivity evaluation

When the pattern was formed by the above (II), the residual pattern was evaluated as being good (○), and when the image was not resolved, it was evaluated as defective (×). The evaluation results are shown in Table 3.

(V) Evaluation of the shape of the spacer

The cross-sectional shape of the pattern obtained in the above (II) was observed by a scanning electron microscope, and any of A and B shown in Fig. 1 was evaluated. At this time, as shown in A, when the spacer has a circular shape, the upper portion of the spacer is easily deformed, and when the TFT plate and the CF plate are bonded, the amount of deformation is sufficiently increased, and the tolerance of the liquid crystal dropping step is improved. Further, as shown in B, when the shape of the spacer is close to the mesa shape, the spacer is not easily deformed, and the tolerance of the liquid crystal dropping step is insufficient. The evaluation results are shown in Table 3.

(VI) Evaluation of the shape of the spacer

The cross-sectional shape of the pattern obtained in the above (II) was observed by a scanning electron microscope, and when the surface of the spacer was uniform, it was evaluated as good (○), and when phase separation or agglomerates were generated, it was evaluated as defective (Δ). The evaluation results are shown in Table 3.

(VII) Evaluation of compression displacement

With respect to the pattern obtained in the above (II), a small compression tester (DUH-201, manufactured by Shimadzu Corporation) was used to measure the amount of deformation when a load of 50 mN was applied by a flat head having a diameter of 50 μm at a measurement temperature of 23 °C. When the value is 0.5 or more, the amount of compression displacement is evaluated as good. The evaluation results are shown in Table 3.

(VIII) Evaluation of heat resistance

The pattern obtained in the above (II) was evaluated in the oven at 230 ° C for 20 minutes, and was evaluated as good (○) when the height of the spacer was less than 4%, and was evaluated as bad at 4% or more ( ×). The evaluation results are shown in Table 3.

(IX) Evaluation of abrasion resistance

A liquid crystal alignment agent AL3046 (trade name, manufactured by JSR Corporation) was applied onto a substrate on which the pattern obtained in the above (II) was formed, and then dried at 180 ° C for 1 hour to form a dry film thickness. A coating film of a 0.05 μm alignment agent. Thereafter, the coating film was subjected to a rubbing treatment using a friction machine having a roll of a polyamide cloth, and the number of revolutions of the rolls was 500 rpm, and the moving speed of the table was 1 cm/sec. At this time, the pattern was evaluated for cutting or peeling. The evaluation results are shown in Table 3.

(X) Evaluation of adhesion

A cured film was formed in the same manner as in the above (II) except that the photomask of the residual pattern was not used. Then, it was evaluated by the checkerboard tape method of 8.5.2 in the adhesion test of JIS K-5400 (1900) 8.5. At this time, the number of the chessboards remaining in the 100 chessboards is as shown in Table 3.

(XI) Evaluation of voltage retention

The prepared liquid composition is spin-coated on the surface to form a SiO ₂ film which prevents sodium ions from being dissolved, and then an ITO (indium-tin oxide alloy) electrode is evaporated onto a soda glass substrate of a predetermined shape, and then, at 90 ° C The room was prebaked in a clean room for 10 minutes to form a coating film of 2.0 μm.

Next, using a high-pressure mercury lamp, the radiation containing the wavelengths of 365 nm, 405 nm, and 436 nm was exposed to a coating film at a exposure amount of 200 J/m ² without using a photomask. Then, the substrate was immersed in a developing solution of a 0.04% by weight aqueous potassium hydroxide solution at 23 ° C for 1 minute. After development, it was washed with ultrapure water and air-dried, and then baked at 230 ° C for 30 minutes to coat. The film is hardened to form a cured film.

Next, the substrate on which the pixel was formed was adhered by a sealant of a glass ball of 0.8 mm, and the substrate on which only the ITO electrode was vapor-deposited into a predetermined shape, and then injected into a liquid crystal MLC-6608 (trade name) manufactured by MERCK Co., Ltd. to prepare a liquid crystal cell.

Then, this liquid crystal cell was placed in a thermostat at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system VHR-1A (trade name) manufactured by Toyo Technic. The voltage applied at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio means a value of a liquid crystal cell potential difference after 16.7 msec/voltage applied at 0 msec. The results are shown in Table 3. When the voltage holding ratio of the liquid crystal cell is 90% or less, the voltage of the liquid crystal cell is 16.7 msec, the applied voltage cannot be maintained at a predetermined level, and the liquid crystal is not sufficiently aligned, and there is a high possibility that "burning" occurs.

(XII) Evaluation of coating properties (uneven stripes, uneven fogging, stitching)

The prepared composition solution was applied to a 550 x 650 mm chromium film-forming glass using a slot die coater. After drying under reduced pressure to 0.5 Torr, a coating film was formed by prebaking at 100 ° C for 2 minutes on a hot plate, and exposed to an exposure amount of 200 J/m ² to form a film thickness of 4 μm from the surface of the chromium film-forming glass. Membrane.

The surface of the film was irradiated with a sodium lamp, and the surface of the coated film was visually confirmed. It is possible to clearly confirm the unevenness of the stripes (the coating direction or the line forming one or more of them in the direction of the intersection is uneven), the unevenness of the mist (uneven clouds), and the stitches (the points generated on the substrate supporting pins) In the case of the case of the case, the evaluation was ×, and the case where the permission was confirmed was Δ, and the case where it was almost impossible to confirm was ○, and the unevenness of the streaks, the unevenness of the mist, and the evaluation of the stitching were ◎.

(III) Evaluation of coatability (uniformity)

The film thickness of the coating film on the chromium film-forming glass produced as described above was measured using a needle contact type measuring machine (AS200 manufactured by KLA Tencor Co., Ltd.).

The uniformity was calculated from the film thickness of the nine measurement points. The nine measurement points mean that the short axis direction of the substrate is X, the long axis direction is Y, and (X[mm], Y[mm]) are (275, 20), (275, 30), (275, 60). , (275, 100), (275, 325), (275, 550), (275, 590), (275, 620), (275, 630).

The calculation formula of the uniformity is shown by the following formula (3). FT(X,Y)max of the following formula (3) is the maximum thickness of the film at nine measurement points, and FT(X,Y)min is the minimum value of the film thickness at nine measurement points, FT(X, Y) avg is the average value of the film thicknesses among the nine measurement points. When the uniformity is less than 2% (<2%), it is evaluated as ◎, when 2% or more (2% ≦) is less than 3% (<3%), it is evaluated as ○, and 3% or more (3% ≦) is less than 5 When it was % (<5%), it was evaluated as Δ, and when it was 5% or more (5% ≦), it was evaluated as ×.

Uniformity (%)={FT(X,Y)max-FT(X,Y)min}×100/{2×FT(X,Y)avg} (3)

The results are shown in Table 4.

(XIV) Determination of viscosity

It was measured at 25 ° C using an E-type viscometer (VISCONIC ELD.R manufactured by Toki Sangyo Co., Ltd.). The results are shown in Table 4.

Fig. 1 is a schematic view showing the sectional shape of a spacer.

Claims (11)

A spacer-forming radiation sensitive linear resin composition comprising: (A) a block copolymer (B) a polymerizable unsaturated compound and (C) a radiation radiation linear polymerization initiator. The sensitive radiation linear resin composition of claim 1, which further contains (D) an epoxy group-containing compound. A radiation sensitive linear resin composition according to claim 1 or 2, wherein the (A) block copolymer has two or more block segments, at least one of which has an alkali-soluble portion. The sensitive radiation linear resin composition of claim 3, which contains a carboxyl group as an alkali-soluble portion. The sensitive radiation linear resin composition of claim 1 or 2, wherein the (A) block copolymer contains at least (a1) an unsaturated carboxylic acid having a radical polymerizable property, an unsaturated carboxylic acid anhydride, and the like. At least one of a group of carboxylic acid protecting compounds, a first block segment composed of a radical polymerizable compound other than (a2) (a1), and a second block composed only of (a1) or (a2) Block segment. The sensitive radiation linear resin composition of claim 1 or 2, wherein the (A) block copolymer is obtained by living radical polymerization. The sensitive radiation linear resin composition according to claim 1 or 2, wherein the (A) block copolymer is a thiocarbonylthio compound represented by the following formula (1), (2) or (3) as a molecular weight controlling agent To polymerize a polymerizable unsaturated compound, [In the formula (1), Z ¹ represents 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, and a total of carbon atoms and hetero atoms. A monovalent heterocyclic group of 3 to 20 atoms, -OR, -SR, -N(R) ₂ , -OC(=O)R, -C(=O)OR, -C(=O)N(R ₂ , -P(=O)(OR) ₂ , -P(=O)(R) ₂ , or a monovalent group having a polymer chain, and each R group 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 heterocyclic group having 3 to 18 carbon atoms in total of a carbon atom and a hetero atom, and an alkyl group having 1 to 20 carbon atoms; The monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, and the R group may be substituted, and R ¹ is an alkyl group having 1 to 20 carbon atoms when p=1. An alicyclic hydrocarbon group having a carbon number of 3 to 20, an aromatic hydrocarbon group having a carbon number of 6 to 20, a monovalent heterocyclic group having 3 to 20 carbon atoms and a hetero atom, and -OR, -SR, -N(R) ₂ or a monovalent group having a polymer chain, and each R group independently represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and 1 to 6 carbon atoms. Avalent aromatic hydrocarbon group or a total of 3 to 18 valences of a total of 3 to 18 carbon atoms and hetero atoms The ring group, p≧2, represents a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a total number of atoms derived from a carbon atom and a hetero atom. a p-valent group of a heterocyclic compound of 3 to 20 or a p-valent group having a polymer chain, an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having a carbon number of 3 to 20, and a carbon number of 6 a monovalent aromatic hydrocarbon group of ~20, a monovalent heterocyclic group of 3 to 20 in total, R, a p-valent group derived from an alkane having 1 to 20 carbon atoms, an aromatic hydrocarbon derived from a carbon number of 6 to 20. The p-valent group, the p-valent group of the heterocyclic compound having a total of 3 to 20 atoms from the carbon atom and the hetero atom, respectively, may be substituted] [In the formula (2), Z ² represents a m-valent group derived from an alkane having 1 to 20 carbon atoms, a m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a total of carbon atoms and hetero atoms. a m-valent group of a heterocyclic compound having 3 to 20 atoms or a group having a m-valent group of a polymer chain, the above-mentioned alkyl group derived from a carbon number of 1 to 20, and an aromatic hydrocarbon derived from a carbon number of 6 to 20. The m-valent group and the m-valent group of the heterocyclic compound having a total of 3 to 20 atoms may be substituted, and R ² is derived from an alkyl group having 1 to 20 carbon atoms and a monovalent alicyclic group having 3 to 20 carbon atoms. a hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a total of 3 to 20 monovalent heterocyclic groups of carbon atoms and hetero atoms, -OR, -SR, -N(R) ₂ or having a polymer The monovalent group of the chain, each R independently of each other 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 total atom of a carbon atom and a hetero atom. The monovalent heterocyclic group of 3 to 18, the alkyl group having 1 to 20 carbon atoms, the alicyclic hydrocarbon group having a carbon number of 3 to 20, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the total atom The number of 3 to 20 monovalent heterocyclic groups and R can be substituted respectively] [In the formula (3), Z ³ and Z ⁴ each independently represent a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. a monovalent heterocyclic group having 3 to 20 atoms in total with a hetero atom, -OR ³ , -SR ³ , -OC(=O)R ³ , -N(R ³ )(R ⁴ ), -C(=O )OR ³ , -C(=O)N(R ³ )(R ⁴ ), -P(=O)(OR ³ ) ₂ , -P(=O)(R ³ ) ₂ or having a polymer chain The valence group, R ³ and R ⁴ are each independently represent 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 atom of a carbon atom and a hetero atom. a monovalent heterocyclic group of 3 to 18, an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having a carbon number of 6 to 20, a total of 3 to 20 carbon atoms and a hetero atom of a hetero atom The ring group, R ³ and R ⁴ systems can be substituted respectively]. The sensitive radiation linear resin composition of claim 1 or 2, wherein the polystyrene-equivalent weight average molecular weight (Mw) and polystyrene-equivalent arithmetic of the (A) block copolymer are determined by gel permeation chromatography. The ratio (Mw/Mn) of the average molecular weight (Mn) is 2.5 or less. A spacer formed by forming a sensitive radiation linear resin composition according to any one of claims 1 to 8. A method for forming a spacer, comprising the steps of (a) to (d), (a) forming a film of a sensitive radiation linear resin composition according to any one of claims 1 to 8 on a substrate. And (b) the step of exposing at least a part of the film, (c) the step of developing the film after the exposure, and the step of heating the film after the development. A liquid crystal display element characterized by having a spacer of the ninth application of the patent application.