TWI432894B - Radiation-sensitive resin composition for formation of a spacer, spacer, method of producing a spacer, and liquid crystal display device - Google Patents

Description

Method for forming radiation-sensitive resin composition for spacer formation, spacer, spacer, and liquid crystal display device

The present invention relates to a radiation sensitive resin composition for spacer formation, a spacer, a method of forming a spacer, and a liquid crystal display element.

Conventional liquid crystal display devices have been widely used for displaying high quality image display devices. In general, a liquid crystal display device includes a liquid crystal layer, which is defined by a predetermined alignment between a pair of substrates to enable image display. This substrate spacing, that is, uniformly maintaining the thickness of the liquid crystal layer, is one of the factors determining image quality. To this end, spacers for fixing the thickness of the liquid crystal layer are provided. In general, the thickness between the substrates is referred to as "liquid crystal cell thickness". The thickness of the liquid crystal cell generally indicates the thickness of the liquid crystal layer, in other words, the distance between the two electrodes that have applied an electric field to the liquid crystal display region.

Conventionally, spacers have been formed by scattering of glass beads. In recent years, photosensitive compositions have been gradually used, and spacers having high positional accuracy have been formed by photolithography. A spacer formed using such a photosensitive composition is referred to as a photo spacer.

The radiation from the mercury lamp used as the light source in photolithography is usually around 436 nm (g line), around 404 nm (h line), around 365 nm (i line), near 335 nm, near 315 nm (j line), and around 303 nm. The radiation-sensitive linear polymerization initiator contained in the radiation-sensitive resin composition is usually selected to have a spectrum having a maximum absorption wavelength in the wavelength range of the high-intensity spectrum. In most cases, based on the viewpoint of transparency, a radiation-sensitive polymerization initiator having a maximum absorption wavelength in a region having a wavelength below the i-line will be used (for example, refer to Japanese Laid-Open Patent Publication No. 2005-208360).

When a radiation-sensitive polymerization initiator having a maximum absorption wavelength near the g-line or the h-line having a longer wavelength than the i-line is used, since the radiation-type polymerization initiator has absorption in the wavelength region close to the visible light, it contains The radiation sensitive linear resin composition of the radiation polymerization initiator will be colored, and the transparency of the formed coating film will be lowered.

When the transparency of the coating film is low, the curing reaction proceeds to the surface of the film at the time of exposure, and the hardening reaction toward the depth direction of the coating film becomes insufficient. As a result, the shape of the spacer obtained after development is an inverted tapered shape (the cross-sectional shape is an inverted triangle whose side of the film surface is longer than the side of the substrate side), and will become the subsequent alignment film smoothing treatment. The reason for the peeling of the spacer.

On the other hand, in the case of an actual spacer forming process, when a spacer is formed on a transparent substrate usable, for example, a color filter or the like by photolithography, a proximity type exposure machine is often used. In recent years, mercury lamps having high illuminance have generally been used due to an increase in the yield of the proximity type exposure machine. In this case, although the yield will be improved, once the mercury lamp having a high illuminance is directly used, since the life of the lens used in the exposure machine is lowered, a filter is used to filter out radiation having a high energy of a short wavelength of less than 350 nm. There are many situations. However, most of the conventional radiation-based polymerization initiators have a maximum absorption wavelength of less than 350 nm, and once the radiation of a wavelength lower than 350 nm is filtered, radicals necessary for the hardening of the radiation-sensitive resin composition cannot be sufficiently generated. The active species, the hardening reaction will become insufficient, and it will become difficult to obtain a size or shape of the spacer that can be satisfied.

Further, since the radiation-sensitive polymerization initiator of the prior art is poor in the preservability of the solution, there is an operability problem that the coating liquid must be stored in the refrigeration, or the effect of the cost increase caused by the coating is applied. Problems such as stability over time on the rear glass substrate.

According to the present invention, there is provided a radiation sensitive linear resin composition for a spacer having high sensitivity and excellent storage stability. Further, another object of the invention is to provide a spacer formed using the radiation-sensitive resin composition, a method of forming the spacer, and a liquid crystal display device including the spacer.

The specific means to achieve this problem are as follows:

<1> A radiation sensitive resin composition for forming a spacer, which comprises:

(A) a resin having a branched structure and/or an alicyclic structure, an acidic group, or an ethylenically unsaturated group bonded to the main chain via an ester group in at least one side chain;

(B) a polymerizable unsaturated compound;

(C) contains a (C1) hexaarylbiimidazole compound, a (C2) aromatic mercapto compound, and a (C3) auxiliary.

<2> The radiation sensitive linear resin composition for forming a spacer according to <1>, wherein the (C3) auxiliary comprises a thioxanthone compound, a coumarin compound, a diphenyl ketone compound, and an acridone compound At least one of the selected ones.

<3> The radiation sensitive linear resin composition for spacer formation according to <1>, wherein the (C1) hexaarylbiimidazole compound is a compound represented by the following formula (1) or formula (2):

In the formula (1), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms; and A represents a substituted or unsubstituted carbon group having 1 to 12 carbon atoms; Alkoxy or -COO-R (wherein R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms); n is an integer of 1 to 3; each m is an integer of 1 to 3 ;

In the formula (2), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms; X ¹ and X; ² is not represented by a hydrogen atom when it is different from two or more of X ³ .

<4> The radiation sensitive resin composition for spacer formation according to <1>, wherein the branched structure and/or the alicyclic structure is dicyclopentyl, dicyclopentenyl, cyclohexyl, tricyclopentane At least one selected from the group consisting of a tricyclopentenyl group, an adamantyl group, a norbornyl group and an isodecyl group.

<5> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the alicyclic structure is a group derived from a monomer represented by the following formula (3):

In the formula (3), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group.

<6> The radiation-sensitive resin composition for spacer formation according to <5>, wherein the divalent organic linking group is one selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group. Base or combination.

<7> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the alicyclic structure is a group derived from a monomer represented by the following formula (4):

In the formula (4), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group.

<8> The radiation-sensitive resin composition for spacer formation according to <7>, wherein the divalent organic linking group is one selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group. Base or combination.

<9> The radiation sensitive resin composition for spacer formation according to <1>, wherein the branching structure is a branched alkyl group having 3 to 12 carbon atoms.

<10> The radiation sensitive resin composition for spacer formation according to <1>, wherein the (A) resin further contains a structural unit derived from styrene.

<11> The radiation sensitive resin composition for spacer formation according to <1>, wherein a composition ratio (x) of the branching structure and/or the alicyclic structure in the (A) resin is 10 to 70 m %, the composition ratio (y) of the acidic group is 5 to 70 mol%, and the composition ratio (z) of the ethylenically unsaturated group is 10 to 70 mol%.

<12> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the mass ratio of the (B) polymerizable compound to the (A) resin is [(B)/(A) ratio] is 0.5 to 2.5 .

<13> A spacer formed by using the radiation sensitive resin composition for spacer formation according to any one of <1> to <12> above.

<14> A method for producing a spacer, comprising: forming a photosensitive resin layer on a substrate by using the radiation sensitive resin composition for spacer formation according to any one of <1> to <12>;

And exposing at least a portion of the photosensitive resin layer to substantially no radiation having a wavelength lower than 350 nm;

a photosensitive resin layer after development exposure; and

The photosensitive resin layer after development is heated.

<15> A liquid crystal display element comprising the spacer disclosed in <13> above.

According to the present invention, it is possible to provide a radiation sensitive linear resin composition for a spacer having high sensitivity and excellent storage stability. Further, it is possible to provide a spacer formed using the composition, a method of forming the spacer, and a liquid crystal display element including the spacer.

Embodiment of the invention

In the following, the radiation-sensitive resin composition for spacer formation (hereinafter also referred to simply as "radiation-sensitive resin composition"), the spacer, the method for producing the spacer, and the liquid crystal display device will be described in detail.

Method for producing radiation sensitive linear resin composition for spacer formation and spacer

The radiation sensitive resin composition for forming a spacer of the present invention comprises: (A) having a branching structure and/or an alicyclic structure, an acidic group, or a bond to the main group via at least one side chain; a chain-containing ethylenically unsaturated group-containing resin; (B) a polymerizable unsaturated compound; and (C) a (C1) hexaarylbiimidazole compound, (C2) aromatic mercapto compound, and (C3) auxiliary.

According to the above configuration, the radiation-sensitive resin composition for spacer formation of the present invention has high sensitivity and superior developability, and has excellent storage stability. In particular, even if it does not contain a wavelength having a wavelength of less than 350 nm, it is highly sensitive, and the hardening reaction is good and superior in development.

Further, the spacer manufactured by the radiation-sensitive resin composition has high compressibility and high dimensional recovery, and can eliminate display unevenness in the display element and/or the display device.

Further, the method for producing a spacer of the present invention is a method for manufacturing the spacer in a liquid crystal display device having the following structure: at least two substrates, a liquid crystal material disposed between the substrates, and an electric field applied to the liquid crystal Two electrodes of material and spacers that limit the thickness of the liquid crystal cell between the substrates. A layer forming step of forming a radiation-sensitive resin composition layer (hereinafter also referred to as "photosensitive resin layer") containing the radiation-sensitive resin composition of the present invention on one side of the two substrates.

Layer formation step

The layer forming step in the present invention is a step of forming a photosensitive resin layer on a substrate by using the photosensitive resin composition of the present invention.

The photosensitive resin layer is subjected to other steps such as a pattern forming step to be described later, and the spacer of the present invention which is excellent in deformation recovery property and can uniformly maintain the thickness of the liquid crystal cell is formed. By using the spacer, especially in accordance with variations in the thickness of the liquid crystal cell, display unevenness in the liquid crystal display device in which display unevenness is likely to occur is effectively eliminated.

Examples of the method of forming the photosensitive resin layer on the substrate include (a) a method of applying the radiation sensitive resin composition of the present invention; and (b) using a photosensitive transfer material having the photosensitive resin layer, A transfer method or the like for laminating and transferring a photosensitive resin layer by heating and/or pressurization.

(a) Coating method

The coating of the radiation sensitive resin composition can be carried out by a conventional coating method, for example, a spin coating method, a curtain coating method, a dip coating method, an air knife coating method, a roll coating method, a wire bar coating method, a gravure coating method, Alternatively, an extrusion coating method or the like using a hopper disclosed in the specification of U.S. Patent No. 2,681,294 is used. Among them, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767, JP-A-2002-79163 A coating method of a slit nozzle or a slit coater such as No. 2001-310147.

(b) Transfer method

The transfer system is a film-like photosensitive resin layer formed on a temporary carrier by using a photosensitive transfer material, and is bonded to a surface of a carrier (or substrate) by pressure or heat by a roll or a flat plate. Thereafter, the photosensitive resin layer is transferred onto the carrier in accordance with the peeling of the temporary carrier. Specifically, a laminating machine and a laminating method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. . From the viewpoint of low contaminants, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 7-110575 is preferably used.

In the case where the photosensitive resin layer is formed, an oxygen blocking layer (hereinafter also referred to as "oxygen barrier layer" or "intermediate layer") may be further provided between the photosensitive resin layer and the temporary carrier. Thereby, the exposure sensitivity can be improved. Moreover, in order to improve transferability, a thermoplastic resin layer having a cushioning property may be provided.

For the temporary carrier, the oxygen barrier layer, the thermoplastic resin layer, the other layer or the photosensitive transfer material constituting the photosensitive transfer material, the paragraph number of the Japanese Patent Laid-Open Publication No. 2006-23696 can be used. 0024] to [0030] The structure and manufacturing method disclosed.

(a) The coating method and (b) the transfer method are all applied to form a photosensitive resin layer, and the layer thickness thereof is preferably from 0.5 μm to 10.0 μm, more preferably from 1 μm to 6 μm. When the layer thickness is in this range, the occurrence of pinholes at the time of coating formation at the time of production is prevented, and it is not necessary to perform display removal of the unexposed portion for a long period of time.

a substrate on which a photosensitive resin layer is formed, for example, a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also referred to as a substrate) A color filter substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. In general, the thickness of the substrate is preferably from 700 μm to 1200 μm.

Radiation-sensitive resin composition

Next, the radiation sensitive resin composition will be described.

The radiation sensitive resin composition of the present invention comprises: (A) having a branched structure and/or an alicyclic structure, an acidic group, or an ethylene group bonded to the main chain via an ester group in at least one side chain. (A) a polymerizable unsaturated compound; and (C) a (C1) hexaarylbiimidazole compound, (C2) aromatic mercapto compound, and (C3) auxiliary.

In addition, if necessary, other components may be further included.

(A) Resin

(A) The resin has a branching structure and/or an alicyclic structure, an acidic group, or an ethylenically unsaturated group bonded to the main chain via an ester group in at least one side chain.

The branching structure and/or the alicyclic structure, the acidic group, and the ethylenically unsaturated group in the resin of the component (A) may be contained in different side chains, and at least two of these may be combined. In the same side chain, all of them may be contained in the same side chain.

Further, in the present specification, the (meth)acrylonitrile group means an acryloyl group or a methacryl group, and the (meth)acrylate means an acrylate or a methacrylate, and a (meth)acryl group. It means an acryl group or a methacryl group, (meth) acrylamide means acrylamide or methacrylamide, and (meth) propylene oxime means propylene aniline or methacryl aniline.

Branching structure and / or alicyclic structure

The branching structure and/or the alicyclic structure will be described.

The (A) resin in the present invention contains at least one branching structure and/or alicyclic structure in the side chain.

The branched structure and/or the alicyclic structure may contain a plurality of the same side chains of the resin (A). Further, the branching structure and/or the alicyclic structure may contain an acidic group or an ethylenically unsaturated group in the same side chain of the resin (A).

Further, the branching structure and/or the alicyclic structure may be directly bonded to the main chain of the resin (A), and the side chain of the resin (A) may be formed only by the branching structure and/or the alicyclic structure, or may be separated. A bivalent organic linking group is bonded to the main chain of the resin (A), and a branch having a branched structure and/or an alicyclic structure may constitute a side chain of the resin (A).

Examples of the branching structure include an alkyl group having 3 to 12 branched carbon atoms, and examples thereof include an isopropyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and an isopentyl group. Neopentyl, 2-methylbutyl, isohexyl, 2-ethylhexyl, 2-methylhexyl, isopentyl, tertiary pentyl, 3-octyl, tertiary octyl, etc., and the like The basis. Among these alkyl groups, isobutyl, secondary butyl, tert-butyl, isopentyl and the like, and the like, and further preferably isopropyl, secondary butyl, and the like are preferred. a butyl group or the like, and having such a group.

Examples of the alicyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, and an isoindole group. An alkyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentyl group, a tricyclopentenyl group, a tricyclopentyl group, or the like, and at least one selected from the group consisting of these groups. Among these alicyclic hydrocarbon groups, preferred are cyclohexyl, norbornyl, isodecyl, adamantyl, tricyclopentenyl, tricyclopentyl, dicyclopentenyl, dicyclopentane At least one selected from the group and the like, and further preferably a cyclohexyl group, an isodecyl group, a dicyclopentenyl group, a dicyclopentyl group, etc., and at least one selected from the group consisting of .

Examples of the divalent organic linking group include one or a combination selected from the group consisting of an alkyl group, an extended aryl group, an ester group, a decylamino group and an ether group.

Examples of the alkylene group include an alkylene group having a total carbon number of 1 to 20, more preferably an alkylene group having a total carbon number of 1 to 10. Specific examples thereof include a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a decyl group, a decyl group, and the like. It may also have a branched structure, a cyclic structure or a functional group, more preferably a methylene group, an ethyl group or a octyl group.

Examples of the aryl group include an extended aryl group having a total carbon number of 6 to 20, more preferably an extended aryl group having a total carbon number of 6 to 12. Specific examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group and the like. These aryl groups may have a branched structure or a functional group, and more preferably a phenyl group or a biphenyl group.

Examples of the monomer for introducing the branched structure and/or the alicyclic structure into the (A) resin side chain include (meth) acrylates, vinyl ethers, vinyl esters, and (meth) acrylamide. The class or the like is preferably a (meth) acrylate, a vinyl ester or a (meth) acrylamide, and more preferably a (meth) acrylate.

Specific examples of the monomer for introducing the branched structure into the (A) resin side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, and n-butyl (meth)acrylate. Tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, tertiary amyl (meth)acrylate, diethyl amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate, trioctyl (meth)acrylate, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, (meth)acrylic acid are preferred. Further, a tertiary butyl ester or the like is further more preferably isopropyl (meth)acrylate or isobutyl (meth)acrylate.

Specific examples of the monomer for introducing the alicyclic structure into the (A) resin side chain include 5 to 20 alicyclic hydrocarbon group (meth) acrylates. Specific examples include (meth)acrylic acid (bicyclo[2,2,1]hept-2-yl) ester, (meth)acrylic acid-1-adamantyl ester, (meth)acrylic acid-2-adamantate, 3-methyl-1-adamantyl (meth)acrylate,-3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyl-1-adamantyl (meth)acrylate , (meth)acrylic acid-3-methyl-5-ethyl-1-adamantyl ester, (meth)acrylic acid-3,5,8-triethyl-1-adamantyl ester, (meth)acrylic acid-3 , 5-dimethyl-8-ethyl-1-adamantyl ester, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, ( 3-hydroxy-1-adamantylmethyl methacrylate, octahydro-4,7-methylenedihydrofurfuryl (meth) acrylate-5-ester, octahydro-4,7-(meth)acrylate Methylene dihydrofurfuryl ester-1-yl methyl ester, (meth)acrylic acid-1-menthyl ester, tricyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, (methyl) 3-hydroxy-2,6,6-trimethylbicyclo[3.1.1]heptyl acrylate,-3,7,7-trimethyl-4-hydroxy[4.1.0](meth)acrylate, N-methyl decyl methacrylate, isodecyl (meth) acrylate, decyl (meth) acrylate, 2,2,5-trimethyl (meth) acrylate Hexyl ester, (meth) acrylate and the like. Among these (meth) acrylates, cyclohexyl (meth) acrylate, n- decyl (meth) acrylate, isodecyl (meth) acrylate, (meth) acrylate-1 is preferred. -adamantyl ester, 2-adamantyl (meth)acrylate, decyl (meth)acrylate, 1-menthyl (meth)acrylate, tricyclodecyl (meth)acrylate, etc., especially Cyclohexyl acrylate, tricyclopentenyl (meth) acrylate, n-northyl (meth) acrylate, isodecyl (meth) acrylate, and 2-adamantyl (meth) acrylate are particularly preferred.

Further, in order to introduce the alicyclic structure into the monomer of the (A) resin side chain, in the following formula (3) or (4), X represents a divalent organic linking group, and y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group.

In the general formula (3) or (4), it is preferably y = 1 or 2, and n = 0 to 4, and more preferably n = 0 to 2.

The divalent organic linking group may have a substituent. Examples of the divalent organic linking group include a group or a combination selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group. .

Examples of the alkylene group include an alkylene group having a total carbon number of 1 to 20, and more preferably 1 to 10. Specifically, examples thereof include a methylene group, an ethylidene group, a propyl group, a butyl group, a pentyl group, a hexyl group, a decyl group, a dodecyl group, an octadecyl group, and the like. The alkyl group may have a branched structure, a cyclic structure or a functional group, and more preferably a methylene group, an ethyl group, or a octyl group.

Examples of the aryl group include a aryl group having a total carbon number of 6 to 20, and more preferably a total carbon number of 6 to 12. Specific examples thereof include a phenyl group, a biphenyl group, a naphthyl group, a fluorenyl group and the like. These aryl groups may have a branched structure or a functional group, and more preferably a phenyl group or a biphenyl group.

Examples of the substituent which the divalent organic linking group may have include an alkyl group, a hydroxyl group, an amine group, a halogen group, an aromatic ring group, and a group having an alicyclic structure.

Among them, a compound represented by the formula (3) or (4) is preferred from the viewpoint of superior development and a superior deformation recovery ratio, and specific examples thereof include the following compounds D-1 to D. -11, T-1 ~ T-12.

A monomer which is suitably produced can be used for introducing the alicyclic structure into the monomer of the (A) resin side chain, and a commercially available product can also be used.

Examples of the commercially available product include FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, and H-TCPD. -M, TOE-A, TOE-M, H-TOE-A, H-TOE-M (all of which are trade names, manufactured by Hitachi Chemical Co., Ltd.). Among these commercial products, FA-512A(S) and FA-512M are preferable from the viewpoint of superior development and excellent deformation recovery rate.

Acid base (A) The resin contains at least one acidic group in the side chain.

The acidic group may also contain a plurality of the same side chain. Further, the acidic group may contain a branching structure and/or an alicyclic structure in the same side chain of the (A) resin, and an ethylenically unsaturated group bonded via an ester group.

Further, the acidic group may be directly bonded to the main chain of the resin (A), and the side chain of the resin (A) may be formed only by an acidic group, or may be bonded to the resin via a divalent organic linking group ( The main chain of A), which has an acidic group, constitutes a side chain of the resin (A). Here, examples of the divalent organic linking group include a divalent organic linking group exemplified in the description of the branching structure and/or the alicyclic structure item, and the preferred range is also the same.

The acidic group is not particularly limited and can be appropriately selected from conventional acidic groups. Examples thereof include a carboxyl group, a sulfonic acid group, a sulfonylamino group, a phosphoric acid group, and a phenolic hydroxyl group. Among these acidic groups, a carboxyl group or a phenolic hydroxyl group is preferred from the viewpoint of development properties and water resistance of the cured film.

The monomer for introducing the acidic group into the side chain of the (A) resin is not particularly limited, and examples thereof include (meth) acrylates, vinyl ethers, vinyl esters, and (meth) acrylamides. The (meth) acrylates, vinyl esters, (meth) acrylamides, and more preferably (meth) acrylates.

Specific examples of the monomer in which the acidic group is introduced into the side chain of the (A) resin can be appropriately selected from conventional monomers, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, and maleic acid. Addition reaction of maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-amino cinnamic acid, acrylic acid dimer, monomer having hydroxyl group and cyclic acid anhydride , ω-carboxy polycaprolactone mono (meth) acrylate, and the like. As the monomer, a monomer which is suitably produced can be used, and a commercially available product can also be used.

The monomer having a carboxyl group which can be used for the reaction of the monomer having the hydroxyl group with the cyclic acid anhydride, for example, 2-hydroxyethyl (meth)acrylate or the like can be mentioned. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride.

In order to introduce an acidic group into the monomer of the (A) resin side chain, a commercially available product may be exemplified by: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M. -5600 (all are trade names); Japan Nakamuramura Chemical Industry Co., Ltd.: NK ester CB-1, NK ester CBX-1 (all trade names); Japan Kyoritsu Oil & Fat Chemical Industry Co., Ltd.: HOA -MP, HOA-MS (all are trade names); Osaka Organic Chemical Industry Co., Ltd.: Biscoat #2100 (trade name). Among these monomers, acrylic acid or the like is preferred from the viewpoint of superior development and low cost.

Ethylene unsaturated group

The side chain of the (A) resin is bonded to the "ethylenically unsaturated group" of the main chain via an ester group, and is not particularly limited, and examples thereof include a (meth)acryl fluorenyl group. The ester group (-COO-) is bonded to the main chain of the ethylenically unsaturated group and the (A) resin.

In the patent specification of the present invention, the ethylenically unsaturated group bonded to the main chain via an ester group means that the atomic group containing an ethylenically unsaturated group is directly bonded to the main chain of the resin by the ester group. . Therefore, although the ester group is directly bonded to the main chain, the ethylenically unsaturated group may be directly bonded to the ester group, or may be bonded via a linking group linking the two.

The method of introducing an ethylenically unsaturated group into the (A) resin side chain can be appropriately selected from the conventional methods. For example, a method of adding a (meth) acrylate having an epoxy group to a repeating unit containing an acidic group; and a method of adding a (meth) acrylate having an isocyanate group to a repeating unit containing a hydroxyl group A method of adding a (meth) acrylate having a hydroxyl group to a repeating unit containing an isocyanate group.

Among them, a method of adding an epoxy group-containing (meth) acrylate to a repeating unit containing an acidic group is most easily produced, and is preferable from the viewpoint of low cost.

The (meth) acrylate having the epoxy group is not particularly limited as long as it is an epoxy group-containing (meth) acrylate. For example, a compound represented by the following structural formula (1) is preferably used. The compound represented by the following structural formula (2).

In the structural formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents an organic group.

In the structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. The W system represents an aliphatic hydrocarbon group of 4 to 7 membered rings.

Among the compounds represented by the structural formula (1) and the compounds represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulae (1) and (2), L ¹ and L ^{2 are more} preferably independent alkyl groups having 1 to 4 carbon atoms.

The compound represented by the structural formula (1) and the compound represented by the structural formula (2) are not particularly limited, and examples thereof include the following exemplified compounds (1) to (10):

Other monomer

In the (A) resin, other monomers may be used to introduce other groups.

The other monomer is not particularly limited, and examples thereof include (meth) acrylate having a branched structure and/or an alicyclic structure, styrene, vinyl ether group, dibasic acid anhydride group, and vinyl ester. A monomer such as a base or an olefin group.

The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group and the like.

The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.

The vinyl ester group is not particularly limited, and examples thereof include vinyl acetate and the like.

The olefin group is not particularly limited, and examples thereof include a butadienyl group and an isoprene group.

The content of the other monomer in the (A) resin is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass.

(A) Specific examples of the resin, for example, compounds represented by the following structures (exemplified compounds P-1 to P-57).

Further, x, 1, y, z, and St in the exemplified compound represent the composition ratio (mass ratio) of each repeating unit, and are preferably in the form of a range described later.

Synthetic method (A) The resin can be synthesized from a step of (co)polymerization of a monomer and a two-stage step of introducing a ethylenically unsaturated group. First, the (co)polymerization reaction is not particularly limited as long as the (co)polymerization reaction of each monomer, and can be appropriately selected from conventional (co)polymerization reactions. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, and the like can be appropriately selected for the active species to be polymerized. Among these (co)polymerization reactions, the synthesis is easy, and from the viewpoint of low cost, radical polymerization is preferred. Further, the polymerization method is not particularly limited, and can be appropriately selected from the conventional methods. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or the like can be appropriately selected. Among these methods, a solution polymerization method is more preferred. Carbon number

From the viewpoint of the modulus of elasticity (hardness), the total carbon number of the resin (A) is preferably 10 or more. Among them, the total carbon number is preferably from 10 to 30, particularly preferably from 10 to 15.

Molecular weight

The molecular weight of the resin (A) is preferably from 10,000 to 100,000, more preferably from 12,000 to 60,000, particularly preferably from 15,000 to 45,000. When the weight average molecular weight is within this range, it is preferable from the viewpoint of suitability and development of a resin (preferably a copolymer). Further, it is preferable from the viewpoint that the shape formed by the decrease in the melt viscosity is difficult to be deformed, the viewpoint that it is difficult to cause crosslinking failure, and the residue of the spacer shape in the absence of development.

The weight average molecular weight was measured by a gel permeation chromatography (GPC). The GPC is described in detail in the example items described later. Glass transition temperature

The glass transition temperature (Tg) of the resin (A) is preferably from 40 to 180 ° C, more preferably from 45 to 140 ° C, particularly preferably from 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

Acid price

(A) The acid value of the resin is preferably in the range of 20 mg KOH/g or more, more preferably 40 mg KOH/g or more, particularly 50 to 130 mg KOH / based on the molecular structure which can be employed. g is especially ideal. If the acid value is within the preferred range, a spacer having good developability and mechanical strength will be obtained.

Tg

The glass transition temperature (Tg) of the (A) resin is preferably from 40 to 180 ° C, and the weight average molecular weight is preferably from 10,000 to 100,000, based on a spacer having good developability and mechanical strength. The Tg is more preferably from 45 to 140 ° C, and the weight average molecular weight is more preferably from 12,000 to 60,000; particularly preferably, the Tg is from 50 to 130 ° C, and the weight average molecular weight is particularly preferably from 15,000 to 45,000.

Further, a preferred example of the (A) resin is more preferably a combination of the molecular weight, the glass transition temperature (Tg) and the acid value.

In the present invention, the resin (A) has a branching structure and/or an alicyclic structure, an acidic group, and an ethylene group which is disposed adjacent to the main chain in the repeating unit (copolymerizing unit). It is preferable to copolymerize the above copolymer with a ternary bond of a saturated bond from the viewpoint of a deformation recovery ratio, a development residue, and wrinkles when forming a pattern structure (for example, a spacer for a color filter).

Specifically, the (A) resin preferably has at least a repeating unit containing a branched structure and/or an alicyclic structure: X (x mole %); and a repeating unit containing an acidic group: Y (y mole %) And a copolymer containing a repeating unit of an ethylenically unsaturated bond to which an ester group is disposed at a distance from the main chain: Z (z mole %) is copolymerized with the above. Furthermore, if necessary, other repeating units may also be included: L (l mole %).

For example, such a copolymer can be a monomer having a branched structure and/or an alicyclic structure; a monomer having an acidic group; and an ethylenically unsaturated bond interposed between the main chain and an ester group. Monomer; and if necessary, copolymerization with other monomers. In particular, the monomer having at least the branched structure and/or the alicyclic structure is preferably represented by the general formula (4), from the viewpoint of improving the compressive elastic modulus and the elastic recovery property by using a functional group having a large volume. The monomer is copolymerized to introduce a copolymer having a branch structure and/or an alicyclic structure. In this case, the (A) resin has a structural unit derived from the monomer represented by the general formula (4) in the main chain.

The copolymerization composition ratio in the case where the (A) resin is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generalized, the composition ratio of the copolymer can be set to the following range:

The composition ratio (x) of the repeating unit having a branched structure and/or an alicyclic structure in the resin (A) is preferably from 10 to 70 mol%, more preferably from 15 to 65 mol%, particularly from 20 to 60. Moor% is especially ideal. When the composition ratio (x) is within this range, good development performance is obtained, and the image forming liquid withstandability in the image portion is also good.

The composition ratio (y) having an acidic group in the resin (A) is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, particularly preferably from 20 to 50 mol%. When the composition ratio (y) is within this range, good hardenability and developability can be obtained.

The composition ratio (z) of the resin having "the ethylenically unsaturated bond to the ester group interposed between the main chain" in the resin is preferably from 10 to 70 mol%, more preferably from 20 to 70 mol%. %, especially 30 to 70 mol% is particularly desirable. When the composition ratio (z) is within the range, the pigment dispersibility is excellent, and the sensitivity and the polymerization hardenability are also good, so that the solution preservability after solution preparation and the long-term state in the dry film state after coating are obtained. The stability over time will be good.

Further, the (A) resin is preferably a composition ratio (x) of 10 to 70 mol%, a composition ratio (y) of 5 to 70 mol%, and a composition ratio (z) of 10 to 70 mol%; More preferably, the composition ratio (x) is 15 to 65 mol%, the composition ratio (y) is 10 to 60 mol%, and the composition ratio (z) is 20 to 70 mol%; particularly desirable case: composition ratio (x) is 20 to 50 mol%, the composition ratio (y) is 20 to 50 mol%, and the composition ratio (z) is 30 to 70 mol%.

The content in the photosensitive resin composition of the (A) resin is preferably from 5 to 70% by mass, and more preferably from 10 to 50% by mass, based on the total solid content of the composition.

(A) The resin can be used in combination with other resins to be described later, and it is preferred to use only the resin (A).

Other resin

The resin which can be used in combination with the (A) resin is preferably a compound which exhibits swelling property to an alkaline aqueous solution, and more preferably a compound which is soluble in an aqueous alkaline solution.

The resin which exhibits swelling property or solubility in an alkaline aqueous solution is, for example, a resin having an acidic group. Specific examples thereof include a compound in which an ethylenically unsaturated double bond and an acidic group are introduced into an epoxide (for example, an epoxy acrylate compound), and a vinyl copolymer having a (meth) acrylonitrile group and an acidic group in a side chain. A mixture of an epoxy acrylate compound, a vinyl copolymer having a (meth)acrylonyl group and an acidic group in a side chain, a maleic acid-based copolymer, or the like.

The acidic group is not particularly limited, and can be appropriately selected depending on the intended purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these acidic groups, those based on raw material availability and the like are preferred. A carboxyl group is mentioned.

In the case where the photosensitive resin layer is formed on the substrate by the transfer method, in particular, the (A) resin may be used in combination with other resins. In this case, the total content (solid content) of the resin which can be used in combination with the (A) resin is preferably from 5 to 70% by mass, and more preferably from 10 to 50% by mass, based on the total solid content of the photosensitive resin layer. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the wrinkle property of the surface of the photosensitive resin layer can be favorably maintained. When the content is 70% by mass or less, the exposure sensitivity is improved.

(B) Polymeric unsaturated compounds

The photosensitive composition of the present invention contains both the (A) resin and the (B) polymerizable unsaturated compound.

The polymerizable unsaturated compound can be used after being selected from the components constituting the conventional composition, and examples thereof include those disclosed in paragraphs [0010] to [0020] of JP-A-2006-23696, or Japan. The components disclosed in paragraphs [0027] to [0053] of JP-A-2006-64921.

In the relationship with the (A) resin, the mass ratio of the (B) polymerizable compound to the (A) resin [(B)/(A) ratio] is preferably 0.5 to 2.5, more preferably 0.6 to 2.2. Especially suitable for 0.8 to 1.9. When the ratio of (B) / (A) is within this range, a spacer having good developability and mechanical strength can be obtained.

(C) Photopolymerization initiator (C1) hexaarylbiimidazole compound

The radiation-sensitive resin composition (C) component of the present invention contains at least a (C1) hexaarylbiimidazole compound because of the increase in the sensitivity of the long wavelength.

The hexaarylbiimidazole-based compound may, for example, be 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4 ',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetra (4 -ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis (2 ,4,6-trichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2', bis(2-cyanophenyl)-4 , 4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5,5'-tetra (4 -phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2, 2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-methylphenyl) -4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole, 2,2'-bis(2-B Phenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5, 5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenyl) Biimidazole, 2,2'-bis(2-phenylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis (2) -phenylphenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-phenylphenyl)-4,4', 5,5'-tetrakis(4-phenoxycarbonylphenyl)biimidazole; 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-methoxy Phenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)biimidazole, 2,2'-bis ( 2-chlorophenyl)-4,4',5,5'-tetrakis(3,4-dimethoxyphenyl)biimidazole; 2,2'-bis(2,4-dichlorophenyl)- 4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole , 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-tribromobenzene -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dicyanophenyl)-4,4',5,5'-tetraphenyl Biimidazole , 2,2'-bis(2,4,6-tricyanophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dimethyl Phenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-trimethylphenyl)-4,4',5,5' -tetraphenylbiimidazole, 2,2'-bis(2,4-diethylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis (2, 4,6-Triethylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-diphenylphenyl)-4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-triphenylphenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2 A biimidazole compound such as '-bis(2-fluorophenyl)-4,4',5,5'-tetraphenylbiimidazole or the like.

Among the above, particularly preferred compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (trade name: B-CIM, Japan) 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4-dimethoxyphenyl)biimidazole (trade name: HABI1311) , manufactured by Siber Hegner, Japan, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured by Nippon Black Gold Chemical Co., Ltd.).

These compounds are used singly or in combination of two or more.

(C2) aromatic mercapto compound

In order to improve the spectral sensitivity, the radiation sensitive resin composition of the present invention contains a (C2) aromatic mercapto compound.

Examples of the aromatic mercapto compound which can be used in the radiation sensitive resin composition of the present invention include a compound having a benzene ring or a heterocyclic ring as a core, and having one or two mercapto groups. In the case of having two such fluorenyl groups, the thiol group on one side may be substituted by an alkyl group, an aralkyl group or a phenyl group, or may be a dimer or a disulfide form in which an alkyl group is interposed therebetween. Dimer.

Among the above, examples of the aromatic mercapto compound include, for example, 2-mercaptobenzothiazole and 2-mercaptobenzoene. Oxazole, and N-phenylmercaptobenzimidazole and the like. These compounds are used singly or in combination of two or more.

(C3) additives

In order to further improve the sensitivity, the radiation sensitive resin composition of the present invention contains a (C3) auxiliary.

The (C3) auxiliary agent is not particularly limited as long as it can improve the sensitivity. Among them, a thioxanthone compound, a coumarin compound, a diphenyl ketone compound, or a diphenyl ketone compound is preferable from the viewpoint of the sensitivity improvement effect. And at least one selected from the acridone compound.

(C3-1) thioxanthone compound

In the present specification, the thioxanthone compound means a thioxanthone which may have a substituent.

The substituent may, for example, be a halogen atom having a carbon number of 1 to 10, preferably a linear or branched alkyl group having 1 to 4 carbon atoms, or a fluorine atom, a chlorine atom or an iodine atom. The position of the substituent is not particularly limited, and is preferably 2 and/or 4 positions.

The thioxanthone compound, specifically, thioxanthone, 2-ethylthioxanthone, 2-propylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthene Alkyl-substituted thioxanthone such as ketone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-methylethylthioxanthone, etc.: 2-chlorothioxanthene A halogenated thioxanthone such as a ketone or the like.

Among the above, preferred are 2-isopropylthioxanthone, 2,4-diethylthioxanthone, or 2-chlorothioxanthone.

(C3-2) coumarin compound

The coumarin compound may, for example, be a compound represented by the formula (I), (II) or (III).

In the formula (I), R ¹ and R ² may be the same or different and each represents a hydrogen atom, an amine group, a dialkylamine group, a monoalkylamine group, an N-substituted amine alkyl group, a halogen atom or an alkane. Oxygen. Here, an alkyl group having 1 to 4 carbon atoms and an alkoxy group are preferred.

In the formula (II), R ³ represents an alkylene group having 1 to 7 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms. R ⁴ and R ⁵ may be the same or different and each represents a hydrogen atom independently or an alkyl group having 1 to 7 carbon atoms. R ⁴ or R ⁵ represents an alkyl group, and preferably represents an alkyl group of 1 to 4.

In the formula (III), R ⁶ and R ⁷ may be the same or different, and each represents a hydrogen atom independently selected, an alkyl group having 1 to 7 carbon atoms (preferably 1 to 4), or a carbon number of 1 to 4; Alkoxy.

Examples of the coumarin compound, specifically, 7-{{4-chloro-6-(diethylamino) secondary three -2-yl}amino}-3-phenylcoumarin, 7-{{4-methoxy-6-(diethylamino) secondary three -2-yl}amino}-3-phenylcoumarin, 7-{{4-methoxy-6-(diethylaminopropylamino) secondary three -2-yl}amino}-3-phenylcoumarin, N-(γ-dimethylaminopropyl)-N'-{3-phenylcoumarin-(7)}urea, 3 -Phenyl-7-(4'-methyl-5'-n-butoxybenzotriazol-2-yl)coumarin. Among these compounds, 7-{{4-chloro-6-(diethylamino) secondary three is preferred. -2-yl}amino}-3-phenylcoumarin.

The coumarin compound may, for example, be a compound represented by the following formula (VIII) which is a 3-aryl-substituted coumarin compound.

In the formula (VIII), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group. R ⁹ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a group represented by the following formula (VIIIA), preferably a methyl group, an ethyl group, a propyl group, or the like. The butyl group or the group represented by the formula (VIIIA) is particularly preferably a group represented by the formula (VIIIA).

R ¹⁰ and R ¹¹ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon number 6 which may be substituted. ～10 aryl, amine, -N(R ¹⁶ )(R ¹⁷ ) or a halogen atom. Here, examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group. Examples of the haloalkyl group having 1 to 8 carbon atoms include a chloromethyl group, a fluoromethyl group, and a trifluoromethyl group. Examples of the alkoxy group having 1 to 8 carbon atoms include a methoxy group, an ethoxy group, and a butoxy group. The aryl group having 6 to 10 carbon atoms which may be substituted may, for example, be a phenyl group. Examples of the halogen atom include -Cl, -Br, and -F. Among them, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, or -N(R ¹⁶ )(R ¹⁷ ) or -Cl is preferable.

R ¹² represents an aryl group having 6 to 16 carbon atoms which may be substituted, and specific examples thereof include a phenyl group, a naphthyl group, a tolyl group, and a p-isopropylbenzyl group. Examples of the substituent which may be introduced into the aryl group include an amine group, -N(R ¹⁶ )(R ¹⁷ ), and an alkyl group having 1 to 8 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, octyl group). a haloalkyl group having 1 to 8 carbon atoms (for example, a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, etc.) or an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, an ethoxy group, or a butyl group) Oxy), hydroxy, cyano, halogen (eg, -Cl, -Br, -F).

R ¹³ , R ¹⁴ , R ¹⁶ and R ¹⁷ each represent an independently hydrogen atom and an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group). R ¹³ and R ¹⁴ may also be bonded to each other while forming a heterocyclic ring with a nitrogen atom (for example, piperidine ring, piperidine) Ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.). R ¹⁶ and R ¹⁷ may also be bonded to each other while forming a heterocyclic ring with a nitrogen atom (for example, piperidine ring, piperidine) Ring, morpholine ring, pyrazole ring, diazole ring, triazole ring, benzotriazole ring, etc.). R ¹⁵ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group), and an alkoxy group having 1 to 8 carbon atoms (for example, a methoxy group, Ethoxy group, butoxy group), an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an amine group, -N(R ¹⁶ )(R ¹⁷ ), or a halogen (for example, -Cl, -Br, -F).

Zb represents =O, =S or =C(R ¹⁸ )(R ¹⁹ ).

R ¹⁸ and R ¹⁹ represent independently cyano groups, -COOR ²⁰ and -COR ²¹ . R ²⁰ and R ²¹ each independently represent an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl) or a haloalkyl group having 1 to 8 carbon atoms (for example, chlorine). An alkyl group having 6 to 10 carbon atoms (for example, a phenyl group), a heterocyclic ring or a benzene ring which may be substituted with a methyl group, a fluoromethyl group or a trifluoromethyl group.

Further, examples of the other coumarin compound include compounds represented by the following formula (IV).

In the above formula (IV), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an amine group, a dialkylamino group, a monoalkylamino group or an N-substituted amin. Base, halogen, alkyl or alkoxy. Here, the alkyl group and the alkoxy group are preferably those having 1 to 4 carbon atoms. R ⁵ and R ⁶ may be bonded to each other to form a ring, and may also form a condensed ring with the adjacent Z.

Z is preferably =O, =S, =C(CN) ₂ , especially =O is particularly desirable.

Further, examples of the coumarin compound represented by the compound represented by the formula (IV), for example, the following compounds 1 to 3, or NKX 1316, 1317, 1767, 1768 obtained according to the catalog of the Linyuan Biochemical Research Institute of Japan, 1320, 1769, 1319, 1770, 1771, 846, 3502, 1619, commercially available products are also commercially available. Among them, NKX 1767, 1768, and 1619 (trade name: manufactured by Japan Linyuan Biochemical Research Institute) are preferred.

In the above compound 1, R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group (preferably having a carbon number of 1 to 5).

(C3-3) diphenyl ketone compound

Examples of the diphenyl ketone compound include diphenyl ketone, benzamidine benzoic acid, 4-phenyl diphenyl ketone, 4,4-diethylaminodiphenyl ketone, and 3,3'- Dimethyl-4-methoxydiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, and the like.

(C3-4) acridone compound

Examples of the acridone compound include the compounds disclosed in paragraphs [0032] to [0042] of JP-A-2007-41082, wherein an example of a particularly desirable compound is 10-n-butyl-2. - Chloramphenidone (trade name: NBCA, manufactured by Japan Black Gold Chemical Co., Ltd.).

The content of the component (C) in the radiation sensitive resin composition of the present invention relative to all solid components of the radiation sensitive resin composition (all solid components of the photosensitive resin layer) (that is, the total of C1 to C3) The content) is preferably from 0.5 to 25% by mass, more preferably from 0.5 to 15% by mass. When the content is within this range, it is possible to prevent a decrease in the light sensitivity or the strength of the spacer, and it is possible to improve the performance such as the deformation recovery property required for the spacer.

When necessary, the radiation sensitive resin composition of the present invention can contain other photopolymerization initiators other than the component (C). Examples of other photopolymerization initiators include an aminodiphenylketone-based compound, a phosphinylphosphine-based compound, and an oxime ester-based compound.

Specific examples of the aminodiphenyl ketone compound include IRGACURE (Irg) 369, IRGACURE (Irg) 379, and IRGACURE (Irg) 907 (all of which are trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).

Specific examples of the bismuth oxide-based phosphine-based compound include DAROCURE TPO and IRGACURE (Irg) 819 (all of which are trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).

Specific examples of the oxime ester-based compound include IRGACURE (Irg) OXE1 or CG1242 (all of which are trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.).

Other ingredients

The photosensitive composition of the present invention contains at least the (A) resin, (B) a polymerizable unsaturated compound, and (C) a photopolymerization initiator, and may further contain other components (if necessary) D) Particles, etc.).

The other components can be selected from the components constituting the conventional composition. For example, the components disclosed in paragraphs [0010] to [0020] of JP-A-2006-23696, JP-A-2006 The components disclosed in paragraphs [0027] to [0053] of the '6491 publication.

(D) particles

In the case where the photosensitive resin layer on the substrate is formed by the transfer method, the photosensitive composition preferably contains fine particles.

(D) The fine particles are not particularly limited, and may be appropriately selected depending on the purpose. For example, the filler pigments disclosed in paragraphs [0035] to [0041] of JP-A-2003-302639, wherein From the viewpoint of a spacer having good developing power and mechanical strength, a cerium oxide colloid is preferred.

The volume average particle diameter of the (D) fine particles is preferably from 5 nm to 50 nm, more preferably from 10 nm to 40 nm, particularly preferably from 15 nm to 30 nm, from the viewpoint that a spacer having high mechanical strength can be obtained.

From the viewpoint of obtaining a spacer having high mechanical strength, in the photosensitive resin layer (that is, a spacer) of the (D) fine particles with respect to all solid components (mass) in the photosensitive resin layer (spacer) The content is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, particularly preferably from 15 to 30% by mass.

Exposure step, development step, and heating step

In the method for producing a spacer according to the present invention, at least a part of the photosensitive resin layer (coating film) formed on the substrate after the layer forming step is subjected to a step of substantially not containing radiation having a wavelength lower than 350 nm (exposure) Step), a step of developing the exposed photosensitive resin layer (developing step), and a step of heating the photosensitive resin layer after development (heating step).

According to the manufacturing method of the present invention, it is possible to produce a spacer having a superior deformation recovery rate.

The step of forming a pattern by exposing and developing the photosensitive resin layer formed on the substrate is referred to as a "pattern forming step".

Examples of the "radiation" in the present invention include ultraviolet rays, far ultraviolet rays, X-rays, electron lines, molecular lines, γ lines, synchrotron radiation, proton beam lines, and the like.

Exposure step

In the exposure step of the present invention, at least a part of the photosensitive resin layer (coating film) formed in the layer forming step is exposed to substantially no radiation having a wavelength lower than 350 nm.

Here, the term "substantially does not contain a wavelength lower than 350 nm" means that the irradiation intensity is higher than the wavelength of 350 nm or more, and may have a wavelength of less than 350 nm, and has an irradiation intensity which is substantially negligible. In other words, it is also possible to include a wavelength that does not adversely affect the life of the exposure machine lens described later.

When a part of the photosensitive resin layer is partially exposed, it is exposed through a predetermined pattern mask. In the present invention, by filtering out short-wavelength radiation having a high energy of less than 350 nm, it is possible to effectively suppress a decrease in the life of a lens which has been used in an exposure machine.

For the radiation used for the exposure, visible light, ultraviolet light, far ultraviolet light, or the like can be used.

Examples of the light source used for light irradiation include a medium pressure to an ultrahigh pressure mercury lamp, a xenon lamp, a metal halide lamp, and the like.

If radiation having a wavelength shorter than a short wavelength of 350 nm is substantially not contained, it is preferred to use radiation in the range of from 190 to 450 nm and to filter out a wavelength of less than 350 nm.

The exposure amount of the radiation is measured by an illuminometer (trade name: OAI model 365, manufactured by OAI Optical Associates Inc.) to measure the intensity value in the exposed radiation wavelength (for example, 365 nm), and is usually 20 to 50,000 J/m. ^{2 is} preferably 20 to 1,500 J/m ² .

The method of filtering out the wavelength of the radiation below 350 nm is not particularly limited, and for example, a method using a filter can be adopted.

For example, the filter can be a UV-transfer filter "UV-35" (trade name) manufactured by Toshiba Glass Co., Ltd., Japan.

Imaging step

In the developing step of the present invention, the photosensitive resin layer (coating film) after the exposure is developed.

The developing liquid used for the development processing may be a thin aqueous solution of a basic substance, or a small amount of an organic solvent which is miscible with a water may be further added to the diluted aqueous solution.

Before the development, it is preferred to spray the pure water with a shower nozzle or the like to uniformly wet the surface of the photosensitive resin composition layer or the oxygen barrier layer.

Examples of suitable basic substances include alkali metal hydroxides (for example, sodium hydroxide, potassium hydroxide), alkali metal carbonates (for example, sodium carbonate, potassium carbonate), and alkali metal bicarbonates (for alkali metal bicarbonates). For example, sodium bicarbonate, potassium bicarbonate), alkali metal silicates (eg, sodium citrate, potassium citrate), alkali metal bismuth phthalates (eg, sodium metasilicate, potassium metasilicate), Triethanolamine, diethanolamine, monoethanolamine, morpholine, tetraalkylammonium hydroxide (for example, tetramethylammonium hydroxide), trisodium phosphate, and the like. The concentration of the alkaline substance is preferably from 0.01 to 30% by mass, and the pH is preferably from 8 to 14.

The "organic solvent mixed with water" is, for example, suitably selected from the group consisting of methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, and ethylene glycol single. Ethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethyl Acetamide, hexamethylphosphoniumamine, ethyl lactate, methyl lactate, ε-caprolactone, N-methylpyrrolidone, and the like. The concentration of the organic solvent which is miscible with the water in the developing liquid is preferably from 0.1 to 30% by mass. A conventional surfactant may be further added, and the concentration of the surfactant in the developing solution is preferably from 0.01 to 10% by mass.

The developing solution can also be used as a solution or as a spray liquid. In the case where the uncured portion of the photosensitive resin composition layer is removed, it is possible to combine it in a developing liquid, and to wipe the photosensitive resin composition layer or the like by a rotating brush or a wet sponge. The temperature of the solution of the developing solution is preferably from about room temperature (20 ° C) to 40 ° C. The development time is usually about 10 seconds to 2 minutes in accordance with the composition of the photosensitive resin composition layer, the alkalinity or temperature of the developing solution, the kind and concentration in the case of adding an organic solvent, and the like. If it is too short, the development of the non-hardened portion (the negative portion is a non-exposed portion) will become insufficient; if it is too long, the hardened portion (the negative portion is the exposed portion) will also be etched. It is also possible to add a water washing step after the development process. In this developing step, the spacers will form the desired shape.

Heating step

In the heating step in the present invention, the heat treatment (also referred to as baking treatment) is a pattern image (or spacer) composed of the photosensitive transfer material obtained in accordance with the development step.

The heat treatment is performed by heating the pattern image (spacer pattern) formed by exposure and development. Thereby, the spacer of the present invention can be obtained.

The method of heat treatment can employ various methods known in the art. For example, a method of accommodating a plurality of substrates in a loading case, a method of treating them by a convection oven, a method of treating them one by one with a hot plate, and a method using an infrared heater may be mentioned.

The heating temperature in the heating step is usually from 150 ° C to 280 ° C, preferably from 180 ° C to 250 ° C. Although the heating time varies depending on the heating temperature, in the case where the baking temperature is 240 ° C, it is preferably 10 minutes to 120 minutes, more preferably 30 minutes to 90 minutes.

Further, in the method for producing a spacer, it is also possible to perform the exposure and the display before the heating step, based on the viewpoint of preventing the film from being uneven and preventing the precipitation of components such as the UV absorber contained in the photosensitive resin layer. Post-exposure of the spacer pattern formed by the steps. Once the post-exposure is performed before the heat treatment is performed, it is possible to effectively prevent the minute contaminants mixed during lamination from expanding to become defects.

Post exposure

The light source for post-exposure can be appropriately selected and used if it is a light source capable of irradiating light (for example, 365 nm or 405 nm) in the wavelength range of the photosensitive resin layer.

Specific examples thereof include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a metal halide lamp.

The exposure amount is preferably an amount of exposure for compensating the exposure, and is usually 50 mJ/cm ² to 5,000 mJ/cm ² , preferably 200 mJ/cm ² to 2,000 mJ/cm ² , and more preferably 500 mJ/cm ² to 1,000 mJ. /cm ² .

The spacer of the present invention can be formed by forming a color filter including a black mask portion such as a black matrix or a colored portion such as a color image.

The black masking portion, the coloring portion, and the spacer are applied in a coating method in which a photosensitive composition is applied in combination, and a transfer method in which a transfer material having a photosensitive resin layer composed of a photosensitive composition is used.

The black shielding portion and the colored portion and the spacer can be formed of respective photosensitive compositions. For example, by applying the photosensitive composition of the liquid directly onto the substrate, after forming the photosensitive resin layer, exposure and development are performed to form the black shielding portion and the colored portion in a pattern, and then The photosensitive composition of the other liquid is provided on another substrate (temporary carrier) different from the substrate to form a transfer material produced by the photosensitive resin layer, and the transfer material is brought into close contact with the black shielding portion. The substrate of the coloring portion can form a spacer by performing exposure and development after transferring the photosensitive resin layer. In this manner, a color filter provided with a spacer can be produced.

Substrate for liquid crystal display device

In the present invention, the substrate for a liquid crystal display device includes the spacer of the present invention. The spacer is preferably formed on a black mask portion of a black matrix or the like formed on the carrier or on a driving element such as a TFT. In addition, a black conductive portion such as a black matrix or a driving element such as a TFT may be present, and a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may be present between the spacer and the spacer.

For example, in the case where a spacer is provided on the black shielding portion or the driving element, the black shielding portion (black matrix or the like) or the driving element pre-arranged on the carrier is covered, for example, the photosensitive is turned The photosensitive resin is laminated on the surface of the carrier, and the photosensitive resin layer is peeled off and transferred to form a photosensitive resin layer, and then a spacer is formed by exposure, development, heat treatment, or the like to form a substrate for a liquid crystal display device.

In the same manner as described above, for example, after the photosensitive composition of the liquid is directly applied onto the substrate to form a photosensitive resin layer, exposure and development are performed, and the black shielding portion and the colored portion are patterned. By using a photosensitive composition of another liquid on another substrate (temporary carrier) different from the substrate to form a transfer material made of a photosensitive resin layer, the transfer material is brought into close contact with the formation. After the photosensitive resin layer is transferred by the substrate having the black shielding portion and the colored portion, the spacer can be patterned by exposure and development. In this manner, a substrate for a liquid crystal display device provided with a spacer can be produced.

On the substrate for a liquid crystal display device, if necessary, colored pixels such as red (R), blue (B), and green (G) may be further provided.

Liquid crystal display element

In the present invention, a liquid crystal display element can be configured by providing a substrate for a liquid crystal display device. In one embodiment of the liquid crystal display device, at least one side having a light transmittance, a carrier (including a substrate for a liquid crystal display device of the present invention), and a liquid crystal layer and a liquid crystal driving means between the carriers (including simple Components of matrix drive mode and active matrix drive mode).

In this case, the substrate for a liquid crystal display device of the present invention can be used as a color filter substrate having a plurality of RGB pixel groups and separating pixels constituting the pixel group from each other by a black matrix. In the color filter, since a spacer having a high elastic recovery rate and a load deformation amount and high deformation recovery property is provided, the liquid crystal display element including the color filter substrate can effectively prevent color filter from being caused by color filter The variation of the liquid crystal cell gap (liquid crystal cell thickness) between the sheet substrate and the counter substrate causes unevenness in color unevenness due to uneven distribution of the liquid crystal material, low-temperature foaming, and the like. Thereby, the produced liquid crystal display element can display a vivid image.

In addition, as another form of the liquid crystal display device, at least one side having a light transmittance, a carrier (including a substrate for a liquid crystal display device of the present invention), and a liquid crystal layer and a liquid crystal driving means between the carriers may be used. The liquid crystal driving means has an active element (for example, a TFT) and an element having a high elastic recovery ratio and a load deformation amount between the pair of substrates, and a predetermined width is limited. In this case, the substrate for a liquid crystal display device of the present invention can also be used as a color filter substrate having a plurality of RGB pixel groups and separating the pixels constituting the pixel group from each other by a black matrix.

Examples of the liquid crystal which may be used in the present invention include nematic liquid crystal, cholesteric liquid crystal, smectic liquid crystal, and ferroelectric liquid crystal.

Further, the pixel group of the color filter substrate may be formed by two-color pixels that exhibit mutually different colors, or may be composed of three-color pixels or four or more pixels. For example, in the case of three colors, it is composed of three colors of red (R), green (G), and blue (B). In the case of arranging RGB three-color pixel groups, it is preferable to arrange them in a mosaic shape such as a mosaic or a triangle, and in the case of arranging a pixel group of four or more colors, any configuration is possible. For example, the color filter substrate may be formed by forming a black matrix as described later to form a pixel group of two or more colors, and conversely, a pixel group may be formed after forming a black matrix. For the formation of RGB pixels, Japanese Patent Laid-Open Publication No. 2004-347831 and the like can be referred to.

Liquid crystal display device

The liquid crystal display device includes the substrate for the liquid crystal display device. Further, the liquid crystal display device includes the liquid crystal display element. That is, as described above, the spacers of the present invention are used to limit the predetermined width so that the spacers are disposed opposite to each other, and the liquid crystal material is sealed (referred to as a liquid crystal layer). The gap is limited so that the thickness of the liquid crystal layer (the thickness of the liquid crystal cell) is maintained to a desired uniform thickness.

Examples of the liquid crystal display mode in the liquid crystal display device include STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and the like. Various other liquid crystal display modes.

In the liquid crystal display device, it is desirable to display a display mode in which display unevenness is likely to occur depending on the thickness variation of the liquid crystal cell, and the liquid crystal cell thickness is preferably a VA type display mode of 2 μm to 4 μm. IPS type display mode, OCB type display mode.

In the example of the configuration of the liquid crystal display device, (a) a driving side substrate in which a driving element such as a thin film transistor (TFT) and a pixel electrode (conductive layer) are arranged to face each other with a spacer interposed therebetween, and The opposite substrate of the counter electrode (conductive layer) is formed by enclosing the liquid crystal material in the gap portion: (b) arranging the drive substrate opposite to each other with the spacer interposed therebetween, and facing the opposite electrode (conductive layer) The substrate is formed by enclosing a liquid crystal material in a gap portion thereof. The liquid crystal display device can be applied to various liquid crystal display devices.

For the liquid crystal display device, for example, it has been disclosed in "Next Generation Liquid Crystal Display Technology (Editor Uchida Natsuo, Japan Industrial Investigation Association, issued in 1994)". In addition to the liquid crystal display device of the present invention or the substrate for a liquid crystal display device, the liquid crystal display device of the present invention is not particularly limited. For example, the liquid crystal display device of various modes disclosed in the "next generation liquid crystal display technology" can be configured. Among them, a liquid crystal display device constituting a color TFT system is particularly effective. A liquid crystal display device for a color TFT system has been disclosed, for example, in "Color TFT Liquid Crystal Display (Japan Kyoritsu Publishing Co., Ltd., issued in 1996)".

In addition to the above-described substrate for a liquid crystal display device or a liquid crystal display device, the liquid crystal display device can generally be an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, or the like. It is composed of various members such as a light-diffusing film and an anti-glare film. For these components, for example, it has been disclosed in "'94 Liquid Crystal Display Peripherals/Chemical Markets (Japan Island Kentaro, Co., Ltd., CMC, 1994)", "2003 LCD Related Markets Status and Future Outlook (下下Volume) (Formian Liangji), Japan (shares) Fuji Kimera, and 2003.

Example

Hereinafter, the present invention will be described in more detail based on the examples, and the present invention is not limited by the following examples. Also, as long as there is no special statement, "%" and "parts" are quality benchmarks.

Resin synthesis

Hereinafter, an example in which the (A) resin is shown is a synthesis example in which a structural unit derived from styrene is added to the compound P-4+St in the above compound P-4. However, the monomer ratio in the compound P-4 is changed by the above-described ones.

Synthesis Example 1

7.48 parts of 1-methoxy-2-propanol (trade name: MFG, Japan emulsifier) was added to the reaction vessel in advance, and the temperature was raised to 90 ° C. In a nitrogen atmosphere, styrene (st; w ) 3.1 parts, tricyclopentenyl methacrylate (TCPD-M (trade name) manufactured by Hitachi Chemical Co., Ltd.; x) 4.28 parts, methacrylic acid (MMA; y) 11.7 parts, azo polymerization A mixed solution of 2.08 parts of a starter (V601, manufactured by Nippon Wako Pure Chemical Industries, Ltd.) and 55.2 parts of 1-methoxy-2-propanol was dropped into a reaction container of 90 for 2 hours. After the dropwise addition, the reaction was carried out for 4 hours to obtain an acrylic resin solution.

Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution, and then 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added. It took 2 hours to drip (GLM-MAA; z). After the dropwise addition, the solvent was also injected at 90 ° C for 4 hours, and then the solvent was added to a concentration of 45% to add 1-methoxy-2-propyl acetate (MMPGAc, Daisel Chemical Industry ( (manufacturing)), a resin solution of the compound P-4+St ((A) resin) having an unsaturated group was obtained (solid content acid value: 76.0 mgKOH/g, Mw: 25,000, 1-methoxy-2-propene) Alcohol / 1-methoxy-2-propyl acetate 45% solution) (X: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol%).

Here, GLM-MAA-based glycidyl methacrylate is bonded to methacrylic acid (hereinafter, the same).

Further, the molecular weight Mw of the compound P-4+ styrene compound (compound P-4+st) represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC method).

GPC system uses HLC-8020GPC (manufactured by Toso Co., Ltd.), and the column system uses three TsK gels, super Multipore HZ-H (manufactured by Toso Co., Ltd., 4.6 mm ID × 15 cm), and the eluent is THF (tetrahydrofuran). ). In addition, the conditions were set such that the sample concentration was 0.35/min, the flow rate was 0.35 ml/min, the sample injection amount was 10 μl, and the measurement temperature was 40° C., using an IR detector. In addition, the calibration line is "standard sample TSK standard, polystyrene" made by Toso (share): "F-40", "F-40", "F-20", "F-4", " 8 samples of F-1", "A-5000", "A-2500", "A-1000", and "n-butylbenzene" were produced (the same applies hereinafter).

Hereinafter, the other compound of the resin (A) is a synthesis example in which the above compounds P-1 to P-4, P-9, P-10, P-25, P-53 and P-57 are synthesized; Synthesis Examples (Synthesis Example 2 to Synthesis Example 8 and Synthesis Example 10 to Synthesis Example 11) in which a compound of any of these compounds was added to the structural unit; and a synthesis example of the copolymer for comparison (Synthesis Example 9).

Synthesis Example 2

The synthesis of the above compound P-4 was carried out in the following manner. However, the monomer ratio in the compound P-4 is changed by the one shown previously.

In Synthesis Example 1, TCPD-M(x) and methacrylic acid (y) were changed so that x:y:z=34 mol%:27 mol%:39 mol% in the compound P-4 except that styrene was not used. In addition to the addition amount of GLM-MMA (z), it was synthesized by the same method as in Synthesis Example 1 to obtain a resin solution of the compound P-4 ((A) resin) having an unsaturated group (solid content acid value: 72.5 mgKOH) /g, Mw: 22,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 3

The synthesis of the compound P-3+st in which the structural unit derived from styrene was added to the compound of the above compound P-3 was carried out in the following manner. However, the monomer ratio in compound P-3 was changed from what was previously shown.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.) to make x:y:z in the compound P-3+st. :w is changed to 25 mol%: 25 mol%: 40 mol%: 10 mol%, and the amount of cyclohexyl methacrylate (x), methacrylic acid (y), GLM-MMA (z), and styrene added is changed. The same procedure as in Synthesis Example 1 was carried out to obtain a resin solution of the compound P-3+st ((A) resin) having an unsaturated group (solid content acid value: 84.9 mgKOH/g, Mw: 26,000, 1-methoxy Base-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 4

The synthesis of the above compound P-3 was carried out in the following manner. However, the monomer ratio in compound P-3 was changed from what was previously shown.

In Synthesis Example 1, except that styrene was not used, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and x in the compound P-3 was used. :y:z is changed to 32 mol%: 25 mol%: 43 mol%, and the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MMA (z) is changed, and the same synthesis example is used. The method of 1 was synthesized to obtain a resin solution of the compound P-3 ((A) resin) having an unsaturated group (solid content acid value: 80.9 mgKOH/g, Mw: 21,000, 1-methoxy-2-propanol) /1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 5

The synthesis of the above compound P-53 was carried out in the following manner. However, the monomer ratio in the compound P-53 was changed from what was previously shown.

In Synthesis Example 1, except that styrene was not used, tricyclopentenyl methacrylate was changed to dicyclopentenyloxyethyl methacrylate (Fancryl FA-512M, manufactured by Hitachi Chemical Co., Ltd., Japan) )), FA-512M (x), methacrylic acid (y), and GLM-MMA (z) were changed in such a manner that x:y:z=46.2 mol%: 24.3 mol%: 29.5 mol% in the compound P-53 In addition to the addition amount, the same procedure as in Synthesis Example 1 was carried out to obtain a resin solution of the compound P-53 ((A) resin) having an unsaturated group (solid content acid value: 70.2 mgKOH/g, Mw: 30,000) , 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 6

The synthesis of the compound P-10+st constructed by adding a structural unit derived from styrene to the compound of the above compound P-10 was carried out in the following manner. However, the monomer ratio in the compound P-10 is changed by the one shown previously.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to dicyclopentanyl methacrylate (Fancryl FA-513M (trade name) manufactured by Hitachi Chemical Co., Ltd.), and styrene was added to Compound P. -10: x: y: z: w is 25 mol%: 25 mol%: 40 mol%: 10 mol% to change FA-513M (x), methacrylic acid (y) and GLM-MMA (z) and styrene In addition to the addition amount, the same procedure as in Synthesis Example 1 was carried out to obtain a resin solution of the compound P-10+st ((A) resin) having an unsaturated group (solid content acid value: 78.7 mgKOH/g, Mw: 28,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 7

The synthesis of the compound P-1+St in which the structural unit derived from styrene was added to the compound of the above compound P-1 was carried out in the following manner. However, the monomer ratio in the compound P-1 is changed by the one shown previously.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to ADMA (manufactured by Nippon Ignaku Co., Ltd.) so that x:y:z:w in the compound P-1+St was 30 mol%: 24 mol%: 38 mol. In the same manner as in the synthesis example 1, except that the amount of ADMA (x), methacrylic acid (y), GLM-MMA (z) and styrene added was changed in an amount of 8 mol%, an unsaturated group was obtained. Resin solution of compound P-1+St ((A) resin) (solid content acid value: 74.1 mgKOH/g, Mw: 29,000, 1-methoxy-2-propanol/1-methoxy-2-propyl Acetate 45% solution).

Synthesis Example 8

The synthesis of the compound P-2+St in which the structural unit derived from styrene was added to the compound of the above compound P-2 was carried out in the following manner. However, the monomer ratio in Compound P-2 was changed from what was previously shown.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to isodecyl methacrylate (IBXMA, manufactured by Nippon Wako Pure Chemical Industries, Ltd.) to make x:y:z in the compound P-2+St: w is the same as in Synthesis Example 1 except that the amount of IBXMA (x), methacrylic acid (y), GLM-MMA (z), and styrene is changed by 34 mol%: 24 mol%: 36 mol%: 6 mol%. The method was synthesized to obtain a resin solution of the compound P-2+St ((A) resin) having an unsaturated group (solid content acid value: 72.9 mgKOH/g, Mw: 29,000, 1-methoxy-2-propanol) /1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 9 (for comparison)

The resin used in the comparison was synthesized in the following manner.

In Synthesis Example 6, GLM-MAA was changed to glycidyl methacrylate (GLM; manufactured by Tokyo Chemical Industry Co., Ltd.) so that x:y:z:w in the copolymer 1 became 27 mol%: 25 mol. %: 40 mol%: 8 mol%, the amount of addition of dicyclopentanyl methacrylate (x), methacrylic acid (y), GLM (z) and styrene was changed, and the same method as in Synthesis Example 6 was used. Synthesis, a resin solution of copolymer 1 having no unsaturated group was obtained (solid content acid value: 95.9 mgKOH/g, Mw: 18,000, 1-methoxy-2-propanol/1-methoxy-2-propene) Base acetate 45% solution).

Synthesis Example 10

The synthesis of the above compound P-57 was carried out in the following manner.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.) to make x:y:z:MMA in the compound P-57. The amount of cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MMA (z) and styrene added was changed to 40.1 mol%: 26.6 mol%: 31.3 mol%: 2.0 mol%. The synthesis was carried out in the same manner as in Synthesis Example 1 to obtain a resin solution of the compound P-57 ((A) resin) having an unsaturated group (solid content acid value: 97.6 mgKOH/g, Mw: 31,300, 1-methoxy) Base-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

Synthesis Example 11

The synthesis of the above compound P-25 was carried out in the following manner.

In Synthesis Example 1, tricyclopentenyl methacrylate was changed to cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.) to make x:y:z:MMA in the compound P-25. The cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MMA (z) and methyl methacrylate were changed to 46.0 mol%: 20.0 mol%: 32.0 mol%: 2.0 mol%. In the same manner as in the addition, the same procedure as in Synthesis Example 1 was carried out to obtain a resin solution of the compound P-25 ((A) resin) having an unsaturated group (solid content acid value: 74.3 mgKOH/g, Mw: 33,600, 1) -Methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

[Example 1]

Example 1: Coating method (method using liquid resist)

Production of color filter substrate

A color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel is fabricated according to the method disclosed in paragraphs (0084) to [0095] of Japanese Patent Laid-Open Publication No. 2005-3861. The light sheet (hereinafter referred to as a color filter substrate) is used, and the size of the color filter substrate is 400 mm × 300 mm.

Next, on the R pixel, the G pixel, the B pixel, and the black matrix of the obtained color filter substrate, a transparent electrode of ITO (indium tin oxide) is further formed by sputtering.

Formation of photo spacers

A glass substrate coating machine MH-1600 (trade name: manufactured by FAS Asia Co., Ltd.) having slit-shaped nozzles on an ITO transparent electrode on which a color filter substrate having the above-described ITO transparent electrode is formed is sputtered, slit A coating liquid for a photosensitive resin layer obtained by the formulation shown in the following Table 1 (C1: C2: C3 = 3.7: 1:1 (weight ratio) of Formula 1 in Example 1) was applied. Next, using a vacuum dryer VCD (trade name; manufactured by Tokyo Chemical Industry Co., Ltd.), one part of the solvent was dried for 30 seconds to lose the fluidity of the coating film, and then prebaked on a hot plate at 90 ° C for 3 minutes. A photosensitive resin layer having a film thickness of 5.2 μm was formed (layer formation step).

Next, using a proximity type exposure machine having an ultrahigh pressure mercury lamp (manufactured by Hitachi Hightech Electronic Engineering Co., Ltd.), a circular mask having a circular pattern of 15 μm in diameter (a quartz exposure mask having an image pattern) is vertically erected in parallel, and In the state of the color filter substrate in which the mask and the thermoplastic resin layer are opposed to each other, the distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm, and the 364 nm is used via the mask. The intensity (exposure amount) of 250 W/m ^{2 was} penetrated through a UV-transparent filter "UV-35" (trade name) manufactured by Toshiba Glass Co., Ltd. in 10 seconds.

Next, use a sodium carbonate-based imaging solution (using water to contain 0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% dibutylnaphthalenesulfonate sodium, anionic surfactant) , defoamer and stabilizer; trade name: T-CD1 (made by Japan Fuji Film Co., Ltd.) diluted to 10 times solution), at 29 ° C, using a cone nozzle pressure of 0.15MPa, sprayed for 30 seconds Form a pattern like the image. Next, using pure water to use a detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (made by Fujifilm Co., Ltd.)) The solution was diluted to 10 times, and the residue of the formed pattern image was removed by a shower nozzle at a pressure of 0.02 MPa at 33 ° C for 20 seconds to form a spacer interval of 300 μm × 300 μm. To form a cylindrical spacer pattern (pattern shape step).

Next, at 220 ° C, a photo spacer was formed on the color filter substrate by performing a 60-minute heat treatment (heat treatment step) on the color filter substrate provided with the spacer pattern.

Here, using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Co., Ltd., type: New View 5022), the highest position of the highest spacer of the obtained 1000 photo spacers was measured from the glass substrate side (n=20). , set the average value to the height (average height). Further, the bottom area measurement of the obtained photo spacer was carried out using an SEM photograph. As a result, the photo spacer was cylindrical with a diameter of 15.1 μm and an average height of 4.7 μm.

Production of liquid crystal display device

In another embodiment, a glass substrate is prepared for the opposite substrate system, and a pattern for PVA mode is formed on the transparent electrode of the color filter substrate obtained above and the opposite substrate, and further formed of polyimine. Alignment membrane.

Thereafter, the color filter pixel group is surrounded, and the sealing agent of the ultraviolet curable resin is applied by spraying to a position corresponding to the surrounding black matrix frame, and the PVA mode liquid crystal is dropped and aligned. The substrates are bonded together. Thereafter, the bonded substrate is irradiated with UV, and then heat-treated to cure the sealant. A polarizing plate HLC2-2518 (trade name) manufactured by Sanritsu Co., Ltd. was attached to both sides of the liquid crystal cell obtained in this manner.

Next, the red (R) LED uses FR1112H (trade name; wafer type LED manufactured by Stanley Electric Co., Ltd.), and the green (B) LED system uses DG1112H (trade name; wafer type LED manufactured by Stanley Electric Co., Ltd.). The blue (G) LED is formed by using a DB1112H (trade name; wafer type LED manufactured by Stanley Electric Co., Ltd.) to form a backlight of a side edge light type, and is disposed on the back side of the liquid crystal cell on which the polarizing plate is provided to form a liquid crystal. Display device.

Evaluation Deformation recovery rate

The measurement and evaluation of the following methods were carried out by using a microhardness tester (trade name: DUH-W201, manufactured by Shimadzu Corporation, Japan). For the measurement, a conical table indentation of 50 μmφ was used, and a maximum load of 21 mN and a holding time of 5 seconds were set, and the load-discharge test method was used. From the measured values, the deformation recovery rate [%] was obtained according to the following formula and evaluated according to the following evaluation criteria. The measurement was carried out in an environment of 22 ± 1 ° C and 50% RH.

Deformation recovery rate (%) = (recovery amount after load release [μm] / deformation amount at load [μm]) × 100

Evaluation basis

5: The deformation recovery rate is over 90%.

4: The deformation recovery rate is 87% or more and less than 90%.

3: The deformation recovery rate is 85% or more and less than 87%.

2: The deformation recovery rate is 80% or more and less than 85%.

1: The deformation recovery rate is 75% or more and less than 80%.

0: The deformation recovery rate is less than 75%.

Elastic coefficient at 15% compression at 25°C

In a room adjusted to 25 ° C, the load is applied at a load of 10 mN/s, and the spacer is compressed to a height H ₁ [mm] corresponding to 85% of the initial height H ₀ [mm], and the height H ₁ is read. The load F ₁ [N] is calculated from the following equation: The spring constant at 15% compression (skew amount = (H _{0 -} H ₁ ) / H ₀ ) is calculated from the following equation.

Elastic coefficient = (load F ₁ / bottom area of the spacer S [mm ² ]) / skew amount

Imaging

In the "production of photo spacers", after exposure, the development was carried out in the same manner as in the development conditions of the respective examples, and SEM observation of the peripheral portion of the formed photo spacer was performed to confirm the residue around the spacer. There is no.

Evaluation basis

5: The residue was not observed at all.

4: A little residue was observed around the pattern.

3: The residue was observed around the pattern.

2: Residue was observed on the substrate around the pattern and the pattern.

1: The residue was confirmed everywhere on the substrate.

Sensitivity

In the coating liquid for a photosensitive resin layer used in each of the examples, under the above development conditions, an exposure development process in which a spacer pattern is formed when the exposure amount is variously changed is similarly performed, and a possible pattern formation is observed by SEM observation. The minimum exposure is set to sensitivity and is evaluated according to the following evaluation criteria.

Evaluation basis

A: The exposure amount is less than 60 mJ/cm ² , and pattern formation is possible.

B: The exposure amount is 60 mJ/cm ² or more and less than 150 mJ/cm ² , and pattern formation is possible.

C: 150mJ / cm ² or more, lower than the exposure amount of 300mJ / cm ^2, the pattern formed as necessary to.

D: An exposure amount of 300 mJ/cm ² or more is necessary for pattern formation. Solution stability over time (preservation)

The coating liquid for the photosensitive resin layer obtained by the above-mentioned thieves was naturally passed over (25 ° C) for 180 days, and the coating liquid for a photosensitive resin layer was placed in an oven at 60 ° C for 2 weeks, and then the coating liquid was used. The same operation as the above sensitivity evaluation was performed, and the evaluation was performed in accordance with the following criteria.

Evaluation basis

A: The exposure amount is less than 60 mJ/cm ² , and pattern formation is possible.

B: Exposure amount of 60mJ / cm ² or more and less than 150mJ / cm ^2, the pattern formed as possible.

C: an exposure amount of 150 mJ/cm ² or more and less than 300 mJ/cm ² is necessary for pattern formation.

D: An exposure amount of 300 mJ/cm ² or more is necessary for pattern formation. Examples 2 to 4, Examples 6 to 16, and Comparative Examples 1 to 7

In the first embodiment, the liquid crystal display device was produced in the same manner as in Example 1 except that the (A) resin and the (C) photopolymerization initiator were changed as shown in Tables 1 to 3.

For the obtained liquid crystal display device, the evaluation similar to that of Example 1 (evaluation (including development) in the manufacturing steps of the spacer) was performed. The evaluation results are shown in Table 3. The resulting spacers were all cylindrical having a diameter of 15.1 μm and an average height of 4.7 μm.

Examples 5, 17 and 18: Transfer method

In the first embodiment, the compound P-1 ((A) resin) prepared in the coating liquid for a photosensitive resin layer, the fine particles, the formation method, and the like are modified as shown in the following Tables 1 and 4 (C1: C2: C3). =1:1.7:1 (weight ratio)) and the method shown in Table 3 were changed, except that the coating liquid for the photosensitive resin layer was replaced, and the photosensitive material was transferred using the spacer shown below. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the printing film was transferred to form a photosensitive resin layer. The resulting photo spacers were all cylindrical with a diameter of 15.1 μm and an average height of 4.7 μm.

Fabrication of spacers with photosensitive transfer film

On a polyethylene terephthalate film temporary carrier (PET temporary carrier) having a thickness of 75 μm, the thermoplastic resin layer obtained from the following formulation A was applied and dried to form a dry layer having a thickness of 15.0 μm. A plastic resin layer.

Formulation A for coating liquid for thermoplastic resin layer

● Methyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate / methacrylic acid copolymer... 25.0 parts (= 55/11.7/4.5/28.8 [mr ratio], weight Average molecular weight 90,000)

● Styrene / acrylic copolymer ... 58.4 parts (= 63 / 37 [mr ratio], weight average molecular weight of 8,000)

● 2,2-bis[4-(methacryloxypolyethoxy)phenyl]propane ... 39.0 parts

●The following surfactants 1 ... 10.0 parts

●Methanol...90.0 parts

● 1-methoxy-2-propanol ... 51.0 parts

●Methyl ethyl ketone ...700 parts

* surfactant 1

●The following structures 1 ... 30%

●Methyl ethyl ketone ...70%

PO: propylene oxide EO: ethylene oxide)

Next, on the formed thermoplastic resin layer, the intermediate layer coating liquid obtained by the following Formulation B was applied and dried, and an intermediate layer having a thickness of 1.5 μm was deposited by dry etching.

Formulation B for the coating liquid for the intermediate layer

●Polyvinyl alcohol ... 3.22 parts (trade name: PVA-205 (saponification rate 80%), (share) made by Claire)

●Polyvinylpyrrolidone ... 1.49 parts (trade name: PVP K-30, manufactured by ISP Japan Co., Ltd.)

●Methanol...42.3 parts

●Distilled water ...524 parts

Then, a coating liquid for a photosensitive resin layer (resin (A) is a compound in Table 3) prepared by the formulation 2 shown in the following Table 1 was further applied and dried on the formed intermediate layer, and the layer was dried and layered. A photosensitive resin layer of 5.2 μm.

In the above manner, the laminated structure of the PET temporary carrier/thermoplastic resin layer/intermediate layer/photosensitive resin layer (the total thickness of the three layers: 21.5 μm) is formed, and further heated and added on the surface of the photosensitive resin layer. The film made of polypropylene having a film thickness of 12 μm was attached and attached to obtain a photosensitive transfer film for a spacer.

Production of light spacers

The obtained spacer was peeled off with a photosensitive transfer film, and the surface of the exposed photosensitive resin layer was superposed on the ITO transparent layer on which the color filter substrate of the ITO transparent electrode produced in the same manner as in Example 1 was formed by sputtering. On the electrode, a laminator type Lamic II type [product name: manufactured by Hitachi Industrial Co., Ltd.) was used, and the bonding speed was 2 m/min at a line pressure of 100 N/cm and 130 ° C under pressure and heating. Thereafter, the PET temporary carrier is peeled off from the interface with the thermoplastic resin layer, and the photosensitive resin layer is simultaneously transferred to the thermoplastic resin layer and the intermediate layer (layer formation step).

Next, using a proximity type exposure machine having an ultrahigh pressure mercury lamp (manufactured by Hitachi Hightech Electronic Engineering Co., Ltd.), a circular mask having a circular pattern of 15 μm in diameter (a quartz exposure mask having an image pattern) is vertically erected in parallel, and In the state of the color filter substrate in which the mask and the thermoplastic resin layer are opposed to each other, the distance between the mask surface and the surface of the intermediate layer side of the photosensitive resin layer is set to 100 μm. The photomask, from the side of the thermoplastic resin layer, was irradiated with a UV-transparent filter made of Toshiba Glass (Japan) with a intensity of 365 nm (exposure amount) of 250 W/m ² for 10 seconds. "(Product name).

Next, at 30 ° C, a flat nozzle pressure of 0.04 MPa was used, and a three-ethanolamine-based developing solution was sprayed for 50 seconds (using pure water to contain triethanolamine 30%, trade name: T-PD2 (Japan Fuji Film) The system was diluted to 12 times (a solution of 1 part of T-PD2 mixed with 11 parts of pure water) to remove the thermoplastic resin layer and the intermediate layer. Next, air was blown onto the glass substrate to completely remove the solution, and the pure water was washed by spraying for 10 seconds, and the pure water was sprayed and sprayed, and air was blown to reduce the accumulation of the solution on the substrate.

Next, a sodium carbonate-based developing solution (using pure water to contain 0.38 mol/liter of sodium hydrogencarbonate, 0.47 mol/liter of sodium carbonate, 5% of dibutylnaphthalenesulfonate sodium, anionic interface activity) Agent, defoamer and stabilizer; trade name: T-CD1 (made by Japan Fuji Film Co., Ltd.) diluted to 10 times solution), sprayed at 30 ° C for 30 seconds using a cone nozzle pressure of 0.15 MPa The image is formed by imaging. Next, using pure water to use a detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (made by Fujifilm Co., Ltd.)) The solution was diluted to 10 times, and the residue of the formed pattern image was removed by a shower nozzle at a pressure of 0.02 MPa at 33 ° C for 20 seconds to form a spacer interval of 300 μm × 300 μm. To form a cylindrical spacer pattern (pattern shape step).

Next, at 220 ° C, a photo spacer was formed on the color filter substrate by performing a 60-minute heat treatment (heat treatment step) on the color filter substrate provided with the spacer pattern. The resulting photo spacers were cylindrical with a diameter of 15.1 μm and an average height of 4.7 μm.

Then, a PVA mode liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate on which a photo spacer was formed.

The abbreviations of the compounds used in the above examples and comparative examples are shown below:

B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (manufactured by Japan Hodogaya Chemical Industry Co., Ltd.)

HAB11311: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4-dimethoxyphenyl)biimidazole (manufactured by Siber Hegner Co., Ltd.)

●Methylbiimidazole: 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole (made by Nippon Black Gold Chemical Co., Ltd.)

●IRG907: 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one (IRGACURE 907, manufactured by Ciba Specia 1 Ty Chemicals Co., Ltd.)

●MBI: 2-mercaptobenzimidazole

●MBT: 2-mercaptobenzothiazole

●EAB: diethylaminodiphenyl ketone

●NKX-1619: Coumarin compound (manufactured by Japan Institute of Biochemistry, Japan)

●MIBK-St: 30 wt% methyl isobutyl ketone dispersion of cerium oxide gel (manufactured by Nissan Chemical Co., Ltd.)

●NBCA: 10-n-butyl-2-chloroacridone (made by Japan Black Gold Chemical Co., Ltd.)

●NPhMBI: N-phenylmercaptobenzimidazole

DETX-S

As is clear from Table 3, the radiation-sensitive resin composition and the spacer of the examples were excellent in any of the evaluation items of sensitivity, deformation recovery rate, and solution storage stability as compared with the comparative examples.

Claims (9)

A radiation-sensitive resin composition for forming a spacer, comprising: (A) having at least: a repeating unit containing an alicyclic structure, a repeating unit containing an acidic group, a repeating unit containing an ethylenically unsaturated group, and a benzene derived from benzene a resin of a copolymer of a repeating unit derived from ethylene, wherein an ethylenic group in the repeating unit of the ethylenically unsaturated group is disposed with an ester group interposed therebetween; (B) a polymerizable unsaturated compound; (C) containing (C1) hexaarylbiimidazole compound, (C2) aromatic mercapto compound and (C3) auxiliary; wherein the ethylenically unsaturated group is a (meth) acrylate having an epoxy group a group introduced into a repeating unit containing an acidic group; the alicyclic structure is a group derived from a monomer represented by the following formula (3): In the formula (3), X represents a divalent organic linking group, y represents 1 or 2, n represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group. The radiation-sensitive resin composition for forming a spacer according to the first aspect of the patent application, wherein the (C3) auxiliary comprises a thioxanthone compound, a coumarin compound, a diphenyl ketone compound, and an acridone compound. Select at least one of them. The spacer-forming radiation-sensitive resin composition according to the first aspect of the invention, wherein the (C1) hexaarylbiimidazole compound is a compound represented by the following formula (1) or formula (2): In the formula (1), X represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms; and A represents a substituted or unsubstituted carbon group having 1 to 12 carbon atoms; Alkoxy or -COO-R (wherein R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms); n is an integer of 1 to 3; each m is an integer of 1 to 3 ; In the formula (2), X ¹ , X ² and X ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms; X ¹ and X; ² is not represented by a hydrogen atom when it is different from two or more of X ³ . A spacer-forming radiation-sensitive resin composition according to the first aspect of the invention, wherein the divalent organic linking group is selected from an alkyl group, an aryl group, an ester group, an anthranyl group and an ether group. Or a combination. The radiation sensitive linear resin composition for spacer formation according to the first aspect of the invention, wherein the composition ratio (x) of the repeating unit containing the alicyclic structure in the (A) resin is 10 to 70 mol%, The composition ratio (y) of the repeating unit containing an acidic group is 5 to 70 mol%, and the composition ratio (z) of the repeating unit containing the ethylenically unsaturated group is 10 to 70 mol%. The radiation-sensitive linear resin composition for spacer formation according to the first aspect of the invention, wherein the mass ratio ((B)/(A) ratio) of the (B) polymerizable compound to the (A) resin is 0.5 to 2.5. A spacer formed by using a radiation sensitive resin composition for spacer formation according to any one of claims 1 to 6. A method for producing a spacer, comprising: forming a photosensitive resin layer on a substrate by using a radiation sensitive resin composition for spacer formation according to any one of claims 1 to 6; At least a part of the resin layer is exposed to substantially no radiation having a wavelength of less than 350 nm; a photosensitive resin layer after development exposure; and a photosensitive resin layer after heating and development. A liquid crystal display element comprising a spacer as in item 7 of the patent application.