TW200931177A - Radiation-sensitive resin composition for formation of a spacer, spacer, method of producing a spacer, and liquid crystal display device - Google Patents

Abstract

Disclosed is a radiation-sensitive resin composition for spacers, which has high sensitivity and excellent storage stability. Also disclosed are a spacer formed by using such a radiation-sensitive resin composition, a method for forming such a spacer, and a liquid crystal display device comprising such a spacer. Specifically disclosed is a radiation-sensitive resin composition for forming spacers, which contains (A) a resin having, in a side chain, a branched structure and/or an alicyclic structure, an acidic group, and an ethylenically unsaturated group bonded to the main chain through an ester group, (B) a polymerizable unsaturated compound, and (C) a hexaarylbiimidazole compound (C1), an aromatic mercapto compound (C2) and an assistant (C3).

Description

[Technical Field] 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. [Prior Art] A conventional liquid crystal display device has been widely used for displaying a display device of high definition image. 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, and the substrate is spaced apart, that is, the thickness of the liquid crystal layer is uniformly maintained to determine the image quality. First, for this purpose, 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 which 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. The 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 43 6iun (g line), around 404 nm (h line), around 3 65 nm (i line), around 3 35 nm, and around 315 nm (j line). A spectrum having a high intensity, such as in the vicinity of 3 03 nm, and a radiation-sensitive polymerization initiator contained in the radiation-sensitive resin composition are generally selected to have a compound 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, see Japanese Patent Laid-Open Publication No. 2005-208360). . When a radiation-sensitive polymerization initiator having a wavelength of longer than the i-line or a maximum absorption wavelength near the h-line is used, 'the radiation-type polymerization initiator has absorption in the wavelength range close to the visible light, as 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 curing reaction in the depth direction of the coating film is insufficient. As a result, the spacer obtained after the development is obtained. The shape 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 the spacer film is peeled off after the alignment film is subjected to the flat grinding treatment. On the other hand, in the case of an actual spacer forming process, a spacer is often used in a transparent substrate which can be used for, for example, a color filter or the like by photolithography, and a proximity type exposure machine is often used. In recent years, mercury lamps having high illuminance have been generally used due to an increase in the yield of the proximity type exposure machine. In this case, although the yield will increase, once the mercury lamp with high illuminance is directly used, the filter is used to filter out the short wavelength of less than 350 nm with high energy due to the reduced lifetime of the lens used in the exposure machine. There are many situations in which radiation is used. 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. In addition, the conventional radiation-based polymerization initiator has poor operability in solution storage 200931177, and there is an operational problem that it is necessary to preserve the coating liquid in refrigeration, or an effect on the cost increase caused by the problem. Problems such as stability over time on a coated glass substrate, etc. [Explanation] According to the present invention, a spacer having high sensitivity and superior preservability is composed of a radiation sensitive resin. Things. 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 for solving the problem is as follows: <1> A radiation-sensitive resin composition for forming a spacer, comprising: (A) having at least one side chain a branched structure and/or an alicyclic structure, an acidic group, or a resin bonded to an ethylenically unsaturated group of a main chain via an ester group; © (B) a polymerizable unsaturated compound; and (C) a C1) a hexaarylbiimidazole compound, a (C2) aromatic mercapto compound, and a (C3) adjuvant. <2> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the (C3) auxiliary contains a thioxanthone compound, a coumarin compound, a diphenyl ketone compound, and At least one selected from the acridone compound. <3> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the (c 1 ) hexaarylbiimidazole compound is represented by the following formula (1) 200931177 or formula (2) Compound

(A)m (1) -Ο"2

(X)n 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 carbon number of 1 to 12; a substituted or unsubstituted alkoxy group or -C 00-R (wherein R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 9 carbon atoms); 11 is an integer of 1 to 3; each m system An integer from 1 to 3;

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 when two or more of X1, X2 and X3 are different, they are represented by a hydrogen atom. The radiation-sensitive resin composition for spacer formation according to &lt;1&gt;, wherein the branching structure and/or the alicyclic structure is a dicyclopentyl group, a dicyclopentenyl group, or a ring At least one selected from the group consisting of hexyl, tricyclopentyl, tricyclopentenyl, adamantyl, norbornyl and isodecyl. <5> The radiation-sensitive resin composition for spacer formation according to <1>, wherein the alicyclic structure is a base derived from a monomer represented by the following formula (3): °fX' 0 0 η

-C-C=Chb Formula Ο) IR In the formula (3), X represents a divalent organic linking group, y represents 1 or 2, η represents an integer of 0 to 15, and R represents a hydrogen atom or methyl. <6> The radioactive resin composition for spacer formation according to <5>, wherein the divalent organic linking group is an alkyl group, an aryl group, an ester group, a decyl group, and an ether group. One of the bases or combinations selected. <7> The radiation-sensitive resin composition for spacer formation according to &lt;1&gt;, 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 200931177 1 or 2, η 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 an alkyl group, an aryl group, an ester group, an anthranyl group, and an ether group. One of the bases or combinations selected. <9> The radiation-sensitive resin composition for spacer formation according to &lt;1&gt;, 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 &lt;1&gt;, wherein the (A) resin further contains a structural unit derived from styrene. 〇 &lt; ιιι > is disclosed in the interval of &lt;ι&gt; a radiation-sensitive resin composition for forming a substance, wherein a composition ratio (X) of the branching structure and/or an alicyclic structure in the (A) resin is 1 〇 to 70 mol%, and a composition ratio of the acidic group ( y ) 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 [(B) / (A) ratio] is 0.5 ~2.5. The &lt;13&gt; is a spacer which is formed by using a radiation sensitive resin composition for spacer formation according to any one of the above items <1> to <12>. &lt;14&gt; The method for producing a spacer comprising: forming a photosensitive resin composition on the substrate by using the radiation sensitive resin composition for spacer formation disclosed in any one of the above &lt;1&gt; to &lt;12&gt; a resin layer; at least a portion of the photosensitive resin layer, the exposure does not substantially contain radiation having a wavelength lower than 35 nm; -10-200931177 photosensitive resin layer after development exposure; and photosensitive resin after heating development Floor. &lt;15&gt; A liquid crystal display device comprising the spacer disclosed in the above &lt;13&gt;. Advantageous Effects of Invention According to the present invention, it is possible to provide a radiation sensitive 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 device having the spacer. [Embodiment] The present invention relates to a radiation-sensitive resin composition for spacer formation according to the present invention (hereinafter, simply referred to as "radiation-sensitive linear resin composition J"), a method for producing a spacer, a spacer, and The liquid crystal display element is described in detail. The method for producing a radiation-sensitive resin composition for spacer formation and a spacer, the radiation-sensitive resin composition for spacer formation of the present invention contains: (A) having at least one side chain a branched structure and/or an alicyclic structure, an acidic group, or a resin bonded to an ethylenically unsaturated group of a main chain via an ester group; (B) a polymerizable unsaturated compound; and (c) a (C1) a hexaarylbiimidazole compound, a (C2) aromatic mercapto compound, and a (C3) auxiliary agent. With the above structure, the spacer-forming radiation sensitive resin composition of the present invention is highly sensitive and superior in appearance. It is image-like and has excellent preservation. Especially, even if it does not contain wavelengths below 350nm, -11-200931177 is high sensitivity, and the hardening reaction is good and superior. Further, the spacer manufactured by the radiation-sensitive resin composition can have high deformation recovery property due to superior compressibility, and can eliminate display unevenness in display elements and/or display devices. 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 material a two-electrode electrode and a spacer U for limiting the thickness of the liquid crystal cell between the substrates, and having a radiation-sensitive resin composition layer containing the radiation-sensitive resin composition of the present invention on one side of the two substrates ( Hereinafter, a layer forming step of a "photosensitive resin layer" is also referred to. Layer forming 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 a spacer having a good deformation recovery property and capable of uniformly maintaining the thickness of the liquid crystal cell will be formed. By using the spacer, especially according to the liquid

III. Variation in the cell thickness, display unevenness in the liquid crystal display device in which 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 (" using a photosensitive transfer material having the photosensitive resin layer, The transfer method of laminating and transferring the photosensitive resin layer by heating and/or pressurization, etc. (a) Coating of the coating method The radiation sensitive resin composition can be carried out by a conventional coating method, for example, a spin coating method, Curtain coating method, dip coating method, gas coating method, gas coating method, roll coating method, wire bar coating method, gravure coating method, or extrusion coating using a hopper disclosed in the specification of U.S. Patent No. 2,681,294 For example, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-164787, JP-A-2003-10767 A coating method of a slit nozzle or a slit coater such as JP-A-2001-310147 (b) Transfer printing is performed on a temporary carrier by using a photosensitive transfer material. Formed The photosensitive resin layer is bonded to the surface of the carrier (or substrate) by pressure or heat by a roll or a flat plate, and then the photosensitive resin layer is transferred onto the carrier in accordance with the peeling of the temporary carrier. 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. No. Hei. From the viewpoint of the low-contamination, it is preferably used in the method disclosed in Japanese Laid-Open Patent Publication No. Hei 7-110575. In the case of forming a photosensitive resin layer, an oxygen barrier layer can be further provided between the photosensitive resin layer and the temporary carrier. (hereinafter, also referred to as "oxygen barrier layer" or "intermediate layer"). Thereby, the exposure sensitivity can be improved. Further, in order to improve the transfer property, a thermoplastic resin layer having a cushioning property may be provided. A temporary carrier of a photosensitive transfer material, an oxygen barrier layer, a thermoplastic resin layer, another layer, or a method for producing the photosensitive transfer material can be used in Japanese Patent Laid-Open No. 2006-23696 The structure and production method of the paragraphs [0024] to [0030] are shown. (a) The coating method and (b) the transfer method are all applied to form the photosensitive resin layer-13-200931177, and the layer thickness thereof is preferably 〇. .5em~lO.Oem, more preferably lym~6ym. When the layer thickness is in this range, pinhole generation at the time of coating formation at the time of manufacture is prevented, and display removal of an unexposed portion can be performed without a long 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 called a substrate) It is a color filter substrate), a driving 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 700 #m~ ❹ 1 2 0 0 // m. Radiation-sensitive resin composition Next, the radiation-sensitive resin composition will be described. The radiation sensitive resin composition of the present invention contains: (A) 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 resin having an unsaturated group; (B) a polymerizable unsaturated compound; and (C) a (C1) hexaarylbiimidazole compound, (C2) an aromatic mercapto compound, and (C3) an auxiliary.

Further, if necessary, other components may be further contained. (A) The resin (A) resin has a branching structure and/or an alicyclic structure, an acidic group, or a bond via an ester group in at least one side chain. An ethylenically unsaturated group attached to the main 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. -14- 200931177 Also, in the present specification, (meth)acryloyl group means acryl fluorenyl or methacryl fluorenyl group, and (meth) acrylate means acrylate or methacrylate, (A The acrylic group represents an acryl group or a methacryl group, the (meth) acrylamide refers to acrylamide or methacrylamide, and the (meth) acryl anilide represents acryl aniline or methacryl oxime. aniline. Branching structure and/or alicyclic structure The branching structure and/or 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 branching structure and/or the alicyclic structure may contain a plurality of the same side chain 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. The bivalent organic linking group is bonded to the main chain of the resin (A), and the branching structure and/or the 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, an isobutyl group, a secondary butyl group, a tert-butyl group, an isopentyl group and the like, and the like, and further preferably an isopropyl group, a secondary butyl group, and a third group are preferable. a butyl group or the like, and having such a group. -15- 200931177 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, and a reduced decane group. At least one selected from the group consisting of a base, an isodecylalkyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentyl group, a tricyclopentenyl group, a tricyclopentyl group, and the like . Among these alicyclic hydrocarbon groups, preferred are cyclohexyl, norbornyl, isodecyl, adamantyl, tricyclopentenyl, tricyclopentyl, dicyclopentenyl, dicyclopentane And at least one selected from the group consisting of, and more preferably, a cyclohexyl group, an isodecyl group, a bicyclo g-pentenyl group, a dicyclopentyl group, etc., and at least selected from the group having such a group One. 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, and more preferably an alkylene group having a total carbon number of 1 to 10. Specific 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 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. &amp; examples of the aryl group include an extended aryl group having a total carbon number of 6 to 20, and more preferably an extended aryl group having a total carbon number of 6 to 12. Specific examples thereof include a phenylene 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 side chain of the resin 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 side chain of the resin may be exemplified by isopropyl (meth)acrylate, isobutyl (meth)acrylate, and (meth)acrylic acid. Butyl butyl ester, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, tertiary amyl (meth) acrylate, diethyl amyl (meth) acrylate, (meth) acrylate-2 - octyl ester, 3-octyl (meth)acrylate, trioctyl (meth)acrylate, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, ( Further, methyl methacrylate butyl acrylate or the like is more preferably isopropyl (meth) acrylate or isobutyl (meth) acrylate. _ In order to introduce the alicyclic structure into the monomer of the (A) resin side chain, the alicyclic hydrocarbon group (meth) acrylate having 5 to 20 carbon atoms is mentioned. Specific examples thereof include (meth)acrylic acid (bicyclo[2,2,1]heptyl-2-yl)ester, (meth)acrylic acid-1-adamantyl ester, (meth)acrylic acid-2-carboxylated ester, 3-methyl-1-adamantyl (meth)acrylate, -3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyl-indole-adamantyl (meth)acrylate , (meth)acrylic acid-3-methyl-5-ethyl-1-adamant, (meth)acrylic acid-3,5,8-triethyl-1-adamant, (meth)acrylic acid-3 ,5·Dimethyl-8-ethyl-1-adamantate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, (meth)acrylic acid_3_hydroxy-1-adamantyl ester, octahydro-4,7-methylenedihydrofurfuryl (meth) acrylate-5-ester, octahydro-4,7 (meth)acrylate -methylenedihydrofurfuryl ester-1-ylmethyl ester, (meth)acrylic acid-1-menthyl ester, tricyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, (methyl Acetic acid-3_hydroxy-2,6,6-trimethylbicyclo[3.1.1]heptyl ester, (meth)acrylic acid-3,7,7-trimethyl• 4-carbyl [4.1_0] ester, ( Acetyl n-decyl acrylate, isobutyl methacrylate, decyl (meth) acrylate, 2,2,5-trimethylcyclohexanol (meth) acrylate, (meth) acrylate ring Hexyl ester and the like. Among these (meth) -17- 200931177 acrylates, preferred are (meth)acrylic acid cyclohexanol, (meth)acrylic acid n-decyl ester, (meth)acrylic acid isodecyl ester, (methyl) Acrylic acid-1·adamantyl ester, (meth)acrylic acid-2-adamantyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid-1-menthyl ester, (meth)acrylic acid tricyclodecyl ester, etc. Cyclohexyl (meth)acrylate, tricyclopentenyl (meth)acrylate, n-northyl (meth)acrylate, isodecyl (meth)acrylate, 2-adamantyl (meth)acrylate Especially ideal. Further, in the following formula (3) or (4), in order to introduce the alicyclic structure into the monomer of the (A) resin side chain, the lanthanoid system represents a divalent organic linking group, and the y system represents 1 Or 2, η represents an integer of 〇 15 and R represents a hydrogen atom or a methyl group. In the general formula (3) or (4), it is preferable that y = 1 or 2, η = 〇 〜 4, and more preferably η = 0 〜 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. . The example of the alkylene group is preferably a substrate having a total carbon number of 1 to 2 0, 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, an octyl group, a dodecyl group, an octadecyl group, and the like. The alkyl group may also have a branched structure, a cyclic structure or a functional group 'further more preferably a methylene group, an exoethyl group or a octyl group. The example of the aryl group may be, for example, preferably an extended aryl group having a total carbon number of 6 to 20, and still 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. -18- 200931177 The substituents 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, a structural group, and the like. Among them, the compound represented by the formula (3) or (4) is preferably a compound represented by the formula (3) or (4) based on the viewpoint of superior development and superior deformation, and the following compounds D-1 to D-1, T- 1~T -1 2.丫 =ch2

R example, which can have a specific example of the alicyclic recovery rate, general formula (3)

H2c=ch-c-o II 〇 D— 3 c=ch2

R CH3 IH2〇=C—C-O-CH2CH2_o 0

H2c=ch-c-o 〇 D- 4 D — 2 ch3 h2c=ch-c-o II〇 D- 5 General formula (4) m βοm -19- 200931177 H2C=C-C-〇CH2CH2CH2—οο

D- 6

D-7 CHg H2C=i-C-〇CH2CH2CH2CH2—Ο Ο 〇 ch3h 2c =c -c -oc h2c h2〇ch 2c h2—ο o

-QO D 8 ch3

H2C=0-jj-〇CH2CH2OCH2CH2—D~9 O H24h-—one—one 0 D- 1 0 ❹ ch3 h2c=c-c-och2ch- II I 0 ch3 -o -〇〇 D- 1 -20- 200931177

Ch3 H2C —C —C —OCH2CH2OCH2CH2 —o_ o

T-9

CH3 H2C =C _C_OCH2CH2OCH2CH2—O~

T- 1 0

T- 1 1 o ch3 H2C =C _〇~ΟΟΗ2〇Η - II | 0 ch3 CH3 H2〇=C—C—OCH2CH—o—ch3

T- 1 2 -21 -

200931177 A commercially available product can also be used in order to introduce the alicyclic structure into the monomer of the (A) resin side chain. Examples of the commercially available product include FA-51 1A, FA-FA-512M, FA-513A, FA-513M, TCPD-A, H-TCPD-A'H-TCPD-M'TOE-A'TOE -M'H-TOE- (All of the products are sold under the trade name of Japan Hitachi Chemical Co., Ltd.). Based on the superior imageability and superiority, FA-512A(S) is preferred. , FA-512M. The acidic group (A) resin contains at least one acidic group in the side chain. The acidic group may also contain a plurality of individual groups in the same side chain or may be contained in the same side chain of the (A) resin. / or alicyclic structure, and ethylene is not saturated with the ester group, the acidic group can be directly bonded to the resin (A) to form the side chain of the resin (A) with an acidic group, or a 2-linking group bonded to a main chain of a resin (A) and having a side chain of an acidic group (A). Here, examples of the divalent organic linking group are in the branched structure and/or the alicyclic structure. The acidic linking group is not particularly limited, and can be appropriately selected from a conventional acid, and examples thereof include a carboxyl group, a sulfonic acid group, a phosphoric acid group, and the like. Among the acidic groups, a carboxyl group or a phenolic hydroxyl group is preferred. For the purpose of introducing an acidic group into the monomer of the (A) resin side chain, an example thereof may be used. For example, (meth) acrylates, vinyl esters, (meth) acrylamides, etc., preferably (5 1 2 A (S), TCPD-M 'A' H-TOE-M can be used. And the recovery rate of these deformations. In addition, the main chain of the acid branching structure and the base group, the organic group of only the valence constitutes a tree, and the sulfonamide group is added to the bis-valent group. , : Sexual viewpoint, there is no special vinyl ether, methyl) propylene-22- 200931177 acid ester, vinyl ester, (meth) acrylamide, further preferably (meth) acrylate . 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 g, a monomer which is suitably produced may be used, or a commercially available product may 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 edge cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexane dicarboxylic anhydride. In order to introduce an acidic group into the monomer of the (Α) resin side chain, a commercially available product is exemplified by: Japan East Asia Synthetic Chemical Industry Co., Ltd. · Aronix Μ-5 3 00, Aronix M-5 400, Aronix M- 5 500, Aronix M-5 600 (all ^ is the trade name); Japan New Nakamura Chemical Industry Co., Ltd.: NK ester CB-1, NK ester CBX-1 (all are trade names); Japan Kyoritsu Oil & Fat Chemicals Industrial (stock) system: HOA-MP, HOA-MS (all are trade names); Osaka Organic Chemical Industry Co., Ltd.: Bisco at #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 (meth)acryl oxime. base. The ester group (-COO-) is bonded to the main chain of the ethylenically unsaturated group and the -23-200931177 (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.方法 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 a (meth) acrylate having an epoxy group 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) and The following structural formula (2)

Structural Formula (1) In the structural formula (1), 'R1' represents a hydrogen atom or a methyl group L1 represents an organic group. -24- 200931177 R2

Show organic base. w 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), L1 and L2 are more preferably independent from each other having a carbon number of 1 to 4. 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):

-25- 200931177

Other monomers 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 branching structure and/or an alicyclic structure of -26 to 200931177, styrene, vinyl ether group, and dibasic acid anhydride. A monomer such as a vinyl group, a vinyl ester group 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. Specific examples of the resin (A) are, for example, compounds represented by the following structures (exemplified compounds P-1 to P-57). Further, in the exemplified compound, x, 1, y, z and St indicate that the composition ratio (mass ratio) of each repeating unit is suitably formed by the range described later -27-200931177

Coo

〇

/y COOH COO

OH I

Co〇,

COOH COO P-1 x:y:z=41:24:35 〇 P-2 x:y:z=48:22:30 Ο

COOH n p_3 OH I x:y:z=45:20:35 〇

, seven coo COOH C

O

OH x:y:z=40:25:35 ❹

OH I 〇 P-5 x:y:z=42:26:32

-28- 200931177

OH I 〇 P-7 x:y:z=40:25:35

P-8 〇

COO

Cooh p-io x:y:z=50:24:26 ❹

COO coo^^X)

COOH

HO XX〇x^ P-11 x:y:z=40:25:35

Co〇〈^

COOH P-12λλλ^ x:y:z=30:30:40

C〇〇^s n HO -29- 200931177

x:y:z=45:15:40

Ο

COO L C〇〇H

Fy

C〇〇v C〇〇H

COO^Y^O OH 〇 P-15 x:y:z=45:30:25

COO

❹

Fy COOH

〇 P-16

〇Y x:y:z=45:20:35

Xcoo

y COOH

Zcoo HO

P-17 〇 x:y:z=45:25:30 -30- 200931177

^ Fork / p-18

Nu I x:y:z=40:25:35

x:y:z=40:30:30

P-21

r»-i I

x:y:z=45:20:35

x:y:z=40:20:40 200931177

y COOH

Coo^q

COOMe COOH ΟΟΟ^^'Ύ^Ο OH

〇Λ- P-25 x:I:y:z=46:2:20:32 〇 coo

P-26 x:l:y:z=45.5:2:19:33. 5

COOH

P-27 nu I ❹ x:y:z=48:22:30 coo

Ό

y COOH

P-28 x:y:z=51.5:18.5:30 -32 200931177

X coo

COOH P~29 OH x:y:z=40:25:35 〇

〇

Cooi^O

COOH OH丨 〇 P-30 byi coo CH2CH2-0

COOH

x:y:z=41:24:35 〇 COO^Y^A^ P-31 OH ' x:y:z=39:26:35 ❾

, seven coo COOH C

广〇Λ^ P-32 OH丨 x:y:z=35:30:35

OH P-33 x:y:z=42:28:30 -33 200931177

X COO

y COOH

〇

P_34 OH x:y:z=37:28:35 〇

COO

Fy COOH

COO^^Y^O OH 〇 々 P-35 x:y:z=39:26:35 -34- 200931177

x:y:z=40:25:35 〇

P-38 OH 1

x:y:z=40:20:40 COOH

COO

C〇〇H

-35- 200931177

COOH

x:y:z=30:25:45

COO^^Y^O OH

P-45

x:y:z=30:30:40

x:y:z:St=30:24:38:8 -36- 200931177

COO COOH

P-47 x:y:z:St=34:24:36:6

X \ /y COO COOH

Fst 〇 0 P-48 x:y:z:St=40:23:35:2

Rx

C〇〇^q

y COOH

COO 〇 P-49 ^γ^σ OH x:y:z=32:25:43

COO . COOH X) OH 1 〇 P-50

x:y:z:St=25:25:40:IO

COO ° COOH ΟΟΟ^^γ^Ο

u V P-51 x:y:z=34:27:39 -37 200931177

〇 GOO ch2ch2-〇

COOH

m P-53 x:y:z=46. 2:24. 3:29. 5

OH I

P-54 x:y:z:St=25:25:40:10

:y : z = 46 : 24 : 30 P-5 5 -38- 200931177

-o

-GO :46:24:30 P- 5 6

y : z=40_ 1:2.0:26.6:31. ❹

O Synthetic Method (A) The resin can be synthesized by a two-stage step of the step of (co)polymerization of the monomer, the step of ethylenically unsaturated groups. First, the (co)polymerization reaction is exemplified by various monomers (the reaction is not particularly limited, and can be appropriately selected from conventional (co)polymerization. For example, for the active species of the polymerization, it is possible to carry out radical polymerization, In the (co)polymerization reaction such as cationic polymerization, anionic polymerization, or coordination polymerization, the synthesis is easy, and based on the low viewpoint, it is preferably a radical polymerization. Further, the polymerization method is not limited, and can be obtained from a conventional method. Among them, the bulk polymerization method, the suspension polymerization method, the emulsion polymerization method, etc. are appropriately selected. Among these methods, the solution polymerization method is more preferable. . There is no such thing as cost, solution, solution -39- 200931177 Carbon number Based on the modulus of elasticity (hardness), (A) the total carbon number of the resin is preferably 10 or more. Among them, the total carbon number is preferably 10 to 30, especially 10 to 15 is particularly desirable. The molecular weight (A) of the resin preferably has a weight average molecular weight of 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 preferred 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 (A) The glass transition temperature (Tg) of the resin is preferably from 40 to 180 ° C, more preferably from 45 to 140 ° C, particularly preferably from 50 to 130 ° C. If the glass transition temperature (Tg) is within the preferred range, a spacer having good imaging properties and mechanical strength can be obtained. The acid value of the acid value (A) resin is preferably in the range of 20 mg KOH/g or more, more preferably 40 mg KOH/g or more, particularly 50 to 50, depending on the molecular structure which can be employed. 130 mg KOH/g is particularly desirable. If the acid value is within the preferred range, a spacer having good developability and mechanical strength will be obtained.

Tg -40- 200931177 Based on the spacer having good developing property and mechanical strength, the glass transition temperature (Tg) of the (A) resin is preferably from 40 to 180, and the weight average molecular weight is preferred. 1〇, 〇〇〇~1〇〇, 〇〇〇; Tg is more preferably 45 to 140 ° C, and the weight average molecular weight is more preferably 12,000 to 60,000; especially Tg is 50 to 130 ° C, and the weight average A molecular weight of 15,000 to 45,000 is particularly desirable. 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 (copolymerization 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 having a branched structure and/or an alicyclic structure: X (x mole %): 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. Further, if necessary, other repeating units may be contained: L (1 mol%). 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 monomers are copolymerized to introduce a copolymer having a branched structure and/or an alicyclic structure of -41 - 200931177. In this case, the (A) resin has a structural unit derived from the monomer represented by the above 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 arbitrarily determined that the copolymerization composition ratio can be set to the following range: (A) The composition ratio (X) of the repeating unit having a branched structure and/or an alicyclic structure in the resin is preferably 10 to 70 moles. Ear %, more preferably 15 to 65 mole %, especially 20 to 60 mole % is particularly desirable. When the composition ratio (X) is within this range, good development performance is obtained, and the image forming liquid of 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 1 7 to 70% by mole, more preferably from 20 to 70. Moer% 'especially 30~70 mol% is especially ideal. 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 (^ is "~70 mol%, a composition ratio (y) is 5 to 70 mol%, and a composition ratio (z) is 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 ideal case: composition ratio (X) is 20 to 50 mol%, -42 to 200931177, composition ratio (y) is 20 to 50 mol%, and composition ratio (z) is 30, ear %. With respect to all solid components of the composition, The content of the resin composition (A) is preferably 5 to 70% by mass, more preferably 50% by mass. (A) The resin can be used in combination with other resins described later, preferably the resin (A) In the case of the resin, the resin which can be used for the resin (A) is preferably a compound which exhibits swelling property to an alkali liquid, more preferably a compound which is an alkaline aqueous solution. It exhibits swelling property to an alkaline aqueous solution or The resin which is soluble is exemplified by a resin having an acidic group. Specific examples thereof include a compound in which an unsaturated double bond and an acidic group are introduced into an epoxide ( a mixture of a vinyl copolymer having a (meth) acrylonitrile group in a side chain, an epoxy acrylate compound, and a vinyl copolymer of an acryl fluorenyl group and an acidic group in a side chain, The acid group is not particularly limited, and can be selected depending on the purpose. For example, an acidic group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group may be used, and the raw material availability may be used. From the viewpoint of the preferred embodiment, the photosensitive resin layer shape is formed on the substrate by a transfer method, and in particular, the (A) resin can be used together with other resins. This inertness is relative to all solid components of the photosensitive resin layer. The total content (solid content) of the resin to be used with (A) is preferably 5 to 70 mass - 70 moles of photosensitive specific 10 0 to be only suitable for water solubility, such as ethylenic, epoxy and acid L There is (meth) cis-butene, such as: in the case of carboxy, the amount of resin %, -43- 200931177 is more preferably 10 to 50% by mass. If the content is 5% by mass or more, the sensitization can be maintained. Film of resin layer In addition, the wrinkle property of the surface of the photosensitive resin layer can be favorably maintained. When the mass is less than or equal to the mass%, the exposure sensitivity is improved. (B) Polymerizable unsaturated compound The photosensitive composition of the present invention contains both (A) Resin and (B) a polymerizable unsaturated compound. The polymerizable unsaturated compound can be used by selecting a component constituting a conventional composition. For example, JP-A-2006-23 696 The components disclosed in paragraphs [0010] to [0020], or the components of the paragraphs [0027] to [0053] of JP-A-2006-64921, are not disclosed. In the relationship with the (A) resin, the mass ratio ((B) / (A) ratio) of the (B) polymerizable compound to the (A) resin is preferably 〇_5 to 2.5', more preferably 0.6. ~2.2, especially 0.8~1.9 is especially ideal. When the ratio of (B) / (A) is within this range, a spacer having good developing power and mechanical strength can be obtained. (C) photopolymerization initiator (C1) hexaarylbiimidazole compound having a long wavelength, the radiation sensitive linear resin composition (C) component of the present invention contains at least (C1) hexaarylbiimidazole compound . 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) hydrazine-44 - 200931177 oxazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylbenzene Bismuthimide, 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-cyano) Phenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)biimidazole, 2,2'-bis(2-cyanophenyl)-4,4',5,5 '-tetrakis(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'- (4-ethoxycarbonylphenyl)-linked imidazole, 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetrakis(4-phenoxycarbonylphenylhydrazolyl) Imidazole, 2,2'-bis(2-ethylphenyl)-4,4',5,5'-tetrakis(4-methoxycarbonylphenyl)biimidazole, 2,2'-bis(2-B Phenyl)-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-methoxycarbonylbenzene Bismuthimide, 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; etc.; 2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetrakis(4-methoxyphenyl)biimidazole, 2,2'- ◎ bis(2-chlorophenyl)-4,4',5,5'-tetrakis(3-methoxy Biphenyl)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-tribromophenyl)-4,4',5,5'-tetraphenyl Imidazole, 2,2'-bis(2,4-dicyanophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4,6-three Cyanophenyl) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,4-dimethylphenyl)-4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(2,4,6-trimethylphenyl)-45- 200931177 -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'-bis(2-fluorophenyl)-4, a biimidazole compound such as 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: 8-(:1) ]^, 曰本保土谷化学工业), 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetrakis(3,4-dimethoxyphenyl)biimidazole (trade name: ΗΑΒΙ131 1, 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 kinds. (C2) Aromatic fluorenyl compound The radiation sensitive resin composition of the present invention contains (C2) an aromatic fluorenyl compound in order to improve the spectral sensitivity. Examples of the aromatic mercapto compound of 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 this case, 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. The dimer of the above-mentioned 'aromatic mercapto compound, for example, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, N-phenylmercaptobenzimidazole, etc. The compound is used singly or in combination of two or more kinds. (C3) Auxiliary-46-200931177 In order to further improve the sensitivity, the radiation sensitive tree system of the present invention contains (C3) an auxiliary agent. The agent is not particularly limited as long as it is a substance capable of improving the sensitivity, and at least one selected from the group consisting of a ketone compound, a coumarin compound, a diphenyl ketone compound, and a compound is preferred from the viewpoint of the sensitivity enhancement effect. -1) Thioxanthone compound In the present specification, the thioxanthone compound means a thioxanthone having a substituent. 0 The substituent may, for example, be a carbon number of 1 to 10, preferably a straight or branched alkyl group of ~4, and a fluorine atom, a chlorine atom or a halogen atom of Yao. The position of the dare base is not particularly limited, preferably and/or 4. The thioxanthene compound, specifically For example, thiazolone, thioxanthone, 2-propyl Tons of ketone, 2-isopropylthioxanthone, 2,4-dimethylketone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2,4. An alkyl-substituted thioxanthone such as a ketone; a ketone or the like of 2-chlorothioxanthone or the like. Among the above, preferred are 2-isopropylthioxanthone, 2,4 thioxanthone, or 2 - chlorothioxanthone. (C3-2) Coumarin Compound The coumarin compound may be exemplified by the formula (I), (II) or (the compound shown. The lipid composition is not specifically determined by the thiazolone. &amp; carbon number 1 atom is equal to 2 position 2-ethyl thioxanthene - methyl thioxanthen • diethyl hydrazine) -47- 200931177

In the formula (I), R1 and R2 may be the same or different, and each independently has a hydrogen atom, an amine group, a dialkylamino group, a monoalkylamino group, an N-aminoalkyl group, a halogen atom or an alkoxy group. Here, a carbon number of 1 to an alkyl group and an alkoxy group are preferable. In the formula (II), R3 represents an alkylene group having 1 to 7 carbon atoms and an alkylene group having 1 to 4 carbon atoms. R4 and R5 may be the same or different and represent an independent hydrogen atom or an alkyl group having 1 to 7 carbon atoms. In the case of the R4 or R5 group, it is preferred to represent an alkyl group of 1 to 4. In the formula (III), R6 and R7 may be the same or different from each other, and each independently has a hydrogen atom, a carbon number of 1 to 7 (preferably 1 to 4) or an alkoxy group having 1 to 4 carbon atoms. Examples of the coumarin compound include, in particular, 7 - {{ 4 -(diethylamino)ditrimethylene-2-yl}amino}-3-phenylcoumarin, and 7 represents a substitution. 'The best of the four is the show of each hospital, the statement base 'chloro-6 --{{4- -48- 200931177 methoxy-6-(diethylamino) secondary three tillage-2-yl} amine }-3-phenylcoumarin, 7-{{4-methoxy-6-(diethylaminopropylamino) secondary triton-2-yl} aminyl 3-phenylcoumarin, N-(7-dimethylaminopropyl)-Ν'-{3-phenylcoumarin--(7)}urea, 3-phenyl-7-(4'-methyl-5'-positive Butoxy benzotriazol-2-yl) coumarin and the like. Among these compounds, 7-{{4-chloro-6-(diethylamino) ternary trimethyl-2-yl}amino phenyl 3-phenylcoumarin is preferred. The coumarin compound may, for example, be a compound represented by the following formula (VIII) which is a 3-aryl-substituted coumarin compound.

❹ 〇 R12 General formula (VIII)

Zb In the formula (VIII), R8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and 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. R9 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 a butyl group. The group represented by the formula or the formula (VIIIA) is particularly preferably a group represented by the formula (VIIIA).

R1G and R11 of the formula (VIIIA) are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a haloalkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, which may be substituted. An aryl group, an amine group having 6 to 10 carbon atoms, -N(R16) (R17) or a tooth-49-200931177 atom. Here, the alkyl group having 1 to 8 carbon atoms may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group or 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. The alkoxy group having 1 to 8 carbon atoms, for example, may be exemplified by a methoxy group, an ethoxy group or a butoxy group. The aryl group having 6 to 10 carbon atoms which may be substituted, for example, may be a phenyl group. The halogen atom, for example, may be -C, -Br or -F. Among them, a hydrogen atom, a methyl group, an ethyl group, a methoxy group, a phenyl group, or -N(R16)(R17) or -Cl is preferable. R12 represents an aryl group having 6 to 16 carbon atoms which may be substituted, and specifically, for example, a phenyl group, a naphthyl group, a tolyl group, a p-isopropylidene group or the like. Examples of the substituent which may be introduced into the aryl group include an amine group, -N(R16) (R17), a fluorenyl group having a carbon number of j 8 (for example, methyl group, ethyl group, propyl group, butyl group, octyl group). a halogen group having 1 to 8 carbon atoms (for example, chloromethyl, fluoromethyl, trifluoromethyl, etc.), an alkoxy group having 1 to 8 carbon atoms (for example, methoxy, ethoxy, butoxy) ), hydroxy, cyano, halogen (eg, -Cl, -Br, -F). R13, R14, R16 and R" represent independently hydrogen atoms and alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl). Q Rl3 and Rl4 may also be mutually Bonding and simultaneously forming a heterocyclic ring with a nitrogen atom (for example, a piperidine ring, a piperazine ring, a morpholine ring, a pyrazole ring, a diazole ring, a triazole ring, a benzotriazine ring, etc.). Bonding to each other while forming a heterocyclic ring with a nitrogen atom (for example, a piperidine ring, a piperazine ring, a morpholine ring, a pyrazole ring, a diterpene ring, a triterpene ring, a benzotriazine ring, etc.), the eR15 system represents a hydrogen atom. 1 alkyl having 1 to 8 (for example, methyl, ethyl, propyl, butyl, octyl), alkoxy having 1 to 8 carbon atoms (for example, methoxy, ethoxybutoxy) An aryl group having 6 to 10 carbon atoms (for example, a phenyl group), an amine group, -N (R16) (R17), or a halogen (for example, -ci, _Br, or _F) may be substituted.

Zb is not = 〇, = 8 or = (: (11 丨 8) (Ri9). -50- 200931177 R18 and R19 are independent cyano groups, -COOR20, -COR21. R2G and R21 are independent. Alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, octyl), haloalkyl having 1 to 8 carbon atoms (for example, chloromethyl, fluoromethyl, trifluoro) a methyl group or the like, an aryl group having 6 to 10 carbon atoms (for example, a phenyl group), a heterocyclic ring or a benzene ring which may be substituted. Further, examples of other coumarin compounds include the following general formula (IV); The compound shown.

In the above formula (IV), R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom, an amine group, a dialkylamino group, a monoalkylamine group, an N-substituted amine alkyl group, a halogen group or an alkyl group. Or alkoxy. Here, the alkyl group and the alkoxy group are preferably those having 1 to 4 carbon atoms. R5 and R6 may be bonded to each other to form a ring, and may also form a condensed ring with the adjacent Z. Z is preferably =0, =S, =C(CN) 2, especially =0 is particularly desirable. Further, examples of the coumarin compound represented by the compound represented by the above formula (IV), for example, the following compounds 1 to 3, or NKX 1316, 1317, 1767, 1768 obtained according to the catalogue of the Forest Research Institute of Biochemistry of Japan. , 1320' 1769, 1319 ' 1770, 1771 ' 846 ' 3502 ' 1619, commercially available products are also available. Among them, NKX 1767 and 1768' 1619 (trade name: manufactured by Japan Linyuan Biochemical Research Institute) are preferred. -51 - 200931177 Compound 1 Compound 2 Compound 3

In the above compound 1, R1, R2, R3 and R4 each independently represent a hydrogen atom or an alkyl group (preferably, carbon number 1 to 5). (C3-3) Examples of the diphenyl ketone compound diphenyl ketone compound include diphenyl ketone, benzamidine benzoic acid, 4-phenyldiphenyl ketone, and 4,4-diethylamino group. Diphenyl ketone, 3,3'-dimethyl-4-methoxydiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, and the like. &lt; (C3-4) An acridinone compound acridinone compound, which is exemplified by the disclosure of the paragraphs [〇〇32] to [0042] of Japanese Patent Laid-Open Publication No. 2007-41082, wherein An example of a particularly desirable compound is 10-n-butyl-2-chloroacridone (trade name: NBC A, manufactured by Nippon Kasei Kasei 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, the light sensitivity or the strength of the spacer can be prevented from being lowered, so that the performance such as the recovery property required for the spacer can be improved. 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 are -52 to 200931177, and examples thereof include an aminodiphenylketone-based compound, a phosphinylphosphine-based compound, and an oxime ester-based compound. Specific examples of the aminodiphenylketone-based compound include IRGACURE (Igg) 3 69 or IRGACURE (Irg) 3 79, and IRGACURE (Irg) 907 (all are trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.) ). Specific examples of the cerium oxide 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 (Ig) OXE1 or CG1 242 (all of which are trade names; manufactured by Ciba Specialty Chemicals Co., Ltd.). Other components The photosensitive composition of the present invention comprises at least the (A) resin, (B) a polymerizable unsaturated compound, and (C) a photopolymerization initiator, and may further contain other materials if necessary. Ingredients ((D) particles, etc.). The other components can be selected from the components constituting the conventional composition. For example, the components disclosed in paragraph numbers [〇〇1〇] to [0020] of JP-A-2006-23696, The components disclosed in paragraphs [0272] to [0053] of JP-A-2006-64921. (D) Fine Particles The photosensitive composition preferably contains fine particles by a transfer method to form a photosensitive resin layer on a substrate. (D) The fine particles are not particularly limited and can be appropriately selected depending on the purpose. For example, it is preferably disclosed in paragraphs [〇〇35] to [0041] of JP-A-2003-302639-53-200931177. The enamel pigment 'where' is preferably a oxidized political colloid based on the viewpoint of a spacer having good developing power and mechanical strength. 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, based on the viewpoint that a spacer having high mechanical strength can be obtained. From the viewpoint of obtaining a spacer having high mechanical strength, the content of the photosensitive resin layer (that is, the spacer) of the (D) fine particles is higher than that of all the solid components (mass) in the photosensitive resin layer (spacer). It is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, particularly preferably 15 to 30% by mass. Exposure step, development step, and heating step The method for producing a spacer according to the present invention includes at least a part of the photosensitive resin layer (coating film) formed on the substrate after the layer forming step is substantially free a step of exposing radiation of less than 35 Onm wavelength (exposure step), a step of developing the photosensitive resin layer after exposure (development 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, is ultraviolet rays, X-rays, electron lines, molecular lines, r lines, synchrotron radiation, proton beam lines, and the like. Exposure Step -54- 200931177 In the exposure step of the present invention, at least a portion of the photosensitive resin layer (coating film) formed in the layer forming step is exposed to radiation substantially free of radiation having a wavelength lower than 350 nm. Here, "substantially does not contain a wavelength of less 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. That is, it is also possible to include a wavelength which does not adversely affect the life of the exposure machine lens described later. When a portion 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 the decrease in the life of the lens which has been used in the 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 ultra-high 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 absent, it is preferred to use radiation in the range of from 190 to 450 nm and to filter out wavelengths lower than 350 nm. The amount of exposure of the radiation is measured by an illuminometer (trade name: OAImodel 365, manufactured by OAI Optical Associates Inc.) to measure the intensity of the exposed radiation wavelength (for example, 365 nm) 通常 'usually 20 to 50,000 J/m 2 . Preferably, it is 20 to 1,500 J/m2. The method of filtering out the wavelength of the radiation lower than 35 nm is not particularly limited, and for example, a method using a filter can be employed. For example, the filter can be a purple-55-200931177 external transmission filter "UV-35" (trade name) manufactured by Toshiba Glass Co., Ltd., Japan. Developing Step In the developing step of the present invention, the exposed photosensitive resin layer (coating film) is developed. The developing liquid used for the development treatment may be a thin aqueous solution of a basic substance. Further, a small amount of an organic solvent which is miscible with the 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 citrates (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 0.01 to 30% by mass, and the pH is preferably 8 to 14. The "organic solvent mixed with water" is, for example, suitably listed as: methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol single Ethyl ether, ethylene glycol mono-n-butyl ether, benzyl alcohol, acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, 7&quot;-butyrolactone, dimethylformamide, dimethyl Ethyl acetamide, hexamethylphosphoniumamine, ethyl lactate, methyl lactate, ε-caprolactone, hydrazine-methylpyrrolidone, and the like. The concentration of the organic solvent in the developing solution which is miscible with the water is preferably from 0.1 to 30% by mass. Further, a conventional surfactant may be further added, and the concentration of the surfactant in the developing solution is preferably 0.01 to 10% by mass. -56- 200931177 This developing solution can also be used as a solution or as a spray solution. In the case where the uncured portion of the photosensitive resin composition layer is removed, a method in which a photosensitive resin composition layer or the like is wiped by a rotating brush or a wet sponge can be used in combination with a developing solution. 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, and the kind and concentration thereof in the case of adding an organic solvent. If it is too short, the development of the non-hardened portion (the negative portion is the non-exposed portion) will become insufficient; if it is too long, the hardened portion (the negative portion will be exposed) will also be engraved with uranium. 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 between 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, and a method of treating them one by one using a hot plate may be used. The heating temperature in the heating step is usually from 150 ° C to 280 ° C, preferably from 180 ° C to 2 50 ° C. Although the heating time varies depending on the heating temperature, in the case where the baking temperature is 240 ° C, it is preferably from 1 minute to 120 minutes, more preferably from 30 minutes to 90 minutes. -57- 200931177 In addition, at intervals &lt; In view of reducing or preventing photosensitivity, it is also possible to perform a post-exposure small contaminant to expand and then expose the pupil in the wavelength region of the layer for post-exposure before the interval formed by the step. A chemical lamp or the like can be cited. The amount of exposure is preferably ～5,000 mJ/cm 2 , more preferably 500 mJ/cm 2 ′. The black masking portion of the photosensitive resin layer coated with the black photosensitive composition such as the spacer portion and the colored image of the present invention Sexual composition is formed. For example, the substrate is coated on the substrate, and the other substrate is shielded by the other color (in the manufacturing method of the temporary carrier, the exposure is based on preventing the UV absorber contained in the non-fat layer from being equal to the heating step). Post-exposure of the pattern. Once implemented, it can effectively prevent the source of defects during lamination. If it is light capable of illuminating a hardenable sensation (for example, 365 nm or 405 nm): ultra-high pressure mercury lamp, high-pressure mercury lamp The exposure amount for the exposure is usually preferably 200 mJ/cm 2 to 2,000 mJ/crrT or 1,100 mJ/cm 2 °. The color filter can be formed after forming a color portion including a black matrix, and the coloring portion and the coloring portion can be formed. The method of transferring the spacer to the spacer and using the transfer method having the photosensitive member transfer material, and the coloring portion and the spacer can be formed by, for example, forming the photosensitive resin layer by the photosensitive group of the liquid. The developing portion and the coloring portion are patterned, and then the photosensitive composition is provided on the substrate, and the film component and the image forming heat treatment which are uniform in the photosensitive resin layer are mixed. Micro-light resin: source, metal halide 5 OmJ/cm2 2, further black. The sensitized product obtained by combining the coated products is directly exposed and displayed, and the transfer material is adhered to the black masking portion and the coloring portion formed by using a different printing material manufactured by the same -58-200931177 After the substrate is transferred, the photosensitive resin layer is transferred, and a spacer can be formed by exposure and development. In this manner, a color filter provided with a spacer can be produced. 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. Further, a black conductive portion such as a black matrix or a driving element such as a TFT may be used, 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. And using the photosensitive composition of another liquid on another substrate (temporary carrier) different from the substrate to form a transfer material made of the photosensitive resin layer, and 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. -59- 200931177 On the substrate for a liquid crystal display device, if necessary, color elements such as red (R), blue (B), and green (G) may be provided. Liquid crystal display element In the present invention, a liquid crystal display element can be formed 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 'separating the respective elements 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 is uneven due to uneven color 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 using a black matrix to isolate pixels constituting the pixel group from each other - 60-200931177. In the present invention, examples of the liquid crystal which may be used 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 of 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 four color groups of 0 or more, any configuration is possible. For example, the color filter substrate can be formed by forming a black matrix as described later to form a pixel group of two or more colors, and conversely, forming a pixel group 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, &lt; aligning one of the substrates to each other in a manner opposite to each other, the spacer of the present invention is used to limit the predetermined width, and the liquid crystal material is sealed (the enclosed portion is called The gap defined by the liquid crystal layer is configured so that the thickness (liquid crystal cell thickness) of the liquid crystal layer is maintained at 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. Among them, in the liquid crystal display device, it is desirable to cause a display mode in which the display is not -61 to 200931177, depending on the thickness of the liquid crystal cell, and the thickness of the liquid crystal cell is preferably 2/zm. 4/zm VA display mode, IPS type display mode, OCB type display mode. In the example of the configuration of the liquid crystal display device, (a) a spacer, a device such as a thin film transistor (TFT), a driving side substrate on which a pixel electrode (conductive layer) is formed, and a counter electrode ( a conductive substrate), a liquid crystal material is sealed in a gap portion thereof; (b) a driving substrate is disposed opposite to the spacer, and a counter substrate is disposed on the directional electrode (conductive layer), and the liquid crystal material is sealed In the meantime, it constitutes something. The liquid crystal display device can be applied to various liquid crystal displays. In the liquid crystal display device, for example, it is disclosed in the next generation of the liquid crystal display technology, which is published in the liquid crystal display device of the present invention in addition to the substrate for the liquid crystal display element crystal display device of the present invention. There is no particular limitation, for example, a display device of various modes disclosed in the "next generation liquid crystal display technology". Among them, a liquid crystal display constituting a color TFT system is particularly effective. For a liquid crystal display device of a color TFT type, for example In the liquid crystal display device, in general, the electrode substrate, the film, and the phase can be used. Various components such as a poor film, a backlight, a spacer, a viewing angle compensation thin anti-reflection film, a light-diffusing film, an anti-glare film, etc., are well-oriented for such members, for example, as disclosed in "94 LCD Peripheral/Chemical Market (Japan Island Kentaro, (share) CMC, 1994 issued f "2003 LCD The status quo and future prospects of the joint market (volume) (the type of display shows the display of the gap display by the drive-to-electricity) j 0 or the liquid-structured liquid crystal device has been exposed to the 1996 plate or the polarizing film, I into the material. ;", 良良-62-200931177 吉), Japan (shares) Fuji Kimera, 2003, 2003, etc. _ EMBODIMENT Hereinafter, the present invention will be described more specifically based on examples, as long as the gist of the present invention is not It is defined by the examples. There are no special declarations, "%" and "parts" are the basis of the quality of the resin. The following shows that the (A) resin is a compound P from the styrene to the above compound P-4. The synthesis q of -4 + St is that the monomer ratio in the compound P-4 is obtained by the above-described composition. i Synthesis Example 1 1-methoxy-2-propanol is previously added (trade name: MFG, Japan ( 7.74 parts of the system) was added to the reaction vessel and heated to 90 ° C. In the environment, 3.1 parts of styrene (St; w) and methacrylic acid ester (TCPD manufactured by Sakamoto Kasei Chemical Co., Ltd.) M (quota β X) 4.28 parts, methacrylic acid (MMA; y) 11·7 parts, azo Starting agent (V601 manufactured by Nippon Wako Pure Chemical Industries Co., Ltd.) 2.08 parts of a mixed solution of 5.2methoxy-2-propanol 55.2 parts, which takes 2 small 90 in a reaction vessel. After the dropwise addition, the reaction is carried out. The resin solution was obtained in an hour. Then, 0.15 parts of hydroquinone monomethyl ether and a portion of tetraethylammonium bromide were added to the acrylic resin solution, followed by methacrylic acid esterification (GLM, Tokyo Chemical Industry Co., Ltd.) 26.4 parts of 2 hours of dropwise addition (GLM-MAA; ζ). After the dropwise addition, the air enthalpy was also reacted at 90 ° C for 4 hours, and then the solvent was added to form a solvent to form 1-methoxy-2. -propyl acetate (manufactured by MMPGAc Chemical Industry Co., Ltd.), which gives a compound having an unsaturated group, does not exceed, as long as a single crystal is constructed. But change. Emulsifier ήNitrogen tricyclopentane: name); Polymerization, and 1-time drop of acrylate 0.34 glycerol, cost J, 45%, D aise 1 P-4+St -63- 200931177 ((A Resin solution of resin) (solid content acid value: 76.0 mgKOH/g, Mw: 25,000, 1·methoxy-2-propanol oxime-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 an acrylic 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 T〇S〇), and the column system uses three TSK gels, Super Multipore HZ-H (Toso (manufactured by the company), 4_6mmIDxl5cm). Tetrahydrofuran). In addition, the conditions were set to a concentration of 0.3 5 /min, a flow rate of 〇.35 ml/min, a sample injection amount of 1 〇βΐ, and a measurement temperature of 4 〇 ° C. . In addition, the calibration line is "standard sample TSK standard, polystyrene" made by toso (share): rF_4〇, "F_4〇", "F-20", "F-4", "Fl", 8 samples of "A-5000", "a-2 5 00", "A-1000", and "n-butylbenzene" (the same applies hereinafter). The following '(A) other compounds of the resin are examples of the synthesis of the above-mentioned compounds P_9, P-io, P-25' P-53 and Ρ·57; and the structural unit derived from phenylethyl is added to these compounds - Synthesis examples (synthesis example 2 to synthesis example 8 and synthesis example 1 〇 to synthesis example 11) of the synthesis of the compound of the species and a synthesis example of the copolymer for comparison (synthesis example 9). Synthesis Example 2 The synthesis of the above compound Ρ_4 was carried out in the following manner. However, the monomer ratio in the compound Ρ-4 was changed from what was previously shown. -64- 200931177 In Synthesis Example 1, except that styrene was not used, the X: y : z = 34 mol% : 27 mol % : 3 9 mol % in the compound p-4 was changed to change TCPD-M (X), A In addition to the addition amount of the acrylic acid (y) and GLM-MMA (z), a resin solution (solid form) of the compound P-4 ((A) resin) having an unsaturated group was obtained by the same method as in Synthesis Example 1. Acid value: 72.5 mgKOH/g, Mw: 22,000, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45% solution). Synthesis Example 3 A synthesis of a compound P-3 + St in which a 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 25 mol% : 25 mol % : 40 mol % : lOmol % to change the addition amount of cyclohexyl methacrylate (X), methacrylic acid (y), GLM-MMA (z), and styrene 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 the 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 (CHM A, manufactured by Tokyo Chemical Industry Co., Ltd.), and the compound P-3 was used. X: y: z is changed to 32 mol -65 - 200931177 % : 25 mol% : 43 mol%, and the addition amount of cyclohexyl methacrylate (X), methacrylic acid (y), and GLM-MMA (z) is changed. The same procedure as in Synthesis Example 1 was carried out 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-A) Oxy-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-5 3 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). Trade name)), change the FA-512M(x), methacrylic acid (y) in the compound P-53 by X: y : z = 46.2mol% : 2 4.3 mo 1 % : 2 9.5 mo 1 % 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-53 ((A) resin) having an unsaturated group (solid form acid value: 70.2 mgKOH) /g, Mw: 3 0,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution). Synthesis Example 6 A synthesis of a compound P-10 + St in which a structural unit derived from styrene was added 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. X in -10: y : z : w becomes 2 5 m ο 1 % : 2 5 m ο 1 % : 4 0 m ο 1 % : 1 〇m ο 1 % square -66- 200931177 In the same manner as in Synthesis Example 1, except that the amounts of 513 M (x), methacrylic acid (y), GLM-MMA (z) and styrene were added, a compound P-10 + St having an unsaturated group was obtained. Resin solution of (A) resin) (solid content acid value: 78.7 mgKOH/g, Mw: 2 8,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution ). Synthesis Example 7 A synthesis of a compound P-1 + St in which a 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 Compound P-1 was changed from what was previously shown. In Synthesis Example 1, tricyclopentenyl methacrylate was changed to ADMA (manufactured by Nippon Industrial Co., Ltd.) so that X: y : z: w in the compound P-1 + St became 30 mol%: 24 mol%. : In addition to the addition amount of ADMA (x), methacrylic acid (y), GLM-MMA (z) and styrene, 38 mol% : 8 mol%, the same method as in Synthesis Example 1 was used to synthesize A resin solution of a saturated compound P-l+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 A synthesis of a compound P-2 + St in which a 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 the compound P-2 was changed from what was previously shown. In Synthesis Example 1, tricyclopentenyl methacrylate was changed to isodecyl methacrylate (manufactured by Nippon & Co., Ltd.) to make x in the compound p_2 + st: y: z: w is 34mo1% : 24mo1% : 36mol% : 6mol%, and the same applies to the addition of ΙΒΧΜΑ (X), methacrylic acid-67- 200931177 (y) and GLM-MMA (z) and styrene. The method of Synthesis Example 1 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, 〇〇〇, 1- Methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution). Synthesis Example 9 (Comparative) The resin used for the comparison was synthesized in the following manner. In Synthesis Example 6, GLM-M AA was changed to glycidyl methacrylate (GLM; manufactured by Tokyo Chemical Industry Co., Ltd.) so that X: y: z: w in the copolymerized product 1 became 27 mol. % : 25 mol % : 40 mol % : 8 mol % The same applies to the synthesis example except that the amount of dicyclopentanyl methacrylate (X), methacrylic acid (y ), GLM (z) and styrene is changed. The method of 6 was synthesized to obtain a resin solution of the copolymer 1 having no unsaturated group (solid content acid value: 95.9 mgKOH/g, Mw: 1 8,000, 1-methoxy-2-propanol/1-methoxy Base-2-propyl acetate 45% solution). Synthesis Example 1 〇 B 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 (CHM A, manufactured by Tokyo Chemical Industry Co., Ltd.), and X: y: z in the compound P-57: MMA was changed to 40.1 mol%: 26.6 mol%: 31.3 mol%: 2.0 mol% to change the amount of cyclohexyl methacrylate (X), methacrylic acid (y), and GLM-MMA (z) and styrene. 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-2-propanol / 1-methoxy-2-propyl acetate 45% solution). -68- 200931177 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 (CHM A, manufactured by Tokyo Chemical Industry Co., Ltd.) to make X: y: z in the compound P-25: MMA was changed to 46.0 mol%: 20.0 m〇l % : 32.0 mol% : 2.0 mol% to change cyclohexyl methacrylate (X), methyl propylene acid (y), and GLM-MMA (Z) and A resin solution of the compound P-25 ((A) resin) having an unsaturated group was obtained by the same method as in Synthesis Example 1 except that the amount of the methyl methacrylate was added (solid content acid value: 74.3) mgKOH/g, Mw: 3 3,600, 1-methoxy-2-propanol/1-methoxy-2-propyl acetate 45% solution) [Example 1] Example 1: Coating method (used Method for Liquid Resistor) The color filter substrate is fabricated in accordance with the method disclosed in paragraphs [0084] to [0095] of Japanese Patent Laid-Open Publication No. Hei. No. 200-5-86 1 to produce a black matrix and R (red) pixels. A color filter of G (green) pixels and B (blue) pixels (hereinafter, referred to as a color filter substrate). Here, the size of the color filter substrate is set to 400 mm x 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. For the formation of a photo spacer, a glass substrate coater MH-1600 having a slit nozzle on an I TO transparent electrode on which a color filter substrate having the above-described ITO transparent electrode is formed is sputtered (trade name: FAS Asia) Company-made), slit coating-69- 200931177 The sensitization of the formulation shown in the following Table 1 (in Example 1, Formula 1 Cl: C2: C3 = 3.7: 1: 1 (weight ratio)) A coating liquid for a resin layer. Next, using a vacuum dryer VCD (trade name; manufactured by Tokyo Ohka 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 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.), the reticle of the circular pattern of the diameter of 15 mm is vertically erected in parallel (the quartz pattern with image pattern is exposed to 0 light) 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 Am. The UV-transparent filter "UV-35" (trade name) manufactured by Toshiba Glass Co., Ltd. was used for exposure to a thickness of 365 nm (exposure amount) of 250 W/m2 for 10 seconds. Next, using a sodium carbonate-based developing solution (using water to contain 0.38 mol/liter of sodium hydrogencarbonate, 0.47 mol/liter of sodium carbonate, 5% of dibutylnaphthalene-sulfonic acid sodium, anionic interface activity) Agent, defoamer and stabilizer; trade name: T-CD1 (made by Fujifilm Co., Ltd.) diluted to 10 times), sprayed at 30 ° C with a cone nozzle pressure of 0.15 MPa at 30 ° C The image is formed by immersion. Next, using pure water to dilute the detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3C Japan Fuji Film Co., Ltd.) 10 times the solution 'at 33 ° C, using a cone nozzle pressure of 0.02 MPa, 20 seconds of spray rinsing to remove the residue of the pattern like the surrounding, to become 300 pieces of m × 3 00 vm The spacer spacer pattern is used to form a cylindrical spacer pattern (pattern shape step). • 70-200931177 Next, at 60 ° C, a photo spacer is 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 the three-dimensional surface structure analysis microscope (manufacturer: ZYGO Co., Ltd., type: New View 5 022), the highest position of the highest spacer of the obtained 1 000 photo spacers was measured from the glass substrate side (n = 20), set its average 値 to height (average height). Further, the measurement of the bottom area of the obtained photo spacer was carried out using an SEM photograph. As a result, the photo spacers were cylindrical with a diameter of 15.1/zm and an average height of 4.7//Π1.其他 In another method of fabricating a liquid crystal display device, a glass substrate is prepared for the opposite substrate system, and a pattern for PVA mode is formed on the transparent electrode provided on the color light-emitting sheet obtained above and on the opposite substrate, and further thereon An alignment film composed of polyimine is provided. 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 is FR1 1 12H (trade name; wafer type LED manufactured by Stanley Electric Co., Ltd.), and green (B) LED is DG1112H (trade name; Stanley Electric Co., Ltd.) ), the blue (G) LED is used as a backlight of the side edge light type using DB1 1 12H (trade name; wafer type LED manufactured by Stanley Electric Co., Ltd.), and is disposed on the back surface of the liquid crystal cell on which the polarizing plate is provided. On the side, a liquid crystal display device is fabricated. -71-200931177 Evaluation of the 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). The measurement was carried out using a conical table indentation of 50 μmφφ, setting a maximum load of 21 mN and a holding time of 5 seconds, using a load-deloading test method. From this, the deformation recovery rate [%] was determined 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 [^m] / deformation amount at load [//m]) X100 Evaluation Jihua 5: Deformation recovery rate is 90% or more. 4: The deformation recovery rate is 87% or more and less than 90%. 3: The deformation recovery rate is 8 5 % or more and less than 8 7 % ° 2: The deformation recovery rate is 80% or more and less than 85%. 1 : The deformation recovery rate is 7 5 % or more and less than 80 % ° 〇 : The deformation recovery rate is less than 75 %. The elastic modulus at 1 5 % compression at 5 °C is adjusted to 25. (:In the room 'with a load speed of 1〇mN/s', the spacer is compressed to a height Hi [mm] corresponding to 85% of the initial height H〇[mm], and the load at the height of the mountain is read. [N]' The elastic coefficient of 15% compression (skew amount = (Ho-H!) / H〇) is calculated by the following formula: Elastic coefficient = (load weight Fi / spacer bottom area S [mm2]) / skew amount Development-72-200931177 In the "production of photo spacers", after exposure exposure, development was carried out by the same method as the development conditions of the respective examples, and SEM observation of the peripheral portion of the formed photo spacer was performed. The presence or absence of the residue around the spacer was confirmed. Evaluation criteria 5: The residue was not observed at all. 4: A small amount of residue was observed around the pattern. 3: The residue was observed around the pattern. 2: Around the pattern and The residue was observed on the substrate in the vicinity of the pattern. 1: Residue was observed in the entire substrate. Sensitivity The coating liquid for the photosensitive resin layer used in each example was similarly exposed under the above development conditions. Whether the spacer map can be formed when the amount is changed The exposure display treatment was formed, and the minimum exposure amount of the possible pattern formation was set as the sensitivity by SEM observation, and evaluated according to the following evaluation criteria. Evaluation Reference A: The exposure amount was less than 60 mJ/cm 2 , and pattern formation was possible. The amount of the film is 60 mJ/cm 2 or more and less than 150 mJ/cm 2 , and pattern formation is 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 : 3 00 m J/cm 2 or more The amount of exposure is necessary for pattern formation. Stability of the solution over time (preservability) The above-mentioned obtained coating liquid for the photosensitive resin layer of the dense plug is naturally passed over time (25 ° C) for 180 days, and will be photosensitive. After the coating liquid for a resin layer was placed in an oven at 60 ° C for 2 weeks, the same coating operation as in -73 - 200931177 was carried out using the coating liquid, and the evaluation was performed according to the following criteria. Evaluation Standard A: Low exposure Pattern formation is possible at 60 mJ/cm 2 B: The exposure amount is 60 mJ/cm 2 or more and less than 150 mJ/cm 2 , and pattern formation is possible. C: Exposure amount of 150 mJ/cm 2 or more and less than 300 m: T/Cm 2 For pattern shape D: The 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 Example 1, as shown in Tables 1 to 3 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. The same liquid crystal display device was used as in Example 1. Evaluation (evaluation (including imaging) within the manufacturing steps of the spacer). The evaluation results are shown in Table 3. The resulting spacers were all cylindrical with a diameter of 15.1/zm and an average height of 4.7 ym. 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 changed as shown in Table 1 below. In the formulas 2 and 4 (C1: C2: C3 = l: 1.7: 1 (weight ratio)), and in the manner shown in Table 3, the coating is applied in place of the coating liquid for the photosensitive resin layer. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the photosensitive transfer film was transferred by using a photosensitive transfer film as described below. The resulting photo spacers were all cylindrical in shape having an average diameter of 4.7/zm. • 74- 200931177 Preparation of a photosensitive transfer film for spacers A thermoplastic resin layer made of the following formulation A was coated on a polyethylene terephthalate film temporary carrier (PET temporary carrier) having a thickness of 75 μm. The liquid was applied and dried to form a thermoplastic resin layer having a dry layer thickness of 15.0 μm.

Formulation of coating liquid for thermoplastic resin layer A *Methyl methacrylate / methacrylic acid · 2 - ethylhexyl ester / benzyl methacrylate / methacrylic acid copolymer... 25.0 parts win (= 55 / 1 1.7/4.5/28.8 [Morby], weight average molecular weight 90,000) styrene/acrylic acid copolymer...58·4 parts (=63/37 [mole ratio], weight average molecular weight 8,000) • 2 , 2-bis[4-(methylpropenyloxypolyethoxy)phenyl]propene... 3 9.0 parts...1 0·0 parts... 90.0 parts...5 1 . 0 parts...700 parts...30% ...70% *The following surfactants 1 *Methanol©« 1-methoxy-2-propanol *methyl ethyl ketone * surfactant 1 *The following structures 1 ♦ Methyl ethyl ketone-75- 200931177 Construct 1 [CH2*^〇H)4d—* 0*C〇CH2CH2CnF2n+

—{CHi-OHV

(P〇) 7H one (ch2-〒h&gt; "6(ΕΟ)τΗ (Πβ=6'ώ:ϋ3Π〇: Mw/Mn = 2.55 PO: propylene oxide EO: ethylene oxide) Next, at 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 layer thickness of 1.5 m/zm was deposited.

Formulation B of the coating solution for the intermediate layer. 3.3.2 parts of polyvinyl alcohol... (trade name: PVA-205 (saponification ratio: 80%), (manufactured by Claire)), polyvinylpyrrolidone... 1.49 parts (trade name: PVP K-30) , ISP Japan Co., Ltd.) Lumethanol...42.3 parts © • Distilled water: 524 parts Next, the photosensitive resin layer obtained by formula 2 shown in the following Table 1 was further applied and dried on the formed intermediate layer. The coating liquid (resin (A) is a compound in Table 3) was laminated to a photosensitive resin layer having a dry layer thickness of 5.2/m. 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; am) is formed, and then further heated on the surface of the photosensitive resin layer. The pressure was applied as a film made of polypropylene having a film thickness of 12/zm, and -76-200931177 was obtained as a photosensitive transfer film for spacers. The photosensitive spacer is formed by peeling off the spacer, and the surface of the light-sensitive resin layer is superposed on the electrode of the color filter substrate on which the ITO transparent electrode produced in the same manner as the actual method is formed. In the laminating machine, the Lamic II type (trade name: manufactured by Nippon Kogyo Co., Ltd.) was used, and the bonding was carried out at a line speed of 100 N/cm and 130 ° C under pressure and heating at a conveying speed of 2 m/min. Thereafter, the PET temporary carrier is peeled off at the interface with the thermoplastic resin, and the photosensitive resin layer is laminated to the thermoplastic resin layer and the intermediate layer (layer forming step). Next, using a proximity-type exposure Hitachi Hightech Electronic Engineering Co., Ltd. with an ultra-high pressure mercury lamp, a circular mask having a circular pattern of approximately 15 μm in diameter (a mask having an image pattern), and making the mask and thermoplastic In the state of the color filter substrate in which the resin layer is disposed to face each other, the distance between the intermediate layer side surfaces of the photomask surface-attachable resin layer is set to 100/zm, and from the side of the thermoplastic resin layer, 3 65 nm is used. The intensity is 25 0 W/m2, and the UV-transparent filter "UV-35" (trade name) of Toshiba-Shiban is penetrated by a 10 second exposure. Then, at 30 ° C, a three-ethanolamine-based developing solution was sprayed with a flat nozzle pressure of 0.04 MPa (using pure water to contain 30%, trade name: T-PD2 (Japan Fuji Film Co., Ltd.) 12 times ( The thermoplastic resin layer and the intermediate layer were removed by mixing 1 part of T-PD2 in a ratio of 1 part of pure water. Then, the upper surface of the substrate was sprayed with air to completely remove the solution, and the feeling was revealed by spraying for 10 seconds. In the case of the ITO transparent (strand) of the bottle example 1, the resin layer is simultaneously transferred to the machine (the Japanese vertical erected quartz exposure method is in contact with the light, and the light is exposed (exposure amount) [glass' (share), 50 seconds Dilute triethanolamine) diluted into 5 solutions), blow this glass clock to wash pure -77- 200931177 water, wash with pure water spray, spray air to reduce the accumulation of solution on the substrate. Next, use sodium carbonate imaging solution ( Using pure water to contain 〇·38 mol/L of sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% dibutyl naphthalene sulfonate, anionic surfactant, antifoaming agent and stabilizer ; Product name: T-CD1 (Japan Fujifilm (stock) system) diluted to 10 times dissolved Using a cone nozzle pressure of 0.15 MPa at 29 ° C, a pattern image was formed by spray development for 30 seconds. Next, using pure water to remove the detergent (containing phosphate, citrate, non-ion) Sexual surfactant, defoamer, stabilizer; 〇 Trade name: T-SD3 (made by Fujifilm Co., Ltd.)) diluted to 10 times solution at 33 ° C, using a cone nozzle pressure of 0.02 MPa, After 20 seconds of shower rinsing, the formed pattern image was removed by the surrounding residue, and a cylindrical spacer pattern (pattern shape step) was formed by 300 spacers of m 00 #mx 300. Next, At 60 ° 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 obtained photo spacer was 1 5 in diameter. A cylindrical shape of 1 / zm and an average height of 4.7 V m. 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. -78 - 200931177 Table 1] Photosensitive resin Coating solution for forming layer 1 Formulation 2 Formulation 4 Formulation 5 Formulation 6 Examples 1 to 4, 6 to 14, Comparative Examples 1 to 5 Examples 5 and 17 Example 18 Comparative Example 6 Comparative Example 7 1-methoxy group -2-propyl acetate 26 23.35 23.35 37.275 19.43 methyl ethyl ketone 28 28 28 28 28 colloidal cerium oxide dispersion (colloidal cerium oxide: 30 parts, methyl isobutyl ketone: 70 parts, Nissan Chemical Co., Ltd. Industrial MIBKst) ; (D microparticles) 0 14.1 14.1 0 0 Solsperse 20000 0.42 0.42 0.42 0 0 DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2-propyl acetate: 24 parts): (B) Polymerizable unsaturated compound 18.2 14.37 14.37 18.2 8.667 (A) A solution of the resin (however, (A) resin is a compound disclosed in Table 3) 20.5 26.98 26.98 0 36.6 Methacrylic acid/allyl methacrylate copolymerization (Mole ratio) = 20/80 (weight average molecular weight = 36,000) 0 0 0 9.225 0 (C) Starting agent 0.227 0.227 0.227 0.227 0.227 Hydroquinone monomethyl ether 0.0036 0.0036 0.0036 0.0036 0.0036 Surfactant 1 (Megafac F-780-F, Great Japan Ink Industrial Co., Ltd.) 0.032 0.032 0.032 0.032 0.032 Victoria Pure Blue NAPS (Nippon Hodogaya Chemical Industry Co., Ltd.) 5% methanol solution 2.05 2.05 0 0 0 Pigment dispersion CIPB 15 : 6 (manufactured by Toyo Ink Co., Ltd.) : 11.92 parts, methacrylic acid / benzyl methacrylate copolymer (mole ratio) = 30 / 70 (weight average molecular weight = 30,000) 5.96 parts, 1-methoxy-2-propyl acetate: 82.12 parts 0 0 2.05 0 0 [Table 2] Formulation solution 3 for photosensitive resin composition layer Example 15 and 16 1-methoxy-2-propyl acetate 36.53 Diethylene glycol ethyl methyl ether 28.43 DPHA solution (Dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2-propyl acetate: 24 parts) 15.75 (A) Resin solution (however, (A) resin is a compound disclosed in Table 3) 17.74 (C) Starting agent 1.27 Hydroquinone monomethyl ether 0.05 Surfactant 2 (Megafac F-781-F, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 0.02 decane coupling agent 1 (KBM-403) , Japan Shin-Etsu Chemical Industry Co., Ltd.) 0.2 Unit: Quality Part -79-200931177

200931177 The following is abbreviated as a compound used in the above examples and comparative examples: • B-CIM: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylene Imidazole (manufactured by Japan Hodogaya Chemical Industry Co., Ltd.) • HABI1311: 2,2,-bis(o-chlorobenzene. 'yl)-4,4',5,5'-tetra(3,4-dimethoxy Phenyl)biimidazole (manufactured by Siber Hegner Co., Ltd.) • Methylbiimidazole: 2,2'-bis(2-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole ( Japan Black Gold Chemical Co., Ltd.) Ο · IRG907: 2-methyl-1-[4-(methylthio)phenyl]-2·morpholinylpropan-1-one (IRGACURE 907, Ciba Specialty Chemicals ( ())), MBI: 2 - mercaptobenzimidazole • MBT: 2-mercaptobenzothiazole _ EAB: diethylaminodiphenyl ketone • NKX-1619: coumarin compound (Japan) MIBK-St: 30wt% methyl isobutyl ketone dispersion of sulphur dioxide gel (manufactured by Sakamoto Chemical Co., Ltd.) • NBCA: 10-n-butyl-2-chloride Acridinone (made by Japan Black Gold Chemical Co., Ltd.) • NPhMBI: N-phenylmercaptobenzopyrene-81- 20 0931177

DETX-S ο C2H5 It is clear from Table 3 that compared with the comparative example, the radiation sensitive resin composition and the spacer of the examples are evaluated in any one of sensitivity, deformation recovery rate, and solution stability. All are excellent. [Simple description of the diagram] None. (: Description of main component symbols) te 〇 j\w

-82-

Claims (1)

200931177 X. Patent application scope: A radiation-sensitive linear resin composition for spacer formation, which comprises: (Α) having a branching structure and/or an alicyclic structure, an acidic group, or a partition in at least a side chain a resin having an ester group bonded to an ethylenically unsaturated group of the main chain; (Β) a polymerizable unsaturated compound; and (C) a (C1) hexaarylbiimidazole compound, (C2) aromatic mercapto compound With (C3) additives. Ο 2· The radiation-sensitive resin composition for forming a spacer according to the first aspect of the patent application, wherein the (C 3 ) auxiliary comprises a thioxanthone compound, a sulphur compound, a diphenyl ketone compound, and a hydrazine At least one selected from the ketone compounds. 3. The radiation-sensitive resin composition for spacer formation according to the first aspect of the patent application' wherein the (C1) hexaarylbiimidazole compound is a compound represented by the following formula (1) or formula (2): Ο -83- 200931177 ～4 alkyl or carbon 6~9 aryl; A is a substituted or unsubstituted alkoxy or -COO-R having a carbon number of 1 to 12 (wherein R represents carbon) An alkyl group having 1 to 4 or an aryl group having 6 to 9 carbon atoms; an integer of 1 to 3; each m is an integer of 1 to 3; (2) 式 In the formula (2), X^X2 and X3 represent an independently 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; X1, X2 When it is different from two or more of X3, it is represented by a hydrogen atom. ^4. The radiation-sensitive resin composition for spacer formation according to the first aspect of the patent application, wherein the branched structure and/or the alicyclic structure is dicyclopentyl, dicyclopentenyl, cyclohexyl, At least one selected from the group consisting of a tricyclopentyl group, a tricyclopentenyl group, an adamantyl group, a norbornyl group, and an isodecyl group. The radiation-sensitive resin composition for spacer formation according to the first aspect of the patent application. Wherein the alicyclic structure is a group derived from a monomer represented by the following formula (3): -84 - 200931177 C—Formula (3) η In the formula (3), the fluorene system represents a divalent organic linking group, the y system represents 1 or 2, the η system represents an integer of 0 to 15, and the R system represents a hydrogen atom or a methyl group. 〇6. A spacer-forming radiation-sensitive resin composition according to the fifth aspect of the patent application, wherein the divalent organic linking group is selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group. The base or the combination of the spacers according to the first aspect of the invention, 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, η represents an integer of 0 to 15, and R represents a hydrogen atom or a methyl group. 8. The spacer-forming radiation-sensitive resin composition according to claim 7, wherein the divalent organic linking group is selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group. A base or combination. 9. The radiation-sensitive resin composition for forming a spacer according to the first aspect of the patent application, wherein the branched structure is a branched alkyl group having 3 to 12 carbon atoms - 85 - 200931177 1 如The spacer of the first aspect forms the radiation sensitive resin composition, wherein the (ruthenium) resin further contains a structural unit derived from styrene. 11. The radiation sensitive linear resin composition for spacer formation according to the first aspect of the invention, wherein the composition ratio (X) of the branch structure and/or the alicyclic structure in the (Α) resin is 10 to 70 The ear %, the composition ratio (y) of the acidic group is 5 to 70 mol%, and the composition ratio (ζ) of the ethylenically unsaturated group is 10 to 70 mol%. 〇12. The radiation-sensitive resin composition for spacer formation according to the first aspect of the invention, wherein the mass ratio of the (B) polymerizable compound to the (A) resin [(B) / (A) ratio] is 0.5. </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; A method of 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 12; At least a part of the photosensitive 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 claim 13 of the patent application. -86- 200931177 VII. Designated representative circle: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ 〇 /\\\ 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: X3