TW200935173A - Photosensitive resin composition, photospacer and method of forming the same, protective film, colored pattern, substrate for display device, and display apparatus - Google Patents

Abstract

The present invention provides a photosensitive resin composition, which comprises [A] the resin with its side chain containing branched chains and/or cycloaliphatic structure, acidic group, and alkyl replacement, wherein the aforementioned alkyl replacement in the resin has two-vinyl unsaturated bonds, [B] the polymerizable compound containing vinyl unsaturated bonds, and [C] the photo-polymerization initiator, which is the pattern-formable structure or photo-sensitive resin composition of protective film with high sensitivity, excellence in liquid-state preservation, and excellence in aging stability of the photo-sensitive film after the film formation.

Description

[Technical Field] The present invention relates to a photosensitive resin composition, a photo spacer, a method for forming the same, a protective film, a colored pattern, a substrate for a display device, and a display device. [Prior Art] In recent years, the size of the liquid crystal display device has increased, and the productivity of the main glass substrate has been increasing. In the conventional substrate size (about 680 x 8 80mm), since the substrate size is smaller than the mask size, it can be used in a batch exposure mode of 0. However, with the recent enlargement of devices, the demand for large substrates (for example, about 1,500×1,800 mm) has increased, but it is almost impossible to prepare a mask size to the same extent as such a substrate. The correspondence between exposure methods is difficult. Therefore, as a large substrate corresponding exposure mode, the stepwise exposure mode is raised. However, in the stepwise exposure mode, since a plurality of exposures are performed on one substrate, positioning is performed each time, so that the time required for stepping movement occurs. 〇 Therefore, compared with the batch exposure method, the step exposure method has a reduced yield. Further, in the batch exposure method, although a patternable exposure sensitivity of about 3,00 (H/m2) is allowed, in the stepwise exposure method, it is required to perform a good pattern at 1,500 J/m2 or less. The exposure sensitivity of the conventional material is difficult to obtain a good spacer shape and film thickness at an exposure amount of 1,500 J/m 2 or less. Further, the requirements relating to the shape of the spacer and the controllability of the film thickness, In recent years, the system has become more and more stringent, and there is room for improvement in the shape and thickness of the 200935173, the shape accompanying the change in the composition solution, and the stability of the film thickness due to the process variation in forming the spacer. In particular, in the exposure range of 1,500 00 J/m 2 or less, there is a problem in the shape of the spacer and the controllability of the film thickness in terms of the exposure amount. Further, in recent years, in the manufacture of a liquid crystal display panel The photosensitive resin composition to be used has a problem that a foreign matter or a contaminated device is generated by crystallization or the like during the storage period or during the use of the component in the composition, and the photosensitive resin composition which is desired to reduce the contamination problem is severely deteriorated. 〇 The photosensitive resin composition has been reviewed variously, and for example, there is disclosed a photosensitive resin composition containing a curable resin composed of a copolymer of an aliphatic cyclic hydrocarbon group, the copolymer having a linkage with an aliphatic group. A molecular structure of a constituent unit of a cyclic hydrocarbon group, a constituent unit having an acidic functional group, and a constituent unit having a radical polymerizable group (see, for example, JP-A-2002-29677 5). Further, a curable resin is disclosed. It is formed of a copolymer containing an aliphatic cyclic hydrocarbon group having a molecular structure of a constituent unit of an aliphatic cyclic hydrocarbon group having a specific structure, a constituent unit having an acidic functional group, and a constituent unit of a radical polymerizable group. For example, the present invention provides a photosensitive resin composition, a photo spacer, a method for forming the same, a protective film, a colored pattern, a substrate for a display device, and a display device. The first aspect provides a photosensitive resin composition containing [A] having a branched chain and/or an alicyclic structure in the side chain, and an acid And a substituted alkyl group resin and the aforementioned substituted alkyl group in the resin has two ethylenically unsaturated bonds, [B] 200935173 a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator, It is a photosensitive resin composition which can form a pattern structure or a protective film which is excellent in the sensitivity of the liquid state, is excellent in the preservability in a liquid state, and is excellent in the stability of the photosensitive film after film formation. The second aspect of this invention is this. A method of forming a photo spacer having a step of forming a film on a substrate using the photosensitive resin composition of the first aspect, and exposing at least a portion of the film to expose the film after exposure And a step of heating the film after the development. The third aspect of the present invention provides a photo spacer, a protective film or a colored pattern formed by using the photosensitive resin composition of the first aspect. According to a fourth aspect of the invention, there is provided a substrate for a display device comprising at least one of a photo spacer, a protective film or a colored pattern of the third aspect, and a display device provided therewith. According to the above-mentioned conventional photosensitive resin composition, when a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) or a protective film is formed on a substrate, it is not necessarily obtained for obtaining. The sensitivity and the polymerization resistance of a good shape and the like are not sufficient in terms of liquid preservability or stability of the photosensitive film after film formation. The present invention has been made in view of the above, and it is an object of the present invention to achieve the following objects. In other words, the object of the present invention is to provide a photosensitive resin composition capable of forming a pattern structure or a protective film which is excellent in sensitivity and liquid state, and which is excellent in stability over time or mechanical properties of a photosensitive film after film formation. . Further, an object of the present invention is to provide a photo spacer which is excellent in height uniformity and uniform cross-sectional shape even when formed with low sensitivity, and a method for producing the same. Further, an object of the present invention is to provide a protective film or a colored pattern which is excellent in film thickness uniformity and uniform cross-sectional shape even when formed with low sensitivity. Further, an object of the present invention is to provide a display device substrate which can suppress display unevenness when used in a display device, and a display device which suppresses display unevenness. The invention relates to a sensible resin composition comprising: [A] a resin having a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in a side chain, and The substituted alkyl group in the resin has two ethylenically unsaturated bonds, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator. The photosensitive resin composition of the above-mentioned <1>, wherein the above-mentioned substituted alkyl group is a group represented by the following formula (1).

(General formula (wherein '* indicates a side bonded to the main chain of the resin, and A1 represents a 2-substituted alkyl group having 1 to 9 carbon atoms: Β1 and Β2 each independently represent a single bond or a urethane bond ( The main chain side: -0-C0-NHR-), the ester bond (main chain side: -CO-O.), and R represents an alkyl group having 1 to 3 carbon atoms; moreover, XI and Χ2 each independently represent an ester bond ( The main chain side: -0-CO-); Ri and R2 each independently represent a 200935173 hydrogen atom or a methyl group. &lt;3&gt; The photosensitive resin composition as described in <1> or <2>, wherein the aforementioned The photosensitive resin composition according to any one of the above-mentioned <1> to <3>, wherein the substituent has a branch and/or Or the base of the alicyclic structure is constituted by the group represented by the following formula (3),

In the formula (3), X represents a divalent organic linking group and may be unsubstituted or substituted; y represents 1 or 2, and η represents an integer of 0 to 15. The photosensitive resin composition as described in any one of the above-mentioned <1>, wherein the above [Α] has a branched chain and/or an alicyclic structure, an acidic group and a substituted alkane in a side chain. The base resin, and the above-mentioned substituted alkyl group in the resin has two ethylenically unsaturated bonds, and the weight average molecular weight is 12, ❹~60,000. The photosensitive resin composition described in any one of the above-mentioned items, wherein the aforementioned [A] has a branched chain and/or an alicyclic structure, an acidic group, and a substituted body in the side chain. The base resin, and the glass transition temperature (Tg) of the above-mentioned substituted alkyl group having two ethylenically unsaturated bonds in the resin is 4 〇 to l8 (rc. &lt;7&gt; as above &lt;1&gt;~&lt;6&gt; The photosensitive resin composition described in the above-mentioned item, wherein the aforementioned [A] has a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in the side chain, and the aforementioned substituted alkyl group in the resin has. The photosensitive resin composition according to any one of the above-mentioned items, wherein the above-mentioned [B] is the above-mentioned [B]. The mass ratio ([B]/[A] ratio) of the polymerizable compound to the above [A] resin is from 0.5 to 2.0. <9> Any of the above &lt;1&gt;~&lt;8&gt; The photosensitive resin composition according to the invention further contains an anthracene pigment having an average particle diameter of 5 to 50 nm. <10> A photo-spacer using the above &lt;1&gt;~ The photosensitive resin composition according to any one of <9>, wherein a method for forming a photo spacer includes at least the following steps (-) to (c), (a) a step of forming a film of the photosensitive resin composition according to any one of the above items <1> to <9>, (2) a step of exposing at least a part of the film, and (3) exposing the film after exposure The step of developing, (4) the step of heating the film after development. <12> A protective film using the photosensitive film described in the above &lt;1&gt;~&lt;9&gt; The resin composition is formed by using the photosensitive resin composition according to any one of the above-mentioned items <1> to <9>. <14> The device substrate is provided with at least one of the photo spacer described in the above <11>, the protective film described in <12>, and the coloring pattern described in <13>. <15> The substrate for a display device according to the above &lt;14&gt; 200935173 [Embodiment] Hereinafter, a photosensitive resin composition of the present invention, a photo spacer using the photosensitive resin composition, a method for forming the same, a protective film, a colored pattern, and a display will be described in detail. A substrate for a device and a display device. <<Photosensitive Resin Composition>> The photosensitive resin composition of the present invention contains [A] a resin having a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in a side chain, and the above-mentioned substituted alkyl group in the resin A compound having two ethylenically unsaturated bonds (hereinafter also referred to as [A] resin), [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator. In general, when a pattern structure (for example, a photo spacer, a colored pattern, or the like, the same applies hereinafter) or a protective film is formed on a substrate by using a photosensitive resin composition, the polymerization hardening is insufficient only by exposure. Further, the storage stability in a liquid state and the stability over time of the photosensitive film after film formation are not necessarily sufficient. Further, in order to ensure the stability over time of the photosensitive film after the film formation, when a high-temperature heat treatment is performed after exposure and development, the pattern structure or the protective film to be formed may be deteriorated or formed. The pattern structure or protective film on the substrate may deteriorate. For example, when a photo spacer is formed on a color filter substrate having a colored pattern, the photo spacer to be formed may be deteriorated, or the colored pattern formed on the substrate may be deteriorated. Therefore, the photosensitive resin composition of the present invention has a high sensitivity, is less likely to cause an increase in viscosity, improves polymerization hardenability at the time of exposure, and is excellent in storage property in a liquid state, and the photosensitive resin composition is a structure of the present invention. 200935173 The photosensitive film after film formation is excellent in stability over time, and can form a pattern structure or a protective film. Hereinafter, (A) a resin, (B) a polymerizable compound having an ethylenically unsaturated bond, [C] a photopolymerization initiator, and other components will be described. &lt;[A] Resin> [A] The resin has a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in the side chain, and the substituted alkyl group has two ethylenically unsaturated bonds (substituted). . The above [A] resin has an acidic group, has developability, and has a substituted alkyl group having two ethylenically unsaturated bonds, and has high polymerization property due to high sensitivity, and has excellent liquid preservability and dry film. The shelf life is preserved, so that the control of the pattern structure to a desired shape and film thickness (height, etc.) can be imparted. Further, since the branched structure and/or the alicyclic structure are provided, the compressive elastic modulus and the elastic recovery property of the compression deformation when the formed pattern structure is subjected to an external force can be improved. Therefore, it is applied to, for example, a pattern structure constituting a photo spacer for a display device. Here, the substituted alkyl group having a branched chain and/or an alicyclic structure, an acidic group, and two ethylenically unsaturated bonds may be contained in different side chains, or may be partially combined in the same side chain. Further, all of them may be contained in the same side chain. In the present specification, (meth)acrylylene group means propylene fluorenyl group or methacryl fluorenyl group, and (meth) acrylate means acrylate or nail. Acrylate, (meth)acryloyl group means propylene fluorenyl or methacryl fluorenyl, (methyl)-10-200935173 acrylamide represents acrylamide or methacrylamide, (meth) propylene oxime The aniline represents acryl anilide or methacryl anilide. (Branch and/or alicyclic structure) [A] The resin is a side chain which is bonded to the resin main chain and contains at least one of a branched chain and/or an alicyclic structure. A plurality of branched and/or alicyclic structures may be contained in the side chain of the [A] resin. Further, the branched chain and/or alicyclic structure may be contained in the side chain of the [A] resin together with an acidic group and/or a substituted alkyl group having two ethylenically unsaturated bonds. Further, the branched and/or alicyclic structure may be directly bonded to the main chain of the [A] resin, and the side chain of the [A] resin may be formed only by the branch and/or alicyclic structure, or may be [ A] The main chain of the resin is bonded via a divalent organic linking group, and the side chain of the [A] resin is formed as a group having a branched chain and/or an alicyclic structure. As the above-mentioned divalent organic linking group, one or a combination selected from an alkyl group, an aryl group, an ester group, a decyl group and an ether group is preferred. The alkylene group is preferably an alkylene group having a total carbon number of from 1 to 20, more preferably from 1 to 10. Specifically, a methylene group, an exoethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a octyl group, a decyl group, an octadecyl group, etc., which may have a branch/ring The structure and the functional group are more preferably a methylene group, an ethyl group or a octyl group. The above-mentioned extended aryl group is preferably an extended aryl group having a total carbon number of 6 to 20, more preferably 6 to 12 parts. Specific examples thereof include a stretching phenyl group, a stretching phenyl group, a stretching naphthyl group, a stretching group, and the like. These may have a branched chain or a functional group, and more preferably a phenyl group or a phenyl group. The branched chain and/or alicyclic structure is preferably a form of a main chain bonded to the [A] resin via at least an ester group (main chain side -COO-) from the viewpoint of developability and elastic recovery. . This form is not limited to the branch and/or alicyclic structure. The form of the main chain bonded to the [A] resin only via the ester group (11 - 200935173 main chain side - COO-) may also be branched and/or branched. The alicyclic structure is bonded to the main chain of the [A] resin via a divalent linking group containing an ester group (main chain side - COO-). That is, other atoms or other linking groups may be contained between the branched chain and/or the alicyclic structure and the ester chain, and/or between the ester chain and the main chain of the [A] resin. Examples of the branched structure include a branched alkyl group having 3 to 12 carbon atoms, and for example, an isopropyl group, an isobutyl group, a second butyl group, a tert-butyl group, an isopentyl group, and a new group are preferable. Butyl, 2-methylbutyl, isohexyl, 2-ethylhexyl, 2-decylmethylhexyl, isopentyl, tert-pentyl, 3-octyl, tert-octyl. Among these, an isopropyl group, a second butyl group, a tert-butyl group, an isopentyl group or the like is more preferable, and an isopropyl group, a second butyl group, a third butyl group or the like is particularly preferable. Examples of the alicyclic structure include an alicyclic hydrocarbon group having 5 to 20 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an borneol group, an isobornyl group, an adamantyl group, and the like. Tricyclic fluorenyl, dicyclopentenyl, dicyclopentanyl, tricyclopentenyl, and tricyclopentanyl, and the like, and the like. Among these, more preferred are dicyclopentenyl, cyclohexyl, borneol, isobornyl, adamantyl, tricyclodecyl, tricyclopentenyl, tricyclopentanyl, and the like. Preferably, it is a dicyclopentenyl group, a cyclohexyl group, an borneol group, an isobornyl group, a tricyclopentenyl group, etc., and particularly preferably a dicyclopentenyl group or a tricyclopentenyl group. In addition, the base having a branched chain and/or an alicyclic structure is preferably a form having a group represented by the following formula (3). -12- 200935173

Ο

\ II 〇-|-C- General formula (3) / η In the general formula (3), X represents a divalent organic linking group, and may be unsubstituted or substituted. y represents 1 or 2, and η represents an integer of 0 to 15. The divalent organic linking group is preferably one or a combination selected from an alkyl group, an aryl group Φ, a acetoxy group, a decylamino group and an ether group, and these may have a substituent. As the above-mentioned stretching, the base is preferably an alkylene group having a total carbon number of from 1 to 20, more preferably an alkylene group of from 1 to 10. Specific examples thereof include a methylene group, an exoethyl 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. These may have Branched/cyclic structure, functional group, more preferably methylene, ethyl, and octyl. The above-mentioned aryl group is preferably an extended aryl group having a total carbon number of 6 to 20, more preferably an arylene group having a Φ of 6 to 12. Specific examples thereof include a stretching phenyl group, a stretching phenyl group, a stretching naphthyl group, a stretching group, and the like, and these may have a branched 'functional group, more preferably a phenyl group or a phenyl group. The substituent at the time of substitution may, for example, be an alkyl group, a hydroxyl group, an amine group, a halogen group, an aromatic ring group or a group having an alicyclic structure. In the synthesis of the [Α] resin, examples of the monomer for introducing a branched chain and/or a lipid raft structure into a side chain include styrenes, (meth)acrylates, vinyl ethers, and vinyl esters. And (meth) acrylamide, etc., preferably (meth) propylene-13-200935173 acid ester, vinyl ester, (meth) acrylamide, more preferably (meth) acrylate . In the synthesis of the [A] resin, as a specific monomer for introducing a branched structure into a side chain, isopropyl (meth)acrylate, isobutyl (meth)acrylate, or (meth)acrylic acid may be mentioned. Second butyl ester, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, third amyl (meth)acrylate, second isoamyl (meth)acrylate, (meth)acrylic acid 2-octyl ester, 3-octyl (meth)acrylate, third octyl (meth)acrylate, etc., among which isopropyl (meth)acrylate, isobutyl (meth)acrylate, A The third butyl acrylate or the like is more preferably isopropyl methacrylate or butyl methacrylate. In the synthesis of the [A] resin, as the monomer for introducing the alicyclic structure in the side chain, a (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms is exemplified. Specific examples thereof include (meth)acrylic acid (bicyclo[2.2.:!] heptyl-2) ester, 1-adamantyl (meth)acrylate, and 2-adamantyl (meth)acrylate, ( 3-methyl-1-adamantylmethyl methacrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, ( ® A Acrylic acid 3_methyl_5·ethyl-1-adamantyl ester, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-di (meth)acrylic acid Methyl-8-ethyl-1-golden vinegar, (meth)acrylic acid 2-methyl-2-goldenate ester, 2-ethyl-2'-adamantyl (meth)acrylate, ( Methyl)acrylic acid 3_hydroxy-obamantane ester, (meth)acrylic acid octahydrate 7-methylene group _5-based vinegar, (methyl) acrylic acid octahydro-4,7-methylene茚-1 -ylmethyl ester, bismuth (meth) acrylate, tricyclodecyl (meth) acrylate, 3-hydroxy-2,6,6-trimethyl-bicyclo(3)[3] . 1 · 1 ]heptyl ester, (meth)acrylic acid 3,7,7-trimethyl-4-hydroxy-bicyclo-14- 200935173 [4.1.0]heptyl ester, (methyl) propyl Acid (original) borneol ester, isobornyl (meth)acrylate, decyl (meth)acrylate, 2,2,5-trimethylcyclohexyl (meth)acrylate, cyclohexyl (meth)acrylate And dicyclopentenyl (meth)acrylate, tricyclopentenyl (meth)acrylate, and the like. Among these (meth) acrylates, cyclohexyl (meth)acrylate and (methyl) are preferred from the viewpoint that the compression elastic modulus and the elastic recovery property of the bulky functional group are improved. Acrylic acid (original) borneol ester, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, decyl (meth)acrylate, (methyl) ) 1-capric acid acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclopentenyl (meth) acrylate, etc., particularly preferably (meth) acrylate Ester, (meth)acrylic acid (original) borneol ester, isobornyl (meth)acrylate, 2:adamantyl (meth)acrylate, dicyclopentenyl (meth)acrylate, (meth)acrylic acid Cyclopentenyl ester. In the synthesis of the [A] resin, a compound represented by the following formula (4) or (5) is exemplified as the monomer for introducing the alicyclic structure in the side chain. Here, in the general formulae (4) and (5), X represents a divalent organic linking group, R represents a hydrogenogen ® or a methyl group; y represents 1 or 2, and η represents 0 to 15. In the general formulae (4) and (5), y = 1 or 2, η = 0 to 8, more preferably y = 1 or 2, and η = 0 to 4 (more preferably η = 0 to 2). ). Preferred examples of the compound represented by the formula (4) or (5) include the following compounds D-1 to D-ll and Τ-1 to Τ-12. In particular, the compound represented by the following formula (4) is preferred from the viewpoint of the elastic recovery rate due to the reactivity of the double bond moiety. -15- 200935173 Formula (4) Formula (5)

In the general formulae (4) to (5), the divalent organic linking group represented by X may be unsubstituted or substituted, and is synonymous with the divalent organic linking group represented by X of the above formula (3). The best is the same. Η H2c=c—C-〇-CH2CH2-〇—H2C=CH-C-〇-^J^y D- 1 D-3 ❹ H2〇=C—C-0-CH2〇H2—O~H2C=CH_Q_0 — D-4 D- 2 H2C=CH-C-〇^^j^ D- 5 -16- 200935173 ch3 H2〇=C_C-OGH2CH2OH2*o °^}〇D-6 _?Hs Γ^ΥτΛ H2C-C —C—OCH2CH2CH2CH2_〇~j~ ) )o D-7 ❹ _?Hs H2C =c—c~OCH2CH2OCH2CH2—o~j~ jyb D-8

-GO ch3 H2C=i-C-OCH2CH2OCH2CH2—〇-o ch3 H2C=i-C-〇CH2CH2OCH2CH2OCH2CH2—〇 〇 D-9

D_10 ❹

D-11 -17- 200935173

• 18 - 200935173 ch3 H2C =C—C—OCH2CH2OCH2CH2 —o—o

T-9 ch3 H2〇=c—C—0CH2CH2OCH2CH2—o 〇

T-10

Ch3 h2c=c-c-och2ch-o-II I 0 CH3

T-11

In the synthesis of the [A] resin, as a monomer for introducing an alicyclic structure into a side chain, a suitable manufacturer can be used. A commercially available product can also be used. As the above-mentioned commercial product, a product of Hitachi Chemical Co., Ltd. can be cited: FA·5 11 A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M, and the like. Among these, it is preferable that FA_512A(S) and 512M are excellent from the viewpoint of excellent developability and excellent deformation recovery rate. ~~Acid group--[A] The resin is at least one type which contains an acidic group in the side chain which is linked to the main chain. A plurality of acidic groups may be contained in the side chain. Further, in the side chain of the [A] resin, the acidic group may have two ethylenic groups with the above-mentioned branched chain and/or alicyclic structure, and between the main chain 19-200935173 via an ester group. The substituted alkyl group of the unsaturated bond is contained together. Further, the acidic group may be directly bonded to the main chain of the [A] resin, and may constitute a side chain of the [A] resin only with an acidic group, or may be bonded to the [A] resin via a divalent organic linking group. The main chain constitutes a side chain of the [A] resin as a group having an acidic group. Here, the divalent organic linking group may be a divalent organic linking group exemplified in the above-mentioned branched chain and/or alicyclic structure, and the preferred range is also the same. The above-mentioned acidic group is not particularly limited, and may be appropriately selected from among those well known, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfonylamino group, a phosphoric acid group, and a phenolic thiol group. Among these, a carboxyl group or a phenolic hydroxyl group is preferred from the viewpoint of excellent developability and water resistance of the cured film. Specific examples of the monomer for introducing the acidic group into the [A] resin are appropriately selected from those skilled in the art, and examples thereof include (meth)acrylic acid, vinylbenzoic acid, maleic acid, and Malay. Addition reaction of acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid diol, monomer having hydroxyl group and cyclic acid anhydride , ω-carboxy-polycaprolactone mono (meth) acrylate, and the like. These may be used by a suitable manufacturer or a commercially available product. The monomer having a hydroxyl group used in the addition reaction of the monomer having a hydroxyl group and the cyclic acid anhydride may, for example, be 2-hydroxyethyl (meth)acrylate. Examples of the cyclic acid anhydride include maleic anhydride, decanoic anhydride, and cyclohexane dicarboxylic anhydride. As a commercial product of a monomer, it can be mentioned by the East Asian Synthetic Chemical Industry Co., Ltd.: -20- 200935173

Aronix M-5 3 00, Aronix M-5400, Aronix M- 5 00, Aronix M-5600, Xinzhongcun Chemical Industry Co., Ltd.: NK ester CB-1, NK ester CBX-1, Kyoeisha oleochemistry Industrial (stock) system: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd.: Biscoat #2100, etc. Among these, (meth)acrylic acid or the like is preferred from the viewpoint of excellent developability and low cost. (Substituted alkyl group having two ethylenically unsaturated bonds) [A] The resin is a side chain bonded to the main chain and contains at least one substituted alkyl group having two ethylenically unsaturated bonds (hereinafter also referred to as "Substituted alkyl") © . In the side chain of the [A] resin, a plurality of the aforementioned substituted alkyl groups may be contained. Further, the substituted alkyl group is contained in the side chain of the [A] resin and is contained in a structural unit different from the above-mentioned branched chain and/or alicyclic structure and acidic group. Further, the substituted alkyl group may be directly bonded to the main chain of the [A] resin, and may constitute a side chain of the [A] resin only by a substituted alkyl group, or may be a divalent organic group in the main chain of the [A] resin. The linking group is bonded to form a side chain of the [A] resin as a group having a substituted alkyl group, and the above-mentioned divalent organic linking group may be further provided between the ester group having a substituted alkyl group and the main chain. The above-mentioned divalent organic linking group is the same as the divalent organic linking group described under the item having a branched chain and/or an alicyclic structure, and the preferred embodiment is also the same. In the above-mentioned, the alkyl group is controlled by the high sensitivity and high polymerization reactivity, the controllability of the film thickness of the pattern structure, the availability of synthetic raw materials, and the suitability for synthesis. It is preferably a form of a main chain bonded to the [A] resin via at least an ester group (main chain side - COO-). This form is not limited to the form in which the substituted alkyl group is bonded to the main chain-21-200935173 of the [A] resin via the ester group (main chain side -COO-), or may be a substituted alkyl group via an ester group (main chain) The 2-valent linking group of the side -COO-) is bonded to the 'main chain' form of the [A] resin. That is, between the substituted alkyl group and the ester group (-COO-), and/or between the substituted alkyl group and the main chain of the [A] resin, it may also contain its atom or other linking group (1 to 9 alkylene oxide). base). ❹ The substituted alkyl group (that is, a substituted alkyl group having two ethylenically unsaturated bonds) is not particularly limited, but the film is characterized by high sensitivity and high polymerization reactivity of the photosensitive resin composition. From the viewpoint of (hardenability, synthetic suitability, and the like), a group represented by the following formula (1) is preferred.

In the formula (1), * represents a side bonded to the main chain of the resin, and A1 represents an alkyl group having 1 to 9 carbon atoms substituted with two substituents having an ethylenically unsaturated bond. Further, A1 is bonded via a main chain and the above ester group (main chain side - C0-0-). In the above formula (1), the alkyl group may be an alkyl group having 1 to 9 carbon atoms, and may be a linear structure, a branched structure or an alicyclic structure. The linear structure may, for example, be a methyl group, an ethyl group, a propyl group, a butyl group or a pentyl group, and is preferably a carbon number of 1 to 9, more preferably a carbon number of 1 to 6. -22-200935173 The branched structure and the branched structure described in the item of the branched chain and/or the alicyclic structure are preferable, and the carbon number is preferably 3 to 8, more preferably 3 to 5 carbon atoms. The alicyclic structure includes an alicyclic structure or the like described under the above-mentioned item of the branched chain and/or alicyclic structure, and preferably has a carbon number of 5 to 20, more preferably a carbon number of 5 to 15 °. In the above, B1 and B2 each independently represent a single bond, a urethane bond (main chain side: -0-C0-NHR-), an ester bond (main chain side: -0-CO-), and R represents a carbon ruthenium. The number of the hospital bases 1 to 3 is preferably B1, preferably a single bond or a urethane bond (main chain side: -0-C0-NHR-), more preferably a single bond. As B2', a single bond or a urethane bond (main chain side: -0-C0-NHR-) is preferred, and a single bond is more preferred. B1 and B2 may be the same or different configurations. In the formula (1), XI and X2 each independently represent (main chain side) - 〇-CO- 〇®. In the formula (1), I and the rule 2 each independently represent a hydrogen atom or a methyl group, and preferably methyl. 1 and R2 may be the same or different configurations. In the synthesis of the [A] resin, a method of introducing a (meth) acrylonitrile group into a side chain can be suitably selected from well-known methods, and for example, (1) a repeating unit having an acidic group is added. a method of (meth) acrylate having an epoxy group, (2) a method of adding a (meth) acrylate having an isocyanate group in a repeating unit having a hydroxyl group, and (3) adding a hydroxyl group to a repeating unit having an isocyanate group The method of (meth) acrylate, and the like. -23- 200935173 Among them, a method of introducing a (meth) acrylate having an epoxy group in a repeating unit having an acidic group is preferred from the viewpoint of easiest production and low cost. In the synthesis of the [A] resin, a method of introducing two (meth) acrylonitrile groups into a side chain can be synthesized, for example, by combining the following methods: (1) having an epoxy group in a repeating unit having an acidic group (meth) acrylate, which is obtained by esterifying a hydroxyl group with (meth) acrylonitrile, etc., and is an isocyanate containing a (meth) acrylate group (for example, Karenz MOI 制 manufactured by Showa Denko Co., Ltd.) , MOIEG, AOI, etc.) A well-known method such as a method of obtaining a hydroxy group by hydroxylation. The (meth)propenoic acid ester having an epoxy group is not particularly limited. For example, a compound represented by the following structural formula (1) and a compound represented by the following structural formula (2) are preferable.

Structural formula (1)

V However, in the above structural formula (1), R1 represents no hydrogen atom or methyl group; and L1 is synonymous with B1 and B2 in the formula (1). -24- 200935173

Structural formula (2) However, in the above structural formula (2), 'r2 represents a hydrogen atom or a methyl group; 12 is synonymous with B1 and B2 of the formula (1); and W represents an aliphatic hydrocarbon group of a 4 to 7 member ring, and The compound represented by the above formula (1) or the compound represented by the structural formula (2) is not particularly limited. For example, the following is the same. Illustrative compounds (1) to (10). -25- 200935173

(1)

(5)

Ο

Ο (10) In the [Α] resin of the present invention, other monomers may be used, and other groups 26-200935173 may be introduced as the other monomer, and are not particularly limited, and examples thereof include (meth)acrylic acid. Monomers such as esters, styrene, vinyl ether, dibasic acid anhydride groups, vinyl ester groups, hydrocarbon alkenyl groups, and the like. The vinyl ether group is not particularly limited, and examples thereof include a butyl vinyl ether group. The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an Ikonic anhydride group. The vinyl ester group is not particularly limited, and examples thereof include vinegar, acid vinyl, and the like. The hydrocarbon alkenyl group is not particularly limited, and examples thereof include a butenyl group and a prenyl group. The content of the other monomer in the above [A] resin is preferably from 1 to 40% by mass, more preferably from 2 to 30% by mass. Specific examples of the [A] resin include compounds represented by the following structures (exemplary compounds PD-1 to PD-56, PU-1 to PU-56), but are not limited thereto. Further, X, y, and Z (and St) in the exemplified compound indicate the composition ratio (mass ratio) of each repeating unit, and the form constituting the preferred range described later is suitable. Further, the form in which the weight average molecular weight of each of the exemplified compounds is in the preferred range described later is also suitable. -27- 200935173

COO^ COOH

〇

COO

x:y:z=42:26:32

V PD-5

x:y:z=40:23:37 〇 PD-6 28- 200935173

COO COOH COO 〇

〇=^Yx

V PD-7 :y:z=40:20:35 coo

COOH

Coo CH2CH2—〇,

〇

❹

COO COOH Ό

-29- 200935173

Coo

Z_ c〇〇, a___?P°

〇

O x:y:z=35:30:35 PD-14

COOv person COOH 0=0-/ 〇 PD-15 x:y:z=45:30:25 ❿

COO^

y COOH

〇

V PD-16 x:y:z=45:20:35

COOv COOH

PD-17 〇 x:y:z=45:25:30 -30- 200935173

C〇〇H

COOH

x:y:z=40:20:40 -31 - 200935173

x:y:z=44:16:40

COO

PD-25

COO丫]COOMe COOH COO

x:I:y:z=46:2:20:32 〇 》PD-26

X-1 : z=45.5-2M9-33.5

y C〇〇H

COO 〇 o=6-j^ x:y:z=48:22:30 PD-27

x:y :ζ=51· 5M8· 5:30 -32- 200935173

Coo

COOH COO 〇

x:y:z=40:25:35

V PD-29

Coo m

COOH

Coo ch2ch2-o

Rv COOH

y COOH

COO

❹

〇

COO

x:y:z=42:28:30

V PD-33 -33 200935173

x:y:z=37:28:35 〇

PD-34

x:y:z=39:26:35 〇

V PD-35

-34 200935173

COOH

x:y:z=40:25:35 ο=όγ

COOH

COO

COOH

C〇〇, /\

COOH

-35- 200935173

Coo.

y C〇〇H

Coo.

❹

y C〇〇H

〇 〇 PD-43 x:y:z=35:30:35

COO

y C〇〇H

〇 FD-44 x:y:z=30:25:45 ❹

Ry

fZ 〇

COOH COO

PD-45 x:y:z=30:30:40

V -36- 200935173

Coo

Rx

PD-46 C〇〇H 0=0-(^ I x:y:z:St=30:24:38:8

Ry

COO COOH COO

Fy

© COOH

ο

x:y:z:St=34:24:36:6

〇 V

PD-47

COO. COOH

PD-48 y:z:St=40:23:35:2 COO^Y^O 〇

V PD-49 0=6/ x:y:z:=32:25:43

Rv COO /^C〇〇H u 0=6 丫

St PD-50 x:y:z:St=25:25:40:10 -37- 200935173

Coo

COOH

O

PD-52 0=0-/ I x:y:z:St=30:27:37:6 ❹

COO

Ch2ch2-o

COOH

PD-53 〇

COO x:y:z=46.2:24.3:29. 5

COOH COO \

PD-54 o=0V I x:y:z:St=25:25:40:10 ❹

COO COOH I ch2ch2och2ch2-o· off and COO eight people 0=0-j^x:y:

V PD-55 z=46:24:30

COO

y COOH ch2ch-〇-03 CH, 〇

38- 200935173

-39- 200935173

Coo COOH COO PU-8

Ch2ch2-o ❹

x:y:z=42:23:35 〇, seven coo COOH C ch2ch2-o

x:y:z=41:24:35 O PU-9

Fy coo 0〇

COOH COO^V^O^ 〇PU-1〇

G

COO COOl·Ό Χσ

x:y:z=50:24:26 PU-11

y COOH

O x:y:z=40:25:35 PU-12 H coo^-\ 〇 〇/ x:y:z=30:30:40

-40 200935173 〇 coo.

Human COO

&gt;A

H ,N ^COOH〇〇^CO°

O PU-13 ❹ x:y:z=45:15:40

〇

COO.

〇 coo,

y COOH

COO, zcoo

V PU-17 〇 x:y:z=45:25:30 -41 - 200935173 coo

Z_ COOH

PU-18 x:y:z=40:25:35 ,ΧΧγ pu-19 x:y:z=45:20:35 ❹ coo

H zcoo

△ COOH

〇 Nb

〇 PU-20 coo

y COOH

Coo^^y^o O x:y:z=40:30:30 〇

/ PU-21

&gt;Y ❹ 〇=C-N&quot;&quot;^ H x:y:z=45:20:35

y COOH

Coo

〇 o s, c/(b

〇 PU-22 x:y:z=35:25:40

COO

〇 Ύ COOH O-^s

000 〇 PU-23 -N -C A 乂〇人乂〇人〆 x〇 x:y:z=40:20:40 -42- 200935173

Η χI - yz=45. 5 ' 2'19 ' 33.5

COO

COOH C〇〇H

x ' y-z=51.5-18. 5 -30 -43- 200935173

Coo

C〇〇H

C〇〇,丫,〇 PU-30

COO

❹ 〇

COO CH 2CH2-〇

C〇〇H COO^V^O O x:y:z=41:24:35 〇 PU-31

〇Χ〇Χ&gt;

Fx 10

COO

〇=C-N_ H x:y:z=39:26:35

C〇〇H

Coo^Y^o I 0=C-N H X'y:z=35:30:35 O όΛ^ PU-33 x:y:z=42:28:30 -44 - 200935173

Ch3 -45- 200935173

Ο

❿ -46- 200935173

X coo.

Coo.

y COOH y COOH

❹

Coo.

PU-40 ❹

Coo

y COOH

H z coo

C-O 〇

〇 x:y:z=45:20:35

COOH COO Λ II 〇 O 〇

PU-41

〇 x:y:z=40:20:40 -47- 200935173

V x:y:z=40:25:35 PU-42

Coo

〇 x:y:z=35:30:35

〇 PU-44

COO

x: y: z=30:25 ·· 45 C〇〇H

48 200935173

COO COOH

❿ coo

PU-49 x:y:z:=32:25:43

-49- 200935173 &lt;Synthesis method&gt; [A] The resin may be combined by a two-stage step or a three-stage step in the step of (co)polymerization of the monomer with the step of introducing two ethylenically unsaturated groups. . First, the '(co)polymerization reaction is produced by (co)polymerization of various monomers' is not particularly limited, and can be suitably selected from those skilled in the art. For example, as the active species to be polymerized, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, or the like can be suitably selected. Among these, © is preferably a radical polymerization from the viewpoint of ease of synthesis. Further, the polymerization method is not particularly limited and can be appropriately selected from those skilled in the art. For example, a bulk polymerization method, a suspension polymerization method, an emulsification polymerization method, a solution polymerization method, or the like can be suitably selected. Among these, a solution polymerization method is more preferred. &lt;Cyclic number&gt; The total carbon number of the [A] resin is preferably 10 or more from the viewpoint of the modulus of elasticity (hardness). The total carbon number is more preferably 10 to 30, particularly preferably 10 to &lt;molecular weight&gt; The molecular weight of the [A] resin is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, based on the weight average molecular weight. Good for 15,000 to 45,000. When the weight average molecular weight is within the above range, it is preferred that the resin (preferably a copolymer) is suitable for the production and development. Further, it is preferable from the point that the shape formed is not easily destroyed by the decrease in the melt viscosity, or the point where the crosslinking is not easily formed, and the residue having no spacer shape at the time of development is considered. The weight average molecular weight is determined by gel permeation chromatography (GPC). The GPC is displayed in detail under the item of the embodiment to be described later. &lt;Glass transfer temperature&gt; The glass transition temperature (Tg) of the resin [A] is preferably 40 to 18 (TC, more preferably 45 to 140 ° C, particularly preferably 50 to 130 ° C. Glass transition temperature (Tg) If it is within the above preferred range, a spacer having good developability and mechanical strength is obtained. 酸 <acid value> [A] The preferred range of the acid value of the resin is in accordance with the molecular structure that can be obtained. The fluctuation is generally preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and particularly preferably 50 to 130 mgKOH/g. If the acid value is within the above preferred range, good development and mechanical properties are obtained. The spacer of the strength [A] resin, the glass transition temperature (Tg) is preferably 40 to 180 ° C from the viewpoint of obtaining a spacer having good developability and mechanical strength, and the weight average molecular weight is higher. Preferably, it is 10,000 to 100,000, and the Tg is preferably 45 to 140 ° C (more preferably 50 to 130 ° C), and the weight average molecular weight is preferably from 12,000 to 60,000 (more preferably from 1 to 5,000 to 45,000). In a preferred embodiment of the [A] resin, a preferred group of the aforementioned molecular weight, glass transition temperature (Tg) and acid value is more preferred. The [A] resin in the present invention has a branched chain and/or an alicyclic structure, an acidic group, and a content 2 which is disposed between the main chain and the ester group in a different repeating unit (copolymerizing unit). Three-membered copolymerization of a substituted alkyl group having an ethylenically unsaturated bond; the above-mentioned copolymer's deformation recovery rate and development residue when forming a pattern structure (for example, a spacer for color filter -51 - 200935173 sheet) Preferably, the above-mentioned [A] resin preferably has at least a repeating unit having a branched chain and/or a lipid raft structure: χ (χ 耳 %), having an acidic group Repeating unit: Y (y mole %), repeating unit having a substituted alkyl group having two ethylenically unsaturated bonds disposed via an ester group with a main chain: Z (z mole %) of 3 yuan Copolymerizing the above copolymer. Further, other repeating units may be used as needed: L (1 mol%). Such a copolymer may, for example, be a monomer having a branched chain and/or an alicyclic structure. a monomer having an acidic group and having two B groups disposed via an ester group throughout the main chain The monomer of the substituted alkyl group having an ethylenically unsaturated bond and, if necessary, another monomer are copolymerized, and the compression elastic modulus and the elastic recovery property are improved from a bulky functional group. In the monomer having at least the above-described branched chain and/or alicyclic structure, it is preferred to copolymerize the monomer represented by the above formula (4) and introduce a group having a branched chain and/or an alicyclic structure. In the case of the copolymer, the [A] resin has a constituent unit derived from the monomer represented by the above formula (4) in the main chain. The copolymerization composition in the case where the above [A] resin is a copolymer is determined in consideration of the glass transition temperature and the acid value, and it cannot be clarified, but may be in the following range. The composition ratio (X) of the repeating unit having a branched chain and/or an alicyclic structure in the resin is preferably from 10 to 70 mol%, more preferably from 1 to 65 mol%, particularly preferably from 2 0. ～60 摩尔%»If the composition ratio (X) is within the above range, good development performance is obtained, and the image forming liquid resistance of the image portion is also good. • 52- 200935173 [A] The composition ratio (y) of the repeating unit having an acidic group in the resin is preferably 5 to 70 mol%, more preferably 1 〇 to 6 〇 mol%, and particularly preferably 2 〇 5 〇 Moer %. When the composition ratio (y) is within the above range, good hardenability and developability are obtained. The composition ratio (Z) of the repeating unit having the "substituted alkyl group having two ethylenically unsaturated bonds disposed via an ester group between the main chain" in the resin is preferably from 1 to 70. Ear %, preferably 20 to 70 mol %, particularly preferably 30 to 70 mol %. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, and the sensitivity and the polymerization hardenability are good, and the liquid storage property after liquid adjustment and the stability with time in the dry film state after application for a long period of time are changed. good. Further, as the [A] resin, the composition ratio (X) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly preferably 20 to 50 mol%), and the composition ratio (y) is 5. ~70 mole % (better 10 to 60 mole %, especially good 30 to 70 mole %), composition ratio (z) is 10 to 70 mole % (more preferably 20 to 70 mole %, The case of particularly preferably 30 to 70 mol% is preferred. The content of the above [A] resin in the photosensitive resin composition is preferably from 5 to 70% by mass, more preferably from 10 to 50% by mass, based on the total solid content of the composition of the composition. The resin of the [A] may be used in combination with other resins to be described later, but it is preferably a case of only the above-mentioned [A] resin. - Other resin - The resin which can be used for the resin of the above [A] is preferably a compound which exhibits swelling property in an aqueous test solution, and more preferably a compound which is soluble in an aqueous alkaline solution. -53- 200935173 As a resin which exhibits swellability or solubility in an aqueous alkaline solution, for example, an acid group is suitably used. Specifically, it is preferred to introduce an ethylenically unsaturated double bond and an acidic group into the epoxy compound. a compound (epoxy acrylate compound), a vinyl copolymer having a (meth)acrylic acid group and an acidic group in a side chain, an epoxy acrylate compound, and a (meth) acrylonitrile group in a side chain; The mixture of the acidic group-containing vinyl copolymer and the maleic acid-based copolymer is not particularly limited as the acidic group ', and may be appropriately selected according to the purpose, and examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. In the above, etc., from the viewpoint of obtaining raw materials, etc., a carboxyl group is preferable. When the above [A] resin and other resins are used, the total content (solid content) of the resin [A] resin and the usable resin is preferably 5 to 70 with respect to the total solid content of the photosensitive resin layer. The mass% is more preferably 10 to 50% by mass. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the surface adhesiveness of the photosensitive resin layer can be favorably maintained. When the content is 70% by mass or less, the exposure sensitivity is improved. © [B] polymerizable compound The photosensitive resin composition of the present invention contains at least one of polymerizable compounds having an ethylenically unsaturated bond. The polymerization reaction is carried out by the action of a radical derived from a photopolymerization initiator to be described later to form a cured film. The polymerizable compound can be selected from the group of the polymerizable compounds of the known constituents, and examples thereof include those described in paragraphs [〇〇1〇] to [〇〇20] of JP-A-2006-23696. The component is in the range of -54 - 200935173 as described in paragraphs [0027] to [0053] of JP-A-2006-64921. The mass ratio of the [B] polymerizable compound to the [A] resin ([B]/[A] ratio) in the relationship with the above [A] resin is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.4. Very good is 0.7~1.2. When the ratio of [B]/[A] is within the above range, a spacer having good developing ability and mechanical strength is obtained. [C] Photopolymerization initiator The photosensitive resin composition of the present invention contains at least one kind of photopolymerization initiator.光 The photopolymerization initiator in the present invention is not particularly limited, and a well-known photopolymerization initiator can be used. As a known photopolymerization initiator, for example, paragraph number [0010] to [0020] of JP-A-2006-23696 or paragraph number [0027] of JP-A-2006-6492 No. 1 [[53] The initiator described in ]. As an example of a known photopolymerization initiator, it is preferred to contain an aminoacetophenone-based compound, a mercaptophosphine oxide-based compound, an oxime ester-based compound, and a combination of six aromatics in addition to the above. A mixed type II initiator of a bi-imidazole compound/aromatic mercapto compound/auxiliary. Specific examples of the aminoacetophenone-based compound include IRGACURE (Irg) 90 7 (made by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the mercaptophosphine oxide-based compound include DAROCUR TPO or IrgaCure (Irg) 819 (above, Ciba Specialty Chemicals Co., Ltd.). Further, specific examples of the oxime ester-based compound include IRGACURE (Irg) OXE01 or CG I 242 (the above is manufactured by Ciba Specialty Chemicals Co., Ltd.). As a mixed type of hexaarylbisimidazole compound/aromatic fluorenyl compound/auxiliary compound-55-200935173, 2,2'-bis(2-chlorophenyl)-4,4' can be mentioned. 5,5'-Tetraphenylbisimidazole (B-CIM, Baotu Valley Chemical Industry)/2-mercaptobenzimidazole/4,4-diethylaminobenzophenone. The construction of these initiators is shown below. &lt;Amino acetophenone-based compound&gt;

Irg 907

❹

Irg 819 &lt; mercaptophosphine oxide compound&gt;

DAROCUR TPO

&lt;肟 ester compound&gt; Irg OXE 01

-56-200935173 The total amount of the photopolymerization initiator in the photosensitive resin composition is preferably from 0.5 to 25% by mass, more preferably from 1 to 20% by mass, based on the total solid content of the photosensitive resin composition. . The photopolymerization initiator is not easily sublimated under heating at the time of pattern formation, and it is possible to suppress contamination of the calciner or the reticle, and the polymerization reaction can be carried out by using the resin A, and the shape and film can be further improved. Thick control. Thereby, even in a low exposure amount range of, for example, 1 500 J/m2 or less, good sensitivity and adhesion are obtained. For example, when a spacer for a color filter is formed, a spacer having a good adhesion to the ruthenium substrate and forming a desired shape can be obtained. Further, the photopolymerization initiator described in the present invention means an active species capable of initiating polymerization of the above specific polymerizable compound by exposure to visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. Ingredients. &lt;Microparticles&gt; The photosensitive resin composition of the present invention contains a resin, a polymerizable compound, and a photopolymerization initiator, and preferably contains at least one kind of fine particles from the viewpoint of mechanical strength. The fine particles are not particularly limited, and can be appropriately selected according to the purpose. For example, the anthraquinone pigments described in JP-A-2003-03902 [0035] to [0041] are preferably obtained. From the viewpoint of a good developer and mechanical strength photo spacer, colloidal vermiculite is preferred. The average particle diameter of the fine particles is preferably from 5 to 50 nm, more preferably from 10 to 40 nm, from the viewpoint of obtaining a high mechanical strength in the case of forming a structure in which a photo spacer or the like is easily subjected to an external force. 15~30nm. -57- 200935173 The content of the fine particles in the photosensitive resin composition (formation of the optical spacer (or the photosensitive resin layer constituting the same), from the viewpoint of the optical spacer of the mechanical strength, relative to the photosensitive material The total solid content (mass) is preferably from 5 to 50% by mass of from 10 to 40% by mass, particularly preferably from 15 to 30% by mass. <Others> The photosensitive resin composition of the present invention In addition to the resin, the compound, the photopolymerization initiator, and, if necessary, the fine particles, it is necessary to further contain other components such as a photopolymerization initiation aid. The photosensitive resin composition can be used as an initiator for the addition. The photopolymerization initiation aid is used for the polymerization of a polymerizable compound which promotes photopolymerization polymerization, and can be referred to by photopolymerization. The photopolymerization initiation aid is preferably an amine compound chalk as the amine compound, for example, Triethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, 4-ethyl formate, isoamyl 4-dimethylaminobenzoate, ethyl benzoate, 4-di Methylaminobenzoic acid 2·ethylhexyl ester, hydrazine, Ν-diamine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), ethylamino)benzophenone, 4,4,-bis(ethylmethylamino) Among the diphenyls, 4,4'-bis(diethylamino)benzophenone is preferred. Further, an amine-based or other photopolymerization initiation aid can be used. When the photopolymerization initiation auxiliary agent other than the above is used, for example, a light-based compound, a thioxanthone-based compound, or a coumarin-based spacer has a high resin composition amount, and more preferably a specific polymerizable substance, a combination of initiators of the photopolymerization initiators to make at least one kind of scoop, methyldiethyldimethylaminobenzene 2-dimethylaminomethyl-p-toluene. 4,4,-bis(dimethyl ketone, etc. Examples of the complex number include alkoxides, etc., and -58-200935173 is the alkoxy oxime-based compound, and examples thereof include 9,10-dimethoxyanthracene and 2-ethyl-9,10-dimethylidene. Oxime, 9,10-diethoxyanthracene, 2-ethyl-9,1〇-diethoxyanthracene, etc. As the thioxanthone-based compound, for example, 2-isopropylthioxene is exemplified. Ketone, 4-isopropyl sultoxone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. For the polymerization initiator, a commercially available photopolymerization initiation aid may, for example, be sold under the trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.). Feeling The content of the photopolymerization composition is preferably 0.6 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, based on 1 part by mass of the photopolymerization initiator. The amount of the other components is selected from the components of the well-known constituent components, and the paragraph number [0010] of JP-A-2006-23696 is exemplified. The components described in paragraphs [0027] to [0053] of JP-A-2006-6492, the above-mentioned Japanese Patent Application No. 2006-6492, the composition of the photosensitive resin composition of the present invention is applied to a photo spacer, coloring, and the like. The formation of the pattern and the protective film is also applicable to formation of other pattern structures or films such as partition walls (for example, black matrix) and alignment control protrusions. "Photo spacers and methods of forming the same" The photo spacers of the present invention are used. The photosensitive resin composition of the present invention is formed as described above. The detailed and preferred aspect of the photosensitive resin composition is as described above. -59- 200935173 The photo spacer of the present invention is used for the photosensitivity of the present invention. Since the composition of the fat is formed, it has a uniform cross-sectional shape even at a low exposure, and the variation in height can be suppressed. Further, the photosensitive resin composition of the present invention has a high compression elastic modulus which is required as a photo spacer, In the present invention, the pattern structure such as a photo spacer has a "uniform cross-sectional shape", and is preferably in a plurality of places (preferably three or more places) in the substrate. The cross-sectional shape of the pattern structure is in a shape close to a rectangular shape. The shape of the near-rectangular shape is parallel to the normal direction of the substrate, and is viewed from the normal direction of the substrate of the pattern structure (cylindrical shape). In the plane perpendicular to the structure, when the pattern structure is cut, the line corresponding to the side surface of the pattern structure and the line corresponding to the line below the pattern structure are formed ( The shape which is hereinafter also referred to as "taper angle") of 80 or more and 1 〇〇 or less is more preferable. In this case, the underside of the pattern structure refers to a contact surface between the surface of the pattern structure and the substrate on which the pattern structure is formed. Further, the side surface of the pattern structure means that the surface of the pattern structure does not correspond to the lower surface of the pattern structure or the upper surface of the pattern structure (the surface parallel to the lower surface of the pattern structure, and the surface not in contact with the substrate) ) face. The photo spacer of the present invention can be formed by any method if the method of using the photosensitive resin composition of the present invention is used, but by using the method (steps 1) to (3) shown below (this) The method for forming a photo spacer according to the invention can be formed most suitably. -60-200935173 The method of forming a photo-spacer of the present invention is a step (1) of forming a film of the photosensitive resin composition of the present invention on a substrate (hereinafter also referred to as "film formation step"), (2) a step of exposing at least a part of the film (hereinafter also referred to as "exposure step"), and (c) a step of developing the film after exposure (hereinafter also referred to as "development step"), It is necessary to provide (4) a step of heating the film after development (hereinafter also referred to as "film heating step") or other steps. (1) Film formation step 〇 The film formation step is a step of forming a film of the photosensitive resin composition of the present invention on a substrate. The photosensitive resin layer can be formed as a film, and the photosensitive resin layer constitutes a spacer capable of maintaining a uniform cell thickness via an additional step such as an exposure step, a developing step, or the like. By using the spacer of the present invention, particularly in a display device (especially a liquid crystal display device) in which display unevenness is likely to occur due to variations in cell thickness, display unevenness in an image can be effectively eliminated. As a method of forming a photosensitive resin layer on a substrate, (a) 感光 is applied to a photosensitive resin composition containing at least the above [A] resin, [B] polymerizable compound, and [C] photopolymerization initiator. The coating method and (b) a transfer method in which a photosensitive resin layer having a photosensitive resin layer having the photosensitive resin layer is used to laminate a photosensitive resin layer by heating and/or pressurization to perform transfer. (a) Coating method The coating method of the photosensitive composition can be applied by a well-known coating method, for example, by spin coating, curtain coating, slit coating, dip coating, air knife coating, and roll coating. The bar coating method, the gravure coating method, or the extrusion coating method using a hopper described in the specification of U.S. Patent No. 2,681,294, the disclosure of which is incorporated herein by reference. In particular, JP-A-2004-89851, JP-A-2004-17043, JP-A-2003-170098, JP-A-2003-16078, JP-A-2003-10767, JP-A-2002-79163 A method of a slit nozzle or a slit coater described in Japanese Laid-Open Patent Publication No. 2001-3-1100, and the like is suitable. (b) Transfer method: a photosensitive resin layer is formed on a temporary support using a photosensitive transfer material, and a heated and/or pressurized roll or a roll is used on a desired substrate surface. After the flat plate is bonded or heat-bonded and bonded, the photosensitive resin layer is transferred onto the substrate by peeling of the temporary support. Specifically, a laminator and a lamination method described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. From the viewpoint of low foreign matter, the method described in JP-A-7-110575 is preferably used. When the photosensitive resin layer is formed, an oxygen barrier layer (hereinafter also referred to as "oxygen barrier film" or "intermediate layer") may be further provided between the photosensitive resin layer and the temporary support ® . By this, the exposure sensitivity can be improved. Further, in order to improve transferability, a cushioning thermoplastic resin layer may be provided. For the temporary support, the oxygen barrier layer, the thermoplastic resin layer, the other layer or the photosensitive transfer material constituting the photosensitive transfer material, the paragraph number [0024] of JP-A-2006-23696 can be used. [0030] The composition and production method described therein. When the photosensitive resin layer is formed by the (a) coating method and the (b) transfer method, the thickness of the layer - 62 - 200935173 is preferably 0.5 to ΐΟ. Ο μι», more preferably 1 to 6 μm. When the layer thickness is in the above range, the occurrence of pinholes can be prevented at the time of coating formation at the time of production, and development of the unexposed portion can be prevented from being removed for a long period of time. Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, a ruthenium film), and a substrate with a color filter (also referred to as color filter). A sheet substrate), a drive substrate to which a driving element (for example, a thin film transistor [TFT]) is attached, or the like. The thickness of the substrate is generally preferably from 700 to 1200 μm. 〇 (2) Exposure step • (3) Development step In the exposure step, at least a part of the film formed by the film formation step is exposed to form a latent image. In the subsequent development step, the film exposed by the exposure step is developed to form a spacer pattern of a desired shape. As a specific example of such steps, a paragraph of JP-A-2006-6492 1 can be cited. The step described in the paragraphs [0040] to [0051] of the formation example described in the [0071] to [0077] or the paragraphs [0040] to [0051] of JP-A-2006-2696 is regarded as a suitable example in the present invention. (4) Film heating step In the film heating step, the film after the development of the developing step is heated. The film is hardened by heating to obtain a spacer having high strength, a compressive modulus of elasticity, and excellent elastic recovery. As described above, a substrate for a display device including a photo spacer on a substrate can be produced. The photo spacer is preferably formed on a black light-shielding portion such as a black matrix formed on a substrate or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or an alignment film such as polyimide may be present between a black light-shielding portion such as a black matrix-63-200935173 array or a driving element such as a TFT and a photo spacer. . For example, when the photo spacer is provided on the black light-shielding portion or the driving element, the substrate is covered with a black light-shielding portion (black matrix or the like) or a driving element, for example, a photosensitive resin of a photosensitive transfer material. After the layer is laminated and the photosensitive resin layer is formed by peeling off the transfer surface, exposure, development, heat treatment, or the like is applied to form a photo spacer, and a germanium substrate for a display device can be produced. In the substrate for a display device of the present invention, colored pixels such as red (R), blue (B), and green (G) colors may be provided as needed. The photo spacer of the present invention can be formed later by forming a color filter including a black mask portion of a black matrix or the like and a coloring portion such as a color pixel. In the black masking portion, the coloring portion, and the photo spacer, the coating method of applying the photosensitive resin composition and the transfer method using the transfer material having the photosensitive resin layer formed of the photosensitive resin composition can be arbitrarily combined. To form. The black masking portion, the coloring portion, and the photo spacer may each be formed of a photosensitive resin composition, and specifically, for example, a photosensitive resin is formed by directly applying a liquid photosensitive resin composition on a substrate. After the layer, exposure and development are performed to form the pattern-shaped black shielding portion and the colored portion, and then the photosensitive resin composition of the other liquid is placed on another substrate (temporary support) different from the substrate. The photosensitive resin layer is formed, and the transfer material produced in this manner is used, and the transfer material is adhered to the substrate on which the black shielding portion and the colored portion are formed, and the photosensitive-64 - 200935173 resin layer is transferred and exposed. - Development of a patterned photo spacer, such that a color filter provided with a photo spacer can be fabricated. <<Protective film>> The protective film of the present invention is formed using the above-described photosensitive resin composition of the present invention. Since the protective film of the present invention is formed by using the photosensitive resin composition of the present invention, it is excellent in film thickness uniformity even when formed by low exposure. The protective film of the present invention can be formed by any method using the method of the photosensitive resin composition of the present invention, and can be formed by the same method as the method of forming the photo spacer of the present invention. Here, when the protective film is not subjected to patterning, that is, when the protective film is formed as a full film, the method of fully exposing the film in the above (2) exposure step is suitable. <<Coloring Pattern>> The coloring pattern of the present invention is formed using the photosensitive resin composition of the present invention. Here, the photosensitive resin composition preferably contains at least one of a coloring agent in addition to the above-mentioned respective components. The coloring agent is not particularly limited, and can be appropriately selected from among the well-known coloring agents. Specific examples of the known coloring agent include the pigments and dyes described in JP-A No. 5-17772, and JP-A-2004-36 1447 [〇〇68] ～[〇〇72] The pigment contained in the 曰 、, the coloring agent described in JP-A-2005-17521 [0080] to [〇〇88]. Since the colored pattern of the present invention is constituted by using the photosensitive resin composition of the present invention -65-200935173, even when formed by low exposure, it has a uniform cross-sectional shape and is excellent in film thickness uniformity. Further, when the coloring pattern of the present invention is used as one of the color filters of the coloring pattern having a plurality of colors, the coloring pattern of at least one color may be formed by using the photosensitive resin composition of the present invention. The colored pattern of the present invention can be formed by any method if the method of using the photosensitive resin composition of the present invention is used. For example, the coloring pattern can be formed by the same method as the method for forming a photo spacer of the present invention. form. φ "Substrate for display device" The substrate for a display device of the present invention comprises at least one of the photo spacer of the present invention, the protective film of the present invention, and the colored pattern of the present invention. The substrate for a display device of the present invention is formed using the photosensitive resin composition of the present invention, and has a structure having good cross-sectional shape and uniformity in film thickness (height) (the photo spacer of the present invention, the protective film of the present invention, and When at least one of the color patterns of the present invention is the same as the above, when used in a display device, display unevenness can be suppressed. The substrate for a display device herein refers to at least one of a pair of supports for constituting the display device. The specific example of the substrate for the display device differs depending on the configuration of the display device or the display device. For example, a color filter substrate having a colored pattern (hereinafter also referred to as "colored pixel") may be used. A substrate with a driving means (for example, a simple matrix substrate or an active matrix substrate), a substrate having a partition wall attached to the partition wall (for example, a substrate having a black matrix with a black matrix), and a coloring pattern and a driving means Color filter of the two-66-200935173 The coloring pattern group (coloring pixel group) of the color filter substrate of the substrate on the array, the glass substrate not provided with the pattern structure or the film, etc. Two-color pixels of different colors can be formed by three-color pixels and four or more pixels. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When RGB three-color pixel groups are arranged, it is preferably a configuration such as a mosaic type or a triangle type, and any configuration can be performed when four or more pixel groups are arranged. In the production of the color filter substrate, for example, a black matrix may be formed as described above after forming a pixel group of 2 © or more, and conversely, a black matrix may be formed to form a pixel group. For the formation of RGB pixels, reference is made to JP-A-2004-347831 and the like. <<Display Element>> A display element can be formed using the substrate for a display device of the present invention. One of the display elements includes at least one of a pair of light-transmitting supports (including a substrate for a display device), and at least a liquid crystal layer and a liquid crystal driving means (including a simple matrix driving method and an active matrix driving) Way) Ο -- The LCD shows 75 pieces. In the case of the liquid crystal display device, the substrate for a display device can be used as a color filter substrate having a plurality of RGB pixel groups and each of the pixels of the pixel group being separated from each other by a black matrix. In the color filter substrate, since a structure having a uniform cross-sectional shape and uniform film thickness (height) is provided, the liquid crystal display element including the color filter substrate can effectively prevent color filters from being removed. The unevenness of the color unevenness of the liquid crystal material caused by the variation of the cell gap (cell thickness) between the substrate and the counter substrate, and low temperature foaming, etc. -67-200935173. Thereby, the produced liquid crystal display element can display a clear image. In addition, as a more detailed aspect of the liquid crystal display device, at least one of the pair of supports (including the substrate for a liquid crystal display device) having a light transmissive property includes at least a liquid crystal layer and a liquid crystal driving means, and the liquid crystal driving means The means has an active element (for example, a TFT), and a constituent of a specified width is controlled by a photo spacer between a pair of substrates. <<Display Device>> The display device of the present invention includes the above-described substrate for a display device. In the display device of the present invention, since the substrate for a display device of the present invention having a uniform cross-sectional shape and uniformity in film thickness (height) is provided, it is possible to suppress display unevenness. Examples of the display device include a display device such as a liquid crystal display device, a plasma display device, an EL display device, and a CRT display device. For the definition of the display device or the description of each display device, for example, "Electronic display device (Zuosuke Sasaki, Ltd., issued by the Industrial Research Association in 1989)", "Showing device" (Ibuki Shunzhang, Industrial Book ( The stock is issued in the first year of Heisei). Among the display devices, a liquid crystal display device is preferred. The liquid crystal display device is configured by, for example, controlling a predetermined width between a pair of substrates facing each other with a photo spacer, and sealing a liquid crystal material (referred to as a liquid crystal layer) in the controlled gap. The thickness of the liquid crystal layer (cell thickness) is formed to maintain a desired uniform thickness.

As the liquid crystal display mode of the liquid crystal display device, STN-68-200935173 type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, and the like can be suitably used. ASM type, other various. In particular, in the liquid crystal display device of the present invention, from the viewpoint of most effectively achieving the effects of the present invention, it is desirable to display a display mode in which display unevenness is difficult to occur as the cell thickness of the liquid crystal cell fluctuates. In the VA type display mode, the IPS type display mode, and the 0CB type display mode in which the cell thickness is 2 to 4 μm, the liquid crystal which can be used in the present invention is a nematic liquid crystal, a cholesteric liquid crystal, or the like. Layered liquid crystal, ferroelectric liquid crystal. The basic configuration of the liquid crystal display device includes (a) a driving side substrate in which a driving element such as a thin film transistor (TFT) or the like and a pixel electrode (conductive layer) are arranged, and a counter electrode (conductive). The opposing substrate of the layer is disposed to face each other with the photo spacer interposed therebetween, and the liquid crystal material is sealed in the gap portion, and (b) the driving substrate and the counter substrate having the counter electrode (conductive layer) are separated by a light interval. The liquid crystal display device of the present invention can be suitably used in various liquid crystal display devices, for example, in which the liquid crystal material is sealed in the gap portion. The liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Uchida Natsuo, Side Industry Survey, issued in 1994)". The liquid crystal display device of the present invention is not particularly limited as long as it includes the liquid crystal display device of the present invention, and for example, it can constitute various types of liquid crystal display devices described in the "τ_Generation Liquid Crystal Display Technology". Among them, 'is particularly effective for a liquid crystal display device constituting a color TFT system. The liquid crystal display device of the color TFT type is described, for example, in "Color TFT 'LCD-69-200935173 Display Color" (Kyoritsu Publishing Co., Ltd., issued in 1996). In addition to the photo spacer, the coloring pattern, the protective film, the liquid crystal display device substrate, and the liquid crystal display element, the liquid crystal display device can generally use an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, and a viewing angle. Various components such as a compensation film, an antireflection film, a light diffusion film, and an antiglare film are formed. For these components, for example, "'94 Liquid Crystal Display Peripherals and Chemicals Market (Island Kentaro, Co., Ltd., CMC 1 994)", "2003 Liquid Crystal Related Market Status and Future Outlook (〇下卷) (Table "Good luck, (share) Fuji Chimera, 2003, 2003, etc.)" is documented. In the case of the Japanese Patent Application No. 2007-339917, the entire disclosure of which is hereby incorporated by reference. EXAMPLES Hereinafter, the present invention will be more specifically described by the examples, but the present invention should not be construed as limited to the examples. Furthermore, "parts" are based on quality unless otherwise specified. ® Again, the weight average molecular weight is determined by gel permeation chromatography (GPC). GPC was HLC-8020GPC (manufactured by Tosoh Corporation), and three TSKgels, Super Multipore HZ-H (made by Tosoh Corporation, 4.6 mm ID x 15 cm) were used for the column, and THF (tetrahydrofuran) was used for the eluent. Further, the conditions were: a sample concentration of 4.5% by mass, a flow rate of 0.35 ml/min, a sample injection amount of 10 μl, and a measurement temperature of 40 ° C, which were carried out using an IR detector. In addition, the calibration curve is made by Tosoh Co., Ltd. "Standard sample TSK standard, polystyrene": "F-40", "F-20", "F-4", "Fl"' -70- 200935173 "A- 8 samples of 5000", "A-2500", "A-1000", and "n-propylbenzene" were produced. &lt;Synthesis of [A] Resin&gt; First, as the resin in the photosensitive resin composition, [A] resin (exemplified compounds PD-52, PU-52, PD-51, PD-53, PD-46, Synthesis of PD-47, PU-53). (Synthesis Example 1) (Synthesis of the exemplified compound PD-52) © 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Emulsifier) was added in advance to the reaction vessel, and the temperature was raised to 90. °C, under nitrogen atmosphere, it will take 3.1 hours of styrene (St), 4.28 parts of tricyclopentenyl methacrylate (TCPD-M; X), 1 made by Shengli Chemical Industry Co., Ltd. 1.1 parts of methacrylic acid (MAA; y), 2.08 parts of azo polymerization initiator (made by Wako Pure Chemical Industries, Ltd., V-601), and 55.2 parts of 1-methoxy-2-propene The mixed solution of the alcohol was dropped into a reaction vessel at 90 °C. After the dropwise addition, the reaction was allowed to proceed for 4 hours to obtain an acrylic resin solution. ® Next, after adding 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide to the acrylic resin solution, 26.4 parts of glycidyl methacrylate (GLM, Tokyo Chemical Industry Co., Ltd.) was added in 2 hours. (share) system) (GLM-MAA; z). After the dropwise addition, the air was blown into the side at 9 (TC was allowed to react for 4 hours, and the solvent was added as a solid concentration of 45%, and the solvent 1 -methoxy-2-propyl acetate was added (MMPGAc, Daicel Chemical Industry) (manufactured by the method) to obtain a compound X having one unsaturated group. Further, the compound X is subjected to an addition reaction with methacryloyl chloride (Tokyo Chemical Co., Ltd.) 71-200935173 to obtain an addition reaction. An exemplified resin solution of the compound PD - 5 2 ([A] resin) (solid content acid value: 76.0 mgKOH/g, Mw: 25,000, 1-methoxy-2-propanol/1-methoxy-2-propane 'Base acetic acid vinegar 45% solution) (x: y: z: St = 30 mole %: 27 mole % : 3 7 mole % : 6 mole %) Here ' GLM-MAA is expressed in methacrylic acid The glycidyl methacrylate is bonded (the same applies hereinafter.) The molecular weight Mw of the exemplified compound PD-52 represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by gel permeation chromatography (GPC © method). (Same in the following) (Synthesis Example 2) (Synthesis of the exemplified compound PU-52) ., In the reaction vessel, 7.48 was added in advance. 1-methoxy-2-propanol (MFG, manufactured by Nippon Emulsifier), heated to 90 ° C, under a nitrogen atmosphere, will cost 3.1 parts of styrene (St), 4.28 parts Tricyclopentenyl methacrylate (TCPD-M, manufactured by Hitachi Chemical Co., Ltd.; X), 11.7 parts of methacrylic acid (MAA; y), 2.08 parts of azo polymerization initiator (Wako Pure Chemicals © A mixed solution of V-601) and 55.2 parts of 1-methoxy-2-propanol was dropped into a reaction vessel at 90 ° C. After the dropwise addition, the reaction was allowed to proceed for 4 hours to obtain Next, after adding 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide to the acrylic resin solution, 26.4 parts of glycidyl methacrylate (GLM) was dropped over 2 hours. KGLM-MAA, manufactured by Tokyo Chemical Industry Co., Ltd.; z). After the dropwise addition, the reaction was carried out for 4 hours at 90 ° C while the air was blown, and the solvent was added as a solid component concentration of 4 %. 200935173 Methoxy-2-propyl acetate (MMPGAc, manufactured by Daicel Chemical Industry Co., Ltd.) was prepared to obtain a compound having one unsaturated group. The above compound was subjected to an addition reaction with Karenz MOI (Showa Electric Co., Ltd.) to obtain a resin solution of the exemplified compound PU-52 ([A] resin) (solid content acid value: 76.0 mgKOH/g, Mw: 2 5,000) , 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (\7:2:81 = 30 mol%: 27 mol%: 3 7 mol % : 6 mole % ). Here, GLM-MAA is represented by a methacrylic acid-bonded methacrylic acid-glycidyl ester (the same applies hereinafter). Further, the molecular weight Mw of the exemplified compound PU-5 2 represents a weight average molecular weight, and the measurement of the weight average molecular weight is carried out by using a gel permeation chromatography (GPC method) (the same applies hereinafter). (Synthesis Example 3) (Synthesis of exemplified compound PD-51) Except for the synthesis of the aforementioned exemplified compound PD-5 2, styrene was not used, and x:y:z in the exemplified compound PD-51 was 34 mol%. : 27 mol % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % % The same method was used to synthesize to obtain a resin solution of the exemplary compound PD-5 1 ([A] resin) having an unsaturated group (solid content acid value: 72.5 mgKOH/g, Mw: 22,000, 1-methoxy-2) -propanol / 1-methoxy-2-propyl acetate 45% solution). (Synthesis Example 4) (Synthesis of exemplified compound PD-53) -73- 200935173 In addition to the synthesis of the aforementioned exemplified compound P-52, tricyclopentene methacrylate was replaced with dicyclopentene acrylate without using styrene. Ethyloxyethyl ester (Fancryl FA-512M manufactured by Hitachi Chemical Co., Ltd.), exemplified by the method of 化合物: 丫3 in the compound 〇-53 is 46.2 mol%: 24.3 mol%: 29.5 mol%, The addition of FA-5 1 2M (x), methacrylic acid (y), and GLM-MAA (z) was carried out in the same manner as in the synthesis of the above-exemplified compound PD-52 to obtain an unsaturated group. Resin solution of the exemplified compound PD-5 3 ([A] resin) (solid content acid value: 71.2 mgKOH/g, Mw: 25,500 φ, 1-methoxy-2-propanol/1-methoxy-2) -propyl acetate 45% solution). (Synthesis Example 5) (Synthesis of exemplified compound PD-46) In addition to the synthesis of the above-exemplified compound PD-52, tricyclopentenyl methacrylate was replaced with ADMA (manufactured by Idemitsu Kosan Co., Ltd.) to PD-1 is added with the composition of the structural unit from benzene and s: x: y: z: St is 30 mol%: 24 mol%: 38 mol%: 8 mol%, change ADMA (x) In addition to the addition amount of methacrylic acid (y), GLM-MAA (z) and styrene, the same procedure as in the synthesis of the above-exemplified compound PD-52 was carried out to obtain the exemplified compound PD-46 ([A] Resin solution of 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 6) (Synthesis of exemplified compound PD-47) In addition to the synthesis of the above-exemplified compound PD-52, tricyclopentenyl methacrylate was replaced with borneol methacrylate to constitute x:y: z:St becomes -74- 200935173 34 mole %: 24 mole % : 36 mole % : 6 mole % way, changing methacrylate methacrylate (X), methacrylic acid (y), GLM- A resin solution of the obtained compound PD-47 ([A] resin) was synthesized by the same method as the synthesis of the exemplary compound PD-52 except for the addition amount of MAA (z) and styrene (solid content acid value: 72.9) MgKOH/g, Mw: 29, hydrazine, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution). (Synthesis Example 7) (Synthesis of the exemplified compound PU-53) ❹ In addition to the synthesis of the exemplified compound PU-52 of Synthesis Example 2, it was changed to dicyclopentenyloxyethyl acrylate (manufactured by Hitachi Chemical Co., Ltd.). Fancryl? 八-5 1,2 PCT) 'Change styrene and change the composition of \7::2 to 46.2 mol%: 24.3 mol%: 29.5 mol%, change the dicyclopentenyloxyethyl acrylate (X), methacrylic acid (y), and GLM-MAA (z) were synthesized in the same manner as in the synthesis of the exemplified compound PU-52 to obtain the exemplified compound PU-53 ([A] resin). Resin solution (solid content acid value: 76.0 mg KOH/g, Mw: 25, 500, 1-methoxy-2-propanol / 1-methoxy-2-G propyl acetate 45% solution). (Synthesis Example 8) (Comparative Example) In a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl were charged. Ethyl ether acetate. Next, 5 parts of styrene, 20 parts of methacrylic acid, 25 parts of tricyclo[5·2·1·02,6]癸-8-yl methacrylate, and 25 parts of 3-(methyl group) were charged. Propylene methoxymethyl)-3-ethyloxetane, 20 parts of tetrahydrofurfuryl methacrylate, and 5 parts of 1,3-butadiene, after nitrogen substitution, began to stir slowly. The temperature of the solution was raised to 70 ° C, and the temperature was maintained at this temperature for 5 hours to obtain a polymer solution containing the copolymer 1 . The obtained polymer solution had a solid concentration of 4 5.0%, and the weight of the polymer. The average molecular weight is 18,000. [Example 1]: coating method &lt;Production of color filter substrate&gt; A method having a black matrix was produced by the method described in paragraphs [0084] to [0095] of JP-A No. 2 005 -3 86 1 A color filter of R (red) pixels, G (green) 〇 pixels, and B (blue) pixels (hereinafter referred to as a color filter substrate). Here, the substrate size of the color filter substrate is 550 mm×650 mm, and then formed on the R pixel, the G pixel, and the B pixel and the black matrix of the obtained color filter substrate by sputtering. Transparent electrode of ITO (indium tin oxide). &lt;Formation of Photo Spacer&gt; On the ITO transparent electrode of the color filter sheet substrate on which the ITO transparent electrode was formed by sputtering as described above, the formulation shown in Table 1 below was applied by a spin coater. (Prescription 1 in Example 1) A coating liquid for a photosensitive resin layer. Then, using a vacuum dryer VCD (manufactured by Tokyo Ohka Co., Ltd.), a 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 to form a film thickness of 5 2 μm of a photosensitive resin layer (film formation step). Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp, a photomask (a quartz exposure mask having a circular pattern of diameter -76-200935173), and a mask The color filter substrate disposed so as to face the photosensitive resin layer has a distance between the mask surface and the surface of the photosensitive resin layer in a state of being slightly parallel and vertically erected, and is transmitted through the mask. The ultraviolet light of a 365 nm-intensity 250 W/m2 transmission through a UV-transmissive filter (UV-3 5, manufactured by Toshiba Glass Co., Ltd.) was irradiated for 1 second (exposure step, exposure amount: 250 mJ/cm 2 ). Then, use a sodium carbonate-based imaging solution (containing 0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anion © surfactant, defoamer) And stabilizer, trade name: T-CD 1 (Fuji film (stock)), diluted 10 times with pure water), spray development at 29 ° C, cone nozzle pressure 0.15MPa for 20 seconds, A pattern image is formed (development step). Next, a detergent (containing phosphate, citrate, nonionic surfactant, antifoaming agent, and stabilizer, trade name: T-SD3, manufactured by Fujifilm Co., Ltd.) was diluted 10 times with pure water. The liquid was sprayed by a shower for 20 seconds at 33 ° C and a cone nozzle pressure of 0.02 MPa to remove the residue around the formed pattern image, thereby forming 300 μm χ 3 00 μηη by one spacer interval. Circle © columnar spacer pattern. Then, a light spacer was formed on the color filter substrate by heat-treating the color filter substrate provided with the spacer pattern at 230 ° C for 30 minutes (film heating step). Here, a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, type: New View 5022) was used for one of the obtained photo spacers, and the highest spacer was measured from the ITO transparent electrode formation surface side. Position (n = 2〇), which is averaged as the height (average height). Further, the measurement of the bottom area of the obtained photo spacer -77 to 200935173 was carried out using an SEM photograph. The result was a cylindrical shape with a diameter of 15.1 μηη and an average height of 4.7 μηη. The measurement system is shown in Table 2 below.

Formulation Solution 1 for Photosensitive Resin Layer (Example 3, Examples 5 to 9) Prescription 2 (Comparative Examples 1 and 3) Prescription 3 (Examples 2 and 4) Prescription 4 (Comparative Example 2) 1-methoxy Benzyl-2-propyl acetate 26 26 26 35 methyl ethyl ketone 28 28 28 30 Colloidal vermiculite dispersion (colloidal vermiculite: 3 parts, methyl isobutyl ketone: 70 parts, Nissan Chemical Industry (Stock) system MIBKst) 0 0 14.1 0 Solusbas 20000 0.42 0.42 0.42 0.42 DPHA solution (dipentaerythritol hexaacrylate: 76 parts, 1-methoxy-2-propyl acetate: 24 parts) 18.2 18,2 18.2 18.2 A solution of a resin (however, the resin is a compound described in the following Table 2) 20.5 0 20.5 0 A solution of the resin (however, Synthesis Example 8 - Compound for Comparative Example (weight average molecular weight = 18,000) 0 20.5 0 0 CGI242 (Vapor Ba special chemical (stock) system: photopolymerization initiator) 0.227 0.227 0.227 0.23 hydroquinone monomethyl ether 0.0036 0.0036 0.0036 0.0036 surfactant 1 (Megafae F-80-F, manufactured by Dainippon Ink and Chemicals Co., Ltd.) 0.032 0.032 0.032 0.032 5% methanol solution of Victoria Blue NAPS (made by Hodogaya Chemical Industry Co., Ltd.) 0 0 2.05 0 Units·Parts -78-200935173 &lt;Production of Liquid Crystal Display Device&gt; Further, a glass substrate as a counter substrate is prepared, and a PVA mode is applied to each of the transparent electrode and the counter substrate of the color filter substrate obtained above. Patterning, and then providing an alignment film made of polyimide. Then, at a position other than the black matrix provided around the pixel group surrounding the color filter, in a dispenser manner The sealant for applying the ultraviolet curable resin is applied, and the liquid crystal for PVA mode is dropped, and after bonding to the counter substrate, the bonded substrate is irradiated with UV, and then heat-treated to harden the sealant. Two sides, pasted (shared) SANRITZ polarizing plate HLC2-25 1 8. Next, use FR1., 1 12H (wafer type LED made by STANLEY Electric Co., Ltd.) as red (R) LED, as green ( G) DG1112H of LED (wafer type LED made by STANLEY Electric Co., Ltd.), DB1 1 12 H (wafer type LED made by STANLEY Electric Co., Ltd.) which is blue (B) LED, and constitutes a backlight of the side light type , configured in the above liquid crystal cell with a polarizing plate On the back side, it becomes a liquid crystal display device.评价 <Evaluation> The coating liquid and the photo-spacer for the photosensitive resin layer obtained were subjected to the measurement and evaluation described below. The results of the measurement evaluation are shown in Table 2 below. A deformation recovery ratio _ The obtained photo-spacer was measured by a microhardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was carried out using a 50 μm ηφ round hammer indenter with a maximum load of 5 〇ηηΝ and a holding time of 5 seconds' by a load-loading test method. From this, the deformation recovery ratio [%] obtained by -79-200935173 was obtained by the following formula, and evaluated according to the following criteria. The measurement was carried out in an environment of 22 ± 11 and 50% RH. Deformation recovery rate (%) = (recovery amount after load opening [μπχ] / deformation amount at load [μιη]) χ 1 00 &lt; evaluation criteria &gt; 5 : Deformation recovery rate was 90% or more. 4: The deformation recovery rate is 87% or more and less than 90%. 3: The deformation recovery rate is 85% or more and less than 87%. 〇 2: The deformation recovery rate is 80% or more and less than 85%. 1: The deformation recovery rate is 75% or more and less than 80%. 〇 : The deformation recovery rate is lower than ., 75%. One sensitivity - When the exposure amount of the obtained photosensitive resin layer coating liquid was changed variously, it was observed whether or not a spacer pattern could be formed, and it evaluated based on the following evaluation criteria. <Evaluation Criteria> ❹ ΑΑ: A pattern can be formed at less than 60 mJ/cm 2 . A: A pattern can be formed at 60 to less than 100 mJ/cm2. B: A pattern can be formed at 100 to 200 mJ/cm2. C: The formation of the pattern must exceed the exposure amount of 200 m J/cm 2 . A preservative one (1) liquid storage property is used, and the photosensitive resin layer obtained above is covered with a coating liquid, and after being covered, the natural time (25 ° C) is after 180 days, and the photosensitivity is obtained. In the same manner as the above-mentioned evaluation of the "sensitivity", the coating liquid was evaluated by the following evaluation criteria in the same manner as the above-mentioned evaluation of the "sensitivity" in the coating liquid of the coating liquid-80-200935173. > A: A pattern can be formed at less than 60 mJ/cm2" B: A pattern can be formed at 60 mJ/cm2 or more and less than 150 mJ/cm2 C: The pattern formation must be 150 mJ/cm2 or more and less than 300 mJ/cm2. φ D : The formation of the pattern must be an exposure amount of 300 mJ/cm 2 or more. (2) The stability of the photosensitive resin layer with time stability. The photosensitive resin layer after baking (the color of the photosensitive resin layer is formed) The filter substrate was placed in an oven at 60 ° C for 14 days, and evaluated in accordance with the following evaluation criteria in the same manner as the above evaluation of "sensitivity". <Evaluation Criteria> A: Below 60 mJ/ Cm2 can form a pattern B: A pattern can be formed at 60 mJ/cm2 or more and less than 150 mJ/cm2. φ C : Pattern shape The exposure amount of 1 50 mJ/cm 2 or more and less than 300 mJ/cm 2 is required. D: The formation of the pattern requires an exposure amount of 3.0 0 mJ/cm 2 or more. (Example 3 and Examples 5 to 9 and Comparative Examples 1 to 3): In the coating method, the formulation of the coating liquid for a photosensitive resin layer was changed to the compound PD-52 ([A) used for the preparation of the coating liquid for a photosensitive resin layer, as in the first embodiment. In the same manner as in Example 1, except that the resin, the fine particles, and the initiator were changed to those shown in the following Table 2, a light spacer and a liquid crystal display device were produced in the same manner as in Example 1. The obtained photo spacer was a cylindrical shape. (Examples 2 and 4): In the transfer method, in place of the application of the coating liquid for a photosensitive resin layer (Prescription 1), the transfer method was carried out using a photosensitive transfer film for a spacer described below. A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the photosensitive resin layer was formed. The obtained photo spacer was a columnar shape. The photosensitive transfer film for the spacer- spacer was produced in a thickness. 75 μιη polyethylene terephthalate film temporary support The coating liquid for a thermoplastic resin layer formed by the following prescription A is applied to a holder (PET Pro Support), and dried to form a thermoplastic resin layer having a dry layer thickness of 15·0 μm. [Prescription of a coating liquid for a thermoplastic resin layer Α] • Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer... 25.0 parts ( = 5 5 / 1 1.7 / 4.5 / 2 8.8 [mr ratio], weight Average molecular weight 90,000) ® .styrene/acrylic acid copolymer...58.4 parts (=6 3 /3 7 [mole ratio], weight average molecular weight Μ) 00) .2,2-bis[4-(methylpropionyloxy) Polyethoxy)phenyl]propane 3 9.0 parts 10.0 parts • The following surfactants • Methanol...90.0 parts...5 1.0 parts...7 0 0 parts • 1-methoxy-2-propanol • A Ketyl ketone-82- 200935173 *Interfacial surfactant 1 •The following structure 1 •Methyl ethyl ketone structure 1 —(CH2HpH)4〇-0=C OC^CHgCnF^ —(Ο ί)χ—

:Ρ〇&gt;7« (〇η2— ο®

(η = 6, χ = 55, y = 5, Mw = 3 3 940, Μ w / Mn = 2.5 5 Ρ〇: propylene oxide, hydrazine: ethylene oxide) Next, on the formed thermoplastic resin layer The coating liquid for an intermediate layer prepared by the following formulation was applied, and dried to laminate an intermediate layer having a dry layer thickness. [Prescription B for coating liquid for intermediate layer] Polyvinyl alcohol...3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray). Polyvinylpyrrolidone...1.49 parts (PVP K-30, ISP曰 ( ( . 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇 甲醇[A] Resin is a compound in Table 2), and a photosensitive resin layer having a dry layer thickness of 5. Mm was dried and laminated. As described above, the laminated structure of the PET precursor/thermoplastic resin layer/intermediate layer/photosensitive resin layer (the total thickness of the three layers: 2 L 5 Km) is formed and the 'heating on the surface of the photosensitive resin layer' is further heated. - A film made of polypropylene having a thickness of 12 μm was used as a cover film-83 200935173 to obtain a photosensitive transfer film for spacers. - Preparation of photo spacer - The obtained spacer was peeled off with a cover film of a photosensitive transfer film, and the surface of the exposed photosensitive resin layer was superposed on the surface of the photosensitive resin layer produced in the same manner as in Example 1 to form a transparent electrode. On the tantalum transparent electrode of the color filter substrate, using a laminator type Lamic II type (manufactured by Hitachi Instruments Co., Ltd.), pressurization and heating under the conditions of 100 N/cm and 130 ° C at an on-line pressure of 2 m/min. Fit for fit. Then, the PET precursor is peeled off at the interface with the thermoplastic resin layer to simultaneously transfer the photosensitive resin layer and the thermoplastic resin layer and the intermediate layer (film formation step). Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Co., Ltd.) having an ultrahigh pressure mercury lamp, a reticle (a quartz exposure reticle having an image pattern) is opposed to the reticle and the thermoplastic resin layer. The color filter substrate disposed in a manner of being substantially parallel and vertically erected, the distance between the mask surface and the surface of the side of the intermediate layer attached to the photosensitive resin layer is ΙΟΟμπι, through the reticle, The proximity exposure was performed from the side of the thermoplastic resin layer at an exposure amount of 90 mJ/cm 2 (exposure step). Then, a triethanolamine-based developing solution (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm)) was diluted 12 times with pure water (1 part of T-PD2 and 11 parts of pure water). The liquid of the mixture) was spray-developed at 30 ° C under a flat nozzle pressure of MPa 4 MPa for 50 seconds to remove the thermoplastic resin layer and the intermediate layer. Next, the upper surface of the glass substrate is sprayed with air to remove the liquid, and the pure water is sprayed by the shower for 10 seconds to perform pure water spray cleaning, and the air is blown -84 - 200935173 to reduce the amount of the substrate. Liquid retention. Then, using a sodium carbonate-based imaging solution (containing 0.38 mol/L sodium bicarbonate, 0.47 mol/L sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent and Stabilizer; trade name: T-CD 1 (made by Fujifilm (stock)) diluted with 1〇 of pure water), sprayed for 30 seconds at 29 ° C, 〇 _ 15MPa cone nozzle pressure, A pattern image is obtained (development step). Next, using a detergent (containing phosphate, citrate, nonionic surfactant, defoamer, stabilizer, trade name: T-SD3 (Fuji film)) The diluted liquid was sprayed by a cone sprayer at a pressure of 33 ° C and a cone pressure of 2 MPa for 20 seconds to remove the residue around the formed pattern image to form a spacer interval. After forming a cylindrical spacer pattern of 300 μm χ 300 μm, a heat treatment (film heating step) is performed for 30 minutes at 23 0 t on the color filter substrate provided with the spacer pattern to be applied to the color filter substrate. Make a light spacer on it. The obtained photo spacer was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm. Then, a p V Α mode liquid crystal display device was produced in the same manner as in Example 1 using a color filter substrate Δ in which a photo spacer was formed. -85 - 200935173 [Table 2] [A] Resin microparticle formation method spacer evaluation Synthesis example No. Structure Mw Species average particle size [nm] Deformation recovery rate [%] Height [μιη] Sensitivity [mJ/c m2] Liquid preservation Temporal stability of the dry film Example 1 1 Compound PD-52 25000 ΕΕ Λτττ. m Coating 5 47 AAA Example 2 1 Compound PD-52 25000 ΜΙΒΚ st (") 20 Transfer 5 4.7 AAA Example 3 2 Compound PU-52 25000 Μ ^ττΤ. m Coating 5 4.7 AAA Example 4 2 Compound PU-52 25000 ΜΙΒΚ st (") 20 Transfer 5 4.7 AAA Example 5 3 Compound PD-51 22000 4rrr. INI JWS Coating 5 4.7 AAA Example 6 4 Compound PD-53 25500 No Sister ί\\\ Coating 5 4.7 AA AA Example 7 5 Compound PD-46 29000 m Ατττ. No coating 5 4.7 AAA Example 8 6 Compound PD-47 29000 4τττ. 1 1 II-V»,, without coating 5 4.7 AAA Example 9 7 Compound PU-53 25500 Λτττ. That Airt. 涂布 Coating 5 4.7 AA AA Comparative Example 1 8 Copolymer 1 18000 te No coating 3 4.7 BCC Comparative Example 2 — — — Μ Coating 2 4.7 C C C Comparative Example 31 Compound € X 22500 Μ uncoated 4 4.7 C A A Mw: weight average molecular weight based detailed Examples and Comparative Examples were used as the following embodiment. .CGI-242: Ethylketone, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-, 1-(0-ethylindenyl) [Ciba Specialty Chemicals Co., Ltd.] -86- 200935173 As shown in the above Table 2, the examples obtained higher sensitivity than the comparative examples, and the prepared coating liquid for the photosensitive resin layer was prepared. The storage stability and the stability of the photosensitive resin layer when held in a dry film state after application were also good. Regarding the obtained spacer, the examples were also more highly uniform and the deformation recovery ratio was good as compared with the comparative example. [Example 10] &lt;Formation of Protective Film&gt; In the production of the color filter substrate of Example 1, after forming a black matrix, R pixel, G pixel, and B pixel, the black matrix was formed. Further, the photosensitive resin composition prepared by the above-mentioned prescription 1 is applied to each of the pixels, and exposed (wide-exposure) without passing through a photomask, and heat-treated to form a protective film. Here, the conditions of coating, exposure, and heat treatment are the same as those for coating, exposure, and heat treatment at the time of formation of the photo spacer of Example 1 except that the film is not exposed through the photomask. Next, a transparent electrode of ITO (indium tin oxide) was formed on the resulting protective layer by sputtering. &lt;Formation of Photo Spacer&gt; The same procedure as in Example 1 was carried out except that the photosensitive resin composition used in Example 1 was used as the photosensitive resin composition on the tantalum transparent electrode formed as described above. A photo spacer is formed. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; Next, a liquid crystal display device was produced by the same method as in Example 1 using a color filter substrate on which the photo spacer was formed. From 87 to 200935173, the obtained protective film and liquid crystal display device were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3. [Example 11] &lt;Formation of coloring pattern&gt; In addition to the formation of the color filter substrate in Example 1, a color filter was produced in the same manner as in Example 1 except that the R pixel was formed by the following method. Light sheet substrate. In other words, in the above-mentioned prescription 1, pigment red 254 (19.4 parts) and Φ red material 177 (4.83 parts) were further added to prepare a photosensitive resin composition for R pixel. R-pixels were formed by the same method as the formation of the photo spacers of Example 1, except that the photosensitive resin composition for R pixel prepared and the R. photoreceptor photomask were used as a photomask. After the R pixel, the G pixel, and the B pixel of the color filter substrate to be formed are formed, a transparent electrode of 1το (indium tin oxide) is formed on each pixel by sputtering. &lt;Formation of Photo Spacer&gt; G In the same manner as in Example 1, except that the photosensitive resin composition used in Example 1 was used as the photosensitive resin composition on the ITO transparent electrode formed as described above. To form a photo spacer. &lt;Production and Evaluation of Liquid Crystal Display Device&gt; Next, a liquid crystal display device was produced by the same method as in Example 1 using a color filter substrate ′ on which the photo spacer was formed. The obtained protective film and liquid crystal display device were evaluated by the same method as in Example 1. The evaluation results are shown in Table 3. -88 - 200935173 [Comparative Example 4, 5] In addition to the configuration of PD-52 of [A] resin of Comparative Example 10, except for the use of the copolymer 1 in Comparative Example 4, and in addition to the comparative example 5, an alternative example In the same manner as in Examples 10 and 11, the PD-52 of the resin composition of [1] was used in the same manner as in Examples 10 and 11, and each of the protective film and the coloring material was produced, and the evaluation was carried out in the same manner. 【table 3】

[A] Resin forming method structure (contained or colored pattern) Evaluation Synthesis Example No. Structure Mw Highly uniform adhesion sensitivity [mJ/cm2] Temporal stability of liquid preservative dry film Example 10 1 PD-52 25000 Coated AAAAA Comparative Example 4 (for Example 10) 7 Copolymer 1 18000 Coated BBBCC Example 11 1 PD-52 25000 Coated AAAAA Comparative Example 5 (for Example 11) 7 Copolymer 1 18000 Coat - BCC As shown in Table 3 As shown in the figure, even when the protective film and the colored pattern were formed by the photosensitive resin composition of the present invention, the same results as in the case of forming the photo spacer were obtained. According to the present invention, it is possible to provide a photosensitive resin composition which can form a pattern structure or a protective film which is excellent in preservability in a liquid state and which is excellent in stability over time or mechanical properties of a photosensitive film after film formation. Further, according to the present invention, it is possible to provide a photo spacer which is excellent in uniformity of uniformity even when formed with low sensitivity, and a method for producing the same. Further, according to the present invention, it is possible to provide a protective film or a colored pattern which is excellent in film thickness uniformity and uniform cross-sectional shape even when formed with low sensitivity. Further, according to the present invention, it can be provided for use in The display device substrate for suppressing display unevenness and the display device for suppressing display unevenness when the device is displayed. The above description of the specific aspects of the present invention is provided for the purpose of description and description. It is of course not intended to limit the invention to the disclosed form, or to the invention. This aspect is selected to best illustrate the confession of the present invention or its actual application. Therefore, if the invention is to be understood by others, the manufacturer may make various modifications or variations suitable for the particular use of the application. Of course, the details of the preferred embodiment of the present invention described above can be freely changed to a wide variety of application forms depending on the mode in which the application is intended. The scope of the invention is intended to be determined by the scope of the appended claims [Simple description of the map]

Atrr No 0 〇 [Main component symbol description] New Zealand /1, -90-

Claims (1)

200935173 VII. Patent application scope: 1 · A photosensitive resin composition containing: [A] a resin having a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in a side chain and the substitution in a resin The alkyl group has two ethylenically unsaturated bonds, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator. 2. The photosensitive resin composition of claim 1, wherein the substrate of the formula is a group represented by the following formula (1), (In the formula (1), * represents a side bonded to the main chain of the resin, and A1 represents a 2-substituted alkyl group having 1 to 9 carbon atoms; and B1 and B2 each independently represent a single bond or a urethane bond; (main chain side: -0-C0-NHR-), ester bond (main chain side: -CO-0-)' R represents an alkyl group having 1 to 3 carbon atoms; and, XI and X2 each independently represent an ester bond (Main chain side: -0-C0-); Ri and R2 each independently represent a hydrogen atom or a methyl group). 3. The photosensitive resin composition of claim 3, wherein the substituent of the substituted alkyl group is a (meth) acryloxy group. 4. The photosensitive resin composition according to the ninth aspect of the invention, wherein the base having a branched chain and/or an alicyclic structure has a group represented by the following formula (3), 〇(\11 0-Γ-Χ-〇Ί C General formula (3) y V /n In the general formula (3), X represents a divalent organic linking group, which may be unsubstituted or substituted; y represents 1 Or 2, η represents an integer of 0 to 15. The photosensitive resin composition of claim 1, wherein the [a] has a branched chain and/or an alicyclic structure, an acidic group, and a substitution in the side chain. a resin of an alkyl group, wherein the substituted alkyl group in the resin has a weight average molecular weight of 2 2,000 to 60,000 in the case of having two ethylenically unsaturated bonds. 6. The photosensitive resin composition according to claim 1 of the patent application, Wherein the [Α] is a resin having a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in the side chain, and the substituted alkyl group in the resin has a glass transition temperature (Tg) of two ethylenically unsaturated bonds. And the photosensitive resin composition of the first aspect of the invention, wherein the [A] has a branched chain and/or an alicyclic structure, an acidic group and a substituted alkyl group in the side chain. a resin, and the acid value of the substituted alkyl group in the resin having two ethylenically unsaturated bonds is 20 mgKOH/g or more. The photosensitive resin composition of the first aspect, wherein the mass ratio ([B]/[A] ratio) of the [B] polymerizable compound to the [A] resin is from 0.5 to 2.0. The photosensitive resin composition of the first aspect of the patent, which further contains -92-200935173 an anthracene pigment having an average particle diameter of 5 to 50 nm. 10. A photo spacer, which is used in the first to ninth application patents. A photosensitive resin composition according to any one of the preceding claims. 11. A method for forming a photo spacer, comprising at least the following steps (1) to (3) '(1) forming a patent application range 1 to a step of coating a photosensitive resin composition of any of the nine items, (ii) a step of exposing at least a portion of the film, and (0) a step of developing the film after exposure, (d) A step of heating the film after the film is formed. 12. A protective film formed by using the photosensitive resin composition according to any one of claims 1 to 9. 13. A coloring pattern which is used Photosensitive resin group of any one of claims 1 to 9 A substrate for a display device, comprising at least one of a photo spacer, a protective film, or a colored pattern formed by using a photosensitive resin composition according to any one of claims 1 to 9. 15. A display device comprising a substrate for a display device according to claim 14. -93- 200935173 IV. Designation of representative drawings: (1) The representative representative of the case is: No. (2) Components of the representative figure Brief description of the symbol: Μ 〇j\w V. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: