JP2009122549A - Photosensitive resin composition, spacer and method for forming the same, and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve sensitivity (shape under low exposure energy and controllability of film thickness), preservability in a liquid state and the temporal stability of a photosensitive film after film formation. <P>SOLUTION: A photosensitive resin composition contains a resin having, in a side chain, a group having a branched and/or alicyclic structure, an acidic group and a group having an ethylenically unsaturated bond bonded to a main chain via an ester group, a polymerizable compound having an ethylenically unsaturated bond, and a specific benzoyloxime-based photopolymerization initiator having a carbazole group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a spacer, a method for forming the same, and a liquid crystal display element.

  In recent years, an increase in the size of a mother glass substrate has been promoted due to an increase in the area of liquid crystal display devices and an improvement in productivity. With a conventional substrate size (about 680 × 880 mm), since the substrate size is smaller than the mask size, it was possible to cope with the batch exposure method. However, with the recent increase in the size of the apparatus, the demand for large substrates (for example, about 1,500 × 1,800 mm) is increasing. However, preparing a mask size comparable to such a substrate size is not possible. It is almost impossible, and it is difficult to deal with the batch exposure method.

Therefore, a step exposure method has been proposed as an exposure method for large substrates.
However, in the step exposure method, since a plurality of exposures are performed on a single substrate and alignment is performed each time, time required for step movement occurs. Therefore, in the step exposure method, there is a concern about a reduction in throughput as compared with the batch exposure method. Further, in the batch exposure method, the exposure sensitivity that allows patterning at about 3,000 J / m ² is allowed, but in the step exposure method, an exposure sensitivity that allows good patterning at 1,500 J / m ² or less is required. It has been. However, with existing materials, it is difficult to obtain a good spacer shape and film thickness with an exposure amount of 1,500 J / m ² or less.

In addition, the required values for the controllability of the spacer shape and film thickness have become increasingly severe in recent years, and accompanying changes in the shape and film thickness due to process variations during the formation of the spacer, and changes in the composition solution over time. There is room for improvement in the shape and stability of the film thickness. In particular, in the exposure amount region of 1,500 J / m ² or less, there are problems in the controllability of the spacer shape and film thickness with respect to the exposure amount.

  Furthermore, in recent years, the photosensitive resin composition used in the production of liquid crystal display panels causes foreign matters to be generated due to crystallization of components in the composition during the storage period or during use, thereby contaminating the device. This problem has become serious, and a photosensitive resin composition that can reduce the problem of contamination is desired.

As a technique against the above, a photosensitive resin composition using a copolymer of an ethylenically unsaturated carboxylic acid or the like and an ethylenically unsaturated compound and a specific photopolymerization initiator is disclosed (for example, see Patent Document 1). ). Further, from an aliphatic cyclic hydrocarbon group-containing copolymer having a molecular structure in which a structural unit having an aliphatic cyclic hydrocarbon group having a specific structure, a structural unit having an acidic functional group, and a structural unit having a radical polymerizable group are linked. A curable resin is disclosed (for example, see Patent Document 2).
JP 2007-65607 A Japanese Patent Laid-Open No. 2002-293737

  In the former photosensitive resin composition, although it is estimated that a certain degree of exposure sensitivity can be obtained, since the liquid storage stability is poor, the coating liquid must be stored in the cold after preparation of the coating liquid. In addition to the rebound to the cost due to this, there is also a problem in terms of stability such as fogging with time in the dry film state provided on the object to be coated even after coating.

  In addition, the latter curable resin comprising the aliphatic cyclic hydrocarbon group-containing copolymer does not necessarily provide sensitivity and polymerization reactivity for obtaining a good shape and the like, and liquid storage stability and photosensitivity after film formation. In view of the temporal stability of the conductive film, it is insufficient.

The present invention has been made in view of the above, and has high sensitivity (controllability of shape and film thickness at a low exposure (preferably 1,500 J / m ² or less)), storage stability in liquid state, and composition. Photosensitive resin composition with excellent temporal stability of the photosensitive film after film formation, spacer with low height variation, good shape and stable production, its formation method, and good display characteristics and stable production possible An object of the present invention is to provide a simple liquid crystal display element and to achieve the object.

  The present invention is a system in which a specific oxime-based initiator is used in combination with a resin provided with a branched and / or alicyclic structure and an ethylenically unsaturated bond arranged via an ester group with respect to the main chain, High sensitivity, polymerization reactivity (polymerization curability), excellent storage stability in the liquid state and film formation state are obtained, and it is particularly effective for improving the control of the shape of the pattern to be formed and the required film thickness It was achieved based on this knowledge.

Specific means for achieving the above object are as follows.
<1> [A] a resin having an ethylenically unsaturated bond arranged in the side chain via an ester group between a branched and / or alicyclic structure, an acidic group, and a main chain; and [B] ethylene A photosensitive resin composition containing a polymerizable compound having a polymerizable unsaturated bond and [C] a photopolymerization initiator selected from the group of compounds represented by the following general formula (1) or (2).

In the general formulas (1) to (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ² and R ³ are each independently selected. A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (provided that the carbon number is 7 to In the case where the phenyl group is substituted, the substituent is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom. . R ⁴ represents an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and R ⁵ represents a hydrogen atom, An alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is represented. n represents an integer of 0 to 5, m represents an integer of 0 to 5, l represents an integer of 0 to 6, and n and m satisfy n + m ≦ 5.

<2> The branched and / or alicyclic structure is at least one selected from a dicyclopentenyl group, a cyclohexyl group, a tricyclopentenyl group, an adamantyl group, a norbornyl group, and an isobornyl group. It is the photosensitive resin composition as described in <1>.
<3> The photosensitive resin composition according to <1> or <2>, wherein the branched and / or alicyclic structure is composed of a group represented by the following general formula (3): It is a thing.

In the general formula (3), X represents a divalent organic linking group, which may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents an integer of 0 to 15.
<4> The resin is a copolymer into which a group having the branched and / or alicyclic structure is introduced by copolymerizing a monomer represented by the following general formula (4). (4) The photosensitive resin composition according to any one of <1> to <3>, wherein the main chain includes a structural unit derived from the monomer represented by (4).

In the general formula (4), X represents a divalent organic linking group, which may be unsubstituted or may have a substituent. R represents a hydrogen atom or a methyl group, y represents 1 or 2, and n represents an integer of 0 to 15.
<5> A spacer formed using the photosensitive resin composition according to any one of <1> to <4>.

<6> A spacer forming method including at least the following steps (A) to (D).
(B) A step of forming a film of the photosensitive resin composition according to any one of <1> to <4> on a substrate (b) A step of exposing at least a part of the film (c) Exposure The process of developing the said film after (d) The process of heating the said film after image development <7> It is a liquid crystal display element provided with the spacer as described in said <5>.

According to the present invention, sensitivity (shape and film thickness controllability at a low exposure (preferably 1,500 J / m ² or less) is high), storage stability in a liquid state, and photosensitive film after film formation. A photosensitive resin composition having excellent stability over time can be provided. Also,
According to the present invention, it is possible to provide a spacer having a small height variation and a good shape and capable of stable production, a method for forming the same, and a liquid crystal display element having good display characteristics and capable of stable production.

  Hereinafter, the photosensitive resin composition of the present invention will be described in detail, and a spacer using the photosensitive resin composition, a method for forming the spacer, and a liquid crystal display element will be described in detail.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention has an ethylenically unsaturated bond arranged via an ester group between a branched and / or alicyclic structure, an acidic group, and a main chain on the side chain [A]. A resin, [B] a polymerizable compound having an ethylenically unsaturated bond, and [C] a photopolymerization initiator selected from the group of compounds represented by formula (1) or formula (2) shown below. It is configured using at least. Moreover, you may comprise using another component further as needed.

In the photosensitive resin composition of the present invention, in particular, the [A] resin and a specific structure in which a branched and / or alicyclic structure and an ethylenically unsaturated bond arranged via an ester group with respect to the main chain are arranged. By mixing with the photopolymerization initiator, a synergistic effect on sensitivity and polymerization reactivity can be obtained, so sensitivity is further enhanced and storage stability in liquid state (eg, long-term storage at room temperature) In addition, the temporal stability of the photosensitive film after film formation can be improved, and the controllability of the shape of the pattern to be formed and the film thickness required for it can be improved. Thereby, the mask pattern size when using the mask is faithfully reproduced, and a desired shape and film thickness can be obtained even in exposure in a low exposure amount region of 1500 J / m ² or less, and a desired pattern structure (preferably It is possible to stably form a color filter spacer.
It is also advantageous for improving adhesion when provided on a substrate, and improving strength and heat resistance after curing.

Hereinafter, each component which comprises the photosensitive resin composition of this invention is demonstrated in detail.
[A] Resin The photosensitive resin composition of the present invention has, on the side chain, a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond arranged via an ester group with the main chain. Contains at least one of the resins it contains. This resin has an acidic group and developability, and has an ethylenically unsaturated bond via an ester group with respect to the main chain, thereby having excellent liquid storage stability and high polymerization reactivity. Since it has storability over time in a dry film, it is possible to impart controllability that allows the pattern structure to be controlled to a desired shape and a required film thickness (such as height). Moreover, it has a branched and / or alicyclic structure, and it is possible to enhance the compression elastic modulus and the elastic recovery from the compression deformation when receiving the external force of the formed pattern structure. Thus, it is useful for constructing a pattern structure such as a color filter spacer.

  Here, the ethylenically unsaturated bond arranged via the ester group between the branched and / or alicyclic structure, the acidic group, and the main chain may be contained in different side chains. , Some may be combined and contained in the same side chain, or all may be contained in the same side chain.

  In the present specification, (meth) acryloyl group represents acryloyl group or methacryloyl group, (meth) acrylate represents acrylate or methacrylate, (meth) acryl represents acryl or methacryl, and (meth) acrylamide represents acrylamide. Alternatively, it represents methacrylamide, and (meth) acrylanilide represents acrylanilide or methacrylanilide.

~~ Branched and / or alicyclic structure ~~
[A] The resin contains at least one of a branched and / or alicyclic structure in a side chain bonded to the main chain of the resin. A plurality of branched and / or alicyclic structures may be included in the side chain of the [A] resin. In addition, the branched and / or alicyclic structure is included in the side chain of the resin [A] together with an ethylenically unsaturated bond arranged via an ester group between the acidic group and / or the main chain. It may be.
The branched and / or alicyclic structure may be directly bonded to the main chain of the [A] resin to constitute the side chain of the [A] resin only by the branched and / or alicyclic structure. It may be bonded to the main chain of the resin through a divalent organic linking group, and the side chain of the resin [A] may be constituted as a group having a branched and / or alicyclic structure.

  The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, 1-10 are preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched / cyclic structure or a functional group, and more preferably a methylene group. , Ethylene group and octylene group are preferable. As the arylene group, an arylene group having a total carbon number of 6 to 20 is preferable, and 6 to 12 is more preferable. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.

  The form in which the branched and / or alicyclic structure is bonded to the main chain of the resin [A] via at least an ester group (—COO—) is preferable from the viewpoint of developability and elastic recovery. This form is not limited to the form in which the branched and / or alicyclic structure is bonded to the main chain of the resin [A] only through the ester group (—COO—), and the branched and / or alicyclic structure is an ester group. The form couple | bonded with the principal chain of [A] resin may be sufficient through the bivalent coupling group containing (-COO-). That is, other atoms and other linking groups may be included between the branched and / or 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 branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, and neopentyl group. 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are more preferable, and i-propyl group, s-butyl group, t-butyl group and the like are particularly preferable.

  Examples of the alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, A tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like, and groups having these are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group and the like are more preferable, dicyclopentenyl group, cyclohexyl group, norbornyl Group, isobornyl group, tricyclopentenyl group and the like are more preferable, and dicyclopentenyl group is particularly preferable.

  Furthermore, the form comprised by having group represented by following General formula (3) as group which has a branched and / or alicyclic structure is preferable.

  In the general formula (3), X represents a divalent organic linking group, which may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents an integer of 0 to 15.

The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group, and these may have a substituent.
As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, it is a 1-10 alkylene group. Specific examples include groups such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, and octadecylene, which may have a branched / cyclic structure or a functional group, and more preferably, A methylene group, an ethylene group and an octylene group;
The arylene group is preferably an arylene group having a total carbon number of 6 to 20, more preferably 6 to 12. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.
Examples of the substituent when substituted include an alkyl group, a hydroxy group, an amino group, a halogen group, an aromatic ring group, and a group having an alicyclic structure.

  [A] Monomers for introducing a branched and / or alicyclic structure into the side chain of the resin include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides and the like. (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  [A] Specific monomers for introducing a branched structure into the side chain of the resin include i-propyl (meth) acrylate, i-butyl (meth) acrylate, and s-butyl (meth) acrylate. , T-butyl (meth) acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meta ) 3-octyl acrylate, t-octyl (meth) acrylate, etc. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, etc. are preferable, methacryl More preferred are i-propyl acid and t-butyl methacrylate.

[A] Examples of the monomer for introducing an alicyclic structure into the side chain of the resin include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid 1-adamantyl, (meth) acrylic acid 2-adamantyl, (meth) acrylic acid 3 -Methyl-1-adamantyl, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, ( 3,5,8-triethyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7 (meth) acrylate Mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic acid 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, ( (Meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 2,2,5-trimethylcyclohexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid di Examples include cyclopentenyl and tricyclopentenyl (meth) acrylate.
Among these (meth) acrylic acid esters, bulky functional groups improve compression elastic modulus and elastic recoverability, so that (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic Isobornyl acid, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, fuentyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic Dicyclopentenyl acid, tricyclopentenyl (meth) acrylate and the like are preferable, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, 2-adamantyl (meth) acrylate, (Meth) acrylic acid dicyclopentenyl, (meth) acrylic acid tricyclope Nthenyl is particularly preferred.

[A] Examples of the monomer for introducing an alicyclic structure into the side chain of the resin include compounds represented by the following general formula (4) or (5). Here, in the general formulas (4) and (5), X represents a divalent organic linking group, and R represents a hydrogen atom or a methyl group. y represents 1 or 2, and n represents 0-15. Among general formulas (4) and (5), y = 1 or 2, n = 0 to 8 is preferable, and y = 1 or 2, n = 0 to 4 (more preferably n = 0 to 2). ). Preferred specific examples of the compound represented by the general formula (4) or (5) include the following compounds D-1 to D-11 and T-1 to T-12.
Among these, the compound represented by the following general formula (4) is preferable from the viewpoint of the elastic recovery rate due to the reactivity of the double bond site.

  In the general formulas (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and X in the general formula (3) It is synonymous with the bivalent organic coupling group represented, and its preferable aspect is also the same.

[A] As a monomer for introducing an alicyclic structure into the side chain of the resin, an appropriately produced monomer or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, 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 can be mentioned. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

~~ Acid group ~~
[A] The resin contains at least one acidic group in the side chain linked to the main chain. A plurality of acidic groups may be contained in the side chain. In addition, the acidic group is included in the side chain of [A] resin together with the branched and / or alicyclic structure, and an ethylenically unsaturated bond arranged via an ester group between the main chain. Also good.
The acidic group may be directly bonded to the main chain of the [A] resin to constitute the side chain of the [A] resin only with the acidic group, or the divalent organic linkage to the main chain of the [A] resin. The side chain of [A] resin may be comprised as a group which couple | bonds through group and has an acidic group. Here, examples of the divalent organic linking group include the divalent organic linking groups exemplified in the description of the branched and / or alicyclic structure, and preferred ranges thereof are also the same.

  There is no restriction | limiting in particular as said acidic group, It can select suitably from well-known things, For example, a carboxyl group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group etc. are mentioned. Among these, a carboxy group and a phenolic hydroxyl group are preferable 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 can be appropriately selected from known ones, such as (meth) acrylic acid, vinylbenzoic acid, maleic acid, maleic acid. Acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxyl -Polycaprolactone mono (meth) acrylate and the like. As these, those produced as appropriate may be used, or commercially available products may be used.

  Examples of the monomer having a hydroxyl group used in the addition reaction product of the monomer having a hydroxyl group and a cyclic acid anhydride include 2-hydroxyethyl (meth) acrylate. Examples of the cyclic acid anhydride include maleic anhydride, phthalic anhydride, and cyclohexanedicarboxylic anhydride.

  Commercially available monomers include Toa Gosei Chemical Industry Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin-Nakamura Chemical Co., Ltd .: NK Ester CB -1, NK ester CBX-1, manufactured by Kyoeisha Oil and Chemical Co., Ltd .: HOA-MP, HOA-MS, manufactured by Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100, and the like. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

~~ ethylenically unsaturated bond ~~
[A] The resin contains at least one kind of ethylenically unsaturated bond arranged on the side chain connected to the main chain via an ester group between the resin and the main chain. A plurality of ethylenically unsaturated bonds may be contained in the side chain. Moreover, the ethylenically unsaturated bond may be contained in the side chain of the [A] resin together with the branched and / or alicyclic structure and / or the acidic group.

  The ethylenically unsaturated bond is bonded to the main chain of the [A] resin via at least one ester group (—COO—), and only the ethylenically unsaturated bond and the ester group [A] resin. The side chain may be constituted. Further, [A] a divalent organic linking group may be further provided between the main chain of the resin and the ester group and / or between the ester group and the ethylenically unsaturated bond. The saturated bond may constitute the side chain of the resin [A] as “a group having an ethylenically unsaturated bond arranged via an ester group between the main chain” and [A] resin. Here, the divalent organic linking group includes the divalent organic linking groups exemplified in the description of the branched and / or alicyclic structure, and the preferred range is also the same.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
[A] The method of introducing a (meth) acryloyl group into the side chain of the resin can be appropriately selected from known methods. For example, a (meth) acrylate having an epoxy group in a repeating unit having an acidic group is used. Examples thereof include a method of adding, a method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, and a method of adding a (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

  Although there is no restriction | limiting in particular as (meth) acrylate which has the said epoxy group, For example, the compound represented by following Structural formula (1) and the compound represented by following Structural formula (2) are preferable.

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

However, in said structural formula (2), R ² represents a hydrogen atom or a methyl group. L ² represents an organic group. W represents a 4- to 7-membered aliphatic hydrocarbon group.

Of the compound represented by the structural formula (1) and the compound represented by the structural formula (2), the compound represented by the structural formula (1) is more preferable than the structural formula (2). In the structural formulas (1) and (2), it is more preferable that L ¹ and L ² are each independently an alkylene group having 1 to 4 carbon atoms.

  Although there is no restriction | limiting in particular as a compound represented by the said Structural formula (1) or a structural formula (2), For example, the following exemplary compounds (1)-(10) are mentioned.

~~ other monomers ~~
Other groups may be introduced into the [A] resin in the present invention using other monomers.
The other monomer is not particularly limited, and examples thereof include (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, hydrocarbon alkenyl group and the like. Can be mentioned.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.
The dibasic acid anhydride group is not particularly limited, and examples thereof include a maleic anhydride group and an itaconic anhydride group.
There is no restriction | limiting in particular as said vinyl ester group, For example, a vinyl acetate group etc. are mentioned.
There is no restriction | limiting in particular as said hydrocarbon alkenyl group, For example, a butadiene group, an isoprene group, etc. are mentioned.

  As content rate of the other monomer in said [A] resin, it is preferable that a composition ratio is 1-40 mass%, and it is more preferable that it is 2-30 mass%.

[A] Specific examples of the resin include compounds represented by the following structures (Exemplary Compounds P-1 to P-56).
In addition, x, y, and z in the exemplified compound represent a composition ratio (mass ratio) of each repeating unit, and a form configured in a preferable range described later is preferable. Moreover, the form comprised also in the preferable range mentioned later of the weight average molecular weight of each exemplary compound is suitable.

<Synthesis method>
[A] The resin can be synthesized from a two-stage process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

<Carbon number>
[A] The total carbon number of the resin is preferably 10 or more in terms of elastic modulus (hardness). Especially, as for total carbon number, 10-30 are more preferable, Most preferably, it is 10-15.

<Molecular weight>
[A] The molecular weight of the resin is preferably 10,000 to 100,000 in terms of weight average molecular weight, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of a resin (preferably a copolymer). Further, it is preferable in that the shape formed by the decrease in melt viscosity is difficult to be crushed, in that it is difficult to cause crosslinking failure, and there is no residue in the spacer shape during development.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC will be described in detail in the section of the examples described later.

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

<Acid value>
[A] The preferred range of the acid value of the resin varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 40 mgKOH / g or more, and 50 to 130 mgKOH / g. It is particularly preferred. When the acid value is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

<Tg>
The [A] resin has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000 because a spacer having good developability and mechanical strength can be obtained. Preferably, the Tg is 45 to 140 ° C. (further 50 to 130 ° C.) and the weight average molecular weight is 12,000 to 60,000 (further 15,000 to 45,000). .
Furthermore, the preferable example of said [A] resin has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The resin [A] in the present invention comprises a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond arranged via an ester group between the main chain and separate repeating units ( From the viewpoint of deformation recovery rate, development residue, and reticulation when a pattern structure (for example, a color filter spacer) is formed, it is preferably a copolymer of terpolymerization or higher in the copolymer unit). .
Specifically, the resin [A] includes a repeating unit having a branched and / or alicyclic structure: X (x mol%), a repeating unit having an acidic group: Y (y mol%), a main chain, It is preferable that the copolymer is a terpolymer or more copolymer having at least a repeating unit having an ethylenically unsaturated bond, Z (z mol%), arranged via an ester group. Furthermore, you may have other repeating units: L (1 mol%) as needed.
Such a copolymer is, for example, an ethylenic polymer arranged via an ester group between a monomer having a branched and / or alicyclic structure, a monomer having an acidic group, and a main chain. It can be obtained by copolymerizing a monomer having a saturated bond and, if necessary, another monomer. Among these, a monomer represented by the general formula (4) is used as a monomer having at least the branched and / or alicyclic structure in that the compressive elastic modulus and elastic recoverability are improved with a bulky functional group. It is preferable that the copolymer is a copolymer into which a group having a branched and / or alicyclic structure is introduced. In this case, [A] resin has the structural unit derived from the monomer represented by the said General formula (4) in a principal chain.

The copolymer composition ratio when the [A] resin is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the following ranges can be adopted.
[A] The composition ratio (x) of the repeating unit having a branched and / or alicyclic structure in the resin is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%. . When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
[A] The composition ratio (y) of the repeating unit having an acidic group in the resin is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
[A] The composition ratio (z) of the repeating unit having an “ethylenically unsaturated bond arranged through an ester group with the main chain” in the resin is preferably 10 to 70 mol%, and preferably 20 to 70 mol. % Is more preferable, and 30 to 70 mol% is particularly preferable. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, the sensitivity and the polymerization curability are good, the liquid storage stability after preparation, and the dry film state after application are maintained for a long time. The stability over time is improved.
Furthermore, as the [A] resin, the composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly 20 to 50 mol%), and the composition ratio (y) is 5 to 5 mol%. 70 mol% (more preferably 10 to 60 mol%, especially 30 to 70 mol%), and the composition ratio (z) is 10 to 70 mol% (more preferably 20 to 70 mol%, particularly 30 to 70 mol%). %) Is preferred.

As content in the photosensitive resin composition of said [A] resin, 5-70 mass% is preferable with respect to the total solid of a composition, and 10-50 mass% is more preferable.
[A] The resin can be used in combination with other resins described later, but it is preferable that the resin is composed only of the [A] resin.

~ Other resins ~
The resin that can be used in combination with the resin [A] is preferably a compound that exhibits swelling properties with respect to an alkaline aqueous solution, and more preferably a compound that is soluble in an alkaline aqueous solution.
As the resin exhibiting swellability or solubility with respect to an alkaline aqueous solution, for example, those having an acidic group are preferably mentioned. Specifically, an ethylenically unsaturated double bond and an acidic group are introduced into an epoxy compound. Compound (epoxy acrylate compound), vinyl copolymer having (meth) acryloyl group and acidic group in side chain, epoxy acrylate compound and vinyl copolymer having (meth) acryloyl group and acidic group in side chain And the like, and a maleamic acid copolymer are preferable.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

  When the above [A] resin and another resin are used in combination, the total content (solid content) of the resin that can be used in combination with the [A] resin is based on the total solid content of the photosensitive resin layer. 5 to 70 mass% is preferable, and 10 to 50 mass% is more preferable. When the content is 5% by mass or more, the film strength of the photosensitive resin layer can be maintained, and the tackiness of the surface of the photosensitive resin layer can be maintained well. When the content is 70% by mass or less, the exposure sensitivity is good. become.

[B] Polymerizable compound The photosensitive resin composition of the present invention contains at least one polymerizable compound having an ethylenically unsaturated bond. Under the action of radicals from the photopolymerization initiator described later, a polymerization reaction is caused to form a cured film.

  The polymerizable compound can be selected from polymerizable compounds constituting a known composition and used, for example, the components described in paragraph numbers [0010] to [0020] of JP-A-2006-23696. And the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

  In the relationship with the [A] resin, the mass ratio of the [B] polymerizable compound to the [A] resin ([B] / [A] ratio) is preferably 0.5 to 2.0. It is more preferably 6 to 1.4, and particularly preferably 0.7 to 1.2. When the ratio [B] / [A] is within the above range, a spacer having good developability and mechanical strength can be obtained.

[C] Photopolymerization initiator The photosensitive resin composition of the present invention has at least one selected from the group of compounds represented by the following general formula (1) or general formula (2) as a photopolymerization initiator (hereinafter, “ It may be referred to as “photoinitiator in the present invention”). By using the oxime-based photopolymerization initiator represented by the general formula (1) or (2) together with the [A] resin, the sensitivity is enhanced, the progress of the polymerization reaction is improved, the shape and the necessary for it. The controllability of the film thickness can be further improved. Thereby, good sensitivity and adhesion can be obtained even with a low exposure amount of 1500 J / m ² or less. For example, when forming a color filter spacer, it is possible to obtain a spacer having good adhesion to the substrate and having a desired shape.

  The photopolymerization initiator referred to in the present invention generates an active species capable of initiating the polymerization of the [B] polymerizable compound by exposure with visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. Means ingredients.

In the general formulas (1) to (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group.
R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms. Represents a click group (excluding a cycloalkyl group having 7 to 8 carbon atoms), and the substituent when the phenyl group is substituted is an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms , A phenyl group, or a halogen atom. Here, the number of these substituents may be 1-5.
R ⁴ represents an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms.
R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
N represents an integer of 1 to 5, m represents an integer of 0 to 5, l represents an integer of 0 to 6, and n and m satisfy n + m ≦ 5.

In the general formulas (1) to (2), the alkyl group having 1 to 20 carbon atoms represented by R ¹ may be a linear or branched alkyl group. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

The cycloalkyl group having 3 to 8 carbon atoms represented by R ^1, examples thereof include a cyclopentyl group, a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

Among these, as R ¹ , for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-hexyl group and the like are preferable.

The alkyl group having 1 to 20 carbon atoms represented by R ² and R ³ may be linear or branched, and specific examples thereof include, for example, a methyl group, an ethyl group, and an n-propyl group. I-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , N-undecyl group and n-dodecyl group. Especially, a C1-C10 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

The cycloalkyl group of R ^2, carbon atoms represented by R ³ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group. Among these, a cycloalkyl group having 3 to 6 carbon atoms is preferable, and a cycloalkyl group having 5 to 6 carbon atoms is particularly preferable.

The “alkyl group having 1 to 6 carbon atoms” as the substituent of the substituted phenyl group represented by R ² and R ³ can be a linear, branched or cyclic alkyl group, and specific examples thereof. As methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. Can be mentioned. Especially, a C1-C6 alkyl group is preferable and a C1-C5 alkyl group is especially preferable.

Further, the “C1-C6 alkoxy group” which is a substituent of the substituted phenyl group represented by R ² and R ³ can be linear, branched or cyclic, and specific examples thereof are as follows. Can include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy and the like. Among these, an alkoxy group having 1 to 3 carbon atoms is preferable.

Examples of the halogen atom that is a substituent of the substituted phenyl group represented by R ² and R ³ include a fluorine atom and a chlorine atom.

Examples of the alicyclic group having 7 to 20 carbon atoms represented by R ² and R ³ (excluding a cycloalkyl group having 7 to 8 carbon atoms) include, for example, a bicycloalkyl group, a tricycloalkyl group, a spiroalkyl group, Examples thereof include a ter-cycloalkyl group, a terpene skeleton-containing group, and an adamantyl skeleton-containing group. Among these, alicyclic groups having 9 to 18 carbon atoms are preferable, and 9 to 12 carbon atoms are particularly preferable.

Among the above, R ² is preferably a bicycloalkyl group, a tricycloalkyl group, an adamantyl skeleton-containing group or the like, and R ³ is preferably a tricycloalkyl group, an adamantyl skeleton-containing group or the like.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms represented by R ⁴ include a thiolanyl group, Azepinyl group, dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group , Thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindoryl group, benzofuranyl group , Benzothiophenyl group, indolizini Group, chromenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, thioxanthenyl group, phenazinyl group, phenothiazinyl group, phenoxy group Examples include a satinyl group, a phenoxazinyl group, a thiantenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.
Of these, an oxygen-containing heterocyclic group having 4 to 20 carbon atoms is preferable, and a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.

The alkyl group having 1 to 12 carbon atoms represented by R ⁵ can be a linear, branched or cyclic alkyl group, and specific examples thereof include, for example, a methyl group, an ethyl group, and n-propyl. Group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl Group, n-undecyl group, n-dodecyl group, cyclopentyl group, cyclohexyl group and the like. Especially, a C1-C12 alkyl group is preferable and a C1-C8 alkyl group is especially preferable.

Further, the alkoxy group having 1 to 12 carbon atoms represented by R ^5, straight chain, can be an alkoxy group branched or cyclic, and examples thereof include a methoxy group, an ethoxy group, n- A propoxy group, i-propoxy group, n-butoxy group, t-butoxy, n-pentyloxy group, etc. can be mentioned. Among these, an alkoxy group having 1 to 2 carbon atoms is preferable.

Among these, as R ⁵ , a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, and an ethoxy group are particularly preferable.

  In the general formulas (1) to (2), n is preferably 1. m is preferably any one of 1, 2 and is particularly preferably 1, and 1 is preferably either 0, 1, or 2 and particularly preferably 1.

Among the structures represented by the general formula (1) or (2), while obtaining high sensitivity and polymerization reactivity (curing), liquid storage after preparation and stability over time in a dry film state after film formation From the viewpoint of maintaining controllability, increasing the controllability of the shape of the pattern to be formed and the film thickness required for it, and improving the adhesion to the object, R ¹ is an ethyl group and R ² is a methyl group R ³ is a methyl group, R ⁴ is a tetrahydrofuranyl group, R ⁵ is a methyl group, n is 1, m is 1, l is 1, Some cases are particularly preferred. Furthermore, the structure represented by the general formula (2) is more preferable.

Specific examples of the compound represented by the general formula (1) or (2) include ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.- Carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);

Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime);
Etc.

Of these, in particular, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime); ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) is preferred.
These photopolymerization initiators may be used alone or in combination of two or more.

  [C] The content of the photopolymerization initiator represented by the general formulas (1) to (2) in the photosensitive resin composition is 1 to 20 with respect to 100 parts by mass of the [B] polymerizable compound. A mass part is preferable, More preferably, it is 2-15 mass parts. When the content of the photopolymerization initiator [C] is within the above range, while obtaining high sensitivity and polymerization reactivity (curing), liquid storage stability after preparation, and aging in a dry film state after film formation The stability can be maintained, and the controllability of the shape and film thickness of the pattern to be formed can be improved. Specifically, when the content is 1 part by mass or more, the remaining film ratio at the time of development can be reduced, and when it is 20 parts by mass or less, the solubility of the unexposed part in the alkaline developer at the time of development can be maintained. .

In the photosensitive resin composition of the present invention, sensitivity (shape and film thickness controllability at low exposure (preferably 1,500 J / m ² or less) is improved), storage stability in liquid state and after film formation In terms of further improving the temporal stability of the photosensitive film (dry film), the following combinations are more preferable.
That is, [A] the resin has different repeating units (copolymerization) each having a branched and / or alicyclic structure, an acidic group, and an “ethylenically unsaturated bond arranged through an ester group between the main chain”. In this case, the copolymer is a terpolymer or higher copolymer in the unit), and the [C] photopolymerization initiator is 1) or 2) below.
1) [C] The photopolymerization initiator in the general formula (1) or (2), R ¹ is an ethyl group, R ² is a methyl group, R ³ is a methyl group, R ^A photopolymerization initiator in which ⁴ is a tetrahydrofuranyl group, R ⁵ is a methyl group, n is 1, m is 1 and l is 1.
2) [C] The photopolymerization initiator is represented by the general formula (1) or (2), wherein R ¹ is an ethyl group, R ² is a methyl group, R ³ is a methyl group, and R ^A photopolymerization initiator in which ⁴ is a tetrahydropyranyl group, R ⁵ is a methyl group, n is 1, m is 1 and l is 1.

As the photopolymerization initiator, O-acyloxime photopolymerization initiators other than the general formulas (1) to (2) (hereinafter referred to as “photopolymerization initiator C-2”) may be used in combination. .
Specific examples of the photopolymerization initiator C-2 include 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octadione-1- [ 4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime)) and the like be able to. Of these, 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable.
When using the said photoinitiator C-2 together, it is preferable that the usage-amount of the photoinitiator C-2 shall be 30 mass% or less of a photoinitiator.

Furthermore, you may use together well-known photoinitiators other than the above (photoinitiator C-3). Examples of the photopolymerization initiator C-3 are described in paragraph numbers [0010] to [0020] of JP-A-2006-23696 and paragraph numbers [0027] to [0053] of JP-A-2006-64921. Can be mentioned. As examples of other known photopolymerization initiators, aminoacetophenone compounds, acylphosphine oxide compounds, and oxime ester compounds other than those described above are preferable in terms of sensitivity.
Specific examples of aminoacetophenone compounds include IRGACURE (Irg) 369, IRGACURE (Irg) 379, and IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.). Specific examples of the acylphosphine oxide compound include DAROCUR TPO, Irgacure (Irg) 819 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like. Specific examples of the oxime ester compounds include IRGACURE (Irg) OXE01 (manufactured by Ciba Specialty Chemicals). The structures of these initiators are shown below.

  The photopolymerization initiators C-2 and C-3 can be appropriately used as long as the effects of the present invention are not impaired. 0.5-25 mass% is preferable with respect to the total solid of the photosensitive resin composition, and, as for the total amount in the photosensitive resin composition of a photoinitiator, 1-20 mass% is more preferable.

[D] Fine Particles The photosensitive resin composition of the present invention contains [D] fine particles in terms of mechanical strength together with the [A] resin, [B] polymerizable compound, and [C] photopolymerization initiator. It is preferable.
The fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable, and among them, good development is preferable. Colloidal silica is preferable from the viewpoint of obtaining a spacer having the property and mechanical strength.

  [D] The average particle diameter of the fine particles is preferably 5 to 50 nm, and preferably 10 to 40 nm in that a high mechanical strength can be obtained when forming a structure that is susceptible to external force such as a spacer. More preferably, it is 15-30 nm.

  [D] The content in the photosensitive resin composition of fine particles (when forming the spacer, the spacer (or the photosensitive resin layer constituting the spacer) is a photosensitive resin from the viewpoint of obtaining a spacer having high mechanical strength. The total solid content (mass) in the composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and particularly preferably 15 to 30 mass%.

[E] Others The photosensitive resin composition according to the present invention is necessary in addition to the above [A] resin, [B] polymerizable compound, [C] photopolymerization initiator, and [D] fine particles as required. Accordingly, other components such as a photopolymerization initiation aid may be included.

  The photosensitive resin composition may use a photopolymerization initiation assistant in combination as another additive component. The photopolymerization initiation assistant can be used in combination with a photopolymerization initiator in order to promote polymerization of a polymerizable compound that has been polymerized by the photopolymerization initiator. As the photopolymerization initiation assistant, it is preferable to use at least one amine compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4 Examples include '-bis (ethylmethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone is particularly preferable. Further, a plurality of amine-based and other photopolymerization initiation assistants may be used in combination.
Examples of other photopolymerization initiation assistants other than the above include alkoxyanthracene compounds, thioxanthone compounds, and coumarin compounds. Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. It is done. Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.
Moreover, a commercially available thing can also be used as a photoinitiation adjuvant. Examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).

  As content in the photosensitive resin composition of a photoinitiator adjuvant, 0.6 mass part or more and 20 mass parts or less are preferable with respect to 1 mass part of said photoinitiator, 1 mass part or more and 15 mass parts. Part or less is more preferable, and 1.5 parts by weight or more and 15 parts by weight or less is particularly preferable.

  Further, as other components, they can be selected from components constituting a known composition and used, for example, paragraph numbers [0010] to [0020] of JP-A-2006-23696 and JP-A-2006-64921. Ingredients listed in paragraphs [0027] to [0053] of the gazette.

<Spacer and formation method thereof>
The spacer of the present invention is formed using the above-described photosensitive resin composition of the present invention. Details and preferred embodiments of the photosensitive resin composition are as described above. The spacer of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but the method including the following steps (i) to (d) (the present invention) The spacer can be formed most suitably by using the spacer forming method.

  Since the spacer of the present invention is composed of the photosensitive resin composition of the present invention, the alignment disorder of the liquid crystal due to the mixing of foreign substances and the like is suppressed, and a high compression elastic modulus required as a spacer is achieved. A spacer having good deformation recovery, uniform height and good shape can be obtained.

  The method for forming a spacer of the present invention comprises (a) a step of forming a film of the above-described photosensitive resin composition of the present invention on a substrate (hereinafter also referred to as “film formation step”), and A step of exposing at least a part of the coating (hereinafter also referred to as “exposure step”), (c) a step of developing the coating after exposure (hereinafter also referred to as “developing step”), and (d). A step of heating the film after development (hereinafter also referred to as “film heating step”) is provided, and another step may be provided as necessary.

(A) Film formation process A film formation process forms the film of the photosensitive resin composition of this invention as stated above on a board | substrate. A photosensitive resin layer can be formed as a coating, and this photosensitive resin layer constitutes a spacer capable of maintaining a uniform cell thickness by performing other steps such as an exposure step and a development step described later. By using the spacer of the present invention, display unevenness in an image in a display device (particularly a liquid crystal display device) that tends to cause display unevenness due to variation in cell thickness is effectively eliminated.

  As a method for forming a photosensitive resin layer on a substrate, (a) a photosensitive resin composition containing at least the above-described [A] resin, [B] polymerizable compound, and [C] photopolymerization initiator is applied. Preferable examples include a coating method for coating, and (b) a transfer method for laminating and transferring the photosensitive resin layer by heating and / or pressurization using the photosensitive transfer material having the photosensitive resin layer.

(A) Coating method The photosensitive composition is coated by a known coating method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, It can be carried out by a gravure coating method or an extrusion coating method using a popper described in US Pat. No. 2,681,294. Among them, JP 2004-89851 A, JP 2004-17043 A, JP 2003-170098 A, JP 2003-164787 A, JP 2003-10767 A, JP 2002-79163 A, A method using a slit nozzle or a slit coater described in JP 2001-310147 A is suitable.

(B) Transfer method Transfer is performed using a photosensitive transfer material, for example, a roller or flat plate in which a photosensitive resin layer formed in a film shape on a temporary support is heated and / or pressed on a desired substrate surface. Then, the photosensitive resin layer is transferred onto the substrate by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

In the case of forming the photosensitive resin layer, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) can be further provided between the photosensitive resin layer and the temporary support. Thereby, exposure sensitivity can be improved. In order to improve transferability, a thermoplastic resin layer having cushioning properties may be provided.
Paragraph numbers [0024] to [0024] of Japanese Patent Application Laid-Open No. 2006-23696 describe the temporary support, the oxygen-blocking layer, the thermoplastic resin layer, and other layers constituting the photosensitive transfer material and the method for producing the photosensitive transfer material. The structure and manufacturing method described in [0030] can be applied.

  When the photosensitive resin layer is formed by both the coating method (a) and the transfer method (b), the layer thickness is preferably 0.5 to 10.0 μm, and more preferably 1 to 6 μm. When the layer thickness is in the above range, the generation of pinholes during the formation of coating during production is prevented, and development and removal of unexposed portions can be performed without requiring a long time.

  Examples of the substrate on which the photosensitive resin layer is formed include a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate), and the like. Examples thereof include a drive substrate with a drive element (for example, a thin film transistor [TFT]). The thickness of the substrate is generally preferably 700 to 1200 μm.

(B) Exposure process / development process In the exposure process, at least a part of the film formed in the film formation process is exposed to form a latent image. In the subsequent development step, the coating film exposed in the exposure step can be developed to form a spacer pattern having a desired shape.

  Specific examples of these processes include the formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and paragraph numbers [0040] to [0051] of JP-A-2006-23696. The process described in 1 can be given as a suitable example in the present invention.

(C) Film heating process In the film heating process, the film after development in the development process is heated. Curing of the coating is further accelerated by heating, and a spacer having high strength, good compression elastic modulus and good elastic recovery can be obtained.

  As described above, a substrate for a liquid crystal display device including a spacer on the substrate can be manufactured. The spacer is preferably formed on a black light shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a black light shielding portion such as a black matrix or a driving element such as a TFT and a spacer.

For example, when the spacer is provided on the black light-shielding portion or the driving element, for example, the photosensitive transfer material is exposed so as to cover the black light-shielding portion (black matrix or the like) or the driving element previously disposed on the substrate. A substrate for a liquid crystal display device is manufactured by laminating a photosensitive resin layer on a support surface, peeling and transferring to form a photosensitive resin layer, and then subjecting it to exposure, development, heat treatment, etc. to form a spacer. be able to.
The substrate for a liquid crystal display device of the present invention may further be provided with colored pixels of three colors such as red (R), blue (B), and green (G) as necessary.

The spacer of the present invention can be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding part, the colored part and the spacer are formed by arbitrarily combining a coating method for applying a photosensitive composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive composition. Is possible.
The black shielding part, the colored part and the spacer can each be formed from a photosensitive composition. Specifically, for example, a photosensitive resin layer is formed by directly applying the liquid photosensitive resin composition to a substrate. Later, exposure and development are performed to form the black shielding portion and the colored portion in a pattern, and then the photosensitive resin composition of another liquid is placed on another substrate (temporary support) different from the substrate. After using the transfer material prepared by installing and forming the photosensitive resin layer, this transfer material is closely attached to the substrate on which the black shielding portion and the colored portion are formed, and the photosensitive resin layer is transferred, The spacer can be formed in a pattern by performing exposure and development.
In this manner, a color filter provided with a spacer can be manufactured.

<Liquid crystal display element>
The liquid crystal display device of the present invention is configured by providing the above-described spacer of the present invention. As one of the liquid crystal display elements, at least one of them includes a liquid crystal layer and a liquid crystal driving means (simple matrix driving method and active matrix driving method) between a pair of light transmissive supports (including a liquid crystal display device substrate). ) At least.

  In this case, the substrate for a liquid crystal display device can be used as a color filter substrate having a plurality of RGB pixel groups and each pixel constituting the pixel group being separated from each other by a black matrix. Since this color filter substrate is provided with a high deformation recovery spacer having an excellent elastic recovery rate and weighted deformation amount, a liquid crystal display element including the color filter substrate is provided between the color filter substrate and the counter substrate. It is possible to effectively prevent the occurrence of display unevenness such as color unevenness due to uneven distribution of liquid crystal material due to fluctuations in cell gap (cell thickness) and low temperature foaming. Thereby, the produced liquid crystal display element can display a vivid image.

  As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes at least a liquid crystal layer and a liquid crystal driving means between a pair of light-transmitting supports (including a substrate for a liquid crystal display device). An active element (for example, TFT) is included, and a pair of substrates is configured to be regulated to a predetermined width by a highly deformable spacer having an excellent elastic recovery rate and weighted deformation amount. Also in this case, the substrate for a liquid crystal display device of the present invention has a plurality of RGB pixel groups, and is used as a color filter substrate in which each pixel constituting the pixel group is separated from each other by a black matrix.

Examples of liquid crystals that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.
In addition, the pixel group of the color filter substrate may be composed of two-color pixels exhibiting different colors, or may be composed of three-color pixels, four-color pixels or more. For example, in the case of three colors, it is composed of three hues of red (R), green (G), and blue (B). When arranging pixel groups of three colors of RGB, arrangement of mosaic type, triangle type, etc. is preferable, and when arranging pixel groups of four colors or more, any arrangement may be used. For producing the color filter substrate, for example, a black matrix may be formed as described above after forming a pixel group of two or more colors, or conversely, a pixel group may be formed after forming a black matrix. Good. Regarding the formation of RGB pixels, JP 2004-347831 A can be referred to.

<Liquid crystal display device>
A liquid crystal display device can be configured by providing the above-described liquid crystal display device substrate. Further, the liquid crystal display device can be configured by providing the liquid crystal display element. That is, as described above, the space between the pair of substrates arranged to face each other is regulated to a predetermined width by the spacer of the present invention, and the liquid crystal material is enclosed in the regulated gap (the enclosed portion is referred to as a liquid crystal layer). The thickness of the liquid crystal layer (cell thickness) is maintained at a desired uniform thickness.

  The liquid crystal display mode in the liquid crystal display device includes STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. Preferably mentioned. Among them, in the liquid crystal display device of the present invention, from the viewpoint of exhibiting the effect of the present invention most effectively, a display mode that easily causes display unevenness due to fluctuations in the cell thickness of the liquid crystal cell is desirable, and the cell thickness is 2 to 4 μm. The VA display mode, the IPS display mode, and the OCB display mode are preferably configured.

  The basic configuration of the liquid crystal display device includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). A counter substrate is arranged with a spacer interposed therebetween and a liquid crystal material is sealed in the gap, and (b) a drive substrate and a counter substrate having a counter electrode (conductive layer) are interposed with a spacer. The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices.

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the liquid crystal display element of the present invention. For example, the liquid crystal display device can be configured as various types of liquid crystal display devices described in the “next-generation liquid crystal display technology”. . In particular, it is effective in constructing a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., issued in 1996)”.

  The liquid crystal display device includes an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and the like except that the spacer, the liquid crystal display device substrate, and the liquid crystal display element are provided. It can generally be configured using various members such as a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

  The weight average molecular weight was measured by gel permeation chromatography (GPC). For GPC, HLC-8020GPC (manufactured by Tosoh Corporation) is used, TSKgel, Super Multipore HZ-H (manufactured by Tosoh Corporation, 4.6 mm ID × 15 cm) are used as columns, and THF (tetrahydrofuran) is used as an eluent. ) Was used. The conditions were as follows: the sample concentration was 0.35 / min, the flow rate was 0.35 ml / min, the sample injection amount was 10 μl, the measurement temperature was 40 ° C., and an IR detector was used. In addition, the calibration curve is “standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, It produced from eight samples of "A-2500", "A-1000", and "n-propylbenzene".

(Synthesis of resin)
[A] Resin was synthesized as shown below.
-Synthesis Example 1
Example compound P-52 in which a structural unit derived from styrene was added to the example compound P-51 described above was synthesized as follows. In addition, about the synthesis | combination of exemplary compound P-51, it shows in the following synthesis example 2.
In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Emulsifier Co., Ltd.) was added in advance, the temperature was raised to 90 ° C., 3.1 parts of styrene (St), tricyclopentenyl meta Acrylate (TCPD-M; manufactured by Hitachi Chemical Co., Ltd.) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Industries, Ltd., V-601) ) A mixed solution consisting of 2.08 parts and 55.2 parts of 1-methoxy-2-propanol was dropped into a 90 ° C. reaction vessel over 2 hours under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, 0.15 part of hydroquinone monomethyl ether and 0.34 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was added for 2 hours. (GLM-MAA; z). After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by Daicel Chemical Industries, Ltd.) is added so that the solid concentration is 45%. A resin solution (solid content acid value; 76.0 mgKOH) of Exemplified Compound P-52 ([A] resin) obtained by adding a structural unit derived from styrene to the aforementioned Exemplified Compound P-51 having an unsaturated group / G, Mw; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) (x: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol%).
Here, GLM-MAA indicates a compound in which glycidyl methacrylate is bonded to methacrylic acid (the same applies hereinafter).
In addition, molecular weight Mw of exemplary compound P-52 showed the weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatograph method (GPC method) (hereinafter the same).

  Hereinafter, [A] Synthesis Examples (Synthesis Examples 2 to 9, Synthesis Examples 12 to 13) for synthesizing Exemplified Compound P-46 to Exemplified Compound P-56 described above as other compounds of the resin, and Comparative Examples The synthesis example (synthesis examples 10-11) of a polymer is shown.

-Synthesis Example 2-
The above-described exemplary compound P-51 was synthesized as follows.
In Synthesis Example 1, without using styrene, TCPD-M (x), methacrylic acid (y), and so that x: y: z in Exemplified Compound P-51 is 34 mol%: 27 mol%: 39 mol%, and Except for changing the addition amount of GLM-MAA (z), the resin solution (solid content acid value) of Exemplified Compound P-51 ([A] resin) having an unsaturated group was synthesized by the same method as in Synthesis Example 1. 72.5 mg KOH / g, Mw; 22,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis Example 3-
Example Compound P-50, in which a structural unit derived from styrene was added to Example Compound P-49 described above, was synthesized as follows. In addition, about the synthesis | combination of exemplary compound P-49, it shows in the following synthesis example 4. FIG.
In Synthesis Example 1, tricyclopentenyl methacrylate was replaced with cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and composition x: y: z: St in which structural unit derived from styrene was added to exemplary compound P-49 Except that the addition amount of cyclohexyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and styrene (St) is changed so that is 25 mol%: 25 mol%: 40 mol%: 10 mol% A resin solution (solid content acid value) of Exemplified Compound P-50 ([A] Resin) synthesized by the same method as in Synthetic Example 1 and adding an styrene-derived structural unit to Exemplified Compound P-49 having an unsaturated group 84.9 mg KOH / g, Mw; 26,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis Example 4-
The above-described exemplary compound P-49 was synthesized as follows.
In Synthesis Example 1, styrene was not used and tricyclopentenyl methacrylate was replaced with cyclohexyl methacrylate (CHMA, manufactured by Tokyo Chemical Industry Co., Ltd.), and x: y: z in Exemplified Compound P-49 was 32 mol%: 25 mol. %: Synthesized by the same method as in Synthesis Example 1 except that the amount of cyclohexyl methacrylate (x), methacrylic acid (y), and GLM-MAA (z) was changed so as to be 43 mol%. Resin solution (solid acid value: 80.9 mg KOH / g, Mw; 21,000, 1-methoxy-2-propanol / 1-methoxy-2-) of exemplary compound P-49 ([A] resin) having a saturated group Propyl acetate 45% solution) was obtained.

-Synthesis Example 5-
The above-described exemplified compound P-53 was synthesized as follows.
In Synthesis Example 1, styrene was not used, and tricyclopentenyl methacrylate was replaced with dicyclopentenyl methacrylate (Hanchlor FA-512M manufactured by Hitachi Chemical Co., Ltd.), and x: y in exemplary compound P-53: Except for changing the addition amount of FA-512M (x), methacrylic acid (y), GLM-MAA (z) so that z is 46.2 mol%: 24.3 mol%: 29.5 mol%, Resin solution (solid content acid value: 71.2 mg KOH / g, Mw; 25,500, 1-) of an exemplary compound P-53 ([A] resin) having an unsaturated group, synthesized by the same method as in Synthesis Example 1. Methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

-Synthesis Example 6
Example compound P-54 in which a structural unit derived from styrene was added to compound P-10 described above was synthesized as follows.
In Synthesis Example 1, a composition in which tricyclopentenyl methacrylate is replaced with dicyclopentanyl methacrylate (funcryl FA-513M manufactured by Hitachi Chemical Co., Ltd.) and a structural unit derived from styrene is added to exemplary compound P-10. The addition amounts of FA-513M (x), methacrylic acid (y), GLM-MAA (z), and styrene were adjusted so that x: y: z: St was 25 mol%: 25 mol%: 40 mol%: 10 mol%. Except for the change, the resin solution of Exemplified Compound P-54 ([A] resin) synthesized by the same method as in Synthetic Example 1 and added with the structural unit derived from styrene to Exemplified Compound P-10 having an unsaturated group ( Solid content acid value: 78.7 mg KOH / g, Mw; 28,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution It was obtained.

-Synthesis Example 7-
Example compound P-46, in which a structural unit derived from styrene was added to compound P-1 described above, was synthesized as follows.
In Synthesis Example 1, tricyclopentenyl methacrylate was replaced with ADMA (manufactured by Idemitsu Kosan Co., Ltd.), and the composition x: y: z: St was 30 mol%: 24 mol% with the addition of a structural unit derived from styrene to compound P-1. : 38 mol%: synthesized by the same method as in Synthesis Example 1 except that the addition amount of ADMA (x), methacrylic acid (y), GLM-MAA (z), and styrene was changed so as to be 8 mol%. Resin solution of an exemplified compound P-46 ([A] resin) obtained by adding a structural unit derived from styrene to the exemplified compound P-1 having an unsaturated group (solid content acid value: 74.1 mgKOH / g, Mw; 29, 000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis Example 8-
Example compound P-47 in which a structural unit derived from styrene was added to compound P-2 described above was synthesized as follows.
In Synthesis Example 1, the composition x: y: z: St in which tricyclopentenyl methacrylate was replaced by isobornyl methacrylate (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.) and a structural unit derived from styrene was added to compound P-2. Except that the addition amounts of IBXMA (x), methacrylic acid (y), GLM-MAA (z), and styrene were changed so that the ratio was 34 mol%: 24 mol%: 36 mol%: 6 mol%. Resin solution (solid content acid value: 72.9 mgKOH / g) of Compound P-2 ([A] resin) synthesized by the same method and having a structural unit derived from styrene added to compound P-2 having an unsaturated group Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis Example 9-
Example compound P-48 in which a structural unit derived from styrene was added to compound P-2 described above was synthesized as follows.
In Synthesis Example 1, tricyclopentenyl methacrylate was replaced with isobornyl methacrylate (IBXMA, manufactured by Wako Pure Chemical Industries, Ltd.), and x: y: z: St in compound P-2 was 40 mol%: 23 mol%: 35 mol. %: Synthesized in the same manner as in Synthesis Example 1 except that the addition amount of isobornyl methacrylate (x), methacrylic acid (y), GLM-MAA (z), and styrene was changed so as to be 2 mol%. Resin solution of the compound P-48 ([A] resin) obtained by adding a structural unit derived from styrene to the compound P-2 having an unsaturated group (solid content acid value: 67.7 mgKOH / g, Mw; 25,000) 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis example 10 (Comparative copolymer 1)-
As a comparative resin, copolymer 1 was synthesized as follows.
In Synthesis Example 6, glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added together with dicyclopentanyl acrylate, etc., and glycidyl methacrylate added to the acrylic resin solution was not added. Dicyclopentanyl methacrylate (x), methacrylic acid (y), GLM (z), and styrene so that x: y: z: St in coalescence 1 is 27 mol%: 25 mol%: 40 mol%: 8 mol% The resin solution of the copolymer 1 having no unsaturated group (solid content acid value: 95.9 mg KOH / g, Mw; 18,000) 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution).

-Synthesis example 11 (Comparative copolymer 2)-
As a comparative resin, copolymer 2 was synthesized as follows.
A flask equipped with a condenser and a stirrer was charged with 7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate. Subsequently, 5 parts of styrene, 20 parts of methacrylic acid, 25 parts of tricyclo [5.2.1.02,6] decane-8-yl methacrylate, 25 parts of 3- (methacryloyloxymethyl) -3-ethyloxetane, methacrylic acid After 20 parts of tetrahydrofurfuryl and 5 parts of 1,3-butadiene were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C. and kept at this temperature for 5 hours to obtain a polymer solution containing the copolymer 2.
The resulting polymer solution had a solid content concentration of 30.0%, and the weight average molecular weight of the polymer was 18,000.

-Synthesis Example 12-
The above-described exemplified compound P-55 was synthesized as follows.
In Synthesis Example 1, styrene was not used, and tricyclopentenyl methacrylate was replaced with the aforementioned compound D-8 (a compound represented by the general formula (4)), and x: y in the exemplified compound P-55: The same as in Synthesis Example 1 except that the addition amount of D-8 (x), methacrylic acid (y), and GLM-MAA (z) was changed so that z was 46 mol%: 24 mol%: 30 mol%. Resin solution (solid content acid value: 71.0 mgKOH / g, Mw; 28,500, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

-Synthesis Example 13-
The above-described exemplary compound P-56 was synthesized as follows.
In Synthesis Example 1, styrene was not used, and tricyclopentenyl methacrylate was replaced with the aforementioned compound D-11 (a compound represented by the general formula (4)), and x: y in Exemplary Compound P-56: The same as in Synthesis Example 1 except that the addition amount of D-8 (x), methacrylic acid (y), and GLM-MAA (z) was changed so that z was 46 mol%: 24 mol%: 30 mol%. Resin solution of an exemplified compound P-56 having an unsaturated group ([A] resin) (solid content acid value: 71.5 mg KOH / g, Mw; 24,500, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

(Example 1): Coating method <Preparation of color filter substrate>
A color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel was produced by the method described in paragraph numbers [0084] to [0095] of JP-A-2005-3861. (Hereinafter, this is referred to as a color filter substrate). Here, the substrate size of the color filter substrate was set to 550 mm × 650 mm.
Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the obtained color filter substrate by sputtering.

<Formation of photo spacer>
On the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced as described above was formed by sputtering, a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-shaped nozzle is shown in Table 1 below. A photosensitive resin layer coating solution having the formulation shown in (Prescription 1 in Example 1) was slit-coated. Subsequently, after part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating film, it was pre-baked at 120 ° C. for 3 minutes, and a photosensitive film having a thickness of 5.0 μm A functional resin layer was formed (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the photosensitive resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer is set to 100 μm in a state where the color filter substrate placed on the substrate is substantially parallel and vertical, and the proxy is used with an exposure amount of 300 mJ / cm ² through the mask. Mitty exposure (exposure process).

  Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed (development process). Subsequently, a detergent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) diluted 10 times with pure water Sprayed with a shower at 33 ° C. for 20 seconds at a cone-type nozzle pressure of 0.02 MPa, the residue around the formed pattern image is removed, and a cylindrical spacer pattern is spaced by one spacer every 300 μm × 300 μm. It formed so that it might become.

  Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 230 ° C. for 30 minutes (coating heating step) to produce a photo spacer on the color filter substrate. Here, 1000 photo spacers obtained were measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) to measure the highest position of the highest spacer from the ITO transparent electrode forming surface side ( n = 20), and the average value when averaged was defined as the height (average height). Moreover, the measurement of the bottom area of the obtained photospacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm. The measured values are shown in Table 2 below.

<Production of liquid crystal display device>
Separately, a glass substrate was prepared as a counter substrate, and the PVA mode was patterned on the transparent electrode and the counter substrate of the color filter substrate obtained above, and an alignment film made of polyimide was further provided thereon.

  After that, a UV curable resin sealant is applied by a dispenser method at a position corresponding to the outer periphery of the black matrix provided so as to surround the pixel group of the color filter, and a liquid crystal for PVA mode is dropped and attached to the counter substrate. After bonding, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealant. Polarizing plates HLC2-2518 manufactured by Sanlitz Co., Ltd. were attached to both surfaces of the liquid crystal cell thus obtained.

  Next, FR1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a red (R) LED, DG1112H (chip type LED manufactured by Stanley Electric Co., Ltd.) as a green (G) LED, DB1112H (as a blue [B] LED) A side-light type backlight was constructed using a chip-type LED manufactured by Stanley Electric Co., Ltd. and placed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display device.

<Evaluation>
The obtained photo spacer was subjected to the following measurements and evaluations. The results of measurement evaluation are shown in Table 2 below.

-Deformation recovery rate-
The obtained photo spacer was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
Deformation recovery rate (%)
= (Recovery amount after release of load [μm] / Deformation amount under load [μm]) × 100
<Evaluation criteria>
5: Deformation recovery rate was 90% or more.
4: The deformation recovery rate was 87% or more and less than 90%.
3: The deformation recovery rate was 85% or more and less than 87%.
2: Deformation recovery rate was 80% or more and less than 85%.
1: The deformation recovery rate was 75% or more and less than 80%.
0: Deformation recovery rate was less than 75%.

-Sensitivity-
With respect to the obtained coating liquid for photosensitive resin layer, it was observed whether or not a spacer pattern could be formed when the exposure amount was variously changed, and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Pattern formation was possible at less than 60 mJ / cm ² .
Δ: Pattern formation was possible at 60 to ²⁰⁰ mJ / cm ² .
X: An exposure amount exceeding 200 mJ / cm ² was required for pattern formation.

-Preservability-
(1) Liquid storage stability The coating solution for the photosensitive resin layer obtained above was sealed, and after the natural aging (25 ° C) 180 days after sealing, the coating solution for the photosensitive resin layer was heated to 60 ° C. Each coating solution after 2 weeks in the oven was used and evaluated according to the following evaluation criteria in the same manner as the operation in the evaluation of “sensitivity”.
<Evaluation criteria>
A: Pattern formation was possible at less than 60 mJ / cm ² .
(Triangle | delta): Pattern formation was possible at 60 mJ / cm < ² > or more and less than 150 mJ / cm < ² >.
×: exposure of less than 150 mJ / cm ² or more 300 mJ / cm ² in the pattern formation is required.
XX: An exposure amount of 300 mJ / cm ² or more was required for pattern formation.

(2) Stability over time of photosensitive resin layer The pre-baked photosensitive resin layer (color filter substrate on which the photosensitive resin layer is formed) is placed in an oven at 60 ° C. for 14 days, Similarly, it evaluated in accordance with the following evaluation criteria.
<Evaluation criteria>
A: Pattern formation was possible at less than 60 mJ / cm ² .
(Triangle | delta): Pattern formation was possible at 60 mJ / cm < ² > or more and less than 150 mJ / cm < ² >.
×: exposure of less than 150 mJ / cm ² or more 300 mJ / cm ² in the pattern formation is required.
XX: An exposure amount of 300 mJ / cm ² or more was required for pattern formation.

(Example 2 and Examples 4 to 18, Comparative Examples 1 to 4): Coating Method In Example 1, the formulation of the coating solution for the photosensitive resin layer was changed as shown in Table 1, and the photosensitive resin layer was used. In the same manner as in Example 1, except that the compound P-1 ([A] resin), the fine particles, and the initiator used for preparing the coating liquid were changed as shown in Table 2 below, A liquid crystal display device was produced. The obtained photospacer was cylindrical.

(Example 3): Transfer method In Example 1, instead of applying the photosensitive resin layer coating solution (prescription 1), transfer using a photosensitive transfer film for spacers shown below is performed, whereby a photosensitive resin is obtained. A photospacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the layer was formed. The obtained photospacer was cylindrical.

-Production of photosensitive transfer film for spacers-
On a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, a thermoplastic resin layer coating solution having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 15.0 μm. did.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts, surfactant 1 below 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

* Surfactant 1
・ The following structure 1… 30%
・ Methyl ethyl ketone 70%

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205 (saponification rate 80%), manufactured by Kuraray Co., Ltd.)
・ Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by ISP Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, a photosensitive resin layer coating solution ([A] resin is a compound in Table 2) having the formulation 1 shown in Table 1 above is further applied onto the formed intermediate layer and dried to obtain a dry layer thickness of 5 A photosensitive resin layer of 0.0 μm was laminated.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total thickness of three layers: 21.5 μm), the surface of the photosensitive resin layer is formed. Further, a polypropylene film having a thickness of 12 μm was applied as a cover film by heating and pressing to obtain a photosensitive transfer film for spacers.

-Production of photo spacer-
The cover film of the obtained photosensitive transfer film for spacers was peeled off, and the ITO transparent electrode of the color filter substrate on which the ITO transparent electrode produced in the same manner as in Example 1 was formed by sputtering on the exposed surface of the photosensitive resin layer. The film was laminated on top and laminated using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) under a linear pressure of 100 N / cm and a pressurization / heating condition of 130 ° C. at a conveyance speed of 2 m / min. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

Subsequently, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask surface and the surface of the photosensitive resin layer on the side in contact with the intermediate layer is set to 100 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side at an exposure amount of 90 mJ / cm ² (exposure process).

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by Fujifilm Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water) The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate. Subsequently, a sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer. Containing agent: Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10-fold with pure water, and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa. An image was formed (development process).
Subsequently, a solution obtained by diluting a cleaning agent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (Fuji Film Co., Ltd.)) 10 times with pure water Used, and sprayed with a shower at a cone type nozzle pressure of 0.02 MPa for 20 seconds at 33 ° C. to remove residues around the formed pattern image, and to form a cylindrical spacer pattern with one spacer spacing of 300 μm × 300 μm. It formed so that it might become.
Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 230 ° C. for 30 minutes (coating heating step) to produce a photo spacer on the color filter substrate. The obtained photospacer had a cylindrical shape with a diameter of 15.1 μm and an average height of 4.7 μm.
And the PVA mode liquid crystal display device was produced like Example 1 using the color filter board | substrate with which the photo spacer was produced.

The details of the photopolymerization initiator in Table 2 are as follows.
CGI-242: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) [Ciba Specialty Chemicals Co., Ltd. Made)
C-1: Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime )
C-2: Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime)
C-3: Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime )
C-4: Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime)
C-5: Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime)
Irgacure (IRG) 907: 2-methyl-1- [4- (methylthio) phenyl] -2-monoforinopropan-1-one (manufactured by Ciba Specialty Chemicals)

  As shown in Table 2, in the examples, higher sensitivity was obtained compared to the comparative example, and the liquid storage stability of the prepared coating solution for the photosensitive resin layer, and the dry film state after coating, The time-dependent stability of the photosensitive resin layer when held at was good.

Claims (7)

[A] a resin having an ethylenically unsaturated bond arranged in the side chain via an ester group between a branched and / or alicyclic structure, an acidic group, and a main chain;
[B] a polymerizable compound having an ethylenically unsaturated bond;
[C] a photopolymerization initiator selected from the group of compounds represented by the following general formula (1) or (2);
Containing a photosensitive resin composition.

[In General Formulas (1) to (2), R ¹ represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ² and R ³ are each independently selected. A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (provided that the carbon number is 7 to And a substituent when the phenyl group is substituted is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, or a halogen atom. . R ⁴ represents an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, and R ⁵ represents a hydrogen atom, An alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms is represented. n represents an integer of 0 to 5, m represents an integer of 0 to 5, l represents an integer of 0 to 6, and n and m satisfy n + m ≦ 5. ]   The branched and / or alicyclic structure is at least one selected from a dicyclopentenyl group, a cyclohexyl group, a tricyclopentenyl group, an adamantyl group, a norbornyl group, and an isobornyl group. The photosensitive resin composition as described. The said branched and / or alicyclic structure is comprised by the group represented by following General formula (3), The photosensitive resin composition of Claim 1 or Claim 2 characterized by the above-mentioned.

[Wherein, X represents a divalent organic linking group, y represents 1 or 2, and n represents an integer of 0 to 15. ] The resin is a copolymer in which a group having the branched and / or alicyclic structure is introduced by copolymerizing a monomer represented by the following general formula (4). The photosensitive resin composition according to any one of claims 1 to 3, wherein the main chain has a structural unit derived from a monomer represented by the formula:

[Wherein, X represents a divalent organic linking group, R represents a hydrogen atom or a methyl group, y represents 1 or 2, and n represents an integer of 0 to 15. ]   The spacer formed using the photosensitive resin composition of any one of Claims 1-4. A method for forming a spacer comprising at least the following steps (a) to (d).
(B) A step of forming a film of the photosensitive resin composition according to any one of claims 1 to 4 on a substrate (b) A step of exposing at least a part of the film (c) After exposure (D) a step of heating the coated film after development   A liquid crystal display device comprising the spacer according to claim 5.