JP2009258353A - Photosensitive resin composition and photo-spacer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high storage stability in a liquid state and giving a cured product excellent in compression strength and deformation recovering property after compressive deformation after the composition is cured. <P>SOLUTION: The photosensitive resin composition contains (A) a resin having a branched and/or alicyclic structure, an acidic group and an ethylenically unsaturated bond in side chains, (B) a polymerizable compound, (C) a photopolymerization initiator and (D) a hydrophilic organic solvent having a boiling point of 150°C or higher. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition and a photospacer using the same.

  Conventionally, liquid crystal display devices are widely used in display devices that display high-quality images. In general, a liquid crystal display device is provided with a liquid crystal layer capable of displaying an image with a predetermined orientation between a pair of substrates, and maintaining the spacing between the substrates, ie, the thickness of the liquid crystal layer, is an element that determines image quality. For this purpose, a spacer for keeping the thickness of the liquid crystal layer constant is provided. The thickness between the substrates is generally referred to as “cell thickness”, and the cell thickness usually indicates the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display region. Is.

  Conventionally, the spacer has been formed by bead dispersion, but in recent years, a spacer with high positional accuracy has been formed by photolithography using a photosensitive composition. A spacer formed using such a photosensitive composition is called a photospacer.

  Photo spacers prepared by patterning, alkali development, and baking using a photosensitive composition have a weak compressive strength of the spacer dots, and tend to increase plastic deformation during panel formation. For high-quality image display, it is required that there is no problem that the uniformity cannot be maintained due to the thickness of the liquid crystal layer being smaller than the design value, and that there is no problem of image unevenness. In addition, it is important that no alkali development residue of the photosensitive composition is generated in terms of increasing the accuracy of the liquid crystal display device.

  As a technique related to the above, the use of a resin having an allyl group for spacer formation is disclosed as a spacer formation technique for keeping the thickness (cell thickness) of the liquid crystal layer constant (for example, Patent Document 1). reference). Moreover, the photosensitive composition for photo spacers which was easy to manufacture and was excellent in storage stability is disclosed (for example, refer patent document 2). Furthermore, a composition excellent in cold-heat shock resistance is disclosed (see, for example, Patent Document 3).

Further, as a radiation-sensitive resin composition capable of forming a columnar spacer having high rubbing resistance, heat-resistant dimensional stability, and compressive strength, co-polymerization of unsaturated carboxylic acids, epoxy group-containing unsaturated compounds, and olefinic unsaturated compounds A radiation-sensitive resin composition for spacers containing a coalescence and a 1,2-quinonediazide compound is known (see, for example, Patent Document 4).
JP 2003-207787 A JP 2005-62620 A JP 2002-287354 A JP 2000-327875 A

  However, in the case of a composition containing an epoxy group in the composition, it is considered that a certain degree of compressive strength can be obtained after curing, but due to the activity of the epoxy group itself, stability when stored as a liquid composition is improved. May cause trouble.

  The present invention has been made in view of the above, a photosensitive resin composition having a high storage stability in a liquid state, and a cured product having excellent compression strength and deformation recovery from compression deformation after curing, and It aims at providing the photo spacer excellent in compressive strength and the deformation | transformation recovery property from a compressive deformation, and makes it a subject to achieve this objective.

Specific means for achieving the above object are as follows.
<1> (A) a resin having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in the side chain, (B) a polymerizable compound, (C) a photopolymerization initiator, D) A photosensitive resin composition containing a hydrophilic organic solvent having a boiling point of 150 ° C. or higher.

  <2> The photosensitive resin composition according to <1>, wherein the (A) resin further has an epoxy group in a side chain.

  <3> The photosensitive resin composition according to <1>, further including an (E) epoxy group-containing resin different from the (A) resin.

  <4> A photospacer formed using the photosensitive resin composition according to any one of <1> to <3>.

ADVANTAGE OF THE INVENTION According to this invention, the storage stability in a liquid state is high, and can provide the photosensitive resin composition from which the cured | curing material excellent in the compression strength and the deformation | transformation recovery property from a compression deformation is obtained after hardening.
ADVANTAGE OF THE INVENTION According to this invention, the photo spacer excellent in the compressive strength and the deformation | transformation recovery property from a compressive deformation can be provided.

  Hereinafter, the photosensitive resin composition of the present invention and the spacer using the same will be described in detail.

  The photosensitive resin composition of the present invention comprises (A) a resin having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in the side chain, (B) a polymerizable compound, and (C). It contains a photopolymerization initiator and (D) a hydrophilic organic solvent having a boiling point of 150 ° C. or higher, and is preferably composed of (E) an epoxy group-containing resin different from the (A) resin. Moreover, it can comprise using a microparticle and other components as needed.

The photosensitive resin composition of the present invention includes a resin having a branched and / or alicyclic structure and an ethylenically unsaturated bond, and is made to exist together with a hydrophilic organic solvent having a boiling point of 150 ° C. or higher. Thus, while maintaining the storage stability of the composition in a liquid state (for example, long-term storage at room temperature), a high strength (for example, compressive strength) against the external force of the pattern is obtained after curing, and deformation when compressed and deformed Recoverability can also be improved.
Thus, for example, a structure (for example, a photospacer) excellent in pressure resistance and deformation recovery when subjected to an external force can be obtained.

Hereinafter, each component which comprises the photosensitive resin composition of this invention is explained in full detail.
-(A) Resin-
The photosensitive resin composition of this invention contains at least 1 type of resin which has a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in a side chain. This resin has an acidic group and developability, and preferably has an ethylenically unsaturated bond (preferably via an ester group with respect to the main chain), thereby providing excellent polymerization reactivity. It has liquid storage stability and storage over time in a dry film, and can give controllability that allows the pattern structure to be controlled to a desired shape and film thickness (such as height). Moreover, it has a branched and / or alicyclic structure, and enhances the compression elastic modulus and deformation recovery from compression deformation (hereinafter also referred to as elastic recovery) when subjected to the external force of the formed pattern structure. Can do. Thus, it is useful for constructing a pattern structure such as a color filter spacer.

  Here, the branched and / or alicyclic structure, the acidic group, and the ethylenically unsaturated bond may be contained in different side chains, or a part thereof may be combined and contained in the same side chain. Or all of them 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 resin (A). Moreover, the branched and / or alicyclic structure may be contained in the side chain of (A) resin together with an acidic group and / or an ethylenically unsaturated bond.
In addition, the branched and / or alicyclic structure may be directly bonded to the main chain of the (A) resin to form the side chain of the (A) resin only by the branched and / or alicyclic structure. ) The side chain of the resin (A) may be constituted as a group having a branched and / or alicyclic structure bonded to the main chain of the resin via a divalent organic linking group.

  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) through at least an ester group (—COO—) is preferable from the viewpoints 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 through the bivalent coupling group containing (-COO-) may be sufficient. 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 resin (A). .

  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 represented by X 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) As a monomer for introduce | transducing an alicyclic structure into the side chain of resin, the (meth) acrylate which has a C5-C20 alicyclic hydrocarbon group is mentioned. 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 have better compressive modulus and elastic recoverability, and (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, and (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 tricyclo Nteniru is particularly preferred.

In addition, examples of the monomer (A) 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.
Especially, the compound represented by following General formula (4) is preferable at the point of an elastic recovery factor.

  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 introduce | transducing an alicyclic structure into the side chain of resin, what was manufactured suitably may be used and a commercial item 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 kind of acidic group in the side chain linked to the main chain. A plurality of acidic groups may be contained in the side chain. Moreover, the acidic group may be contained in the side chain of (A) resin with the said branched and / or alicyclic structure, and an ethylenically unsaturated bond.
The acidic group may be directly bonded to the main chain of the resin (A) to constitute the side chain of the resin (A) only with the acidic group, or (A) a divalent organic linkage to the main chain of the resin. You may combine through group and may comprise the side chain of (A) resin as a group which 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 resin (A) 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 ethylenically unsaturated bond in the side chain linked to 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 (A) resin together with the branched and / or alicyclic structure and / or the acidic group. An aspect in which the ethylenically unsaturated bond is bonded to (A) the main chain of the resin via at least one ester group (—COO—) is also preferable.

  The ethylenically unsaturated bond is bonded to (A) the main chain of the resin via at least one ester group (—COO—), and only the ethylenically unsaturated bond and the ester group are used as the (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 through an ester group between the main chain” and (A) the 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.

~~ epoxy group ~~
(A) The resin preferably contains an epoxy group in the side chain connected to the main chain. A plurality of epoxy groups may be contained in the side chain. Moreover, the epoxy group may be contained in the side chain of (A) resin with at least one selected from the branched and / or alicyclic structure, the acidic group, and the ethylenically unsaturated bond.

  The epoxy 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 epoxy group, or (A) a divalent organic linkage to the main chain of the resin. The side chain of (A) resin may be comprised as a group which couple | bonds through group and has an epoxy group.

  The epoxy group may be introduced by polymerizing a monomer for introducing the epoxy group. In this case, examples of the monomer (A) for introducing an epoxy group into the side chain of the resin (hereinafter also referred to as “epoxy group-containing monomer”) include glycidyl acrylate, glycidyl methacrylate, α -Glycidyl ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, -6,7 acrylate -Epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, etc. It is done. Among them, from the viewpoint of further increasing the compression strength after curing (for example, the spacer strength when used as a photospacer), glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl. Ether and p-vinylbenzyl glycidyl ether are preferred.

~~ Other groups ~~
In the (A) resin in the present invention, other groups may be introduced using other monomers. There is no restriction | limiting in particular as another monomer, For example, the monomer etc. which have (meth) acrylic acid ester, styrene, vinyl ether, a dibasic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group, etc. are mentioned. It is done.

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.

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

  (A) As a specific example of resin, the compound (exemplary compound P-1 to P-59) represented by the following structure is mentioned, for example. In addition, x, y, z, St, and Ep in exemplary compounds represent the composition ratio (mass ratio) of each repeating unit, and the form comprised in the preferable range mentioned later is suitable. 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>
The (A) resin can be synthesized and produced by performing a (co) polymerization reaction of monomers. Further, in addition to the (co) polymerization reaction, a step of introducing an ethylenically unsaturated group may be provided and synthesized in a two-step process.
The (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be 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 number of carbon atoms 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) Although the preferable range of the acid value of the resin varies depending on the molecular structure that can be taken, it is generally 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 resin (A) 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, a preferable example of the (A) resin is more preferably a combination of the preferable molecular weight, glass transition temperature (Tg), and acid value.

  In the present invention, the resin (A) is a copolymer having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond, each having a repeating unit (copolymerization unit) as a separate copolymer unit or more. The combination is preferable from the viewpoint of deformation recovery rate, development residue, and reticulation when a pattern structure (for example, a color filter spacer) is formed. Further, when the resin (A) has an epoxy group in the side chain, a branched and / or alicyclic structure, an acidic group, an ethylenically unsaturated bond, and an epoxy group are each represented by different repeating units (copolymerization). The copolymer may be a quaternary copolymer or more in the 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%), and ethylenically unsaturated. It is preferably a copolymer of at least terpolymer having at least a repeating unit having a bond: Z (z mol%). Further, repeating units having an epoxy group: Ep (e _p mol%) is suitable quaternary copolymerization or more copolymers having, if necessary, other repeating units: have the L (l mole%) You may do it.
Such a copolymer includes, for example, a monomer having a branched and / or alicyclic structure, a monomer having an acidic group, and ethylene (preferably arranged via an ester group between the main chain). It can be obtained by copolymerizing a monomer having a polymerizable unsaturated bond and, if necessary, a monomer having an epoxy group and / or another monomer. Among these, a monomer represented by the general formula (4) as a monomer having at least the branched and / or alicyclic structure in that the compressive strength and the deformation recovery property are improved with a bulky functional group. Is preferably a copolymer in which a group having a branched and / or alicyclic structure is introduced, and a monomer further having an epoxy group in terms of further improving the compressive strength and deformation recovery. Is preferably a copolymer in which a group having an epoxy group is introduced.
In this case, the resin (A) has a structural unit derived from the monomer represented by the general formula (4) and a structural unit derived from a monomer having an epoxy group in the main chain.

The copolymer composition ratio when the resin (A) 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 compressive strength and deformation recovery are obtained, and the developer resistance of the cured portion is also good.
(A) As for the composition ratio (y) of the repeating unit which has an acidic group in resin, 5-70 mol% is preferable, 10-65 mol% is further more preferable, and 20-60 mol% is especially preferable. 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 in the resin is preferably from 10 to 70 mol%, more preferably from 15 to 65 mol%, particularly preferably from 20 to 60 mol%. When the composition ratio (z) is within the above range, the sensitivity and curability are good, the liquid storage stability after preparation, and the stability over time when held for a long time in the dry film state after coating are good. Become.
(A) As for the composition ratio (Ep) of the repeating unit which has an epoxy group in resin, 1-35 mol% is preferable, 3-30 mol% is further more preferable, and 5-25 mol% is especially preferable. When the composition ratio (Ep) is within the above range, good compressive strength and deformation recovery can be obtained.
Further, as the (A) resin, the composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly 20 to 60 mol%), and the composition ratio (y) is 5 to 5 mol%. 70 mol% (more 10 to 65 mol%, especially 20 to 50 mol%), and the composition ratio (z) is 10 to 70 mol% (more 15 to 65 mol%, especially 20 to 60 mol%). %), And in addition to these, the composition ratio (Ep) is preferably 1 to 35 mol% (more preferably 3 to 30 mol%, particularly 5 to 25 mol%).

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.
Although (A) resin can be used together with the other resin mentioned later, the case where it consists only of said (A) resin is preferable.

~ Other resins ~
As the resin that can be used in combination with the resin (A), a compound that shows swelling property with respect to an alkaline aqueous solution is preferable, and a compound that is soluble in an alkaline aqueous solution is more preferable.
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 (A) resin and other resin are used in combination, the total content (solid content) of the resin (A) that can be used in combination with the 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 and (C) photopolymerization initiator-
The photosensitive resin composition of the present invention contains at least one polymerizable compound having an ethylenically unsaturated bond and at least one photopolymerization initiator. The polymerizable compound undergoes a polymerization reaction under the action of radicals from the photopolymerization initiator to form a cured film.

  As the polymerizable compound and the photopolymerization initiator in the present invention, components constituting a known composition can be suitably used. For example, in paragraphs [0011] to [0013] of JP-A-2006-23696 And the components described in paragraph numbers [0040] to [0053] of JP-A-2006-64921.

In the relationship with the (A) resin, the content ratio [mass ratio; (B) / (A) ratio] of the (B) polymerizable compound to the (A) resin is preferably in the range of 0.5 to 2.0. The range of 0.6 to 1.4 is more preferable, and the range of 0.7 to 1.2 is particularly preferable. When the ratio (B) / (A) is within the above range, a photospacer having good developability and mechanical strength can be obtained.
As content of the said (C) photoinitiator, the range of 0.1-20 mass% is preferable with respect to (A) resin, and the range of 0.5-10 mass% is more preferable.

-(D) Hydrophilic organic solvent having a boiling point of 150 ° C or higher-
The photosensitive resin composition of the present invention contains at least one hydrophilic organic solvent having a boiling point of 150 ° C. or higher. By containing a hydrophilic organic solvent having a relatively high boiling point, a decrease in storage stability with the lapse of time after preparing the photosensitive resin composition solution can be avoided. For example, residues in the development process after film formation and drying can be avoided. Occurrence can be prevented. When the boiling point of the hydrophilic organic solvent is less than 150 ° C., the storage stability of the photosensitive resin composition in a solution state is deteriorated.

  “Hydrophilic” here means having a polar group in the molecule and having a solubility in water of 0.5% by mass or more.

  The boiling point of the hydrophilic organic solvent is more preferably 150 to 200 ° C. from the viewpoint of storage stability of the photosensitive resin composition solution.

  Examples of hydrophilic organic solvents having a boiling point of 150 ° C. or higher include dimethylformamide (153 ° C.), dimethyl sulfoxide (189 ° C.), 3-methoxybutanol (161 ° C.), cyclohexanol (161 ° C.), diacetone alcohol (169 ° C.). ), Cyclohexanone (156 ° C), ethyl lactate (154 ° C), butyl lactate (187 ° C), diethyl malonate (199 ° C), ethylene glycol (197 ° C), ethylene glycol monoethyl ether acetate (156 ° C), diethylene glycol mono Examples thereof include ethyl ether acetate (217 ° C.), diethylene glycol monobutyl ether acetate (247 ° C.), N-methyl-2-pyrrolidone (204 ° C.), and γ-butyrolactone (203 ° C.).

  Among them, a hydrophilic organic solvent having a boiling point of 150 to 200 ° C. is preferable, and specifically, dimethylformamide (153 ° C.), dimethyl sulfoxide (189 ° C.), and ethyl lactate (154 ° C.) are preferable.

  (D) As content in the photosensitive resin composition of a hydrophilic organic solvent, 2-20 mass% is preferable with respect to all the solvent components, and 5-15 mass% is more preferable. When the content of the hydrophilic organic solvent is 2% by mass or more, the storage stability in the liquid composition is better, and when it is 20% by mass or less, it is advantageous in terms of preventing precipitation of the photosensitive resin composition component. It is.

-(E) Epoxy group-containing resin-
The photosensitive resin composition of the present invention preferably contains at least one epoxy group-containing resin. In the present invention, in addition to the resin (A) containing an epoxy group in the form added to the (A), a development residue in an uncured part is generated during development by including a resin (epoxy group-containing resin) different from the resin (A) containing an epoxy group. In addition to preventing the reduction of the thickness of the cured part and the hardened part, it also improves the compressive strength of the structure after hardening and the recovery from deformation when it is deformed. Can be secured.

  The epoxy group-containing resin is not particularly limited as long as it is an epoxy group-containing resin, and examples thereof include a resin obtained by polymerizing an epoxy group-containing monomer and a resin obtained by introducing an epoxy group into a polymer. In the present invention, for example, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (hereinafter also referred to as “compound a”) and an epoxy group-containing unsaturated compound (hereinafter also referred to as “compound b”). And a copolymer of an olefinic unsaturated compound (hereinafter also referred to as “compound c”) other than the compound a and the compound b can be suitably used.

Examples of the compound a include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid, and anhydrides of these dicarboxylic acids. Can be preferably mentioned.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of polymerization reactivity, solubility in an aqueous alkali solution, and availability.

  As a content rate in the epoxy group containing resin of the structural unit derived from the compound a, 5-40 mass% is preferable with respect to the sum total of the structural unit derived from the compound a, the compound b, and the compound c, More preferably, 10 -30 mass%. When the content of the structural unit is 5% by mass or more, the dissolution in the alkaline aqueous solution is good, and when it is 40% by mass or less, the solubility in the alkaline aqueous solution does not become too large. This structural unit is used individually by 1 type or in combination of multiple types.

Examples of the compound b include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, and 3,4-epoxybutyl acrylate. , Methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl ether M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.
Among them, from the viewpoint of further increasing the compression strength after curing (for example, the spacer strength when used as a photospacer), glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl. Ether and p-vinylbenzyl glycidyl ether are preferred, and glycidyl methacrylate is particularly preferred.

  As for the content rate in the epoxy group containing resin of the structural unit derived from the compound b, 10-70 mass% is preferable with respect to the sum total of the structural unit derived from the compound a, the compound b, and the compound c, More preferably, 20- 60% by mass. When the content ratio of the structural unit is 10% by mass or more, the compression strength and deformation recovery of the structure after curing (for example, photospacer) become better, and when it is 70% by mass or less, the epoxy group-containing resin itself. Can maintain good storage stability. This structural unit is used individually by 1 type or in combination of multiple types.

Examples of the compound c include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, and t-butyl methacrylate; acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; cyclohexyl methacrylate, Methacrylic acid cyclic compounds such as 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.02,6] decan-8-yl methacrylate (so-called dicyclopentanyl methacrylate), dicyclopentanyloxyethyl methacrylate, and isobornyl methacrylate Alkyl ester; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.02,6] decane -8-yl acrylate (so-called dicyclopentanyl acrylate), acrylic acid cyclic alkyl esters such as isobornyl acrylate; methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; and styrene, α-methylstyrene, m-methylstyrene, p-methyl Styrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic De, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.
Of these, styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, and 1,3-butadiene are preferable in view of polymerization reactivity and solubility in an alkaline developer during development. . This structural unit is used individually by 1 type or in combination of multiple types.

  As for the content rate in the epoxy group containing resin of the structural unit derived from the compound c, 10-70 mass% is preferable with respect to the sum total of the structural unit derived from the compound a, the compound b, and the compound c, More preferably, 15- 50% by mass. When the content ratio of the structural unit is 10% by mass or more, the storage stability of the epoxy group-containing resin itself is good, and when it is 70% by mass or less, the solubility of the epoxy group-containing resin itself in an aqueous alkali solution during development. Can be maintained.

  In such a copolymer, by containing a carboxyl group and / or a carboxylic acid anhydride group and an epoxy group, a good degree of curing can be imparted while the solubility in an alkaline aqueous solution during development is good. Is possible.

The polystyrene-converted weight average molecular weight (Mw) of the epoxy group-containing resin is preferably 2 × 10 ³ to 1 × 10 ⁵ , and more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . When the Mw is 2 × 10 ³ or more, the developability of the film when the film is formed, the remaining film rate, etc. are good, the pattern shape to be formed, the heat resistance, etc. are excellent, and it is 1 × 10 ⁵ or less. High sensitivity can be maintained.

  The epoxy group-containing resin can be synthesized and produced by radical polymerization of compound a, compound b and compound c in a solvent in the presence of a polymerization initiator.

  Solvents used during synthesis and production include, for example, alcohols such as methanol and ethanol; ethers such as tetrahydrofuran; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; methyl cellosolve acetate, ethyl cellosolve acetate and the like. Ethylene glycol alkyl ether acetates; diethylene glycols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether; propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether Propylene glycol monoalkyl ethers such as propylene glycol butyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate propylene glycol butyl ether acetate; propylene glycol methyl ether propionate Propylene glycol alkyl ether acetates such as propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; aromatic hydrocarbons such as toluene and xylene; methyl ethyl ketone, cyclohexanone, 4- Ketones such as droxy-4-methyl-2-pentanone; and methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, protyl 3-hydroxypropionate Butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, ethoxyacetic acid pro Pyl, butyl ethoxy acetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate Ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl Propionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, 3-propoxypropionate And esters such as ethyl acid, propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate and butyl 3-butoxypropionate It is done.

  Moreover, what is generally known as a radical polymerization initiator can be used as a polymerization initiator used at the time of a synthesis | combination and manufacture. For example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile) Azo compounds such as benzoyl peroxide, lauroyl peroxide, t-butyl peroxypivalate, organic peroxides such as 1,1′-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

When the epoxy group-containing resin is used in combination with the (A) resin, the content ratio (mass ratio; (D) / (A) ratio) of the (D) epoxy group-containing resin to the (A) resin is: The range of 1/10 to 1/1 is preferable, the range of 1/5 to 4/5 is more preferable, and the range of 1/5 to 3/5 is particularly preferable. When the ratio (D) / (A) is 1/10 or more, it is possible to prevent the development residue of the uncured part during development and the reduction of the film thickness of the cured part. The structure (for example, photospacer) with high deformation | transformation recovery property when obtained is obtained, and the storage stability in the liquid state of the photosensitive resin composition can be ensured as it is 1/1 or less.
Epoxy group-containing resins can be used singly or in combination.

As a preferable aspect of the photosensitive resin composition of this invention, the aspect shown to following (1)-(5) is suitable.
(1) The resin (A) is a resin containing at least one structural unit derived from the compound represented by the general formula (4) or the general formula (5), and (D) a hydrophilic organic solvent Is a hydrophilic organic solvent having a boiling point of 150 to 200 ° C.
(2) The resin (A) is a resin containing at least one structural unit derived from the compound represented by the general formula (4), and (D) the hydrophilic organic solvent is dimethylformamide (153 ° C.) , Dimethyl sulfoxide (189 ° C.), and ethyl lactate (154 ° C.).
(3) The resin (A) is at least one of structural units derived from the compound represented by the general formula (4) or the general formula (5) and at least one of structural units derived from the epoxy group-containing monomer. (D) The aspect whose hydrophilic organic solvent is a hydrophilic organic solvent with a boiling point of 150-200 degreeC.
(4) The resin (A) is a resin containing at least one structural unit derived from the compound represented by the general formula (4) or the general formula (5), and (D) a hydrophilic organic solvent Is a hydrophilic organic solvent having a boiling point of 150 to 200 ° C., and includes (E) an epoxy group-containing resin, and the epoxy group-containing resin is an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (compound a) An embodiment wherein the epoxy group-containing unsaturated compound (compound b) is a copolymer of an olefinic unsaturated compound (compound c) other than the compound a and the compound b.
(5) In the above (4), the compound a is acrylic acid, methacrylic acid, and maleic anhydride, and the compound b is glycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether. M-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, wherein the compound c is styrene, t-butyl methacrylate, dicyclopentanyl methacrylate, p-methoxystyrene, 2-methylcyclohexyl acrylate, 1,3- An embodiment that is butadiene.

-(F) Fine particles-
In addition to the above components, the photosensitive resin composition of the present invention preferably contains fine particles in terms of mechanical strength. 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.

  The average particle size of the fine particles is preferably from 5 to 50 nm, more preferably from 10 to 40 nm, in view of obtaining high mechanical strength when forming a structure that is susceptible to external force such as a spacer. Particularly preferably, it is ˜30 nm.

  The content of the fine particle photosensitive resin composition (when forming a structure such as a spacer in the structure (or a layer formed of the photosensitive resin composition constituting the structure) having a high mechanical strength (For example, from the viewpoint of obtaining a spacer), the total solid content (mass) in the photosensitive resin composition is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and 15 It is especially preferable that it is -30 mass%.

-(G) Other ingredients-
The photosensitive resin composition in the present invention further contains other components such as a photopolymerization initiation aid, if necessary, in addition to the above components (A) to (E) and, if necessary, (F) fine particles. You may go out.

  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.

  The other components can be selected from components constituting a known composition and used, for example, paragraph numbers [0014] to [0020] of JP-A-2006-23696 and JP-A-2006-64921. Ingredients listed in paragraphs [0027] to [0039] of the gazette.

  The photosensitive resin composition of the present invention can be used for the production of any cured product, but is suitable for the production of structures in which strength when subjected to external force and recoverability after deformation are positioned as important physical properties. For example, it is useful for producing a pattern structure such as a photo spacer for a color filter which is one of constituent members such as a liquid crystal display device.

  The photo spacer is formed on, for example, a desired substrate, preferably a color filter substrate provided with a colored pattern (for example, colored pixels) such as R (red), G (green), and B (blue). Thus, a substrate with a spacer that constitutes a liquid crystal display element or the like can be obtained.

  The photospacer of the present invention is formed using the above-described photosensitive resin composition of the present invention, and is excellent in compressive strength and deformation recovery when subjected to compression deformation. For this reason, for example, by applying the photo spacer to a display device (for example, a liquid crystal display device) in which display unevenness is likely to occur due to cell gap variation, cell gap variation can be suppressed, and display unevenness is effective. Can be prevented. The photospacer of the present invention includes at least two substrates, a liquid crystal compound provided between the substrates, two electrodes for applying an electric field to the liquid crystal compound, and a cell thickness between the substrates. It can be suitably used as the photospacer in a liquid crystal display device provided with a photospacer.

  As a method for producing a photospacer, for example, a photosensitive film is formed on one of two substrates using the above-described photosensitive resin composition of the present invention (hereinafter referred to as “film formation step”). In other words, at least a part of the formed film is exposed (hereinafter also referred to as “exposure process”), and the exposed film is developed (hereinafter referred to as “development process”). ) Can be formed. Further, after the development step, if necessary, other steps such as heating and curing the developed film (hereinafter sometimes referred to as “film heating step”) can be provided.

(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 film, and this photosensitive resin layer constitutes a photospacer that can maintain a uniform cell thickness by passing through other steps such as an exposure step and a development step described later. By using the photospacer 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 a change in cell thickness is effectively eliminated.

  As a method for forming a photosensitive resin layer on a substrate, (a) a coating method for applying the photosensitive resin composition of the present invention described above, and (b) a photosensitive resin composition of the present invention described above. Preferable examples include a transfer method in which a photosensitive transfer material having a formed photosensitive resin layer is used, and the photosensitive resin layer is laminated and transferred by heating and / or pressing.

(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 photospacer 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 photospacer having high strength, good compression modulus and good elastic recovery can be obtained.

  As described above, a substrate for a liquid crystal display device including a photospacer on the substrate can be manufactured. The photo 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, a driving element such as a TFT, and a photo spacer.

For example, when the photo spacer is provided on the black light shielding portion or the driving element, the black light shielding portion (black matrix or the like) or the driving element previously disposed on the substrate is covered with, for example, a photosensitive transfer material. A photosensitive resin layer is laminated on the support surface, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment, and the like to form a photo spacer, thereby forming a liquid crystal display device substrate. Can be produced.
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 photospacer of the present invention can be formed after forming a color filter including a black shielding portion such as a black matrix and a colored portion such as a colored pixel.
The black shielding part and the colored part and the photo 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. It is possible.
The black shielding part, the colored part, and the photospacer can each be formed from a photosensitive composition. Specifically, for example, the photosensitive resin layer is formed by directly applying the liquid photosensitive resin composition to a substrate. Then, exposure and development are performed to form the black shielding part and the colored part in a pattern, and then the photosensitive resin composition of another liquid is placed on another substrate (temporary support) different from the substrate. A transfer material prepared by forming a photosensitive resin layer on the substrate, and transferring the photosensitive resin layer by bringing the transfer material into close contact with the substrate on which the black shielding portion and the colored portion are formed. By performing exposure and development, the photo spacer can be formed in a pattern.
In this manner, a color filter provided with a photospacer can be manufactured.

As a preferable form of the photospacer of the present invention, for example, a form provided on a substrate for a liquid crystal display device can be mentioned.
Here, as the substrate for the liquid crystal display device, a substrate provided with a display light-shielding portion (for example, a black matrix) or a drive element (for example, TFT) can be used. In this case, the photospacer is preferably formed on a display light-shielding portion such as a black matrix formed on the substrate or on a driving element such as a TFT. The substrate for the liquid crystal display device further includes colored pixels (red (R), blue (B), green (G), etc.), transparent electrodes (transparent conductive layers such as ITO), liquid crystal alignment films (polyimide, etc.), etc. May be provided.

  When the photo spacer is provided on the display light-shielding portion or the driving element, the display light-shielding portion (black matrix or the like) or the driving element previously disposed on the substrate is covered, for example, the photosensitive resin of the present invention. Using a photosensitive transfer film having a photosensitive resin layer using the composition, laminating the photosensitive resin layer on the substrate surface, and then peeling and transferring the photosensitive resin layer to transfer the photosensitive resin. By subjecting the layer to exposure, development, heat treatment, and the like to form a photo spacer, a substrate for a liquid crystal display device can be manufactured.

  A liquid crystal display element can be comprised using the board | substrate for liquid crystal display devices. 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 photo spacer having high compressive strength and deformation recovery property, a liquid crystal display element including the color filter substrate has a cell gap unevenness (between the color filter substrate and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

  Further, for example, at least one of them is provided with at least a liquid crystal layer and a liquid crystal driving means between a pair of light transmissive supports (including a substrate for a liquid crystal display device), and the liquid crystal driving means includes an active element (eg, TFT). And a pair of substrates is configured to be regulated to a predetermined width by a photo spacer having high compressive strength and high deformation recovery. 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.

A liquid crystal display device can be formed by providing the liquid crystal display device substrate or the liquid crystal display element.
As described above, the liquid crystal display device regulates a predetermined width between a pair of substrates facing each other so as to face each other with the photo spacer of the present invention, and encloses a liquid crystal material in the regulated gap (the enclosed portion is liquid crystal). 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). The counter substrate is arranged to be opposed to each other with a photo spacer interposed therebetween, and a liquid crystal material is sealed in the gap, and (b) the driving substrate and the counter substrate having the counter electrode (conductive layer) are arranged as a photo spacer. The liquid crystal display device of the present invention can be suitably applied to various types of 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 photospacer, etc., except that the photo spacer, the liquid crystal display substrate, and the liquid crystal display element described above 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)
As described below, among the resins (A), the exemplified compounds P-57 to P-59 described above were synthesized to obtain resin solutions. In addition, the weight average molecular weight Mw of each resin was measured using the gel permeation chromatograph (GPC).

-Synthesis Example 1
In a reaction vessel, 75 parts of 1-methoxy-2-propyl acetate (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance and the temperature was raised to 90 ° C., and 10 parts of styrene, 45 parts of isopropyl methacrylate, 45 parts of methacrylic acid. , 8 parts of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 75 parts of 1-methoxy-2-propyl acetate were heated to 90 ° C. in a nitrogen gas atmosphere. The reaction vessel was dropped into the reaction vessel over 2 hours. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.

  Next, 0.22 part of hydroquinone monomethyl ether and 0.74 part of tetoethylammonium bromide were added to the obtained acrylic resin solution, and then 30 parts of glycidyl methacrylate was added dropwise over 2 hours. After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a solvent is added so that the solid content concentration is 45% by mass, whereby the resin solution of the exemplified compound P-57 having an ethylenically unsaturated group ( Mw; 12,000, 45 mass% solution of 1-methoxy-2-propyl acetate).

-Synthesis Example 2-
In a reaction vessel, 75 parts of 1-methoxy-2-propyl acetate (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance and the temperature was raised to 90 ° C., and 10 parts of styrene, 50 parts of dicyclopentanyl methacrylate, A mixed solution obtained by mixing 40 parts of an acid, 8 parts of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 75 parts of 1-methoxy-2-propyl acetate was added at 90 ° C. under a nitrogen gas atmosphere. The mixture was added dropwise into the reaction vessel heated to 2 hours over 2 hours. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.

  Next, 0.22 part of hydroquinone monomethyl ether and 0.74 part of tetoethylammonium bromide were added to the obtained acrylic resin solution, and then 30 parts of glycidyl methacrylate was added dropwise over 2 hours. After dripping, after reacting at 90 ° C. for 4 hours while blowing air, a solvent is added so that the solid concentration is 45% by mass, whereby the resin solution of the exemplified compound P-58 having an ethylenically unsaturated group ( Mw; 13,000, 45% by mass solution of 1-methoxy-2-propyl acetate).

-Synthesis Example 3-
In a reaction vessel, 75 parts of 1-methoxy-2-propylacetate (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance, and the temperature was raised to 90 ° C., and 10 parts of styrene, 40 parts of dicyclopentanyl methacrylate, A mixed solution comprising 40 parts of acid, 10 parts of glycidyl methacrylate, 8 parts of an azo polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601) and 75 parts of 1-methoxy-2-propyl acetate was placed under a nitrogen gas atmosphere. The solution was dropped into a reaction vessel at 0 ° C. over 2 hours. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Next, 0.22 part of hydroquinone monomethyl ether and 0.74 part of tetoethylammonium bromide were added to the obtained acrylic resin solution, and then 30 parts of glycidyl methacrylate was added dropwise over 2 hours. After dropping, after reacting at 90 ° C. for 4 hours while blowing air, by adding a solvent so that the solid content concentration is 45% by mass, the above exemplary compounds having an ethylenically unsaturated group and an epoxy group in the side chain A resin solution of P-59 (Mw; 13,000, 45% by mass solution of 1-methoxy-2-propyl acetate) was obtained.

-Synthesis Example 4-
In a reaction vessel, 75 parts of 1-methoxy-2-propyl acetate (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance, and the temperature was raised to 90 ° C., and 25 parts of styrene, 25 parts of methacrylic acid, 50 glycidyl methacrylate were added. Part of the mixture, 8 parts of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 75 parts of 1-methoxy-2-propyl acetate were heated to 90 ° C. in a nitrogen gas atmosphere. It was dripped in the warmed reaction container over 2 hours. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.
Next, a resin solution of compound Q-1 having an epoxy group in the side chain (Mw; 11,000, 45 of 1-methoxy-2-propyl acetate) so that the amount of the solvent is adjusted to a solid content concentration of 45% by mass. Mass% solution) was obtained.

(Example 1)
-Preparation of photosensitive resin composition-
200 parts of resin solution of Exemplified Compound P-57 obtained in Synthesis Example 1 above and DPHA liquid (mixture of 76 parts of dipentaerythritol hexaacrylate and 24 parts of 1-methoxy-2-propyl acetate; (B) polymerization 72 parts, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369, manufactured by Ciba Specialty Specialty Chemicals); (C) photopolymerization started Agent) 22.5 parts is mixed, and after further adding propylene glycol monomethyl ether acetate so that the solid content concentration becomes 30% by mass, dimethylformamide ((D) a hydrophilic organic solvent having a boiling point of 150 ° C. or higher) 30 parts was added and filtered through a Millipore filter having a pore size of 0.2 μm to prepare a photosensitive resin composition (R-1).

-Formation of spacer pattern-
A glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-like nozzle on the ITO film of the glass substrate on which the ITO film is formed by sputtering, the photosensitive resin composition (R -1) was applied. Subsequently, a 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, and then pre-baked at 120 ° C. for 3 minutes to obtain a thickness of 4.0 μm. A photosensitive resin layer was formed (film formation step).

Next, 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 photosensitive resin layer is set to 150 μm in a state where the glass substrate placed on the substrate is set substantially parallel and vertically, and the photosensitive resin layer is proxied through the mask at an exposure amount of 300 mJ / cm ² . Mitty exposure (exposure process). Next, after developing for 1 minute at 25 ° C. with a 0.5% by weight aqueous solution of potassium hydroxide (development process), it was rinsed with pure water for 1 minute. Thus, the unexposed part of the photosensitive resin layer was removed, and the spacer pattern was formed on the glass substrate. Next, the glass substrate provided with the spacer pattern was subjected to heat treatment at 220 ° C. for 60 minutes (coating heating step) to produce a photospacer.
When the diameter of the obtained photo spacer was measured with an optical microscope (Olympus Corporation) and the height of the photo spacer was measured with a surface profiler P-10 (manufactured by TENCOR), the diameter was 26 μm and the average height was 3.6 μm. there were.

-Evaluation-
(1. Breaking load)
A 50 μmφ frustum indenter was applied to the photospacer produced above with a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation), and a load was applied at a constant speed (3.3 mN / sec. ), A load (breaking load) when the photospacer was cracked or broken was measured, and was evaluated according to the following evaluation criteria as an index for evaluating the strength of the photospacer. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH. The value of the breaking load indicates that the larger the numerical value, the higher the strength of the photo spacer.
<Evaluation criteria>
5: The breaking load was 200 mN or more.
4: The breaking load was 190 mN or more and less than 200 mN.
3: The breaking load was 180 mN or more and less than 190 mN.
2: The breaking load was 170 mN or more and less than 180 mN.
1: The breaking load was 160 mN or more and less than 170 mN.
0: The breaking load was less than 160 mN.

(2. Deformation recovery rate)
For the photo spacer prepared above, a micro-hardness meter (DUH-W201, manufactured by Shimadzu Corporation) adopted a frustum-type indenter with a diameter of 50 μm, and the load was removed at a maximum load of 100 mN and a holding time of 5 seconds. The load test method was conducted. The deformation recovery rate [%] was obtained from the obtained measured value 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. The deformation recovery rate indicates that the larger the numerical value, the better the shape recovery.
Deformation recovery rate (%) =
(Recovery amount after weight release [μm] / deformation amount by weight [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%.

(3. Storage stability of photosensitive resin composition)
After the photosensitive resin composition (R-1) prepared above is stored in two environments of 5 ° C. and 30 ° C. for 30 days, a film forming process, an exposure process, a developing process, and a film heating process are performed as described above. In addition to confirming the size of the photospacer produced by performing (change in size from the photospacer produced before storage), the presence or absence of residues around the photospacer by SEM observation is confirmed visually. Storage stability was evaluated. The residue was evaluated according to the following evaluation criteria.
<Evaluation criteria>
5: No residue was seen at all.
4: Although some residue was observed around the pattern, it was in a practically acceptable range.
3: Residue was observed around the pattern.
2: Residues were observed on the periphery of the pattern and on the substrate in the vicinity of the pattern.
1: Residue was confirmed in several places on the substrate.

(Example 2)
In Example 1, except that the resin solution of Exemplified Compound P-57 was replaced with the resin solution of Exemplified Compound P-58 ((A) resin) obtained in Synthesis Example 2, the same procedure as in Example 1 was performed. A photosensitive resin composition (R-2) was prepared, and a photospacer was prepared and evaluated. The evaluation results are shown in Table 1 below.

(Example 3)
In Example 1, the resin solution of Exemplified Compound P-57 was replaced with the resin solution of Exemplified Compound P-59 ((A) resin) obtained in Synthesis Example 3, and the same procedure as in Example 1 was performed. A photosensitive resin composition (R-3) was prepared to produce a photospacer and evaluated. The evaluation results are shown in Table 1 below.

Example 4
In Example 1, except that 200 parts of the resin solution of Exemplified Compound P-57 was replaced with 150 parts of the resin solution of Exemplified Compound P-57 and 50 parts of the resin solution of Resin Q-1 obtained in Synthesis Example 4 above. In the same manner as in Example 1, a photosensitive resin composition (R-4) was prepared, and a photospacer was produced and evaluated. The evaluation results are shown in Table 1 below.

(Example 5)
In Example 4, except that dimethylformamide was replaced with dimethyl sulfoxide ((D) a hydrophilic organic solvent having a boiling point of 150 ° C. or higher), the photosensitive resin composition (R-5) was prepared in the same manner as in Example 1. It was prepared and a photo spacer was produced and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 1)
In Example 1, the photosensitive resin composition (R-6) was prepared in the same manner as in Example 1 except that dimethylformamide ((D) a hydrophilic organic solvent having a boiling point of 150 ° C. or higher) was not added. It was prepared and a photo spacer was produced and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 2)
In Example 4, except that dimethylformamide ((D) a hydrophilic organic solvent having a boiling point of 150 ° C. or higher) was not added, a photosensitive resin composition (R-7) was prepared in the same manner as in Example 4. It was prepared and a photo spacer was produced and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 3)
In the same manner as in Example 1 except that dimethylformamide was replaced with 1-ethoxy-2-propanol (boiling point 133 ° C. (boiling point <150 ° C.)) in Example 1, the photosensitive resin composition (R-8) ), A photospacer was prepared and evaluated. The evaluation results are shown in Table 1 below.

(Comparative Example 4)
In Example 1, a photosensitive resin composition (in the same manner as in Example 1 except that the resin solution of Exemplified Compound P-57 was replaced with the resin solution of Compound Q-1 obtained in Synthesis Example 4 above. R-9) was prepared to produce a photospacer and evaluated. The evaluation results are shown in Table 1 below.

As shown in Table 1, in the examples, a spacer excellent in strength and compression characteristics could be formed, and the prepared photosensitive resin composition was excellent in storage stability. On the other hand, in the comparative example, both strength and compression characteristics were inferior, and the storage stability of the photosensitive resin composition was extremely poor.

Claims (4)

  (A) a resin having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in the side chain, (B) a polymerizable compound, (C) a photopolymerization initiator, and (D) a boiling point A photosensitive resin composition comprising a hydrophilic organic solvent at 150 ° C. or higher.   The photosensitive resin composition according to claim 1, wherein the (A) resin further has an epoxy group in a side chain.   Furthermore, (E) epoxy group containing resin different from said (A) resin is included, The photosensitive resin composition of Claim 1 characterized by the above-mentioned. The photospacer formed using the photosensitive resin composition of any one of Claims 1-3.