KR20090072995A - Photosensitive resin composition, photo spacer and method of forming the same, protective layer, colored pattern, substrate for a display, and display device - Google Patents

Abstract

A photoresist resin composition, and a method for forming a photo-spacer by using the composition are provided to improve the storage stability in liquid state and to enhance aging stability. A photoresist resin composition comprises a resin having a branched and/or alicyclic structure, an acidic group and a substituted alkyl group at the side chain (wherein the substituted alkyl group has two ethylenically unsaturated bonds); a polymerizable compound having an ethylenically unsaturated bond; and a photopolymerization initiator. Preferably the substituted alkyl group is represented by the formula 1.

Description

PHOTOSENSITIVE RESIN COMPOSITION, PHOTO SPACER AND METHOD OF FORMING THE SAME, PROTECTIVE LAYER, COLORED PATTERN, SUBSTRATE FOR A DISPLAY, AND DISPLAY DEVICE}

The present invention relates to a photosensitive resin composition, a photo spacer, a method for forming the same, a protective film, a coloring pattern, a substrate for a display device, and a display device.

In recent years, the mother glass substrate has been enlarged due to the large area of the liquid crystal display device and the improvement of productivity. In the conventional board | substrate size (about 680x880 mm), since a board | substrate size is smaller than a mask size, it was able to respond by the batch exposure system. By the way, the demand for large substrates (for example, about 1,500 × 1,800 mm) is increasing with the increase of the size of the apparatus. However, it is almost impossible to prepare a mask size that is about the same as the substrate size. Response is difficult.

Therefore, the step exposure method is proposed as the exposure method for large substrates.

By the way, in a step exposure system, since it exposes several times in one board | substrate, and performs alignment every time, the time required for step movement arises. For this reason, in the step exposure method, the reduction in throughput is concerned compared with the batch exposure method. Further, in the batch exposure method, an exposure sensitivity capable of patterning at about 3,000 J / m 2 is allowed, but in the step exposure method, an exposure sensitivity in which good patterning is performed at 1,500 J / m 2 or less is required. However, with the existing materials, it is difficult to obtain a good spacer shape and film thickness at an exposure amount of 1,500 J / m 2 or less.

In addition, the required values regarding the shape of the spacer and the controllability of the film thickness have become increasingly strict in recent years, so that the shape due to the variation of the process when forming the spacer, the variation in the film thickness, and the shape according to the change over time of the composition solution In terms of the stability of the film thickness, there is room for improvement. In particular, in the exposure amount area of 1,500 J / m <2> or less, there exists a subject in the controllability of the shape of a spacer with respect to an exposure amount, and a film thickness.

In addition, in recent years, photosensitive resin compositions used in the manufacture of liquid crystal display panels suffer from serious problems such as foreign matters due to crystallization of components in the composition during storage and use, and contaminate the device. There is a need for a photosensitive resin composition that can reduce problems.

 Regarding the photosensitive resin composition, various studies have been made in the prior art, and for example, a molecular structure in which a structural unit having an aliphatic cyclic hydrocarbon group, a structural unit having an acidic functional group, and a structural unit having a radical polymerizable group are linked to each other. The photosensitive resin composition containing curable resin which consists of an aliphatic cyclic hydrocarbon group containing copolymer which has the following is disclosed (for example, refer Unexamined-Japanese-Patent No. 2002-296775). Moreover, curable resin which consists of an aliphatic cyclic hydrocarbon group containing copolymer of the molecular structure which the structural unit which has the aliphatic cyclic hydrocarbon group of a specific structure, the structural unit which has an acidic functional group, and the structural unit which has a radical polymerizable group connected is disclosed (for example, See, for example, Japanese Patent Laid-Open No. 2002-293837).

The present invention provides a photosensitive resin composition, a photo spacer, a method of forming the same, a protective film, a coloring pattern, a substrate for a display device, and a display device. A first embodiment of the present invention is a resin having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the [A] side chain, wherein the substituted alkyl group has two ethylenically unsaturated bonds, and [B] ] Forming a patterned structure or a protective film containing a polymerizable compound having an ethylenically unsaturated bond and a [C] photopolymerization initiator, having high sensitivity, excellent storage stability in a liquid state, and excellent aging stability of the photosensitive film after film formation. It provides a photosensitive resin composition that can be. 2nd Embodiment of this invention is a process of forming a film on the board | substrate using the photosensitive resin composition of the said 1st embodiment, the process of exposing at least one part of the said film, and the process of developing the said film after exposure. And a step of heating the film after development. 3rd Embodiment of this invention provides the photo spacer, protective film, or coloring pattern formed using the photosensitive resin composition of the said 1st Embodiment. A fourth embodiment of the present invention provides a display device substrate provided with at least one of the photo spacer, the protective film, or the coloring pattern of the third embodiment, and a display device provided with the same.

By the way, when forming a pattern structure (for example, a photo spacer, a coloring pattern, etc .. or the same below) or a protective film on a board | substrate using the said conventional photosensitive resin composition, a sensitivity and polymerization reactivity to necessarily obtain a favorable shape etc. are necessarily It was not obtained, but it was also insufficient in terms of liquid retention and time-lapse stability of the photosensitive film after film formation.

This invention reflects the above, and makes it a subject to achieve the following objectives.

That is, an object of the present invention is to provide a photosensitive resin composition capable of forming a pattern structure or a protective film having high sensitivity, excellent storage stability in a liquid state, and excellent seizure stability and mechanical properties of the photosensitive film after film formation. .

Moreover, an object of this invention is to provide the photo spacer which was excellent in height uniformity and uniform cross-sectional shape, and its manufacturing method also when it is formed in low sensitivity.

Moreover, an object of this invention is to provide the protective film or coloring pattern excellent in the film thickness uniformity and uniform cross-sectional shape also when it is formed in low sensitivity.

Moreover, an object of this invention is to provide the board | substrate for display apparatuses which can suppress a display stain when used for a display apparatus, and the display apparatus in which display stain was suppressed.

<1> A resin having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in a side chain of [A], wherein the substituted alkyl group has two ethylenically unsaturated bonds, and a [B] ethylenically unsaturated bond. It contains a polymeric compound which has and a photoinitiator [C], The photosensitive resin composition characterized by the above-mentioned.

<2> The said photosensitive resin composition as described in <1> whose said substituted alkyl group is group represented by following General formula (1).

(In General Formula (1), * represents a side bonded to the main chain of the resin, and A1 represents a disubstituted alkyl group having 1 to 9 carbon atoms. B1 and B2 each independently represent a single bond and a urethane bond (main chain side: -O-CO-NHR-) and an ester bond (backbone side: -CO-O-), R represents an alkyl group having 1 to 3. In addition, X1 and X2 each independently represent an ester bond (backbone side: -O-CO-) R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group.)

<3> The photosensitive resin composition according to <1> or <2>, wherein the substituent of the substituted alkyl group is a (meth) acryloyloxy group.

<4> The photosensitive resin composition according to any one of <1> to <3>, wherein the group having the branched and / or alicyclic structure has a group represented by the following General Formula (3).

In General formula (3), X represents a divalent organic coupling group and may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents the integer of 0-15.

<5> The resin according to any one of <1> to <4>, wherein the substituted alkyl group has two ethylenically unsaturated resins having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain [A]. The weight average molecular weight of resin which has a bond is the range of 12,000-60,000, It is a photosensitive resin composition characterized by the above-mentioned.

<6> The resin according to any one of <1> to <5>, wherein the substituted alkyl group has two ethylenically unsaturated resins having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain [A]. The glass transition temperature (Tg) of resin which has a bond is 40-180 degreeC, The photosensitive resin composition characterized by the above-mentioned.

<7> The resin according to any one of <1> to <6>, wherein the substituted alkyl group has two ethylenically unsaturated resins having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain [A]. The acid value of resin which has a bond is 20 mgKOH / g or more, The photosensitive resin composition characterized by the above-mentioned.

<8> The mass ratio ([B] / [A] ratio) with respect to said [A] resin of the said [B] polymeric compound in any one of said <1>-<7> is 0.5-2.0 It is a photosensitive resin composition characterized by the above-mentioned.

<9> The photosensitive resin composition according to any one of <1> to <8>, further comprising an extender pigment having an average particle diameter of 5 to 50 nm.

<10> It is formed using the photosensitive resin composition in any one of said <1>-<9>, It is a photo spacer characterized by the above-mentioned.

<11> It is the formation method of the photo spacer characterized by including at least the following process (A)-(C).

(A) Process of forming the film of photosensitive resin composition in any one of said <1>-<9> on a board | substrate

(B) exposing at least a portion of the coating;

(C) Process of developing the said film after exposure

(D) heating the film after development

<12> It is a protective film formed using the photosensitive resin composition in any one of said <1>-<9>.

<13> It is a coloring pattern formed using the photosensitive resin composition in any one of said <1>-<9>.

<14> It is the board | substrate for display apparatuses provided with the photo spacer as described in said <11>, the protective film as described in said <12>, and the coloring pattern as described in said <13>.

<15> It is a display apparatus characterized by including the board | substrate for display apparatuses as described in said <14>.

Hereinafter, the photosensitive resin composition of this invention is demonstrated in detail, and also the photo spacer using the said photosensitive resin composition, its formation method, a protective film, a coloring pattern, the board | substrate for display apparatuses, and a display apparatus are also demonstrated.

<< photosensitive resin composition >>

The photosensitive resin composition of this invention is resin which has a branched and / or alicyclic structure, an acidic group, and a substituted alkylester group in the [A] side chain, The resin in which the said substituted alkyl group has two ethylenically unsaturated bonds (following only "(A] resin"), a polymerizable compound having an [B] ethylenically unsaturated bond, and a [C] photopolymerization initiator.

Generally, when a photosensitive resin composition is used to form a pattern structure (for example, a photo spacer, a coloring pattern, etc. or the same) or a protective film on a substrate, polymerization alone is insufficient only by exposure. In addition, the storage stability in the liquid state and the aging stability of the photosensitive film after film formation were not necessarily sufficient.

In addition, in order to ensure the temporal stability of the photosensitive film after the film formation, when the high temperature heat treatment is performed after exposure and development, the pattern structure or protective film to be formed may deteriorate, and the pattern structure or protective film already formed on the substrate deteriorates. In some cases, For example, when forming a photospacer on the color filter substrate which has a coloring pattern, the photo spacer to be formed may deteriorate, and the coloring pattern already formed on the board | substrate may deteriorate.

Therefore, by making the photosensitive resin composition into the structure of the said invention, the photosensitive resin composition of this invention has high sensitivity, it is hard to raise a viscosity, the polymerization curability at the time of exposure improves, and it is excellent in the storage property in a liquid state. Moreover, it becomes possible to form a pattern structure and a protective film which are excellent in the time stability of the photosensitive film after film-forming.

Hereinafter, [A] resin, the polymeric compound which has [B] ethylenically unsaturated bond, [C] photoinitiator, and other components are demonstrated.

<[A] resin>

The resin (A) has a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain, and the substituted alkyl group has two ethylenically unsaturated bonds (substituted).

The above-mentioned [A] resin has an acidic group, has developability, and has a substituted alkyl group having two ethylenically unsaturated bonds. Since the resin (A) has high sensitivity, the resin (A) has high polymerization reactivity, and has excellent liquid retention and dry film. Because of its retention over time, the controllability of controlling the pattern structure to a desired shape and film thickness (height, etc.) can be provided.

Moreover, since it has a branch and / or an alicyclic structure, the compressive elastic modulus at the time of receiving the external force of the formed pattern structure, and elastic recovery from compression deformation can be improved. This is useful for forming a pattern structure such as a photo spacer for a display device, for example.

Here, the branched and / or alicyclic structure, the acidic group, and the substituted alkyl group having two ethylenically unsaturated bonds may be contained in different side chains, some may be included in the same side chain in combination, and all are the same side chains. It may be included in.

In addition, in this specification, a (meth) acryloyl group represents an acryloyl group or a methacryloyl group, (meth) acrylate represents an acrylate or a methacrylate, and (meth) acryl represents an acryl or methacryl (Meth) acrylamide represents acrylamide or methacrylamide, and (meth) acrylanilide represents acrylanilide or methacrylanilide.

(Branch and / or alicyclic structure)

The resin (A) includes at least one branched and / or alicyclic structure in the side chain which is bonded to the main chain of the resin. A plurality of branch and / or alicyclic structures may be included in the side chain of the resin [A]. The branched and / or alicyclic structure may be contained together with a substituted alkyl group having an acidic group and / or two ethylenically unsaturated bonds in the side chain of the resin [A].

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 with only the branched and / or alicyclic structure, and a divalent organic linking group in the main chain of the [A] resin. The side chains of the resin [A] may be formed as a group having a branched and / or alicyclic structure by bonding through a group.

As the divalent organic linking group, one or a combination selected from alkylene group, arylene group, ester group, amide group, and ether group is preferable. As said alkylene group, it is preferable that it is an alkylene group of 1-20 total carbons, More preferably, 1-10 are preferable. Specifically, methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecyl, etc. are mentioned, These may have a branched / cyclic structure and a functional group, More preferably, Methylene group, ethylene group and octylene group are preferable. As said arylene group, it is preferable that it is an arylene group of 6-20 carbon atoms, More preferably, 6-12 are preferable. Specifically, a phenylene group, a biphenylene group, a naphthalene group, an anthracene group, etc. are mentioned, These may have a branch and a functional group, More preferably, a phenylene group and a biphenylene group are preferable.

It is preferable that a branch and / or an alicyclic structure are the form couple | bonded with the main chain of [A] resin through at least an ester group (main chain side -COO-) from a viewpoint of developability and elastic recovery rate. 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] via only the ester group (main chain side -COO-), and the branched and / or alicyclic structure is formed of the ester group ( It may be in the form which is couple | bonded with the main chain of [A] resin via the bivalent coupling group containing main chain side -COO-). That is, other atoms or other linking groups may be contained between the branched and / or alicyclic structure and the ester chain, and / or between the ester chain and the main chain of the [A] resin.

Examples of the branched structure include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl group, t-octyl group, etc. are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group, etc. are more preferable, and i-propyl group, s-butyl group, t-butyl group, etc. are especially preferable.

Examples of the alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, and examples thereof include cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, Tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopentanyl group, and the like, and groups having them are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobonyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group, etc. are more preferable, and a dicyclopentenyl group and a cyclo Hexyl group, norbornyl group, isobonyl group, tricyclopentenyl group, etc. are more preferable, and a dicyclopentenyl group and a tricyclopentenyl group are especially preferable.

Moreover, as a group which has a branch and / or an alicyclic structure, the aspect comprised holding the group represented by following General formula (3) is preferable.

In General formula (3), X represents a divalent organic coupling group and may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents the integer of 0-15.

As said divalent organic linking group, one or a combination chosen from an alkylene group, an arylene group, ester group, an amide group, and ester group is preferable, and these may have a substituent.

As said alkylene group, it is preferable that it is a C1-C20 alkylene group, More preferably, it is an alkylene group which is 1-10. Specifically, groups, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, and octadecyl, are mentioned, These may have a branched / cyclic structure and a functional group, More preferably, , Methylene group, ethylene group and octylene group.

The arylene group is preferably an arylene group having 6 to 20 carbon atoms in total, and more preferably an arylene group having 6 to 12 carbon atoms. Specifically, a phenylene group, a biphenylene group, a naphthalene group, an anthracene group, etc. are mentioned, These may have a branch and a functional group, More preferably, they are a phenylene group and a biphenylene group.

As a substituent in the case of substitution, an alkyl group, a hydroxyl group, an amino group, a halogen group, an aromatic ring group, the group which has alicyclic structure, etc. are mentioned.

In the synthesis of the resin (A), styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like are used as monomers for introducing branched and / or alicyclic structures into side chains. Enumerated, it is preferable that they are (meth) acrylates, vinyl esters, (meth) acrylamides, and it is more preferable that they are (meth) acrylates.

In the synthesis of the resin (A), specific monomers for introducing the branched structure into the side chain include (meth) acrylic acid i-propyl, (meth) acrylic acid i-butyl, (meth) acrylic acid s-butyl and (meth) acrylic acid t -Butyl, (meth) acrylic acid i-amyl, (meth) acrylic acid t-amyl, (meth) acrylic acid sec-iso-amyl, (meth) acrylic acid 2-octyl, (meth) acrylic acid 3-octyl, (meth) acrylic acid t -Octyl etc. are mentioned, Especially, it is preferable that they are i-propyl (meth) acrylic acid, i-butyl (meth) acrylate, t-butyl methacrylate, etc., i-propyl methacrylate, t-butyl methacrylate, etc. Etc. are more preferable.

In the synthesis of the resin (A), examples of the monomer for introducing an alicyclic structure into the side chain include (meth) acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. As specific examples, (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, (meth) acrylic acid 3,5-dimethyl-1-adamantyl, (meth) acrylic acid 3-ethyladamantyl, (meth) acrylic acid 3-methyl-5-ethyl-1-adamantyl , (Meth) acrylic acid 3,5,8-triethyl-1-adamantyl, (meth) acrylic acid 3,5-dimetal-8-ethyl-1-adamantyl, (meth) acrylic acid 2-methyl-2 -Adamantyl, (meth) acrylic acid 2-ethyl-2-adamantyl, (meth) acrylic acid 3-hydroxy-1-adamantyl, (meth) acrylic acid octahydro-4,7-mentanoindene-5 -Yl, (meth) acrylic acid octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylic acid 1-mentyl, (meth) acrylic acid tricyclodecyl, (meth) acrylic acid 3-hydroxy-2, 6,6-trimethyl-bicyclo [3.1.1] heptyl, (meth) acrylic acid 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl, (meth) acrylic acid (nor) bonyl, ( Isobornyl acrylate, pentyl (meth) acrylate, 2,2,5-trimethylcyclohexyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclophene (meth) acrylate Tenyl and the like.

Among these (meth) acrylic acid esters, the compressive modulus and elastic recovery properties of the bulky functional group become good, and cyclohexyl (meth) acrylate, (meth) acrylic acid (nor) bonyl, (meth) acrylic acid isobornyl, (Meth) acrylic acid 1-adamantyl, (meth) acrylic acid 2-adamantyl, (meth) acrylic acid pentyl, (meth) acrylic acid 1-mentyl, (meth) acrylic acid tricyclodecyl, (meth) acrylic acid dicyclopentenyl , (Meth) acrylic acid tricyclopentenyl, etc. are preferable, and (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) yl, (meth) acrylic acid isobornyl, (meth) acrylic acid 2-adamantyl, (meth) Dicyclopentenyl acrylate and tricyclopentenyl (meth) acrylate are particularly preferred.

In addition, in the synthesis | combination of [A] resin, the compound represented by following General formula (4) or (5) is mentioned as a monomer for introduce | transducing alicyclic structure in a side chain. 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), it is preferable that y = 1 or 2 and n = 0-8, More preferably, y = 1 or 2, n = 0-4 (more preferably n =) 0-2). As a preferable specific example of a compound represented by general formula (4) or (5), following general formula D-1-D-11 and T-1-T-12 are mentioned.

Especially, the compound represented by following General formula (4) is preferable at the point of the elastic recovery rate by the reactivity of a double bond site | part.

In the general formulas (4) to (5), the divalent organic linking group represented by X may be unsubstituted or may have a substituent, and is the same as the divalent organic linking group represented by X in the general formula (3). The preferred form is also the same.

In the synthesis | combination of (A) resin, as a monomer for introduce | transducing an alicyclic structure into a side chain, what was suitably manufactured may be used, and a commercial item may be used.

As said commercial item, Hitachi Chemical Co., Ltd. Products: FA-511A, FA-512A (S), FA512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A, H-TCPD-M, TOE-A, TOE-M , H-TOE-A, H-TOE-M and the like. Among these, FA-512A (S) and 512M are preferable at the point which is excellent in developability and excellent in strain recovery rate.

~~ acid group ~~

Resin (A) contains 1 or more types of acidic groups in the side chain connected to a main chain. Two or more acidic groups may be contained in the side chain. The acidic group may be contained together with a substituted alkyl group having two ethylenically unsaturated bonds arranged through the ester group between the branched and / or alicyclic structure and the main chain in the side chain of the resin [A]. .

The acidic group may be directly bonded to the main chain of the resin [A] to form a side chain of [A] using only the acidic group, and may be bonded to the main chain of the resin [A] via a divalent organic linking group to have an acidic group. You may comprise the side chain of [A] resin as a group. Here, about the bivalent organic linking group, the divalent organic linking group illustrated by description in the said branch and / or alicyclic structure is mentioned, A preferable range is also the same.

There is no restriction | limiting in particular as said acidic group, It can select from a well-known thing suitably, For example, a carboxy group, a sulfonic acid group, a sulfonamide group, a phosphoric acid group, a phenolic hydroxyl group, etc. are mentioned. Among these, it is preferable that they are a carboxyl group and a phenolic hydroxyl group from the point which is excellent in developability and the water resistance of a cured film.

As a specific example of the monomer for introduce | transducing the said acidic group into resin [A], it can select from a well-known thing suitably, For example, (meth) acrylic acid, vinylbenzoic acid, maleic acid, the monoalkyl ester of maleic acid, fumaric acid, itaconic acid, Crotonic acid, cinnamic acid, sorbic acid, (alpha)-cyanocinnamic acid, an acrylic acid dimer, addition reaction of the monomer which has a hydroxyl group, and cyclic acid anhydride, (omega)-carboxylic acid- polycaprolactone mono (meth) acrylate, etc. are mentioned. These may use what was manufactured suitably, and may use a commercial item.

As a monomer which has a hydroxyl group used for the addition reaction of the monomer which has the said hydroxyl group, and cyclic acid anhydride, 2-hydroxyethyl (meth) acrylate etc. are mentioned, for example. As said cyclic acid anhydride, maleic anhydride, a phthalic anhydride, a cyclohexanedicarboxylic acid anhydride, etc. are mentioned, for example.

As a commercial item of a monomer, TOAGOSEI CO., LTD. Products: ARONICS M-5300, ARONICS M-5400, ARONICS M-5500, ARONICS M-5600, Shin-nakamura Chemical Corporation Products: NK ester CB-1, NK ester CBX-1, KYOEISHA CHEMICAL Co., Ltd. Products: HOA-MP, HOA-MS, OSAKA ORGANIC CHEMICAL INDUSTRY LTD. Product: BISCOAT # 2100, etc. are listed. Among these, (meth) acrylic acid is preferable at the point which is excellent in developability and low price.

(Substituted alkyl group having two ethylenically unsaturated bonds)

Resin (A) contains 1 or more types of substituted alkyl groups (henceforth only "substituted alkyl groups") which have two ethylenically unsaturated bonds in the side chain connected to a principal chain. Two or more said substituted alkyl groups may be contained in the side chain of [A] resin.

In addition, the substituted alkyl group is a form contained in the structural unit different from the said branch and / or alicyclic structure and acidic group in the side chain of [A] resin.

In addition, the substituted alkyl group may be directly bonded to the main chain of the [A] resin to form a side chain of the [A] resin with only the substituted alkyl group, and bonded to the main chain of the [A] resin via a divalent organic linking group, As a group which has a substituted alkyl group, the side chain of resin [A] may be comprised, and you may further have the said divalent organic coupling group between the ester group and main chain which have a substituted alkyl group.

As said bivalent organic coupling group, it is the same as the bivalent organic coupling group described in the item of group which has a branch and / or an alicyclic structure, and its preferable example is also the same.

Among the above, the substituted alkyl group is at least an ester group (main chain side -COO-) from the viewpoints of controllability such as developability due to high sensitivity and high polymerization reactivity, film thickness of pattern structure, synthetic raw material supplying ability, synthetic aptitude, and the like. It is preferable that it is a form couple | bonded with the main chain of [A] resin by the medium. This form is not limited to the form in which the substituted alkyl group is bonded to the main chain of the resin [A] via only the ester group (main chain side -COO-), and the substituted alkyl group contains the ester group (main chain side -COO-). The form which is couple | bonded with the side chain of [A] resin via a bivalent coupling group may be sufficient.

That is, other atoms or other linking groups (alkylene groups of 1 to 9) are included between the substituted alkyl group and the ester group (-COO-) and / or between the substituted alkyl group and the main chain of the resin [A]. You may be.

Although it does not specifically limit as said substituted alkyl group (that is, substituted alkyl group which has two ethylenically unsaturated bonds), From the viewpoint of the high sensitivity of the photosensitive resin composition and the characteristic of a film | membrane (curability, synthetic aptitude etc.) by high polymerization reactivity, the following general The group represented by Formula (1) is preferable.

In General formula (1), * represents the side couple | bonded with the principal chain of resin, and A1 represents the C1-C9 alkyl group substituted by the 2 substituent which has an ethylenically unsaturated bond. In addition, A 1 bonds with the main chain via the ester group (main side chain -CO-O-).

In general formula (1), as said alkyl group, a C1-C9 alkyl group may be sufficient, and a straight chain structure, a branched structure, an alicyclic structure, etc. are mentioned.

As a linear structure, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc. are mentioned, It is preferable that it is C1-C9, and it is more preferable that it is C1-C6.

As a branched structure, the branched structure etc. which were described in the item of the said branch and / or alicyclic structure are mentioned, It is preferable that it is C3-C8, and it is more preferable that it is C3-C5.

As alicyclic structure, the alicyclic structure etc. which were described in the branch of the said branch and / or alicyclic structure are mentioned, It is preferable that it is C5-C20, and it is more preferable that it is C5-C15.

In General formula (1), B1 and B2 respectively independently represent a single bond, a urethane bond (main chain side: -O-CO-NHR-), and an ester bond (main chain side: -O-CO-), and R is An alkyl group having 1 to 3 carbon atoms is shown.

As B1, it is preferable that it is a single bond and a urethane bond (main chain side: -O-CO-NHR-), and it is more preferable that it is a single bond.

As B2, it is preferable that it is a single bond and a urethane bond (main chain side: -O-CO-NHR-), and it is more preferable that it is a single bond.

B1 and B2 may be the same or may have a different structure.

In General formula (1), X <1> and X <2> respectively independently represent (the main chain side) -O-CO-.

In general formula (1), R <_1> and R <_2> represents a hydrogen atom or a methyl group each independently, Preferably it is a methyl group. It may be the same as R ₁ and R ₂ , or may have a different structure.

In the synthesis | combination of (A) resin, the method of introduce | transducing a (meth) acryloyl group into a side chain can be suitably selected from a well-known method, For example, (1) (meth) which has an acidic group and has an epoxy group in a repeating unit A method of adding an acrylate, (2) A method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxy group, (3) A method of adding a (meth) acrylate having a hydroxyl group to a repeating unit having an isocyanate group And the like can be enumerated.

Especially, the method of adding the (meth) acrylate which has an epoxy group to the repeating unit which has an acidic group is the most easy in manufacture, and it is preferable at the point of low cost.

In the synthesis | combination of (A) resin, as a method of introduce | transducing two (meth) acryloyl groups into a side chain, the (meth) acrylate which has an epoxy group is added to the repeating unit which has the said (1) acidic group, for example. Then, a method of esterifying a hydroxy group with (meth) acrylic acid chloride or the like, and then obtaining a hydroxy group with an isocyanate containing a (meth) acrylate group (e.g., KARENZ MOI, MOIEG, AOI manufactured by SHOWA DENKO KK, etc.) It can synthesize | combine combining well-known methods, such as the method of obtaining by making it.

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

However, in said structural formula (1), R <^1> represents a hydrogen atom or a methyl group. L ¹ has the same meaning as B1 and B2 in General Formula (1).

However, in said structural formula (2), R <^2> represents a hydrogen atom or a methyl group. L <^2> is synonymous with B1 and B2 of General formula (1). W represents a 4-7 membered aliphatic hydrocarbon group, is synonymous with A1 of the said General formula (1), and its preferable example is also the same.

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

~~ Other monomers ...

In this invention, another group may be introduce | transduced into [A] resin using another monomer.

There is no restriction | limiting in particular as said other monomer, For example, the monomer etc. which have a (meth) acrylic acid ester, styrene, a vinyl ether, a dibasic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group, etc. can be mentioned.

There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. can be mentioned.

There is no restriction | limiting in particular as said dibasic acid anhydride group, For example, maleic anhydride group, itaconic anhydride group, etc. are mentioned.

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, butadiene group, an isoprene group, etc. are mentioned.

In the said [A] resin, as content rate of another monomer, it is preferable that it is 1-40 mass%, and it is more preferable that it is 2-30 mass%.

Specific examples of the resin (A) include, but are not limited to, the compounds represented by the following structures (example compounds PD-1 to PD-56 and PU-1 to PU-56).

In addition, x, y, and z (and St) in an exemplary compound show the composition ratio (mass ratio) of each repeating unit, and the aspect comprised in the preferable range mentioned later is suitable. Moreover, the aspect comprised also in the preferable range mentioned later also suitable for the weight average molecular weight of each exemplary compound.

Synthesis

Resin (A) can be synthesize | combined from the two-stage process or the three-stage process of the process of the (co) polymerization reaction of a monomer, and the process of introducing two ethylenically unsaturated groups.

First, the (co) polymerization reaction is made by the (co) polymerization reaction of various monomers, and there is no particular limitation, and it can be appropriately selected from known ones. For example, for the active species of polymerization, radical polymerization, cation polymerization, anion polymerization, coordination polymerization, or the like can be appropriately selected. Among these, synthesis | combination is easy and since it is low cost, it is preferable that it is radical polymerization. Moreover, there is no restriction | limiting in particular also about a polymerization method, It can select from a well-known thing suitably. For example, a bulk polymerization method, suspension polymerization method, emulsion polymerization method, solution polymerization method, etc. can be selected suitably. Among these, it is more preferable that it is a solution polymerization method.

<Carbon number>

The total carbon number of the resin (A) is preferably 10 or more from the point of elastic modulus (hardness). Especially, it is more preferable that total carbon number is 10-30, Especially preferably, it is 10-15.

<Molecular weight>

As molecular weight of (A) resin, 10,000-100,000 are preferable at a weight average molecular weight, 12,000-60,000 are more preferable, 15,000-45,000 are especially preferable. If a weight average molecular weight is in the said range, it is preferable at the point of the manufacturing suitability and developability of resin (preferably a copolymer). Moreover, it is preferable at the point which the shape formed by the fall of melt viscosity is hard to collapse, the point which becomes difficult to become a bridge | crosslinking defect, and the point which has no spacer-shaped residue in image development.

The weight average molecular weight is measured by gel permeation chromatography (GPC). About GPC, it shows in detail in the item of the Example described later.

<Glass transition temperature>

It is preferable that it is 40-180 degreeC, as for the glass transition temperature (Tg) of (A) resin, it is more preferable that it is 45-140 degreeC, and it is especially preferable that it is 50-130 degreeC. If glass transition temperature (Tg) exists in the said preferable range, the spacer which has favorable developability and mechanical strength will be obtained.

<Acid value>

Although the preferable range of the acid value of resin (A) changes with the molecular structure which can be taken, it is generally preferable that it is 20 mgKOH / g or more, It is more preferable that it is 40 mgKOH / g or more, It is especially preferable that it is 50-130 mgKOH / g. Do. If an acid value is in the said preferable range, the spacer which has favorable developability and mechanical strength can be obtained.

Since the said (A) resin can obtain the spacer which has favorable developability and mechanical strength, it is preferable that glass transition temperature (Tg) is 40-180 degreeC, and the weight average molecular weight is 10,000-100,000, and Tg It is preferable that it is 45-140 degreeC (more 50-130 degreeC), and a weight average molecular weight is 12,000-60,000 (more 15,000-45,000).

Moreover, as for the preferable example of said [A] resin, it is more preferable to combine the said preferable molecular weight, glass transition temperature (Tg), and an acid value, respectively.

In the present invention, the resin [A] is a repeating alkyl group containing a branched and / or alicyclic structure, two ethylenically unsaturated bonds disposed between an acidic group and an ester group via an ester group, respectively, respectively. It is preferable that it is a copolymer of ternary copolymer or more which has a unit (copolymerization unit) from a viewpoint of the strain recovery rate, image development residue, and reticulation in the case of forming a pattern structure (for example, the spacer for color filters).

Specifically, the resin [A] is an ester between a repeating unit having a branched and / or alicyclic structure: X (x mol%), a repeating unit having an acidic group: Y (y mol%), and a main chain. Repeating unit having a substituted alkyl group containing two ethylenically unsaturated bonds disposed via a group: It is preferable that the copolymer is a terpolymer or higher copolymer having at least Z (z mol%). As needed, you may have another repeating unit: L (l mol%).

Such a copolymer is, for example, a substituted alkyl group containing two ethylenically unsaturated bonds disposed via an ester group between a monomer having a branched and / or alicyclic structure, a monomer having an acidic group, and a main chain. It can obtain by copolymerizing the monomer which has and the other monomer as needed. Among these, the monomer having the branched and / or alicyclic structure is copolymerized with a monomer represented by the general formula (4) at least in terms of good compressive modulus and elastic recovery with a bulky functional group. Preferred is a copolymer in which a group having an alicyclic structure is introduced. In this case, [A] resin has a structural unit derived from the monomer represented by the said General formula (4) in a principal chain.

About the copolymerization composition ratio when the said [A] resin is a copolymer, it is determined in consideration of glass transition temperature and an acid value. Although it cannot speak uniformly, it can be set as the following range.

In the resin (A), the composition ratio (x) of the repeating unit having a branched and / or alicyclic structure is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, more preferably 20 to 60 mol% Is particularly preferred. If the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image portion is also good.

In the resin (A), the composition ratio (y) of the repeating unit having an acid group is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, particularly preferably 20 to 50 mol%. If the composition ratio y is within the above range, good curability and developability can be obtained.

[A] It is preferable that the composition ratio (z) of the repeating unit which has "the substituted alkyl group containing two ethylenically unsaturated bonds arrange | positioned via the ester group between main chains" in resin is 10-70 mol%, It is more preferable that it is 20-70 mol%, and it is especially preferable that it is 30-70 mol%. If the composition ratio (z) is within the above range, it is excellent in pigment dispersibility, good sensitivity and polymerization curability, good liquid preservation after the crude liquid, and aging stability when retained for a long time in the dry film state after application.

In addition, as resin [A], the composition ratio (x) is 10 to 70 mol% (more preferably 15 to 65 mol%, particularly 20 to 50 mol%), and the composition ratio (y) is 5 to 70 mol% (more 10-60 mol%, especially 30-70 mol%), and the composition ratio z is preferable when it is 10-70 mol% (more 20-70 mol%, especially 30-70 mol%).

As content in the photosensitive resin composition of said [A] resin, it is preferable that it is 5-70 mass% with respect to the total solid of a composition, and it is more preferable that it is 10-50 mass%.

Although resin (A) can be used together with other resin mentioned later, it is preferable that it consists of only said [A] resin.

... other resin ...

As resin which can be used together with said [A] resin, the compound which shows swelling property with respect to alkaline aqueous solution is preferable, and the compound which is soluble with respect to alkaline aqueous solution is more preferable.

As resin which shows swelling property or solubility with respect to alkaline aqueous solution, what has an acidic group is mentioned, for example, Specifically, The compound (epoxy acrylate compound) which introduce | transduced ethylenically unsaturated double bond and acidic group into an epoxy compound, A mixture of a vinyl copolymer having an (meth) acryloyl group and an acid group in the side chain, an epoxy acrylate compound, a vinyl copolymer having a (meth) acryloyl group and an acid group in the side chain, a maleamic acid copolymer, and the like desirable.

There is no restriction | limiting in particular as said acidic group, According to the objective, it can select suitably, For example, a carboxy group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, Among these, a carboxyl group is preferably enumerated from a viewpoint of the availability of a raw material, etc. do.

When using together said [A] resin and other resin, as content (solid content) of the sum total with resin which can be used together with [A] resin, it is 5-70 mass% with respect to the total solid of the photosensitive resin layer. It is preferable and it is more preferable that it is 10-50 mass%. If this content is 5 mass% or more, the film strength of the photosensitive resin layer can be maintained, the adhesiveness of the surface of the said photosensitive resin layer can be kept favorable, and if it is 70 mass% or less, exposure sensitivity will become favorable.

[B] Polymerizable Compound

The photosensitive resin composition of this invention contains 1 or more types of polymeric compounds which have an ethylenically unsaturated bond. The reaction is effected by the action of radicals from a photopolymerization initiator described later to form a cured film.

As said polymeric compound, it can select from the polymeric compound which comprises a well-known composition, and can use, For example, Paragraph No. 0010 of Unexamined-Japanese-Patent No. 2006-23696, The component of Paragraph No. [0027]-[0053] of Unexamined-Japanese-Patent No. 2006-64921 can be enumerated.

In the relationship with said [A] resin, it is preferable that mass ratio ([B] / [A] ratio) with respect to [A] resin of a [B] polymeric compound is 0.5-2.0, and it is 0.6-1.4 More preferably, it is especially preferable that it is 0.7-1.2. If the ratio [B] / [A] is in the above range, a spacer having good developability and mechanical strength is obtained.

[C] photopolymerization initiator

The photosensitive resin composition of this invention contains 1 or more types of photoinitiators.

There is no limitation in particular as a photoinitiator in this invention, A well-known photoinitiator can be used. As known photoinitiators, for example, paragraphs [0010] to [0020] of JP 2006-23696 A and paragraphs [0027] to [0053] of JP 2006-64921 A The initiators described may be enumerated. Examples of known photopolymerization initiators include aminoacetophenone compounds, acylphosphine oxide compounds, oxime ester compounds, and hexaarylbiimidazole compounds / aromatic mercapto compounds / agents other than those described above in terms of sensitivity. It is preferred to contain a mixed initiator.

Specific examples of the aminoacetophenone-based compound include IRGACURE (Irg) 907 (manufactured by Ciba Specialty Chemicals). Specific examples of the acylphosphine oxide compound include DAROCUR TPO, Irgacure (Irg) 819 (above, Ciba Specialty Chemicals), and the like. Moreover, IGRACURE (Irg) OXE01, CGI242, etc. (above, Ciba Specialty Chemicals product) are mentioned as a specific example of an oxime ester type compound. As a mixed initiator combining hexaarylbiimidazole compound / aromatic mercapto compound / adjuvant, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (B- CIM, Hodogaya Chemical Co., LTD.) / 2-mercaptobenzoimidazole / 4,4-diethylaminobenzophenone.

Below, the structure of these initiators is shown.

It is preferable that it is 0.5-25 mass% with respect to the total solid of the photosensitive resin composition, and, as for the total amount in the photosensitive resin composition of a photoinitiator, it is more preferable that it is 1-20 mass%.

This photoinitiator is hard to sublimate under the heating at the time of pattern formation, can suppress the contamination of a baking furnace, a photomask, etc. Moreover, by using together with the said resin A, the progress of a polymerization reaction becomes favorable and a shape and a film thickness are carried out. Controllability can be further improved. Thereby, favorable sensitivity and adhesiveness can be obtained also in the low exposure amount area | region of 1500 J / m <2> or less, for example. For example, when forming a spacer for color filters, the adhesiveness with a board | substrate is favorable and the spacer formed in the desired shape can be obtained.

In addition, the photoinitiator as used in this invention means the component which generate | occur | produces the active species which can start superposition | polymerization of the said specific polymeric compound by exposure by visible rays, an ultraviolet-ray, an ultraviolet-ray, a charged particle beam, X-rays, etc. .

<Particulates>

In this invention, it is preferable that the photosensitive resin composition contains 1 or more types of microparticles | fine-particles from a point of mechanical strength with resin, a polymeric compound, and a photoinitiator.

There is no restriction | limiting in particular as microparticles | fine-particles, Although it can select suitably according to the objective, For example, the extender pigment of Unexamined-Japanese-Patent No. 2003-302639-[0041] is preferable, and the developability which is especially good, Colloidal silica is preferable in that a photo spacer having a mechanical strength can be obtained.

It is preferable that it is 5-50 nm, and, as for the average particle diameter of the said microparticles | fine-particles, when a photo spacer etc. form a structure which is easy to receive external force, it is more preferable that it is 10-40 nm. It is especially preferable that it is 15-30 nm.

As content in the photosensitive resin composition (the photo spacer (or the photosensitive resin layer which comprises this when forming a photo spacer) of the said microparticles | fine-particles), the total solid in the photosensitive resin composition from a viewpoint of obtaining the photo spacer which has high mechanical strength. It is preferable that it is 5-50 mass% with respect to (mass), It is more preferable that it is 10-40 mass%, It is especially preferable that it is 15-30 mass%.

<Others>

In this invention, the photosensitive resin composition may further contain other components, such as a photoinitiation start adjuvant, as needed in addition to resin, a specific polymeric compound, a photoinitiator, and the microparticles | fine-particles contained as needed.

The photosensitive resin composition may use together a photoinitiation adjuvant as another additive component. A photopolymerization start adjuvant can be used in combination with a photopolymerization start adjuvant in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a photoinitiation start adjuvant. As a photoinitiator, it is preferable to use 1 or more types of amine compounds.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate and 2-dimethylamino benzoate. Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively Michler's ketone), 4,4'-bis (diethylamino) Benzophenone, 4,4'-bis (ethylmethylamino) benzophenone, etc. are mentioned, Especially, 4,4'-bis (diethylamino) benzophenone is preferable. Moreover, you may use combining a amine type and other photoinitiator adjuvant.

As other photopolymerization start adjuvant other than the above, an alkoxy anthracene type compound, a thioxanthone type compound, a coumarin type compound etc. are mentioned, for example. As said alkoxy anthracene type compound, 9,10- dimethoxy anthracene, 2-ethyl-9,10- dimethoxy anthracene, 9,10- diethoxy anthracene, 2-ethyl-9, 10- diethoxy anthracene, for example And the like. As said thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro, for example 4-propoxy thioxanthone, etc. are mentioned.

Moreover, what is marketed can also be used as a photoinitiator starting adjuvant. Examples of commercially available photopolymerization initiation aids include trade names "EAB-F" (manufactured by Hodogaya Chemical Co., LTD.).

As content in the photosensitive resin composition of a photoinitiator, it is preferable that they are 0.6 mass part or more and 20 mass parts or less with respect to 1 mass part of said photoinitiators, It is more preferable that they are 1 mass part or more and 15 mass parts or less, Especially 1.5 mass parts It is preferable that it is more than 15 mass parts.

In addition, as other components, it can select and use from the component which comprises a well-known composition, For example, Paragraph No. 2006-23696 of Unexamined-Japanese-Patent No. 2006-23696, and Unexamined-Japanese-Patent No. 2006 The components described in paragraphs [0027] to [0053] of JP-A-64921 can be enumerated.

The photosensitive resin composition of this invention can be used suitably for formation of the photo spacer mentioned later, a coloring pattern, and a protective film, and other pattern structures and coatings, such as a partition (for example, a black matrix) and an orientation control process, etc. It can also be used preferably for formation.

《Photo Spacer and Formation Method》

The photo spacer of this invention is formed using the photosensitive resin composition of this invention mentioned above. The detail and preferable aspect of a photosensitive resin composition are as above-mentioned.

Since the photo spacer of this invention is comprised using the photosensitive resin composition of this invention, it has a uniform cross-sectional shape also in low exposure, and height imbalance is suppressed.

Moreover, the photosensitive resin composition of this invention can obtain the photo spacer which has the high compressive modulus and strain recovery property which are required as a photo spacer.

In the present invention, as a state in which a pattern structure such as a photo spacer has a "uniform cross-sectional shape", the cross-sectional shape of the pattern structure becomes a shape close to a rectangle in a plurality of places (preferably three or more places) in the substrate. Presence is preferable.

As the shape close to the rectangle, a cut surface when the pattern structure is cut in a plane parallel to the substrate normal direction and in a plane parallel to the edge (in the case of a columnar structure, the edge tangent) viewed from the substrate normal direction. WHEREIN: The shape which the angle (henceforth "taper angle" hereafter) which the line | wire corresponded to the pattern structure side surface and the line | surface corresponded to the pattern structure lower surface is 80 degrees or more and 100 degrees or less is more preferable.

Here, the lower surface of the pattern structure means a contact surface with a lower surface on which the pattern structure is formed among the surfaces of the pattern structure. In addition, the pattern structure side surface means a surface which does not correspond to the pattern structure upper surface (surface parallel with the pattern structure lower surface and the surface which does not contact the lower surface) also in the lower surface of the pattern structure among the surface of the pattern structure.

As long as the photo spacer of this invention is a method using the photosensitive resin composition of this invention, although it may be formed by what method, the method including the process (a)-(c) shown below (method of forming the photo spacer of this invention) It can form most preferably by using.

The method of forming the photo spacer of the present invention includes (a) forming a film of the photosensitive resin composition of the present invention on a substrate (hereinafter also referred to as a "film forming step"), and (b) of the film (C) a process of exposing at least a portion (hereinafter also referred to as an "exposure process") and (c) a process of developing the film after exposure (hereinafter also referred to as a "development process"). Therefore, (d) The process of heating the said film after image development (henceforth a "film heating process"), and another process may be provided and comprised.

(A) Film forming process

A film formation process forms the film of the photosensitive resin composition of this invention mentioned above on a board | substrate. A photosensitive resin layer can be formed as a film, and this photosensitive resin layer comprises the spacer obtained by maintaining cell thickness uniformly through other processes, such as an exposure process and image development process mentioned later. By using the spacer of the present invention, display stains in an image in a display device (especially a liquid crystal display device) in which display stains are particularly likely to occur due to variations in cell thickness are effectively eliminated.

As a method of forming a photosensitive resin layer on a board | substrate, (a) the coating method which apply | coats the photosensitive resin composition containing at least [A] resin, a [B] polymeric compound, and a [C] photoinitiator, and ( b) The transfer method of laminating and transferring a photosensitive resin layer by heating and / or pressurization using the photosensitive transfer material which has the said photosensitive resin layer can be mentioned preferably.

(a) Application method

Application of the photosensitive composition is a known coating method, for example, spin coating method, curtain coating method, slit coating method, dip coating method, air knife coating method, roll coating method, wire bar coating method, gravure coating method, or The extrusion coating method using the hopper described in US 2681294 specification, etc. can be performed. Among them, Japanese Patent Laid-Open No. 2004-89851, Japanese Patent Laid-Open No. 2004-17043, Japanese Patent Laid-Open No. 2003-170098, Japanese Patent Laid-Open No. 2003-164787, Japanese Patent Laid-Open No. 2003-10767 The method by the slit nozzle or the slit coater described in Unexamined-Japanese-Patent No. 2002-79163, 2001-310147, etc. is suitable.

(b) transfer method

The transfer is carried out by bonding a photosensitive resin layer formed in a film form on a support using a photosensitive transfer material to a desired substrate surface, for example, by pressing or hot pressing using a roller or a plate that has been heated and / or pressed. The photosensitive resin layer is transferred onto the substrate by peeling off.

Specifically, the laminator and lamination methods described in Japanese Patent Application Laid-Open No. 7-110575, Japanese Patent Laid-Open No. 11-77942, Japanese Patent Laid-Open No. 2000-334836 and Japanese Patent Laid-Open No. 2002-148794 It may be enumerated, and in view of low foreign matter, it is preferable to use the method described in JP-A-7-110575.

In the case of forming the photosensitive resin layer, an oxygen barrier layer (hereinafter also referred to as an "oxygen barrier film" or an "intermediate layer") can be further disposed between the photosensitive resin layer and the branch support. Thereby, exposure sensitivity can be raised. Moreover, in order to improve the transferability, you may arrange | position the thermoplastic resin layer which has cushion characteristics.

For the branch members constituting the photosensitive transfer material, the oxygen barrier layer, the thermoplastic resin layer, other layers, and the manufacturing method of the photosensitive transfer material, paragraphs [0024] to [0030] of [0024] The configuration and production method described in the above can be applied.

When forming a photosensitive resin layer together with (a) application | coating method and (b) transfer method, it is preferable that it is 0.5-10.0 micrometers, and, as for the layer thickness, it is more preferable that it is 1-6 micrometers. If the layer thickness is in the above range, generation of pinholes during coating formation at the time of manufacture is prevented, and development removal of the unexposed portion can be performed without requiring a long time.

As a board | substrate which forms a photosensitive resin layer, it is a board | substrate with a transparent substrate (for example, a glass substrate or a plastic substrate), a board | substrate with a transparent conductive film (for example, ITO membrane), and a color filter (also called a color filter substrate). And a driving substrate with a driving element (for example, a thin film transistor "TFT"). As thickness of a board | substrate, it is generally preferable that it is 700-1200 micrometers.

(B) Exposure process and (c) Development process

In the exposure step, at least a part of the film formed in the film forming step is exposed to form a latent image. In the subsequent development step, the film exposed in the exposure step can be developed to form a spacer pattern of a desired shape.

As a specific example of these processes, Paragraph No. [0071]-[0077] of Unexamined-Japanese-Patent No. 2006-64921, Paragraph No. [0040]-[0051] of Unexamined-Japanese-Patent No. 2006-23696 The process described in the above may be listed as a suitable example in the present invention.

(D) Film heating process

In the film heating step, the film after development in the developing step is heated. By heating, hardening of a film is accelerated | stimulated more, the spacer which has high strength, and is excellent in compressive modulus and elastic recovery property is obtained.

As described above, a display device substrate having a photo spacer on the substrate can be produced. 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. In addition, an alignment film such as a transparent conductive layer (transparent substrate) such as ITO, polyimide, or the like may exist between the black light shielding portion such as the black matrix, the driving element such as the TFT, and the photo spacer.

For example, when the photo spacer is disposed on the black light blocking portion or the driving element, the photosensitive transfer material is covered so as to cover the black light blocking portion (black matrix or the like) or the driving element previously disposed on the substrate. The photosensitive resin layer is laminated on the support surface, peeled and transferred to form the photosensitive resin layer, and then subjected to exposure, development, heat treatment, and the like to form a photospacer, thereby producing a substrate for display device.

In the display device substrate of the present invention, colored pixels such as red (R), blue (B), and green (G) three colors may be further disposed as necessary.

The photo spacer of this invention can be formed after forming the color filter containing black shielding parts, such as a black matrix, and coloring parts, such as a color pixel.

The said black shield part, a coloring part, and a photo spacer can be formed combining arbitrarily the coating method which apply | coats the photosensitive resin composition, and the transfer method using the transfer material which has the photosensitive resin layer which consists of the photosensitive resin composition.

The black shielding part, the coloring part, and the photospacer can be formed from the photosensitive resin composition, and specifically, for example, the photosensitive resin layer is formed by directly applying the liquid photosensitive resin composition to a substrate. Subsequently, exposure and development are carried out, and the black shielding portion and the coloring portion are formed in a pattern form, and then, the photosensitive resin composition of a separate liquid is provided on a substrate (support member) different from the substrate and is photosensitive. Using the transfer material produced by forming the resin layer, the transfer material is brought into close contact with the substrate on which the black shielding portion and the coloring portion are formed to transfer the photosensitive resin layer, and then the photo spacers are exposed and developed. It can be formed in a pattern shape.

In this way, a color filter provided with a photo spacer can be produced.

Shield

The protective film of this invention is formed using the photosensitive resin composition of this invention mentioned above.

Since the protective film of this invention is comprised using the photosensitive resin composition of this invention, it is excellent in film thickness uniformity also when it is formed in low exposure.

The protective film of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention, but can be formed by the same method as the method for forming the photo spacer of the present invention described above. Here, in the case where the protective film is not patterned, that is, when the protective film is formed of a so-called beta film, a method of exposing the entire surface of the coating in the (b) exposure step is preferable.

<< coloring pattern >>

The coloring pattern of this invention is formed using the photosensitive resin composition of this invention mentioned above. Here, the form in which the photosensitive resin composition further contains 1 or more types of coloring agents in addition to each component mentioned above is preferable.

There is no restriction | limiting in particular as said coloring agent, It can select from a well-known coloring agent suitably, and can use. As a known coloring agent, the pigment and dye of Unexamined-Japanese-Patent No. 2005-17716 [0038]-[0054], and the Unexamined-Japanese-Patent No. 2004-361447-[0072] are specifically, described. The pigment, the coloring agent of Unexamined-Japanese-Patent No. 2005-17521, etc. can be mentioned.

Since the coloring pattern of this invention is comprised using the photosensitive resin composition of this invention, even when it is formed in low exposure, it has a uniform cross-sectional shape and is excellent in film thickness uniformity.

In addition, when the coloring pattern of this invention is used as one element of the color filter which has a several color coloring pattern, what is necessary is just to form one or more coloring patterns using the photosensitive resin composition of this invention.

The coloring pattern of the present invention may be formed by any method as long as it is a method using the photosensitive resin composition of the present invention. For example, the coloring pattern may be formed by the same method as the method for forming the photo spacer of the present invention.

<< substrate for display device >>

The substrate for display devices of this invention is comprised including one or more of the photo spacer of this invention, the protective film of this invention, and the coloring pattern of this invention.

The display device substrate of the present invention is a structure having a good cross-sectional shape and film thickness (height) uniformity formed using the photosensitive resin composition of the present invention (photo spacer of the present invention, protective film of the present invention, and coloring pattern of the present invention). Display spots can be controlled when used in a display device.

Here, the display substrate means one or more of a pair of supports for constituting the display apparatus.

As a specific example of the display apparatus substrate, although it changes also with the structure of a display element or a display apparatus, For example, the color filter board | substrate provided with a coloring pattern (henceforth "coloring pixel"), and the drive means provided with a drive means. Both substrates (e.g. simple matrix substrates, active matrix substrates, etc.), spacer walled substrates having separation walls (e.g. black matrix substrates having black matrices, etc.), coloring patterns and driving means Examples thereof include a color filter on array substrate, a glass substrate on which a pattern structure and a film are not provided.

The colored pattern group (colored pixel group) of the color filter substrate may be composed of two colors of pixels representing different colors, or may be composed of pixels of three colors and pixels of four or more colors. For example, in the case of three colors, it consists of three colors, red (R), green (G), and blue (B). When arranging the pixel group of three colors of RGB, it is preferable that it is arrangement | positioning of a mosaic type, a triangle type, etc., and what arrangement may be sufficient when arranging the pixel group of four or more colors. In the production of the color filter substrate, for example, after forming a pixel group of two or more colors, the black matrix may be formed as described above, or conversely, the pixel group may be formed after the black matrix is formed. For the formation of RGB pixels, Japanese Patent Laid-Open No. 2004-347831 can be referred to.

<< display element >>

A display element can be formed using the substrate for display device of this invention.

As one of the display elements, at least one of the liquid crystal layers and the liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) is provided between a pair of optically transparent supports (including a display device substrate). Enumerated are liquid crystal display devices having at least.

In the case of this liquid crystal display element, the display device substrate has a plurality of RGB pixel groups, and each pixel constituting the pixel group can be used as a color filter substrate in which a black matrix is separated from each other. Since a structure having a good cross-sectional shape and a uniform film thickness (height) is disposed on the color filter substrate, the liquid crystal display device having the color filter substrate includes a cell gap (cell) between the color filter substrate and the counter substrate. Due to the variation in thickness), generation of display stains such as color stains due to low temperature foaming, etc., in which the liquid crystal material is unevenly distributed, can be effectively prevented. Thereby, the produced liquid crystal display element can display a clear image.

Further, as a more detailed aspect of the liquid crystal display device, at least one liquid crystal layer and liquid crystal driving means are provided between at least one pair of optically transparent supports (including a substrate for a liquid crystal display device), the liquid crystal driving means It is enumerated that this active element (for example, a TFT) is provided, and a pair of substrates are regulated to a predetermined width by a photo spacer.

<< display device >>

The display device of the present invention includes the above display device substrate.

The display stain of the present invention is suppressed in order to provide the substrate for a display device of the present invention in which a structure having a good cross-sectional shape and a uniform film thickness (height) is provided.

Examples of the display device include a liquid crystal display device, a plasma display display device, an EL display device, a display device such as a CRT display device, and the like. For the definition of the display device and the explanation of each display device, for example, "Electronic display device (Nagasaki Akio, Kogyo Chosakai Publishing Inc. 1990 issuance)", "Display device (Ibuki Junshou, Sangyotosho Inc. Issuance).

Among the display devices, liquid crystal displays are preferred.

The liquid crystal display is configured by, for example, regulating a predetermined width between a pair of substrates facing each other so as to face each other with a photo spacer and enclosing the liquid crystal material at a regulated interval (the encapsulation portion is referred to as a liquid crystal layer). The thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness.

In the liquid crystal display device, as the liquid crystal display mode, STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, semiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types are preferably listed. do. Especially, in the liquid crystal display device of this invention, it is preferable that it is the display mode which is easy to produce a display stain by the change of the cell thickness of a liquid crystal cell from a viewpoint of showing the effect of this invention most effectively, and cell thickness is 2 ~. It is preferable to be comprised of the VA type display mode, IPS type display mode, and OCB type display mode which are 4 micrometers.

Moreover, as a liquid crystal which can be used in this invention, a nematic liquid crystal, a cholesteric liquid crystal, a smectic liquid crystal, and a ferroelectric liquid crystal are mentioned.

As a basic configuration of the liquid crystal display device, (a) a drive element such as a thin film transistor (TFT), a driving side substrate on which a pixel electrode (conductive layer) is arranged, and an opposing substrate including an opposing electrode (conductive layer) is used as a photo spacer. And the liquid crystal material is enclosed in the gap portion, and (b) the driving substrate and the opposing substrate provided with the opposing electrode (conductive layer) are disposed to face each other via a photo spacer. The liquid crystal material enclosed in the liquid crystal material is enumerated, and the liquid crystal display device of the present invention can be preferably applied to various liquid crystal display devices.

About a liquid crystal display device, it describes, for example in "next-generation liquid crystal display technology (Uchida Dachio Editing, Side Industry Association, 1994)." There is no restriction | limiting in particular except the liquid crystal display element of this invention in the liquid crystal display device of this invention, For example, it can comprise with the liquid crystal display device of various systems as described in said "next-generation liquid crystal display technology." Especially, it is effective to comprise the liquid crystal display device of a color TFT system. About the liquid crystal display device of a color TFT system, it describes in a "color TFT liquid crystal display (public publication Co., Ltd., 1996 issuance), for example."

The liquid crystal display device includes an electrode substrate, a polarizing film, a retardation film, a backlight, a photo spacer, a viewing angle compensation film, and antireflection, except that the liquid crystal display device includes the above-described photo spacer, a coloring pattern, a protective film, a liquid crystal display substrate, and a liquid crystal display element. Generally, it can comprise using various members, such as a film, a light-diffusion film, and an anti-glare film. For these members, for example, the market of '94 liquid crystal display peripheral materials and chemicals market (Shima Kentaro, CMC, 1994), the 2003 liquid crystal related market and future prospects (the lower volume) (Omote) Yajima, Fuji Kimera General Federation, 2003, etc.). This application refers to the whole patent application 2007-339917 of a Japanese patent application of December 28, 2007, and claims the priority here.

EXAMPLE

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example, unless the main technical idea of this invention is exceeded. In addition, "part" is a mass reference | standard unless there is particular notice.

In addition, the weight average molecular weight was measured by gel permeation chromatography (GPC). GPC uses TLCgel, 3 Super Multipore HZ-H (4.6mm ID x 15 cm) as a column using HLC-8020GPC (manufactured by Tosoh Corporation), and THF (tetrahydrofuran) as eluent. Was used. As the conditions, the sample concentration was 4.5% by mass, the flow rate was 0.35 ml / min, the sample injection amount was 10 mu l, the measurement temperature was 40 占 폚, and an IR detector was used. In addition, the detection line is a "Sample TSK standard, polystyrene" manufactured by Tosoh Corporation: "F-40", "F-20", "F-4", "F-1", "A-5000", "A -2500 "," A-1000 ", and" n-propylbenzene "were produced from eight samples.

<Synthesis of [A] Resin>

First, [A] resin (example compound PD-52, PU-52, PD-51, PD-53, PD-46, PD-47, and PU-53) was synthesize | combined as resin in the photosensitive resin composition.

Synthesis Example 1

Synthesis of Example Compound PD-52

In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Nyukazai Co., Ltd.) were added in advance, and the temperature was raised to 90 ° C, and 3.1 parts of styrene (St) and tricyclopentenyl methacrylate ( TCPD-M from Hitachi Chemical Co., Ltd., x) 4.28 parts, methacrylic acid (MAA; y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Industries, Ltd. product, V-601) 2.08 parts, And a mixed solution composed of 55.2 parts of 1-methoxy-2-propanol was added dropwise over 2 hours in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.

Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution, followed by 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) for 2 hours. It dripped over (GLM-MAA; z). After dropping, the mixture was reacted at 90 ° C. for 4 hours while blowing air, and then prepared by adding solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by DAICEL CHEMICAl INDUSTRIES, LTD.) So that the solid concentration was 45%. Thus, compound X having one unsaturated group was obtained.

Further, by reacting Compound X with methacrylic acid chloride (Tokyo Chemical Industry Co., Ltd.), a resin solution (solid acid value; 76.0 mgKOH / g, Mw) of the exemplary compound PD-52 ([A] resin) was added. ; 25,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained (x: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol) %).

Here, GLM-MAA shows that glycidyl methacrylate couple | bonded with methacrylic acid (it is the same hereafter).

In addition, the molecular weight Mw of exemplary compound PD-52 showed the weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatography method (GPC method) (it is the same below).

Synthesis Example 2

Synthesis of Example Compound PU-52

In the reaction vessel, 7.48 parts of 1-methoxy-2-propanol (MFG, manufactured by Nippon Nyukazai Co., Ltd.) were added in advance, and the temperature was raised to 90 ° C, and 3.1 parts of styrene (St) and tricyclopentenyl methacrylate ( TCPD-M from Hitachi Chemical Co., Ltd .; x) 4.28 parts, methacrylic acid (MAA: y) 11.7 parts, azo polymerization initiator (Wako Pure Chemical Industries, Ltd. product, V-601) 2.08 parts, And a mixed solution composed of 55.2 parts of 1-methoxy-2-propanol was added dropwise over 2 hours in a reaction vessel at 90 ° C. under a nitrogen gas atmosphere. After dripping, it was made to react for 4 hours and the acrylic resin solution was obtained.

Next, 0.15 parts of hydroquinone monomethyl ether and 0.34 parts of tetraethylammonium bromide were added to the acrylic resin solution, followed by 26.4 parts of glycidyl methacrylate (GLM, manufactured by Tokyo Chemical Industry Co., Ltd.) for 2 hours. It dripped over (GLM-MAA; z). After dropping, the mixture was reacted at 90 ° C. for 4 hours while blowing air, and then prepared by adding solvent 1-methoxy-2-propyl acetate (MMPGAc, manufactured by DAICEL CHEMICAl INDUSTRIES, LTD.) So as to have a solid content of 45%. Thus, compound X having one unsaturated group was obtained.

Further, KARENZ MOI (SHOWA DENKO KK) was added to the compound to react with the resin solution (solid acid value; 76.0 mgKOH / g, Mw; 25,000, 1-methoxy-) of the exemplary compound PU-52 ([A] resin). 2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained (x: y: z: St = 30 mol%: 27 mol%: 37 mol%: 6 mol%).

Here, GLM-MAA shows that glycidyl methacrylate couple | bonded with methacrylic acid (it is the same hereafter).

In addition, the molecular weight Mw of exemplary compound PU-52 showed the weight average molecular weight, and the measurement of the weight average molecular weight was performed using the gel permeation chromatography method (GPC method) (it is the same below).

Synthesis Example 3

Synthesis of Example Compound PD-51

In synthesizing the exemplary compound PD-52, TCPD-M (x), meta, such that x: y: z is 34 mol%: 27 mol%: 39 mol% in the exemplary compound PD-51 without using styrene. Except for changing the addition amount of the acrylic acid (y) and GLM-MAA (z), synthesized by the same method as in the synthesis of the exemplary compound PD-52, the exemplary compound PD-51 having an unsaturated group ([A] A resin solution (solid acid value; 72.5 mg KOH / g, Mw; 22,000, 45% solution of 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate) was obtained.

Synthesis Example 4

Synthesis of Example Compound PD-53

In the synthesis of the exemplary compound PD-52, tricyclopentenyl methacrylate was replaced with dicyclopentenyloxyethyl acrylate (FANCRYL FA-512M from Hitachi Chemical Co., Ltd.) without using styrene. Addition amount of FA-512M (x), methacrylic acid (y), and GLM-MAA (z) so that x: y: z is 46.2 mol%: 24.3 mol%: 29.5 mol% in Exemplary Compound PD-53 Aside from the change, the resin solution (solid acid value; 71.2 mgKOH / g, Mw; 25,500) of the compound PD-53 (resin [A]) having an unsaturated group was synthesized by the same method as the synthesis of the compound PD-52 described above. , 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

Synthesis Example 5

Synthesis of Example Compound PD-46

In the synthesis of the exemplary compound PD-52, tricyclopentenyl methacrylate was replaced with ADMA (manufactured by Idemitsu Kosan Co., Ltd.), and the composition PD-1 was added with a structural unit derived from styrene. X: y : z: St is added except that the addition amount of ADMA (x), methacrylic acid (y), GLM-MAA (z) and styrene is changed to 30 mol%: 24 mol%: 38 mol%: 8 mol%. Resin solution (solid acid value; 74.1 mgKOH / g, Mw; 29,000, 1-methoxy-) of the compound PD-46 ([A] resin) synthesized by the same method as the synthesis of the exemplary compound PD-52. 2-propanol / 1-methoxy-2-propyl acetate 45% solution) was obtained.

Synthesis Example 6

Synthesis of Example Compound PD-47

In the synthesis of the exemplary compound PD-52, tricyclopentenyl methacrylate was replaced with norbornyl methacrylate, and the composition x: y: z: St was 34 mol%: 24 mol%: 36 mol%: 6 Synthesis was carried out by the same method as the synthesis of Exemplary Compound PD-52, except that the addition amounts of norbyl methacrylate (x), methacrylic acid (y), GLM-MAA (z) and styrene were changed to mole%, Resin solution of solid compound PD-47 ([A] resin) (solid acid value; 72.9 mgKOH / g, Mw; 29,000, 1-methoxy-2-propanol / 1-methoxy-2-propyl acetate 45% solution) Got.

Synthesis Example 7

Synthesis of Example Compound PU-53

In the synthesis of the exemplary compound PU-52 of Synthesis Example 2, it was changed to dicyclopentenyloxyethyl arc relate (FANCRYL FA-512M from Hitachi Chemical Co., Ltd.) and composition x: y: Except having changed the addition amount of dicyclopentenyl oxyethyl acrylate (x), methacrylic acid (y), and GLM-MAA (z) so that z may become 46.2 mol%: 24.3 mol%: 29.5 mol%, Synthesis was carried out by the same method as the synthesis of compound PU-52, and a resin solution (solid acid value; 76.0 mgKOH / g, Mw; 25,500, 1-methoxy-2-propanol) of the exemplary compound PU-53 ([A] resin) was synthesized. / 1-methoxy-2-propyl acetate 45% solution) was obtained.

Synthesis Example 8 (for Comparative Example)

In a flask equipped with a cooling tube and a stirrer, 7 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts of propylene glycol monomethyl ether acetate were placed. Subsequently, 5 parts of styrene, 20 parts of methacrylic acid, and tricyclo methacrylic acid [5. 2. 1. 02, 6] 25 parts decan-8-yl, 25 parts 3- (methacryloyloxymethyl) -3-ethyloxetane, 20 parts methacrylic acid tetrahydrofurfuryl, and 1,3- 5 parts of butadiene were added, and after nitrogen-substituting, stirring was started slowly. The temperature of the solution was raised to 70 ° C. and maintained at this temperature for 5 hours to obtain a polymer solution containing copolymer 1.

Solid content concentration of the obtained polymer solution was 45.0%, and the weight average molecular weight of the polymer was 18,000.

Example 1 Coating Method

<Production of Color Filter Boards>

Color filter having a black matrix, an R (red) pixel, a G (green) pixel, and a B (blue) pixel by the method described in paragraphs [0084] to [0095] of Japanese Patent Laid-Open No. 2005-3861. (Hereinafter, referred to as a color filter substrate). Here, the substrate size of the color filter substrate was 550 mm x 650 mm.

Next, transparent electrodes of indium tin oxide (ITO) were further formed on the R pixels, the G pixels, the B pixels, and the black matrix of the obtained color filter substrate by sputtering.

<Formation of Photo Spacer>

The coating liquid for photosensitive resin layers which consists of the prescription | regulation shown in Table 1 (Formulation 1 in Example 1) as a spinner was applied to the ITO transparent electrode of the color filter substrate which sputter | spatter formed the ITO transparent electrode produced above. 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 fluidity of the coating film, and then prebaked on a hot plate at 90 ° C. for 3 minutes to obtain a film thickness of 5.2. A µm photosensitive resin layer was formed (film forming step).

Subsequently, a mask (a quartz exposure mask having a circular pattern having a diameter of 15 µm) and a mask and a photosensitive resin layer face each other using a proximity type exposure machine (IPROS CORPORATION) having an ultra-high pressure mercury lamp. In the state in which the color filter substrates were placed substantially parallel to each other vertically, the distance between the mask surface and the surface of the photosensitive resin layer was set to 100 µm, and the ultraviolet transmissive filter was 250 W / m 2 at 365 nm through the mask. (UV-35, manufactured by Toshiba Glass Co.) was irradiated with ultraviolet light for 10 seconds (exposure step, exposure amount of 250 mJ / cm 2).

Next, Na carbonate developer (0.38 mol / liter sodium hydrogen carbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and tablets containing; trade name: T-CD1 ( FUJIFILM Corporation) was 10 times diluted with pure water, and shower-developed at 29 degreeC for 30 second at cone nozzle pressure of 0.15 Mpa, and the pattern image was formed (development process). Cone nozzle pressure at 33 ° C. for 20 seconds using a cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (liquid diluted 10-fold with FUJIFILM Corporation) in pure water). It sprayed by 0.02 Mpa by shower, and the residue of the periphery of the formed pattern was removed, and the columnar spacer pattern was formed so that it might become one spacer space | interval at 300 micrometer x 300 micrometers.

Next, the photo-spacer was produced on the color filter board | substrate by heat-processing the color filter board | substrate with which the spacer pattern was arrange | positioned at 230 degreeC for 30 minutes (film heating process). Here, 1000 photo spacers obtained were measured using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) to measure the highest position of the highest spacer from the ITO transparent electrode formation surface side (n = 20). The average value at the time of average was made into height (average thickness). In addition, the measurement of the bottom area of the obtained photo spacer was performed using the SEM photograph. As a result, it was a cylindrical shape having a diameter of 15.1 μm and an average height of 4.7 μm. The measured values are shown in Table 2 below.

<Production of Liquid Crystal Display Device>

Separately, a glass substrate was prepared as an opposing substrate, patterned for the PVA mode on the transparent electrode and the opposing substrate of the color filter substrate obtained above, and an alignment film made of polyimide was also provided thereon.

Thereafter, a sealant of an ultraviolet curable resin was applied by a dispenser method to a position corresponding to the outer edge of the black matrix provided around the pixel group of the color filter, and the liquid crystal for PVA mode was dropped and bonded to the counter substrate. Thereafter, the bonded substrate was irradiated with UV, and then heat-treated to cure the sealing agent. Thus, the polarizing plate HLC2-2518 by a SANRITZ CORPORATION product was stuck on both surfaces of the obtained liquid crystal cell.

Next, FR1112H (chip type LED of STANLEY ELECTRIC CO., LTD. Product) as red (R) LED, DG1112H (chip type LED of product STANLEY ELECTRIC CO., LTD. Product), blue (B) LED as green (G) LED As a back light of a side light system using DB1112H (a chip type LED of STANLEY ELECTRIC CO., LTD.), It was arranged on the side which becomes the back surface of the liquid crystal cell provided with the said polarizing plate, and it was set as the liquid crystal display device.

<Evaluation>

The following measurement and evaluation were performed about the obtained coating liquid for photosensitive resin layers and photospacer. The results of the measurement evaluation are shown in Table 2 below.

Deflection Recovery Rate

The obtained photospacer was measured and evaluated as follows with a microhardness tester (DUH-W201, manufactured by Shimadzu Corporation). The measurement was carried out by a load-unloading test method using a cone-shaped indenter of 50 µm phi with a maximum load of 50 mN and a holding time of 5 seconds. The strain recovery rate [%] was calculated | required from this measured value by the following formula, and it evaluated according to the following evaluation criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.

% Strain Recovery

= (Recovery amount [μm] / deformation amount at load [μm] after load release) × 100

<Evaluation Criteria>

5: The strain recovery was 90% or more.

4: Strain recovery was more than 87% and less than 90%.

3: Strain recovery was more than 85% and less than 87%.

2: Strain recovery was more than 80% and less than 85%.

1: Strain recovery was 75% or more and less than 80%.

0: Strain recovery was less than 75%.

-Sensitivity-

The obtained coating liquid for photosensitive resin layers was observed whether or not a spacer pattern could be formed when the exposure amount was varied in various ways, and evaluated according to the following evaluation criteria.

<Evaluation Criteria>

AA: A pattern could be formed in less than 60mJ / cm <2>.

A: The pattern could be formed in less than 60-100mJ / cm <2>.

B: The pattern could be formed in less than 100-200mJ / cm <2>.

C: The exposure amount exceeding 200mJ / cm <2> was needed for pattern formation.

Preservation

(1) liquid retention

After 180 days of spontaneous aging (25 degreeC) after the close-tightness of the coating liquid for photosensitive resin layers obtained above, and putting the coating liquid for photosensitive resin layers in 60 degreeC oven for 2 weeks, respectively, It evaluated in accordance with the following evaluation criteria similarly to operation in the said "sensitivity" evaluation using a coating liquid.

<Evaluation Criteria>

A: A pattern could be formed in less than 60 mJ / cm <2>.

B: A pattern could be formed in 60 mJ / cm <2> or more and less than 150 mJ / cm <2>.

C: The exposure amount of 150 mJ / cm <2> or more and less than 300 mJ / cm <2> was needed for pattern formation.

D: The exposure amount of 300 mJ / cm <2> or more was required for pattern formation.

(2) Time-lapse stability of the photosensitive resin layer

The photosensitive resin layer (color filter substrate in which the photosensitive resin layer was formed) after prebaking was put into the oven of 60 degreeC for 14 days, and it evaluated according to the following evaluation criteria similarly to the operation in the said "sensitivity" evaluation.

<Evaluation Criteria>

A: A pattern could be formed in less than 60 mJ / cm <2>.

B: A pattern could be formed in 60 mJ / cm <2> or more and less than 150 mJ / cm <2>.

C: The exposure amount of 150 mJ / cm <2> or more and less than 300 mJ / cm <2> was needed for pattern formation.

D: The exposure amount of 300 mJ / cm <2> or more was required for pattern formation.

(Example 3, Examples 5-9, Comparative Examples 1-3): Coating method

In Example 1, the prescription of the coating liquid for photosensitive resin layers was changed as shown in the said Table 1, and the compound PD-52 ([A] resin) used for preparation of the coating liquid for photosensitive resin layers, microparticles | fine-particles, And the photo spacer and the liquid crystal display device were produced like Example 1 except having changed the initiator as shown in Table 2 below. The obtained photo spacer was made into the column shape.

(Examples 2 and 4): Transfer method

Example 1 WHEREIN: Except having formed the photosensitive resin layer by performing transfer using the photosensitive transfer film for spacer shown below instead of application | coating of the coating liquid for photosensitive resin layer (prescription 1), In the same manner, a photo spacer and a liquid crystal display device were produced. The obtained photo spacer was columnar.

Fabrication of Photosensitive Transfer Film for Spacer

The coating liquid for thermoplastic resin layers which consists of following formula A was apply | coated and dried on the polyethylene terephthalate film support body (PET support body) of 75 micrometers in thickness, and the thermoplastic resin layer of 15.0 micrometers of dry layer thicknesses was formed.

[Prescription A of Coating Liquid for Thermoplastic Resin Layer]

Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts

(= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)

Styrene / acrylic acid copolymer 58.4 parts

(= 63/37 [molar ratio], weight average molecular weight 8,000)

2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane

… 39.0 parts

The following surfactant 1... 10.0 parts

Methanol. 90.0 parts

1-methoxy-2-propanol... 51.0 parts

Methyl ethyl ketone. 700 copies

* Surfactant 1

Structure 1. 30%

Methyl ethyl ketone. 70%

Next, the coating liquid for intermediate | middle layers which consists of following formula B was apply | coated and dried on the formed thermoplastic resin layer, and the intermediate | middle layer of 1.5 micrometers of dry layer thicknesses was laminated | stacked.

[Prescription B of Coating Liquid for Interlayers]

Polyvinyl alcohol 3.22 parts

  (PVA-205 (80% reduction), KURARAY CO., LTD. Product)

Polyvinylpyrrolidone... 1.49 parts

   (PVA K-30, product of ISP Japan Ltd.)

Methanol. 42.3 Part

·Distilled water … 524 parts

Next, on the formed intermediate | middle layer, the coating liquid for photosensitive resin layers (resin of [A] resin of Table 2) which consists of prescription 3 shown in the said Table 1 is apply | coated and dried, and the photosensitivity whose dry layer thickness is 5.0 micrometers. The resin layer was laminated.

As described above, after forming a laminated structure of the PET support body / thermoplastic resin layer / intermediate layer / photosensitive resin layer (total layer thickness of 3 layers: 21.5 μm), the surface of the photosensitive resin layer was 12 μm thick as a cover film. The polypropylene film was heated and pressed, and the photosensitive transfer film for spacers was obtained.

Production of photo spacers

The cover film of the obtained photosensitive transfer film for spacers was peeled off, and the ITO transparent electrode produced by making the surface of the exposed photosensitive resin layer the same as Example 1 overlaps each other on the ITO transparent electrode of the sputtered color filter substrate, and laminated Lamic Using type II (manufactured by Hitachi Plant Technologies, Ltd.), bonding was carried out at a conveyance speed of 2 m / min under pressure and heating conditions of 100 N / cm linear pressure and 130 ° C. Thereafter, the PET was peeled off at the interface with the thermoplastic resin layer, and the photosensitive resin layer was transferred together with the thermoplastic resin layer and the intermediate layer (film formation step).

Subsequently, a mask (a quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other using a proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp. In a state in which the color filter substrates arranged so as to be viewed upright are placed in parallel with each other, the distance between the mask surface and the surface of the side in contact with the intermediate layer of the photosensitive resin layer is set to 100 µm, and from the thermoplastic resin layer side via the mask. Proximity exposure was carried out at an exposure amount of 90 mJ / cm 2 (exposure step).

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (product of FUJIFILM Corporation) was diluted 12 times with pure water (mixture of T-PD2 in a ratio of 1 part to 11 parts of pure water) was mixed. The shower development was carried out at 30 ° C. for 50 seconds at a flat nozzle pressure of 0.04 MPa to remove the thermoplastic resin layer and the intermediate layer. Subsequently, the air was blown hard to the upper surface of the glass substrate to remove the liquid, and then pure water was blown for 10 seconds by a shower, followed by pure shower cleaning, and air was blown hard to reduce liquid coagulation on the substrate. Subsequently, Na-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer containing; trade name: T-CD1 (FUJIFILM Corporation) Product) was shower-developed at a cone nozzle pressure of 0.15 MPa for 30 seconds at 29 DEG C using a solution obtained by diluting 10 times with pure water to form a pattern image (developing process).

Next, the cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by FUJIFILM Corporation) in a 10-fold dilution in pure water for 20 seconds at a cone type nozzle pressure of 0.02 Blown hard by shower with MPa, the residue of the periphery of the formed pattern was removed, and the columnar spacer pattern was formed so that it may become one spacer space | interval by 300 micrometer x 300 micrometers.

Next, the photospacer was produced on the color filter substrate by heat-processing the color filter substrate in which the spacer pattern was formed for 30 minutes at 230 degreeC (film heating process). The obtained photo spacer was columnar with a diameter of 15.1 μm and an average height of 4.7 μm.

And the PVA mode liquid crystal display device was produced like Example 1 using the color filter board | substrate with which the photo spacer was produced.

The detail of what was used by the Example and the comparative example is as follows.

CGI-242: ethanol, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) [manufactured by Ciba Specialty Chemicals]

As shown in the said Table 2, in the Example, the sensitivity higher than the comparative example is obtained, and the photosensitive resin layer in the case of being maintained in the liquid storage property of the prepared coating liquid for photosensitive resin layers, and the dry film state after application | coating The time stability of the was also good.

Also about the obtained spacer, in the Example, both higher uniformity and strain recovery rate were favorable compared with the comparative example.

Example 10

<Formation of protective film>

In Example 1, in the preparation of the color filter substrate, after forming the black matrix, the R pixel, the G pixel, and the B pixel, the photosensitive resin composition of the above-mentioned formula 1 is further applied on the black matrix and each pixel, and the mask is applied. It exposed without mediation (front exposure), and heat-processed to form the protective film. Here, the conditions of application | coating, exposure, and heat processing are the same as the conditions of application | coating, exposure, and heat processing in formation of the photo spacer of Example 1 except exposing without using a mask.

Next, on the obtained protective layer, the transparent electrode of ITO (Indium Tin Oxide) was further formed by sputtering.

<Formation of Photo Spacer>

On the ITO transparent electrode formed above, the photo spacer was formed by the method similar to Example 1 except having used the photosensitive resin composition used in Example 1 as a photosensitive resin composition.

<Production and Evaluation of Liquid Crystal Display Device>

Next, the liquid crystal display device was produced by the method similar to Example 1 using the color filter substrate in which the said photo spacer was formed.

The protective film and liquid crystal display device obtained were evaluated by the same method as in Example 1. Table 3 shows the results of the evaluation.

Example 11

<Formation of Colored Pattern>

In Example 1, in the preparation of the color filter substrate, a color filter substrate was produced in the same manner as in Example 1 except that the R pixel was formed by the following method.

That is, Pigment Red 254 (19.4 parts) and Pigment Red 177 (4.83 parts) were further added to the above Formula 1 to prepare a photosensitive resin composition for R pixels.

R pixel was formed by the method similar to formation of the photo spacer of Example 1 except having used the prepared photosensitive resin composition for R pixels, and using the photomask for R pixels as a photo mask.

After forming the R pixel, the G pixel, and the B pixel of the produced color filter substrate, a transparent electrode of indium tin oxide (ITO) was further formed on each pixel by sputtering.

<Formation of Photo Spacer>

On the ITO transparent electrode formed above, the photo spacer was formed by the method similar to Example 1 except having used the photosensitive resin composition used in Example 1 as a photosensitive resin composition.

<Production and Evaluation of Liquid Crystal Display Device>

Next, the liquid crystal display device was manufactured by the same method as Example 1 using the color filter substrate in which the said photo spacer was formed.

The protective film and liquid crystal display device obtained were evaluated by the same method as in Example 1. Table 3 shows the results of the evaluation.

[Comparative Examples 4 and 5]

Comparative Example 4 used Copolymer 1 instead of the structure PD-52 of the [A] resin of Example 10, and Comparative Example 5 also used Copolymer 1 instead of the structure PD-52 of the [A] resin of Example 11. Except for using, the protective film and the coloring material were created and evaluated in the same manner as in Examples 10 and 11, respectively.

As shown in Table 3, also when the protective film and the coloring pattern were formed using the photosensitive resin composition of this invention, the favorable result was obtained similarly to the case where a photo spacer was formed.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form a pattern structure and a protective film which is high in sensitivity, excellent in storage property in a liquid state, and excellent in the time-lapse stability and the dynamics characteristic of the photosensitive film after film-forming can be provided.

Moreover, according to this invention, even when formed at low sensitivity, the photo spacer excellent in height uniformity and a uniform cross-sectional shape, and its manufacturing method can be provided.

In addition, according to the present invention, even when formed at a low sensitivity, an excellent protective film or colored pattern can be provided in the film thickness uniformity and uniform cross-sectional shape.

According to the present invention, it is possible to provide a substrate for a display device that can suppress display stains when used in a display device, and a display device in which display stains are suppressed.

The above description of specific embodiments of the present invention is provided for the purpose of description and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. The above embodiments are selected in order to best explain the concept of the present invention and its practical application, whereby various aspects or modifications can be made to suit particular applications intended by others skilled in the art. It is intended to understand the present invention to others skilled in the art.

The details of the preferred embodiment of the present invention is obvious that those skilled in the art can be freely changed to various applications by the aspects intended for the application. It is intended that the scope of the invention be determined based on the following claims and their equivalents.

Claims (15)

As the photosensitive resin composition, [A] A resin having a branched and / or alicyclic structure, an acidic group and a substituted alkyl group in the side chain, wherein the substituted alkyl group has two ethylenically unsaturated bonds, [B] a polymerizable compound having an ethylenically unsaturated bond, (C) Photopolymerization initiator is contained, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, As the photosensitive resin composition, Said substituted alkyl group is group represented by following General formula (1), The photosensitive resin composition characterized by the above-mentioned.

(In General Formula (1), * represents a side bonded to the main chain of the resin, and A1 represents a disubstituted alkyl group having 1 to 9 carbon atoms. B1 and B2 each independently represent a single bond and a urethane bond (the main chain side). : -O-CO-NHR-) and an ester bond (backbone side: -CO-O-), R represents an alkyl group having 1 to 3. In addition, X1 and X2 each independently represent an ester bond (backbone side) : -O-CO-) R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group.) The method of claim 1, As the photosensitive resin composition, The substituent of the said substituted alkyl group is a (meth) acryloyloxy group, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, As the photosensitive resin composition, The group which has the said branch and / or alicyclic structure is comprised holding the group represented by following General formula (3), The photosensitive resin composition characterized by the above-mentioned.

In General formula (3), X represents a divalent organic coupling group and may be unsubstituted or may have a substituent. y represents 1 or 2, and n represents the integer of 0-15. The method of claim 1, As the photosensitive resin composition, A resin having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain [A], wherein the substituted alkyl group has a weight average molecular weight in the range of 12,000 to 60,000. Photosensitive resin composition to be. The method of claim 1, As the photosensitive resin composition, The resin having a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the side chain [A], wherein the substituted alkyl group has a glass transition temperature (Tg) of 40 to 180 ° C. The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, As the photosensitive resin composition, The resin which has a branched and / or alicyclic structure, an acidic group, and a substituted alkyl group in the said [A] side chain, The acid value of resin in which the said substituted alkyl group has two ethylenically unsaturated bonds is 20 mgKOH / g or more, The photosensitive resin characterized by the above-mentioned. Composition. The method of claim 1, As the photosensitive resin composition, The mass ratio ([B] / [A] ratio) with respect to said [A] resin of the said [B] polymeric compound is 0.5-2.0, The photosensitive resin composition characterized by the above-mentioned. The method of claim 1, As the photosensitive resin composition, The extender pigment which is 5-50 nm in average particle diameter is further contained, The photosensitive resin composition characterized by the above-mentioned. It is formed using the photosensitive resin composition of any one of Claims 1-9 as a photo spacer, The photo spacer characterized by the above-mentioned. A method of forming a photo spacer, which comprises at least the following steps (a) to (c). (A) Process of forming the film of the photosensitive resin composition in any one of Claims 1-9 on a board | substrate. (B) exposing at least a portion of the coating; (C) Process of developing the said film after exposure (D) heating the film after development It is formed using the photosensitive resin composition of any one of Claims 1-9 as a protective film, The protective film characterized by the above-mentioned. It is formed using the photosensitive resin composition of any one of Claims 1-9 as a coloring pattern, The coloring pattern characterized by the above-mentioned. A display device substrate comprising at least one of a photo spacer, a protective film, or a coloring pattern formed using the photosensitive resin composition according to any one of claims 1 to 9. A display device comprising the display device substrate according to claim 14.