KR20090013685A - Curable composition, cured film, method of manufacturing photo spacer, substrate for liquid crystal display device, and liquid crystal display device - Google Patents

Abstract

A curing composition, a cured layer formed by the composition, a method for preparing a photospacer by using the composition, a substrate containing the photospacer, and an LCD device containing the substrate are provided to prevent the generation of spot on display, thereby obtaining high definition display. A curing composition comprises a resin which comprises a group having a branched and/or alicyclic structure, a group having an acidic group, and a group having an epoxy group; a polymerizable compound; a photopolymerization initiator; and an interface active photopolymerization initiator. Preferably the interface active photopolymerization initiator is a compound having at least one group selected from a substituted or unsubstituted C3-C30 alkyl group, a substituted or unsubstituted siloxane group and a substituted or unsubstituted fluorinated alkyl group.

Description

Curable composition, cured film, manufacturing method of photo spacer, substrate for liquid crystal display device and liquid crystal display device {CURABLE COMPOSITION, CURED FILM, METHOD OF MANUFACTURING PHOTO SPACER, SUBSTRATE FOR LIQUID CRYSTAL DISPLAY DEVICE, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a curable composition, a cured film, a method for producing a photo spacer, a substrate for a liquid crystal display device, and a liquid crystal display device.

Liquid crystal displays are widely used as display devices for displaying high quality images. In general, a liquid crystal layer is arranged between a pair of substrates to enable image display with a predetermined orientation. Keeping the substrate gap, that is, the thickness of the liquid crystal layer uniformly, is one of the factors that determine the image quality. Therefore, a spacer for keeping the thickness of the liquid crystal layer constant is arranged. The thickness between these substrates is generally referred to as "cell thickness", and the cell thickness usually represents the thickness of the liquid crystal layer, in other words, the distance between two electrodes applying an electric field to the liquid crystal in the display area.

Spacers have been formed by bead dispersion in the past, but in recent years, spacers having high positional accuracy have been formed by photolithography using a curable composition. The spacer formed using such a curable composition is called a photo spacer.

The photo spacers produced through patterning, alkali development, and baking using a curable composition tend to have a low compressive strength of the spacer dots, and have a tendency to increase plastic deformation during panel formation. Due to this, high-quality image display is required to be free from problems such that the thickness of the liquid crystal layer becomes smaller than the design value and thus no uniformity can be maintained or a problem of generating image spots. Moreover, it is also important that the alkali image development residue of a curable composition does not generate | occur | produce from the point of high precision of a liquid crystal display device.

In connection with the above, as a photo spacer formation technique for keeping the thickness (cell thickness) of a liquid crystal layer constant, using resin which has an allyl group for photo spacer formation is disclosed (for example, Unexamined-Japanese-Patent No. 2003-). 207787).

Moreover, the curable composition for photo spacers which is easy to manufacture and excellent in storage stability is disclosed (for example, refer Unexamined-Japanese-Patent No. 2005-62620).

Moreover, the composition excellent in cold-heat shock resistance is also disclosed (for example, refer Unexamined-Japanese-Patent No. 2002-287354).

Moreover, the curable composition containing the surface active photoinitiator which can improve the surface strength of the cured film formed is disclosed (for example, Unexamined-Japanese-Patent No. 2004-515611, Unexamined-Japanese-Patent No. 2004-522819). Japanese Patent Publication No. 2004-525994).

Originally, high strain recovery is required for photo spacers used in liquid crystal cells. In order to realize this, it is possible to increase the crosslinking reaction rate of monomers and the like to increase the strain recovery rate to some extent, but the improvement effect tends to reach a limit point, and further improvement has been required.

This invention is made | formed in view of the above, and has a high strain recovery property after hardening, for example, when the liquid crystal display device is formed, the curable composition which can eliminate a display stain, and the manufacturing method of a cured film, a photo spacer, And it aims at providing the board | substrate for liquid crystal display devices and liquid crystal display device which enable display of a high quality image by preventing a display stain, and aims at achieving the said objective.

The specific means for solving the said subject is as follows.

Curable composition containing the resin which contains group which has a <1> branched and / or alicyclic structure, the group which has an acidic group, the group which has an epoxy group, a polymeric compound, a photoinitiator, and an surface active photoinitiator.

<2> The said surface active photoinitiator is a compound as described in said <1> which is a compound which has at least 1 sort (s) chosen from the C3-C30 alkyl group which may be substituted, the siloxane group which may be substituted, and the fluorinated alkyl group which may be substituted. Curable composition.

<3> The surfactant photopolymerization initiator may be a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or an oxime compound. Curable composition as described in said <1> or <2> which is a compound to contain.

The group which has a <4> above-mentioned alicyclic structure is a group derived from the C6-C25 cyclic compound which may be substituted, The curable composition in any one of said <1>-<3>.

<5> Cured film formed by hardening | curing the curable composition in any one of said <1>-<4>.

<6> The manufacturing method of the photo spacer which has a process of forming a curable composition layer on a support body by apply | coating the curable composition in any one of <1>-<4>.

<7> The board | substrate for liquid crystal display devices provided with the photo spacer manufactured by the manufacturing method of the photo spacer as described in said <6>.

<8> The liquid crystal display device provided with the board | substrate for liquid crystal displays as described in said <7>.

(Effects of the Invention)

According to the present invention, it has a high strain recovery after curing, for example, when a liquid crystal display device is formed, a curable composition capable of eliminating display stains, and a method for producing a cured film, a photo spacer, and display stains are prevented. A liquid crystal display substrate and a liquid crystal display device capable of displaying high quality images can be provided.

Hereinafter, the curable composition of this invention, the cured film, the manufacturing method of a photo spacer, the board | substrate for liquid crystal display devices, and a liquid crystal display device are demonstrated in detail.

<The manufacturing method of a curable composition and a photo spacer>

The curable composition of this invention is photopolymerization with at least 1 sort (s) of resin (A) containing the group which has a branch and / or alicyclic structure, the group which has an acidic group, and the group which has an epoxy group, the polymerizable compound (B), and photopolymerization At least 1 type of initiator (C) and at least 1 type of surfactant photoinitiator (D) are contained at least. Since the photo spacer manufactured by the curable composition of this invention has a high strain recovery property, the display stain in a display apparatus can be eliminated.

In addition, the method of manufacturing the photo spacer of the present invention includes at least two supports, a liquid crystal provided between the support, two electrodes for applying an electric field to the liquid crystal, and a photo spacer for regulating the cell thickness between the supports. It is a method of manufacturing the said photo spacer in the provided liquid crystal display device, and has a layer formation process of forming the curable composition layer using the curable composition of this invention on one of the said two support bodies.

According to the manufacturing method of the photo spacer of this invention, the photo spacer which has a high strain recovery property can be manufactured easily.

Hereinafter, the manufacturing method of the photo spacer of this invention is demonstrated, and the detail of the curable composition of this invention is also described through the said description.

[Layer Forming Step]

The layer formation process in this invention is a process of forming the curable composition layer (henceforth simply a "curable resin layer") included by apply | coating the curable composition of this invention on a support body.

This curable resin layer can comprise the photo spacer which is favorable in a strain recovery property, and can maintain cell thickness uniformly through the patterning process mentioned later. By using the photo spacer, display stains in an image in a display device in which display stains are liable to occur due to variations in cell thickness, in particular, are effectively eliminated.

As a method of forming a curable resin layer on a support body, it laminates by (a) the method of apply | coating the solution containing curable composition of this invention by a well-known coating method, and (b) the transfer method using curable resin transfer material. A method is mentioned preferably. Hereinafter, each will be described.

(a) Application method

Application of the curable composition is known coating methods such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, gravure coating, or US patents. It can carry out by the extrusion coating method etc. which use the popper as described in 262694 specification. Among them, Japanese Patent Publication No. 2004-89851, Japanese Patent Publication 2004-17043, Japanese Patent Publication 2003-170098, Japanese Patent Publication 2003-164787, Japanese Patent Publication 2003-10767, Japanese Patent Publication The method by the slit nozzle or slit coater described in 2002-79163, Unexamined-Japanese-Patent No. 2001-310147, etc. is preferable.

(b) transfer method

In the case of transfer, a roller or flat plate obtained by heating and / or pressing a curable resin layer formed in a film shape on a support body using a curable resin transfer material having at least a curable composition layer on a temporary support member on a support surface. After bonding by crimping | bonding by pressing or heat-pressing, the curable resin composition layer is transferred on a support body by peeling of a support body. Specifically, the laminator and the lamination method described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836 and JP-A-2002-148794 can be mentioned. It is preferable to use the method of Unexamined-Japanese-Patent No. 7-110575 from a low foreign material viewpoint.

When forming curable resin layer on a branch support, an oxygen blocking layer (henceforth an "oxygen barrier film" or an "intermediate layer") can further be formed between curable resin layer and a branch support. For this reason, exposure sensitivity can be raised. Moreover, in order to improve the transferability, you may form the thermoplastic resin layer which has cushion characteristics.

The branch members constituting the curable transfer film, the oxygen barrier layer, the thermoplastic resin layer, other layers, and the manufacturing method of the curable transfer film are described in Japanese Patent Laid-Open No. 2006-23696, paragraphs [0024] to [0030]. It is the same as the structure and production method described.

When both (a) coating method and (b) transfer method apply | coat and form curable resin layer, 0.5-10.0 micrometers is preferable and, as for the layer thickness, 1-6 micrometers is more preferable. When the layer thickness is in the above range, pinholes are generated during coating formation at the time of manufacture, and development removal of the unexposed part can be performed without requiring a long time.

Examples of the support for forming the curable resin layer include a transparent substrate (for example, a glass substrate or a plastic substrate), a substrate with a transparent conductive film (for example, an ITO film), and a substrate with a color filter (also called a color filter substrate). ) And a driving substrate with a driving element (for example, a thin film transistor [TFT]). As thickness of a support body, 700-1200 micrometers is generally preferable.

Curable composition ...

Next, a curable composition is demonstrated.

The curable composition includes a resin having a branched and / or alicyclic structure, a group having an acidic group, a group having an epoxy group (hereinafter, simply referred to as "resin (A)"), a polymerizable compound (B), And a photoinitiator (C) and a surface active photoinitiator (D) at least. Moreover, if necessary, it can comprise using other components, such as a coloring agent and surfactant.

The curable composition is particularly preferably used for photo spacers.

Resin (A)

The resin (A) contains a group: X having a branched and / or alicyclic structure in the side chain, a group: Y having an acidic group, and a group: Z having an epoxy group, and if necessary, other groups (L) You may have it. In addition, two or more X, Y, and Z may be combined in one group of resin (A).

Groups having branched and / or alicyclic structures:

Said "group which has a branch and / or an alicyclic structure" is demonstrated.

First, as the group having a branch, a branched alkyl group having 3 to 12 carbon atoms is represented, for example, 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, t-octyl etc. are mentioned. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group, etc. are preferable, and i-propyl group, s-butyl group, t-butyl group, etc. are more preferable.

Next, the group having an alicyclic structure means an alicyclic hydrocarbon group which may be substituted with 5 to 25 carbon atoms. It is preferable that it is 6-20, and, as for carbon number of the group which has alicyclic structure from a viewpoint of solubility and synthetic aptitude, it is more preferable that it is 6-17.

As a specific example of group which has alicyclic structure, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, isobonyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, A dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, etc. are mentioned. Among these, cyclohexyl group, norbornyl group, isobonyl group, adamantyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group, etc. are preferable, and cyclohexyl group is preferable. More preferred are a group group, a norbornyl group, an isobonyl group, a dicyclopentenyl group, a tricyclopentenyl group, and the like.

Examples of the monomer containing a group having a branched and / or alicyclic structure in the side chain include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, and (meth) acrylamides, and the like (meth) acrylates. And vinyl esters and (meth) acrylamides are preferable, and (meth) acrylates are more preferable.

As a specific example of the monomer containing the group which has a branched structure in the said side chain, (meth) acrylic-acid i-propyl, (meth) acrylic-acid i-butyl, (meth) acrylic acid s-butyl, (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. Among these, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and methacrylic acid i-propyl and t-butyl methacrylate are more preferable.

Next, as a specific example of the monomer containing the group which has an alicyclic structure in the said side chain, it is (meth) acrylate which has a C5-C20, Preferably C6-C20 alicyclic hydrocarbon group. Specific examples include (meth) acrylic acid (2-bicyclo [2.2.1] heptyl), (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-dimethyl-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-mentanoinden-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 (meth) acrylate, pentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, cyclohexyl (meth) acrylate, etc. are mentioned. Among these (meth) acrylates, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) yl, isobornyl (meth) acrylate, (meth) acrylic acid-1-adamantyl, and (meth) acrylic acid-2-a Monomethyl, (meth) acrylic acid-2-methyl-2-adamantyl, (meth) acrylic acid-2-ethyl-2-adamantyl, (meth) acrylic acid-3-hydroxy-1-adamantyl, ( (Meth) acrylic acid pentyl, (meth) acrylic acid-1-mentyl, (meth) acrylic acid tricyclodecyl, etc. are preferable, cyclohexyl (meth) acrylate, (meth) acrylic acid (nor) bonyl, (meth) acrylic acid isobornyl, ( Metha) acrylic acid-2-adamantyl is particularly preferred.

Moreover, the compound represented by following General formula (1) or (2) is mentioned as a specific example of the monomer containing group which has an alicyclic structure in the said side chain. Here, in General formula (1) and (2), x represents 1 or 2, and R represents a hydrogen atom or a methyl group. m and n represent 0-15 each independently. Among general formulas (1) and (2), x = 1 or 2, m = 0-8, n = 0-4 are preferable, and m = 1-4, n = 0-2 are more preferable. The following compound (D-1-D-5, T-1-T-8) is mentioned as a preferable specific example of a compound represented by General formula (1) or (2).

The monomer containing the group which has an alicyclic structure in the said side chain may use what was prepared suitably, and may use a commercial item.

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

-Group having an acidic group: Y-

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.

There is no restriction | limiting in particular as a monomer of the group which has an acidic group in the said side chain, Styrene, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamide, etc. are mentioned, (meth) acrylate Preferred examples thereof include vinyl esters and (meth) acrylamides, and more preferably (meth) acrylates.

As a specific example of the monomer of the group which has an acidic group in the said side chain, it can select from a well-known thing suitably, For example, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid , Sorbic acid, α-cyano cinnamic acid, acrylic acid dimer, addition reaction product of monomer having hydroxy group and cyclic acid anhydride,? -Carboxy-polycaprolactone mono (meth) acrylate, and the like. 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, cyclohexane dicarboxylic anhydride, etc. are mentioned, for example.

As said commercial item, Toago Kosei Kagaku Kogyo Co., Ltd. make: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shinnakamura Kagaku Kogyo Co., Ltd. make: NK ester CB -1, NK ester CBX-1, Kyoesha Yushi Kagaku Kogyo Co., Ltd. make: HOA-MP, HOA-MS, Osaka Yuuki Kagaku Kogyo Co., Ltd. make: biscoat # 2100, etc. are mentioned. Among these, (meth) acrylic acid is preferable at the point which is excellent in developability and low cost.

-Epoxy group: Z-

There is no restriction | limiting in particular as group which has an epoxy group, For example, group derived from the (meth) acrylate compound represented by the following structural formula (1) or structural formula (2) is mentioned preferably.

In Structural Formula (1), R ¹ represents a hydrogen atom or a methyl group, and L ¹ represents a divalent linking group.

In Structural Formula (2), R ² represents a hydrogen atom or a methyl group, L ² represents a divalent linking group, and W represents a 4-7 membered aliphatic hydrocarbon group.

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

Although there is no restriction | limiting in particular as a monomer which has an epoxy group in the side chain of the compound represented by the said Formula (1) or the compound represented by Structural formula (2), For example, the following exemplary compounds (1)-(16) are mentioned.

As a monomer which has an epoxy group in the side chain in this invention, glycidyl (meth) acrylate is preferable from a viewpoint of solubility and synthetic aptitude. In addition, you may use these monomers individually by 1 type or in combination of 2 or more types.

-Other monomers-

There is no restriction | limiting in particular as said other monomer, For example, the monomer which has a (meth) acrylic acid ester, styrene, a vinyl ether, a dibasic acid anhydride group, a vinyl ester group, a hydrocarbon alkenyl group, etc. which do not have a branched and / or alicyclic structure, etc. Can be mentioned.

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

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.

As content rate of the other monomer in the said resin (A), it is preferable that molar composition ratio is 0-30 mol%, and it is more preferable that it is 0-20 mol%.

As a specific example of resin (A), the compound represented by the following compound structure (P-1-P-7) is mentioned, for example. In addition, x, y, z, and l in the following structures represent each composition ratio (mol%).

About the manufacturing method

The said resin (A) can be manufactured including the process of the (co) polymerization reaction of the monomer (monomer) mentioned above at least.

There is no restriction | limiting in particular in the method of a (co) polymerization reaction, It can select from a well-known thing suitably. For example, for the active species of polymerization, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, and the like can be appropriately selected. Among these, it is preferable that it is radical polymerization from a point with easy synthesis and low cost. 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 solution polymerization method.

-Molecular Weight-

As for the weight average molecular weight of the said copolymer preferable as resin (A), 10,000-100,000 are preferable, 12,000-60,000 are more preferable, 15,000-4.5 million are especially preferable. If a weight average molecular weight is in the said range, it is preferable at the point of manufacture suitability and developability of a copolymer. Moreover, it is preferable at the point which the shape formed by the fall of melt viscosity is hard to be damaged, the point which is difficult to become a bridge | crosslinking defect, and the residue in image development can be suppressed.

In addition, a weight average molecular weight is measured using a gel permeation chromatograph (GPC), for example.

Glass transition temperature

It is preferable that glass transition temperature (Tg) preferable as resin (A) is 40-180 degreeC, It is more preferable that it is 45-140 degreeC, It is especially preferable that it is 50-130 degreeC. If the glass transition temperature (Tg) is within the above preferred range, a photo spacer having good developability and mechanical strength is obtained.

Acid value

The preferred acid value of the resin (A) varies depending on the molecular structure that can be taken, but generally the range is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH /. It is especially preferable that it is g. If the acid value is within the above preferred range, a photo spacer having good developability and mechanical strength is obtained.

The glass transition temperature (Tg) of the said resin (A) is 40-180 degreeC, and the weight average molecular weight is 10,000-100,000, It is preferable at the point that the photo spacer which has favorable developability and mechanical strength is obtained.

Moreover, as for the preferable example of the said resin (A), the combination of each of the preferable said molecular weight, glass transition temperature (Tg), and an acid value is more preferable.

The resin (A) in the present invention is at least three member each having a group: X having a branched and / or alicyclic structure in the side chain, a group: Y having an acidic group, and a group: Z having an epoxy group as different copolymerization units, respectively. It is preferable that it is a copolymer more than copolymerization from a viewpoint of a strain recovery rate, image development residue, and reticulation. Specifically, a copolymer obtained by copolymerizing at least one of the monomers constituting the X, Y, and Z is preferable.

The copolymerization composition ratio of each of the above components of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and can not be said uniformly, but the group having a branch and / or an alicyclic structure is preferably 10 to 70 mol%. , 15-65 mol% is more preferable, and 20-60 mol% is especially preferable. If the composition ratio of the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and resistance to the developing solution of the image portion is also good.

Moreover, 5-70 mol% is preferable, as for "group which has an acidic group", 10-60 mol% is more preferable, 20-50 mol% is especially preferable. If the composition ratio of the group having an acidic group in the side chain is within the above range, good curability and developability are obtained.

Moreover, 10-70 mol% is preferable, as for "group which has an epoxy group", 20-70 mol% is more preferable, 30-70 mol% is especially preferable. If the composition ratio of the group which has an epoxy group in a side chain is in the said range, it is excellent in pigment dispersibility and also developable and curable.

As content of the said resin (A), 5-70 mass% is preferable with respect to the said solid composition total solid, and 10-50 mass% is more preferable. Although the curable composition of this invention may contain resin other than resin (A), it is preferable to contain only resin (A).

Resin other than resin (A)

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

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

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

Total content of resin other than resin (A) and resin (A)

As total content of resin other than the said resin (A) and resin (A), 5-70 mass% is preferable with respect to the said solid composition total solid, and 10-50 mass% is more preferable. When the said content is less than 5 mass%, the film strength of the curable resin layer mentioned later becomes easy, the adhesiveness of the surface of the said curable resin layer may deteriorate, and when it exceeds 70 mass%, exposure sensitivity may fall. . In addition, the said content shows things regarding solid content.

-Polymeric compound (B), photoinitiator (C), other components-

In this invention, the component which comprises a well-known composition as a polymeric compound (B), a photoinitiator (C), and another component can be used preferably, For example, Paragraph number of Unexamined-Japanese-Patent No. 2006-23696 The component as described in [0010]-[0020], and the component as described in Paragraph No. [0027]-[0053] of Unexamined-Japanese-Patent No. 2006-64921 are mentioned.

Surface active photopolymerization initiator (D)

As a surfactant photoinitiator (D) in this invention, if it is a compound which has a surfactant action and a photoinitiation action, it can use without a restriction | limiting especially, For example, it has a photoinitiation action and at least 1 sort (s) of the substituent which has a surfactant action. The compound containing at least 1 sort (s) of a substituent in the same molecule is mentioned.

In the curable composition of this invention, the surface property of the cured film formed of a curable composition can be improved and a favorable image development resistance can be improved by further containing a surface active photoinitiator (D) in addition to a photoinitiator (C). For this reason, when the photo spacer which comprises a display apparatus is produced, for example, high strain recovery property is shown.

It is preferable that the substituent which has the said surfactant activity is at least 1 sort (s) chosen from the C3-C30 alkyl group which may be substituted from the viewpoint of the surface characteristic of a cured film, the siloxane group which may be substituted, and the alkyl fluoride group which may be substituted.

As a substituent in the case where these groups have a substituent, a C1-C8 alkyl group, a C1-C8 alkoxy group, a halogen group, an amino group, a cyano group, etc. are mentioned, for example.

As for the C3-C30 alkyl group which may have the said substituent, it is more preferable that it is C4-C20. Specifically, hexyl group, octyl group, dodecyl group, octadecyl group, hexadecyl group, etc. are mentioned, for example.

Moreover, as a siloxane group which may have the said substituent, it is preferable to include the structural unit represented by following General formula (3), for example.

In the formula, R ³¹ represents a hydrogen atom, a hydrocarbon group or -OR ³³ , and R ³² represents a hydrogen atom, a hydrocarbon group or -OR ³⁴ . R ³³ and R ³⁴ each independently represent a hydrocarbon group. As a hydrocarbon group represented by R <^31> -R <^34> , a C1-C8 alkyl group is mentioned, Specifically, a methyl group, an ethyl group, a propyl group, etc. are preferable.

As a repeating number of the structural unit represented by the said General formula (3), it is preferable that it is 2-20 from a viewpoint of the surface characteristic of a cured film, and it is more preferable that it is 2-10.

Moreover, it is preferable that it is a C1-C16 fluoroalkyl group which has the said substituent, and it is more preferable that it is a C3-C12 fluoroalkyl group.

Moreover, as a substituent in the case where an alkyl fluoride group has a substituent, a C1-C8 alkyl group, a C1-C8 alkoxy group, a halogen atom, an amino group, a cyano group, etc. are mentioned, for example.

In this invention, it is preferable that it is an alkyl fluoride group represented by following General formula (4).

In the formula, L ⁴ represents an oxygen atom or a single bond, i represents an integer of 0 to 8, and j represents an integer of 1 to 12. In this invention, it is preferable that i is an integer of 0-6, j is an integer of 1-10, It is more preferable that i is an integer of 1-4 and j is an integer of 2-8.

Specifically, a perfluorofluorohexyloxyethyl group, a perfluorouroctylethyl group, etc. are mentioned, for example.

Moreover, as a substituent which has a photoinitiator action, the substituent derived from the photoinitiator demonstrated as said photoinitiator (C) is mentioned. Especially, it is preferable that it is a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, the (alpha)-amino ketone compound, the (alpha)-hydroxy ketone compound from a viewpoint of photoinitiation activity. .

The surfactant photopolymerization initiator (D) in the present invention may have a linking group between a substituent having a surface active action and a substituent having a photopolymerization start action. There is no restriction | limiting in particular as said coupling group, For example, an oxygen atom (-O-), a sulfur atom (-S-), a nitrogen atom, a carbonyl group, an amide bond, an ester bond, an alkylene group, an alkenylene group, an arylene group, and these The coupling group which consists of a combination of these is mentioned. Moreover, it is not limited to a bivalent coupling group, Trivalent or more coupling group may be sufficient.

Specific examples of the surface active photopolymerization initiator (D) of the present invention include the compounds described in JP-A-2004-515611, JP-A-2004-522819, JP-A-2004-525994, and the following examples. Compound (1-44) is mentioned.

As the surface active photopolymerization initiator (D) in the present invention, a substituent having a surface active effect is selected from a long chain alkyl group which may be substituted, a siloxane group which may be substituted, and an alkyl fluoride group which may be substituted from the viewpoint of the surface properties of the cured film. And at least one substituent having a photopolymerization initiating action is a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-amino ketone compound, an α-hydroxy ketone compound It is preferable that the substituent which has surfactant activity is a C1-C16 alkyl fluoride group, the C2-C20 polymethylsiloxane group, or a C4-C20 alkyl group, and the substituent which has a photoinitiation action are trihalomethyl It is more preferable that it is a -s-triazine compound. Especially, the said exemplary compound 9, 30, 31, etc. are especially preferable.

In the curable composition of the present invention, a resin having an alicyclic structure as a resin (A) is a cyclohexyl group, a tricyclopentenyl group or a dicyclopentenyl group, and an acidic group is a carboxyl group (for example, a compound) from the viewpoint of the surface properties of the cured film. Groups derived from a trihalomethyl-s-triazine compound, a C1-C16 alkyl fluoride group, and a polysilicon of 2-20 It is preferable to use a compound having a methylsiloxane group or an alkyl group having 4 to 20 carbon atoms (for example, Exemplary Compounds 9, 30, 31 and the like), and as the resin (A), a group having an alicyclic structure is a dicyclopentenyl group and is acidic. The group is a carboxyl group (for example, compound structure P-6, etc.), and has a group derived from a trihalomethyl-s-triazine compound and an alkyl fluorinated alkyl group having 1 to 16 carbon atoms as the surfactant compound (D). Compound (e.g. Side, it is more preferable to use the exemplified compound 30, etc.).

In the curable composition of this invention, it is preferable that mass ratio ((B) / (A) ratio) with respect to resin (A) of a polymeric compound (B) is 0.3-1.5, and it is more preferable that it is 0.4-1.4, It is especially preferable that it is 0.5-1.2. If the ratio (B) / (A) is within the above preferred range, a photo spacer having good developability and mechanical strength is obtained.

Moreover, as content of the said photoinitiator (C) from a viewpoint of the mechanical strength of a cured film, 0.1-20 mass% is preferable with respect to resin (A), and 0.5-10 mass% is more preferable.

Moreover, as content of the said surface active photoinitiator (D) from a viewpoint of the mechanical strength of a cured film, 0.1-10 mass% is preferable with respect to a polymeric compound (B), and 0.2-5 mass% is more preferable.

Moreover, as a mass ratio ((D) / (C) ratio) of the said surface active photoinitiator (D) with respect to the said photoinitiator (C), 0.1-1 are preferable.

Particulates

In the curable composition of this invention, microparticles | fine-particles can be contained further. There is no restriction | limiting in particular as said 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] can be used. Among them, colloidal silica is preferable from the viewpoint of obtaining a photo spacer having good developability and mechanical strength.

It is preferable that it is 5-50 nm, It is more preferable that it is 10-40 nm from a viewpoint that the average particle diameter of the said microparticles | fine-particles with a high mechanical strength is obtained, It is especially preferable that it is 15-30 nm.

Moreover, it is preferable that the mass ratio with respect to the total solid in the curable composition in this invention is 5-50 mass%, and, as for content of the said microparticle, from a viewpoint that the photo spacer which has a high mechanical strength is obtained, it is 10-40 mass% It is more preferable, and it is especially preferable that it is 15-30 mass%.

Patterning Process

In this invention, the patterning process of exposing, developing, and patterning curable resin layer formed on the support body can further be included. As a specific example of a patterning process, the formation example of Paragraph No. [0071]-[0077] of Unexamined-Japanese-Patent No. 2006-64921, and the process of Paragraph No. [0040]-[0051] of Unexamined-Japanese-Patent No. 2006-23696 are disclosed. These are mentioned as a preferable example also in this invention.

Since the cured film of this invention is what hardens the said curable composition, it is a cured film with favorable surface characteristics. The cured film of this invention is formed by hardening | curing by irradiation of an active energy ray, after forming curable resin layer by the said layer formation process. In addition to hardening by irradiation of an active energy ray, hardening by heating may be further performed. Moreover, it may be patterned by the said patterning process.

Since the cured film of this invention has favorable surface characteristics, recovery of plastic deformation with respect to external force is favorable, and it can apply suitably to formation of a photo spacer, a colored layer, a protective layer, etc., for example.

The photo spacer in 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 black shielding part, the coloring part, and the photo spacer can be formed by arbitrarily combining a coating method for applying the curable composition and a transfer method using a transfer material having a photosensitive resin layer made of the curable composition.

The black shielding portion, the coloring portion, and the photo spacer may each be formed of a curable composition. Specifically, for example, exposure and development are performed after the curable resin layer is formed by directly applying the liquid curable composition to a substrate. And forming the black shielding portion and the coloring portion in a pattern shape, and then forming the curable resin layer by forming the curable composition of another liquid on a substrate (support) different from the substrate. By using this material, the curable resin transfer material is brought into close contact with the substrate on which the black shielding portion and the coloring portion are formed, and then the photoresist can be formed into a pattern by performing exposure and development after transferring the curable resin layer. In this way, the color filter in which the photo spacer was formed can be manufactured.

Further, the black shielding portion and the coloring portion are brought into close contact with the curable resin transfer material to the substrate, and then the exposure and development are performed after transferring the curable resin layer, and the black shielding portion and the coloring portion are formed in a pattern shape, and then the liquid curable composition. The photo spacers can be formed in a pattern form by directly applying a film, and then forming a curable resin layer on the substrate on which the black shielding portion and the coloring portion are formed, followed by exposure and development. In this way, the color filter in which the photo spacer was formed can be manufactured.

In the manufacturing method of the photo spacer of this invention, it is preferable to include the process of forming a curable resin layer (curable composition layer) by apply | coating the said curable composition on the support body with a black shield part and a coloring part from a viewpoint of display quality.

<Board for liquid crystal display device>

The board | substrate for liquid crystal display devices of this invention is equipped with the photo spacer obtained by the manufacturing method of the photo spacer of the said invention. The photo spacer is preferably formed on a display light shielding portion such as a black matrix formed on a support or on a driving element such as a TFT. Further, a liquid crystal alignment film such as a transparent conductive layer (transparent electrode) such as ITO, polyimide or the like may exist between a light shielding portion for display such as a black matrix, a driving element such as TFT, and a photo spacer.

For example, when the photo spacer is formed on the display light blocking portion or the driving element, the photo light blocking portion (black matrix or the like) or the driving element disposed in advance on the support is coated to cover the photosensitive resin transfer film. After the resin layer is laminated on the support surface and peeled and transferred to form a photosensitive resin layer, the substrate for the liquid crystal display device of the present invention can be produced by forming a photo spacer by performing exposure, development, heat treatment, and the like.

Colored pixels, such as red (R), blue (B), and green (G) three colors, may be further formed in the board | substrate for liquid crystal display devices of this invention as needed.

<Liquid crystal display element>

The liquid crystal display element can be comprised by providing the board | substrate for liquid crystal displays of this invention. As one of the liquid crystal display elements, a liquid crystal layer and liquid crystal driving means (including a simple matrix driving method and an active matrix driving method) between a pair of supports (including the liquid crystal display substrate of the present invention) at least one of which is light transmissive. The thing provided with at least is mentioned.

In this case, the liquid crystal display device substrate of the present invention can be configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is divided into a black matrix. In this color filter substrate, a photo spacer having a uniform height and excellent strain recovery property is formed, so that the liquid crystal display device having the color filter substrate suppresses the occurrence of cell gap variation (cell thickness variation) between the color filter substrate and the counter substrate. This can effectively prevent the generation of display stains such as color stains. For this reason, the produced liquid crystal display element can display a clear image.

Moreover, as another form of a liquid crystal display element, at least one liquid crystal layer and liquid crystal drive means are provided at least between a pair of support bodies (including the board | substrate for liquid crystal display devices of this invention), The said liquid crystal drive means The photo spacer having an active element (for example, a TFT) and having a uniform height between the pair of substrates and having excellent strain recovery properties is configured to be regulated to a predetermined width.

Also in this case, the liquid crystal display substrate of the present invention has a plurality of RGB pixel groups, and each pixel constituting the pixel group is configured as a color filter substrate in which black pixels are separated from each other.

Examples of the liquid crystal that can be used in the present invention include nematic liquid crystals, cholesteric liquid crystals, smectic liquid crystals, and ferroelectric liquid crystals.

The pixel group of the color filter substrate may be composed of two colors of pixels representing different colors, or may be composed of three pixels or four or more pixels. For example, in the case of three colors, it consists of three colors of red (R), green (G), and blue (B). When arranging the pixel group of RGB three colors, arrangement such as mosaic type or triangle type is preferable, and any arrangement may be used 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, a black matrix may be formed as described, or conversely, a pixel group may be formed after a black matrix is formed. For the formation of RGB pixels, Japanese Patent Laid-Open No. 2004-347831 can be referred to.

<Liquid crystal display device>

The liquid crystal display device of this invention is comprised by providing the said liquid crystal display substrate. Moreover, the liquid crystal display device of this invention is comprised by providing the said liquid crystal display element. That is, as described between a pair of substrates arranged to face each other so as to face each other, the photo spacer produced by the manufacturing method of the photo spacer of the present invention is regulated to a predetermined width, and the liquid crystal material is enclosed in the regulated gap (the sealing portion is And the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness.

Examples of the liquid crystal display mode in the liquid crystal display device include STN type, TN type, GH type, ECB type, ferroelectric liquid crystal, antiferroelectric liquid crystal, VA type, IPS type, OCB type, ASM type, and various other types. have. Especially, in the liquid crystal display device of this invention, the display mode which is easy to produce a display stain by the change of the cell thickness of a liquid crystal cell from the viewpoint which shows the effect of this invention most effectively is preferable, VA whose cell thickness is 2-4 micrometers. It is preferable to be comprised of a type display mode, an IPS type display mode, and an OCB type display mode.

As a basic configuration of the liquid crystal display device of the present invention, (a) a driving 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 a counter electrode (conductive layer) (B) Opposing substrates having a drive substrate and an opposing electrode (conductive layer) are disposed to face each other through a photo spacer, and are disposed to face each other via spacers. The thing which enclosed the liquid crystal material in the structure, etc. are mentioned, The liquid crystal display device of this invention can be preferably applied to various liquid crystal display devices.

About a liquid crystal display device, it describes in "next-generation liquid crystal display technology (Tatsuo Uchida editing, side Kogyo Chosakai, 1994 issuance)", for example. 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 the "color TFT liquid crystal display (Kyoritsu Shooting Co., Ltd., 1996 issuance)", for example.

The liquid crystal display device of the present invention is an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle compensation film, an antireflection film, a light diffusion film, and an antiglare except for providing the liquid crystal display device of the present invention described above. It can generally comprise using various members, such as a film. For these members, for example, the market of liquid crystal display peripheral materials and chemicals (Kentaro Shima, CMC, 1994), the present situation of the liquid crystal-related market in 2003 and the future prospects (the lower volume) (Ryomoto Omote) , Fuji Chimera Souken, 2003, etc.).

EXAMPLE

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example, unless the exceeding well-known. In addition, "part" and "%" are mass references | standards unless there is particular notice.

 The synthesis example of the compound represented by compound structures P-1 to P-5 as resin (A) in this invention is shown below.

Synthesis Example 1

In a reaction vessel, 203.9 parts of 1-methoxy-2-propanol (MFG, manufactured by Daicel Kagaku Kogyo Co., Ltd.) were previously raised to 70 ° C under a nitrogen gas atmosphere, 12.5 parts of styrene and 76.8 parts of glycidyl methacrylate. And 66.1 parts of dicyclopentenyl methacrylate, 46.5 parts of methacrylic acid, and 9.5 parts of an azo polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) were added dropwise over 2 hours. A solution (28.6% solution) of resin represented by structure P-1 was obtained.

The weight average molecular weight (Mw) of the resin represented by compound structure P-1 was found to be 31,500 by gel permeation chromatography.

Synthesis Example 2

In the synthesis example 1, except for using 2-adamantyl methacrylate instead of dicyclopentenyl methacrylate, the solution (28.0% solution) of resin represented by the compound structure P-2 similarly to the synthesis example 1 was obtained. Got it.

The weight average molecular weight (Mw) of resin represented by the said compound structure P-2 was 28,700.

Synthesis Example 3

In Synthesis Example 1, a solution (28.6% solution) of resin represented by compound structure P-3 was obtained in the same manner as in Synthesis Example 1 except that isobornyl methacrylate was used instead of dicyclopentenyl methacrylate.

The weight average molecular weight (Mw) of resin represented by the said compound structure P-3 was 34,200.

Synthesis Example 4

In the synthesis example 1, except having used tricyclopentenyl methacrylate instead of dicyclopentenyl methacrylate, it carried out similarly to the synthesis example 1, and obtained the solution (28.2% solution) of resin represented by compound structure P-4. .

The weight average molecular weight (Mw) of resin represented by the said compound structure P-4 was 30,700.

Synthesis Example 5

In the synthesis example 1, except having used cyclohexyl methacrylate instead of dicyclopentenyl methacrylate, it carried out similarly to the synthesis example 1, and obtained the solution (28.6% solution) of resin represented by compound structure P-5.

The weight average molecular weight (Mw) of resin represented by the said compound structure P-5 was 28,100.

Synthesis Example 6

A compound in the same manner as in Synthesis Example 1 except that dicyclopentenyloxyethyl methacrylate (pancryl FA-512M manufactured by Hitachi Kasei Kogyo Co., Ltd.) was used instead of dicyclopentenyl methacrylate. A solution (28.2% solution) of resin represented by structure P-6 was obtained.

The weight average molecular weight (Mw) of resin represented by the said compound structure P-6 was 29,800.

Synthesis Example 7

Compound Synthesis P in the same manner as in Synthesis Example 1 except that tricyclopentenyloxyethyl methacrylate (TCPD-M manufactured by Hitachi Kasei Kogyo Co., Ltd.) was used instead of dicyclopentenyl methacrylate. A solution (28.5% solution) of resin represented by -7 was obtained.

The weight average molecular weight (Mw) of resin represented by the said compound structure P-7 was 31,800.

Production of color filter substrate

A color filter substrate having a black matrix, an R pixel, a G pixel, and a B pixel was produced by the method described in paragraphs [0084] to [0095] of JP-A-2005-3861. Subsequently, 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 color filter substrate by sputtering.

(Example 1)

Coating for curable resin layer which consists of Formula 5 shown in following Table 1 with the coater MS-1600 (made by FACE Asia Co., Ltd.) for glass substrates which have a slit-shaped nozzle on the ITO film | membrane of the color filter board | substrate with which the ITO film | membrane sputtered produced above The liquid was applied. Subsequently, a part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Okasha Co., Ltd.) to remove fluidity of the coating film, and then prebaked at 120 ° C. for 3 minutes to form a curable resin layer having a thickness of 3.8 μm (layer Forming process).

Next, the color filter substrate arrange | positioned so that the mask (quartz exposure mask which has an image pattern) and the said mask and curable resin layer may face using the proximity type exposure machine (made by Hitachi Hi-Tech Denshi Engineering Co., Ltd.) which has an ultrahigh pressure mercury lamp. In a state in which the surface is vertically set in parallel to each other, the distance between the mask and the exposed surface of the curable resin layer was 40 μm, and the exposure was performed at an exposure dose of 300 mJ / cm 2 from the curable resin layer side through the mask.

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 stabilizer); brand name: T-CD1 The solution which dilute | produced by (Corporation Co., Ltd.) with pure water 10 times) was shower-developed by the cone nozzle pressure 0.15 Mpa for 30 second at 29 degreeC, and the pattern image of the photo spacer was obtained.

Subsequently, the cone-type nozzle pressure was used for 20 seconds at 33 ° C using a liquid obtained by diluting the cleaning agent (phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; brand name: T-SD3 (manufactured by FUJIFILM)) 10 times with pure water. The residue around the pattern shape formed by spraying with a shower at 0.02 Mpa was performed, and the desired spacer pattern was obtained.

Next, the color filter substrate in which the spacer pattern was formed was heat-processed at 230 degreeC for 30 minutes (heat processing process), and the photo spacer was produced.

The obtained photo spacer was cylindrical with a diameter of 24 µm and an average height of 3.6 µm. In addition, the average height was measured using the three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) of 1000 photo spacers obtained, and measured the highest position of the highest photo spacer from the transparent electrode formation surface of ITO (n = 20).

<Production of liquid crystal display device>

Separately, a glass substrate was prepared as a counter substrate, and patterned for PVA mode on the transparent electrode and counter substrate of the color filter substrate obtained above, and the alignment film which consists of polyimides was further formed on it.

Thereafter, a sealant of an ultraviolet curable resin was applied by a dispenser method to a position corresponding to the outer frame of the black matrix so as to surround the pixel group of the color filter, and the liquid crystal for PVA mode was dropped and bonded to the counter substrate. The bonded substrate was subjected to UV irradiation and then heat treated to cure the sealing agent. Thus, polarizing plate HLC2-2518 made from Sanlitz Corporation was stuck to both surfaces of the obtained liquid crystal cell.

Subsequently, FR1112H (chip type LED by Stanley Denki Corporation) as a red (R) LED, DG1112H (chip type LED by Stanley Denki Corporation) as a green (G) LED, and DB1112H (Stanley Denki) as a blue (B) LED A side light type backlight was formed using the chip type LED (manufactured by Co., Ltd.), and disposed on the side of the liquid crystal cell provided with the polarizing plate to form a liquid crystal display device.

(Example 2-Example 4, Example 7-Example 11, Comparative Example 2-Comparative Example 4, Comparative Example 6, Comparative Example 7)

In Example 1, the color filter substrate with a photo spacer was produced like Example 1 except having used the prescription shown in following Table 1a and 1b instead of the coating liquid for curable resin layer of Formula 5. The obtained spacer pattern was cylindrical shape of diameter 24micrometer and average height 3.6micrometer.

Subsequently, the liquid crystal display device was produced like Example 1 except having used the color filter substrate obtained above instead of the color filter substrate obtained in Example 1.

(Example 5)

In Example 1, using the prescription 8 shown in Table 1 below instead of the coating liquid for curable resin layers of the prescription 5, it carried out similarly to Example 1 except having changed the exposure dose into 100 mJ / cm <2> instead of 300 mJ / cm <2>. The color filter substrate with a spacer was produced, and the liquid crystal display device was produced using this. The obtained spacer pattern was a cylindrical shape with a diameter of 24 µm and an average height of 3.6 µm.

(Example 6)

In Example 1, except having changed the exposure amount into 100mJ / cm <2> instead of 300mJ / cm <2>, the color filter board | substrate with a photo spacer was produced like Example 1, and the liquid crystal display device was produced using this. The obtained spacer pattern was a cylindrical shape with a diameter of 24 µm and an average height of 3.6 µm.

(Comparative Example 1)

In Example 1, it replaced with the coating liquid for curable resin layers of the prescription 5, and the prescription 1 shown in Table 1 was used, and it carried out similarly to Example 1 except having changed the exposure amount into 100 mJ / cm <2> instead of 300 mJ / cm <2>. The color filter substrate with a spacer was produced, and the liquid crystal display device was produced using this. The obtained spacer pattern was cylindrical shape of diameter 24micrometer and average height 3.6micrometer.

(Comparative Example 5)

In Example 1, using the prescription 4 shown in Table 1 below instead of the coating liquid for curable resin layers of the prescription 5, it carried out similarly to Example 1 except having changed the exposure dose into 100 mJ / cm <2> instead of 300 mJ / cm <2>. The color filter substrate with a spacer was produced, and the liquid crystal display device was produced using this. The obtained spacer pattern was a cylindrical shape with a diameter of 24 µm and an average height of 3.6 µm.

[evaluation]

The following evaluation was performed about the photo spacer and liquid crystal display device obtained above. The evaluation results are shown in Table 2.

Deflection Recovery Rate

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

(%) Strain recovery rate (%)

           (Recovery after weighted opening [µm] / Strain by weight [µm]) × 100

<Evaluation Criteria>

5: 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: The strain recovery rate was 80% or more and less than 85%.

1: The strain recovery rate was 75% or more and less than 80%.

0: Strain recovery was less than 75%.

Phenomenon

In the above-described "manufacturing of photo-spacer", it developed by the method similar to the developing conditions of each Example after proximity exposure, and SEM observation of the formed photo spacer periphery part was performed and it was confirmed whether the residue remained in the periphery.

<Evaluation Criteria>

5: The residue is not seen at all.

4: Some residue was seen around the pattern.

3: The residue was seen around the pattern.

2: The residue was seen on the board | substrate around a pattern and a pattern vicinity.

1: The residue was confirmed in various places on a board | substrate.

Laminate aptitude <lamination bubble> evaluation-

About the state which transferred the curable resin layer to the color filter board | substrate using curable resin transfer material, after a support body peeling, the lamination state was observed with the optical microscope, and the presence or absence of lamination bubble was observed.

<Evaluation Criteria>

3: There is no lamination bubble at all.

2: Lamination bubbles occurred other than the pattern formation point.

1: Lamination bubble generate | occur | produced in the pattern formation part.

Reticulation

The surface of curable resin transfer material after leaving for 24 hours in 45 degreeC / 75% RH environment was observed using the microscope, and visual evaluation was performed according to the following reference | standard.

<Evaluation Criteria>

4: No occurrence of fine "wrinkles" was found at all.

3: Although generation | occurrence | production of the minute "wrinkles" etc. was recognized slightly, it was the degree which can be used practically.

2: The generation | occurrence | production of minute "wrinkles" etc. was confirmed slightly.

1: The generation | occurrence | production of minute "wrinkles" etc. was recognized considerably.

Marking spots

The gray display at the time of inputting the gray test signal with respect to each liquid crystal display device was observed with the naked eye and a magnifying glass, and the presence or absence of generation | occurrence | production of a display stain was evaluated according to the following evaluation criteria.

<Evaluation Criteria>

1: Marking stain was not confirmed at all.

2: Marking spots were slightly confirmed.

3: Marking spots were remarkably confirmed.

It can be seen from Table 2 that the photo spacer produced with the curable composition of the present invention exhibits high strain recovery rate. In addition, when a photo spacer is produced with a low exposure amount, it is similarly exhibiting a high strain recovery rate. Therefore, it is inferred that effective polymerization of the entire curable resin layer is promoted by reducing the influence of oxygen from the surface of the curable resin layer.

Claims (10)

Resin containing a group having a branched and / or alicyclic structure, a group having an acidic group, and a group having an epoxy group; Polymerizable compounds; Photopolymerization initiator; And a surfactant photopolymerization initiator at least. The said surface active photoinitiator is a compound which has 1 or more types chosen from the C3-C30 alkyl group which may be substituted, the siloxane group which may be substituted, and the fluorinated alkyl group which may be substituted. Curable composition.  The method of claim 1, wherein the surface active photopolymerization initiator is derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-amino ketone compound, an α-hydroxyketone compound, or an oxime compound It is a compound containing the substituent to become, The curable composition characterized by the above-mentioned. 3. The surface active photopolymerization initiator according to claim 2, wherein the surface active photopolymerization initiator is derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or an oxime compound It is a compound containing the substituent to become, The curable composition characterized by the above-mentioned. The group which has the said alicyclic structure is group which originates in the C6-C25 cyclic compound which may be substituted, The curable composition of Claim 1 characterized by the above-mentioned. The group which has the said alicyclic structure is group derived from C6-C25 cyclic compound which may be substituted, The curable composition of Claim 2 characterized by the above-mentioned. The cured film formed by hardening | curing the curable composition in any one of Claims 1-6. It has the process of forming a curable composition layer on a support body by apply | coating the curable composition of any one of Claims 1-6, The manufacturing method of the photo spacer characterized by the above-mentioned. The photo spacer manufactured by the manufacturing method of the photo spacer of Claim 8 is provided, The board | substrate for liquid crystal display devices characterized by the above-mentioned. The liquid crystal display device of Claim 9 was provided, The liquid crystal display device characterized by the above-mentioned.