JP2009035642A - Curable composition, curable resin transferring material, curing film, its manufacturing method, substrate for liquid crystal display, and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition forming a curing film improved in its surface property. <P>SOLUTION: This curable composition includes at least a resin (A) having a reactive group and an acid group, a polymerizable compound (B), a photopolymerization initiator (C) and a surface-active photopolymerization initiator (D). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable composition, a curable resin transfer material, a cured film and a method for producing the same, a substrate for a liquid crystal display device, and a liquid crystal display device.

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

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

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

In relation to the above, as a photospacer forming technique for keeping the thickness (cell thickness) of the liquid crystal layer constant, it is disclosed to use a resin having an allyl group for forming the photospacer (for example, Patent Documents). 1).
Moreover, the photosensitive composition for photo spacers which was easy to manufacture and was excellent in storage stability is disclosed (for example, refer patent document 2).
Moreover, the composition excellent in cold-heat shock resistance is also disclosed (for example, refer patent document 3).
Furthermore, the photosensitive composition containing the surface active photoinitiator which can improve the surface strength of the cured film formed as a photosensitive composition is disclosed (for example, refer patent documents 4-6).
JP 2003-207787 A JP 2005-62620 A JP 2002-287354 A JP-T-2004-515611 JP-T-2004-522819 JP-T-2004-525994

  The present invention provides a curable composition capable of forming a cured film having good surface characteristics, a curable resin transfer material, a cured film using these, a method for producing the same, and display unevenness. An object of the present invention is to provide a substrate for a liquid crystal display device and a liquid crystal display device capable of displaying a high-quality image, and to achieve the object.

Specific means for solving the above problems are as follows.
<1> A resin (A) having a reactive group and an acidic group, a polymerizable compound (B), a photopolymerization initiator (C), and a surface active photopolymerization initiator (D) are contained at least. Curable composition.
<2> The surfactant photopolymerization initiator (D) is an optionally substituted alkyl group having 3 to 30 carbon atoms, an optionally substituted siloxane group, and an optionally substituted fluorinated alkyl group. The curable composition according to <1>, wherein the curable composition is a compound having at least one selected from the group consisting of:
<3> The curable composition according to <1> or <2>, wherein the resin (A) further includes a group having a branched and / or alicyclic structure.
<4> The group according to any one of the above <3>, wherein the group having an alicyclic structure is a group derived from an optionally substituted cyclic compound having 6 to 25 carbon atoms. Curable composition.
<5> The curable composition according to any one of <1> to <4>, wherein the reactive group is an ethylenically unsaturated group.

<6> The curable composition according to any one of <1> to <5>, further including a colorant (E).
<7> The curable composition according to any one of <1> to <6>, further comprising fine particles (F).
<8> The curability according to <7>, wherein the fine particles (F) have an average particle diameter of 5 to 50 nm and a mass ratio to the total solid content of 5 to 50% by mass. Composition.
<9> The curable composition according to <7> or <8>, wherein the fine particles (F) are colloidal silica.

<10> A curable resin transfer material having at least a curable composition layer formed using the curable composition according to any one of <1> to <9> on a temporary support.
<11> The curable resin transfer material according to <10>, further comprising an oxygen barrier layer and / or a thermoplastic resin layer between the temporary support and the curable resin layer.

<12> A cured film formed by exposing and developing a curable resin layer formed using the curable composition according to any one of <1> to <9>.
<13> The cured film as described in <12>, which is used for any of a colored layer, a light shielding layer, a photospacer, and a protective film of a color filter.

<14> A method for producing a cured film, which includes a step of forming a curable composition layer on a support by applying the curable composition according to any one of <1> to <9>.
<15> The curable composition layer is transferred onto the support by transferring the curable composition layer by heating and / or pressurization using the curable resin transfer material according to <10> or <11>. The manufacturing method of the cured film which has the process of forming.
<16> A patterning step of forming a pattern by exposing / developing the curable composition layer to produce any one of a colored layer of a color filter, a light shielding layer, a photospacer, and a protective film. The manufacturing method of the cured film as described in said <15> or said <16>.
<17> The method for producing a cured film according to any one of <14> to <16>, wherein the patterning step further includes a heat treatment.

<18> A substrate for a liquid crystal display device comprising a cured film produced by the method for producing a cured film according to any one of <14> to <17>.
<19> A liquid crystal display device comprising the substrate for a liquid crystal display device according to <18>.

  The present invention provides a curable composition capable of forming a cured film having good surface characteristics, a curable resin transfer material, a cured film using these, a method for producing the same, and display unevenness. It is possible to provide a liquid crystal display device substrate and a liquid crystal display device that can display a high-quality image.

<Curable composition>
The curable composition of the present invention comprises a resin (A) having a reactive group and an acidic group, a polymerizable compound (B), a photopolymerization initiator (C), and a surface active photopolymerization initiator (D). And at least. When the curable composition of the present invention is cured, radicals generated by the surface active photopolymerization initiator present in the vicinity of the surface layer quench oxygen in the vicinity of the surface layer. Thereby, the influence of oxygen from the surface layer is reduced, and effective hardening of the film surface layer and the entire film proceeds. For this reason, in the cured film manufactured with the curable composition of this invention, the surface characteristic of a cured film becomes favorable.

  Hereinafter, the manufacturing method of the cured film of this invention is demonstrated, and the detail of the curable composition of this invention is also described through this description.

[Layer formation process]
The method for producing a cured film of the present invention includes a step of forming a curable composition layer containing the curable composition of the present invention (hereinafter sometimes simply referred to as “curable resin layer”) on a support (hereinafter referred to as “the curable resin layer”). It may be referred to as a “layer forming step”).
This curable resin layer can form a cured film through a patterning process described later. For example, the cured film can suitably constitute any one of a colored layer of a color filter, a light shielding layer, a photospacer, and a protective film. These cured films have good surface characteristics and good development resistance because surface hardening effectively proceeds.

  As a method of forming the curable resin layer on the support, (a) a method of applying a solution containing the curable composition of the present invention by a known coating method, and (b) a curable resin transfer material was used. A method of laminating by a transfer method is preferable. Each will be described below.

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

(B) Transfer method In the case of transfer, a curable resin transfer material having at least a curable resin layer on the temporary support is used, and the curable resin layer on the temporary support is heated and / or pressurized on the support surface. After bonding by pressing or thermocompression bonding with a roller or a flat plate, the curable resin layer is transferred onto the support by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

When the curable resin layer is formed on the temporary support, an oxygen barrier layer (hereinafter also referred to as “oxygen barrier film” or “intermediate layer”) is further provided between the curable resin layer and the temporary support. It is preferable. Thereby, the exposure sensitivity can be increased. In order to improve transferability, it is preferable to provide a cushioning thermoplastic resin layer between the curable resin layer and the temporary support.
Regarding the temporary support, the oxygen blocking layer, the thermoplastic resin layer, and other layers constituting the curable resin transfer material and the method for producing the curable resin transfer material, for example, paragraph number of JP-A-2006-23696 [0024] It is the same as the configuration and manufacturing method described in [0030].

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

  As a support for forming the curable resin layer, for example, a transparent substrate (for example, a glass substrate or a plastics substrate), a substrate with a transparent conductive film (for example, an ITO film), a substrate with a color filter (also referred to as a color filter substrate). And a driving substrate with a driving element (for example, a thin film transistor [TFT]). The thickness of the support is generally preferably 700 to 1200 μm.

~ Curable composition ~
Next, the curable composition will be described.
The curable composition of the present invention comprises at least one resin (A) having a reactive group and an acidic group, at least one polymerizable compound (B), and at least one photopolymerization initiator (C). It contains at least a seed and at least one kind of a surface active photopolymerization initiator (D). Moreover, it is preferable to comprise using other components, such as a coloring agent (E), microparticles | fine-particles (F), and surfactant, as needed.

-Resin (A)-
The resin (A) contains at least one group having a reactive group in the side chain: Z (z mol%) and at least one group having an acidic group in the side chain: Y (y mol%). If necessary, it may contain at least one kind of group having a branched and / or alicyclic structure in the side chain: X (x mol%) and other group: L (1 mol%). it can.
Resin (A) is a monomer having a reactive group in the side chain, a monomer having an acidic group in the side chain, and a branched and / or alicyclic structure in the side chain as necessary. It can be obtained by copolymerizing the polymer and other monomers. In addition, a monomer capable of introducing a reactive group into the side chain, a monomer having an acidic group in the side chain, and a monomer having a branched and / or alicyclic structure in the side chain, if necessary, It can be obtained by copolymerizing with other monomers and then introducing a reactive group into the side chain.

  The resin (A) in the present invention further includes a group X having a branched and / or alicyclic structure in the side chain from the viewpoint of imparting a high degree of deformation recovery to a cured film formed using the curable composition. It is preferable to include.

  A plurality of X, Y, and Z in the resin (A) may be combined in one group, or may be included in separate groups. In particular, it is preferable that X, Y, and Z are contained in different groups from the viewpoint of imparting a higher degree of deformation recovery to a cured film formed using the curable composition.

-Group having a reactive group: Z-
There is no restriction | limiting in particular as a reactive group, For example, an ethylenically unsaturated group, an epoxy group, etc. can be mentioned. Among these, from the viewpoint of storage stability, an ethylenically unsaturated group is preferable, and a (meth) acryloyl group is more preferable.
The resin (A) in the present invention has a reactive group in the side chain, but may have a linking group between the reactive group and the main chain. The linking group that links the reactive group and the main chain is not particularly limited as long as it is a divalent linking group, and examples thereof include an ester group, an amide group, a carbamoyl group, and an alkylene group. It may be a divalent linking group in which two or more are combined.

The method of introducing an ethylenically unsaturated group into the side chain can be appropriately selected from known methods, for example, a method of adding a (meth) acrylate having an epoxy group to a group having an acidic group, a hydroxy group And a method of adding a (meth) acrylate having an isocyanate group to a group having a hydroxyl group and a method of adding a (meth) acrylate having a hydroxy group to a group having an isocyanate group.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

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

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

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

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

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

  Moreover, as a method of introducing an epoxy group into the side chain, it can be appropriately selected from known methods, for example, a monomer having an epoxy group, a monomer having an acidic group, and if necessary And a method of copolymerizing with a monomer having a branched and / or alicyclic structure. Examples of the monomer having an epoxy group include (meth) acrylate having the above epoxy group.

-Group having an acidic group: Y-
There is no restriction | limiting in particular as an acidic group, It can select suitably from well-known things, 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, a carboxy group and a phenolic hydroxyl group are preferable from the viewpoint of excellent developability and water resistance of the cured film.

  The monomer having an acidic group in the side chain is not particularly limited, and examples thereof include styrenes, (meth) acrylates, vinyl ethers, vinyl esters, (meth) acrylamides, and the like (meth) acrylates. , Vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  The monomer having an acidic group in the side chain can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itacone. Acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate, etc. Is mentioned. As these, those produced as appropriate may be used, or commercially available products may be used.

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

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

-Group having a branched and / or alicyclic structure: X-
The “group having a branched and / or alicyclic structure” will be described.
First, the branched group means a branched alkyl group having 3 to 12 carbon atoms, 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 group, t-octyl group and the like. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are preferable, and i-propyl group, s-butyl group, t-butyl group and the like are more preferable.

Next, the group having an alicyclic structure means an alicyclic hydrocarbon group having 5 to 25 carbon atoms which may be substituted. From the viewpoints of solubility and suitability for synthesis, the group having an alicyclic structure preferably has 6 to 20 carbon atoms, and more preferably 6 to 17 carbon atoms.
Specific examples of the group having an alicyclic structure include, for example, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a dicyclopentenyl group, a dicyclopentenyl group. Examples include a nyl group, a tricyclopentenyl group, and a tricyclopentanyl group. Among these, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like are preferable, and a cyclohexyl group , Norbornyl group, isobornyl group, tricyclopentenyl group and the like are preferable.

  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, (meth) acrylamides, and the like ( (Meth) acrylates, vinyl esters and (meth) acrylamides are preferred, and (meth) acrylates are more preferred.

  Specific examples of the monomer containing a group having a branched structure in the side chain include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, (meth ) T-butyl acrylate, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, (meth) acrylic acid 3-octyl, t-octyl (meth) acrylate, and the like are mentioned. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate, and the like are preferable, and more preferable. I-propyl methacrylate, t-butyl methacrylate and the like.

  Next, as a specific example of a monomer containing a group having an alicyclic structure in the side chain, an alicyclic hydrocarbon having 5 to 20 carbon atoms, preferably 6 to 20 carbon atoms. (Meth) acrylate having a group. Specific examples include (meth) acrylic acid (2-bicyclo [2.2.1] heptyl), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, and (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 Octahydro-4,7-mentanoinden-5-yl, (meth) acrylic acid octahydro-4,7-mentanoinden-1-ylmethyl, (meth) acrylic acid-1-menthyl, (meth) acrylic acid tricyclo Decyl, (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, (nor) bornyl (meth) acrylic acid, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, (meth) Examples include cyclohexyl acrylate. Among these (meth) acrylic acid esters, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid- 2-adamantyl, (meth) acrylic acid fuentyl, (meth) acrylic acid-1-menthyl, (meth) acrylic acid tricyclodecyl, etc. are preferred, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

  Furthermore, specific examples of the monomer containing a group having an alicyclic structure in the side chain include compounds represented by the following general formula (1) or (2). Here, in the general formulas (1) and (2), x represents 1 or 2, and R represents hydrogen or a methyl group. m and n each independently represent 0-15. Among general formulas (1) and (2), x = 1 or 2, m = 0 to 8, and n = 0 to 4 are preferable, and m = 1 to 4 and n = 0 to 2 are more preferable. Preferable specific examples of the compound represented by the general formula (1) or (2) include the following compounds D-1 to D-5 and T-1 to T-8.

As the monomer containing a group having an alicyclic structure in the side chain, an appropriately produced monomer may be used, or a commercially available product may be used.
As said commercial item, Hitachi Chemical Co., Ltd. product: FA-511A, FA-512A (S), FA-512M, FA-513A, FA-513M, TCPD-A, TCPD-M, H-TCPD-A , H-TCPD-M, TOE-A, TOE-M, H-TOE-A, H-TOE-M and the like. Among these, FA-512A (S) and 512M are preferable because they are excellent in developability and excellent in the deformation recovery rate.

―Other monomers―
The other monomer is not particularly limited, for example, (meth) acrylic acid ester, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group having no branched and / or alicyclic structure in the side chain. And monomers having a hydrocarbon alkenyl group and the like.
There is no restriction | limiting in particular as said vinyl ether group, For example, a butyl vinyl ether group etc. are mentioned.

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

  As content rate of the other monomer in 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%.

  Specific examples of the resin (A) include compounds represented by the following compound structures P-1 to P-42.

-Manufacturing method-
The resin (A) can be produced from a monomer (co) polymerization step and, if necessary, a step of introducing a reactive group, for example, an ethylenically unsaturated group.
Resin (A) which has an ethylenically unsaturated group in a side chain can be manufactured as follows, for example.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

-Molecular weight-
The weight average molecular weight of the copolymer suitable as the resin (A) is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of the copolymer. Moreover, it is preferable at the point which the shape formed by the fall of melt viscosity is hard to be crushed, and also it is hard to become a crosslinking defect.
In addition, a weight average molecular weight is measured using a gel permeation chromatograph (GPC), for example.

-Glass transition temperature-
The glass transition temperature (Tg) suitable as the resin (A) can be 40 to 180 ° C, preferably 45 to 140 ° C, and more preferably 50 to 130 ° C. When the glass transition temperature (Tg) is within the preferred range, a cured film having good developability and mechanical strength can be obtained.

-Acid value-
The acid value suitable as the resin (A) varies depending on the molecular structure that can be taken, but generally it is preferably 20 mgKOH / g or more, more preferably 50 mgKOH / g or more, and 70 to 130 mgKOH / g. It is particularly preferred. When the acid value is within the preferred range, a cured film having good developability and mechanical strength can be obtained.

When the resin (A) has a glass transition temperature (Tg) of 40 to 180 ° C. and a weight average molecular weight of 10,000 to 100,000, a cured film having good developability and mechanical strength can be obtained. This is preferable.
Furthermore, a preferable example of the resin (A) is more preferably a combination of the preferable weight average molecular weight, glass transition temperature (Tg), and acid value.

  The resin (A) in the present invention is a group having the branched and / or alicyclic structure: X (x mol%), a group having an acidic group: Y (y mol%), and a group having a reactive group: From the viewpoint of deformation recovery rate, development residue, and reticulation, a copolymer of at least ternary copolymer having Z (z mol%) in separate copolymer units is preferable. Specifically, a copolymer obtained by copolymerizing at least one of the respective monomers constituting X, Y, and Z is preferable.

There is no restriction | limiting in particular about the copolymerization composition ratio of each said component of the said resin (A), For example, it can determine according to the objective of a cured film in consideration of a glass transition temperature and an acid value.
Generally, from the viewpoint of the surface properties of the cured film, “group having a branched and / or alicyclic structure: X” is 0 to 70 mol%, and “group having an acidic group: Y” is 5 to 70 mol%. , “Group having a reactive group: Z” can be 10 to 70 mol%.

In particular, for example, when a cured film is used as a photospacer, the “group having a branched and / or alicyclic structure” is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and particularly preferably 20 to 60 mol%. preferable. When the group having a branched and / or alicyclic structure is within the above range, good developability is obtained and the developer resistance of the image area is also good.
The “group having an acidic group” is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, and particularly preferably 20 to 50 mol%. When the group having an acidic group is within the above range, good curability and developability can be obtained.
Further, the “group having an ethylenically unsaturated group” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 70 mol%. When the group having an ethylenically unsaturated group is within the above range, pigment dispersibility is excellent, and developability and curability are also good.

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

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

-Ratio of resin (A) to other resins-
The total content of the resin (A) and the resin that can be used in combination is preferably 5 to 70% by mass and more preferably 10 to 50% by mass with respect to the total solid content of the curable composition. When the solid content is less than 5% by mass, the film strength of the curable resin layer described later tends to be weak, and the tackiness of the surface of the curable resin layer may be deteriorated. When it exceeds, exposure sensitivity may fall. In addition, the said content has shown that solid content.

-Polymerizable compound (B), photopolymerization initiator (C), other components-
In the present invention, a polymerizable compound (B), a photopolymerization initiator (C), and other components that constitute a known composition can be suitably used. For example, paragraphs of JP-A-2006-23696 Examples include the components described in numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921.

-Surfactant photopolymerization initiator (D)-
As the surface active photopolymerization initiator (D) in the present invention, any compound having a surface active action and a photopolymerization initiating action can be used without particular limitation. The compound which contains 1 type and at least 1 type of the substituent which has a photoinitiation action in the same molecule can be mentioned.
In the curable composition of the present invention, by further containing a surface active photopolymerization initiator (D) in addition to the photopolymerization initiator (C), polymerization and curing of the surface and inside of the curable composition layer Since the process proceeds efficiently, the surface characteristics of the cured film formed by the curable composition are improved, and good development resistance can be exhibited. Thereby, for example, when a photo spacer constituting the display device is manufactured, a high degree of deformation recovery is exhibited. For example, when a light-shielding layer, a colored layer, or a protective layer is manufactured, fluctuations in the layer thickness due to development can be suppressed, and the surface strength of the cured film can be increased.

From the viewpoint of the surface properties of the cured film, the substituent having a surface-active action may be an alkyl group having 3 to 30 carbon atoms, an siloxane group that may be substituted, and a substituent that may be substituted. It is preferably at least one selected from fluorinated alkyl groups.
Examples of the substituent in the case where these groups have a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, an amino group, and a cyano group. Can do.

  The alkyl group having 3 to 30 carbon atoms which may have the substituent is more preferably 4 to 20 carbon atoms. Specific examples include a hexyl group, octyl group, dodecyl group, octadecyl group, hexadecyl group and the like.

The siloxane group that may have a substituent preferably includes, for example, a structural unit represented by the following general formula (3).
Moreover, as a substituent in case a siloxane 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. be able to.

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. Examples of the hydrocarbon group represented by R ^{31 to} R ³⁴ include an alkyl group having 1 to 8 carbon atoms, and specifically, a methyl group, an ethyl group, a propyl group, and the like are preferable.
The number of repeating structural units represented by the general formula (3) is preferably 2 to 20 and more preferably 2 to 10 from the viewpoint of the surface characteristics of the cured film.

The fluorinated alkyl group which may have a substituent is preferably a fluorinated alkyl group having 1 to 16 carbon atoms, and preferably a fluorinated alkyl group having 3 to 12 carbon atoms. More preferred.
Examples of the substituent when the fluorinated alkyl group has a substituent include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen atom, an amino group, and a cyano group. Can be mentioned.
In the present invention, a fluorinated alkyl group represented by the following general formula (4) is preferable.

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 the present invention, i is an integer of 0-6, j is preferably an integer of 1-10, i is an integer of 1-4, and j is an integer of 2-8. Is more preferable.
Specific examples include a perfluorohexyloxyethyl group and a perfluorooctylethyl group.

  Examples of the substituent having a photopolymerization initiating action include substituents derived from the photopolymerization initiator described as the photopolymerization initiator (C). Among these, from the viewpoint of photopolymerization initiation activity, a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or the like is preferable.

  The surface active 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. The linking group is not particularly limited, and examples thereof include 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 A linking group comprising these combinations can be exemplified. Moreover, not only a bivalent coupling group but a trivalent or more coupling group may be sufficient.

  As the surface active photopolymerization initiator (D) in the present invention, specifically, compounds described in JP-T-2004-515611, JP-A-2004-522819, JP-A-2004-525994, and the like, The following exemplary compounds 1-36 can be mentioned.

  As the surface active photopolymerization initiator (D) in the present invention, from the viewpoint of the surface properties of the cured film, the substituent having a surface active action may be a long chain alkyl group which may be substituted, or may be substituted. At least one selected from a siloxane group and an optionally substituted fluorinated alkyl group, the substituent having a photopolymerization initiating action is a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, α- It is preferable that the substituent is derived from an aminoketone compound or an α-hydroxyketone compound, and the substituent having a surface activity is a fluorinated alkyl group having 1 to 16 carbon atoms, a polymethylsiloxane group having 2 to 20 silicon atoms, Alternatively, the alkyl group having 4 to 20 carbon atoms and the substituent having a photopolymerization initiating action is a trihalomethyl-s-triazine compound. More preferably. Among these, the exemplified compounds 9, 30, 31 and the like are particularly preferable.

  In the curable composition of the present invention, from the viewpoint of the surface characteristics of the cured film, the reactive group as the resin (A) is a (meth) acryloyl group, and the group having an alicyclic structure is a cyclohexyl group or tricyclopentenyl. A trihalomethyl-s-triazine compound as a surface active compound (D) using a resin (for example, compound structure P-4, P-6, etc.), which is a group or dicyclopentenyl group and the acidic group is a carboxy group A compound having a group to be derived and a fluorinated alkyl group having 1 to 16 carbon atoms, a polymethylsiloxane group having 2 to 20 silicon atoms, or an alkyl group having 4 to 20 carbon atoms (for example, exemplified compounds 9, 30, 31 and the like) ), And the reactive group as the resin (A) is a (meth) acryloyl group, the group having an alicyclic structure is a dicyclopentenyl group, and is acidic. A resin derived from a trihalomethyl-s-triazine compound as a surface active compound (D) and a fluorinated alkyl group having 1 to 16 carbon atoms. It is more preferable to use a compound having the compound (for example, exemplified compound 30).

  In the relationship with the resin (A), the mass ratio ((B) / (A) ratio) of the polymerizable compound (B) to the resin (A) is preferably 0.3 to 1.5, and It is more preferably 4 to 1.4, and particularly preferably 0.5 to 1.2. When the (B) / (A) ratio is within the preferred range, a cured film having good developability and mechanical strength can be obtained.

From the viewpoint of the mechanical strength of the cured film, the content of the photopolymerization initiator (C) is preferably 0.1 to 20% by mass, and 0.5 to 10% by mass with respect to the resin (A). More preferred.
Moreover, from the viewpoint of the mechanical strength of the cured film, the content of the surface active photopolymerization initiator (D) is preferably 0.1 to 10% by mass with respect to the polymerizable compound (B), and is preferably 0.2 to 5 mass% is more preferable.
Furthermore, as mass ratio ((D) / (C) ratio) of the said surface active photoinitiator (D) with respect to the said photoinitiator (C), 0.1-1 are preferable.

-Colorant (E)-
The curable composition of the present invention is preferably a colored curable composition containing at least one colorant (E). By including the colorant (E), for example, a colored layer of a color filter can be suitably formed. The colored layer of the color filter can form a colored pixel of the color filter, for example.

  As the colorant in the present invention, known pigments and dyes can be used without particular limitation. For example, in the colored curable composition of (i) R (red), C.I. I. Pigment Red (C.I.P.R.) 254 and C.I. I. Pigment Red (C.I.P.R.) 177 is used in combination, and (ii) G (green) colored curable composition is C.I. I. Pigment Green (C.I.P.G.) 36 and C.I. I. Pigment Yellow (CIPY) 150 is used in combination, and (iii) B (blue) in the colored curable composition is C.I. I. Pigment Blue (C.I.P.B.) 15: 6 and C.I. I. Pigment Violet (CIPV) 23 can be used in combination.

C. in (i) above. I. P. R. The content of 254 is required to be 0.80 to 0.96 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm, and 0.82 to 0.8. more preferably 94 g / ^{m 2,} and particularly preferably 0.84~0.92g / ^{m 2.}
C. in (i) above. I. P. R. The content of 177 is indispensable to be 0.20 to 0.24 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm, and is 0.21 to 0.20. more preferably 23 g / ^{m 2,} and particularly preferably 0.215~0.225g / ^{m 2.}

C. in the above (ii). I. P. G. The content of 36 is indispensable to be 0.90 to 1.34 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm. more preferably 29 g / ^{m 2,} and particularly preferably 1.01~1.23g / ^{m 2.}
C. in the above (ii). I. P. Y. The content of 150 is required to be 0.38 to 0.58 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm, and is 0.40 to 0.00. more preferably 56 g / ^{m 2,} and particularly preferably 0.43~0.53g / ^{m 2.}

C. in (iii) above. I. P. B. The content of 15: 6 is indispensable to be 0.59 to 0.67 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm, and 0.60 to 0.60. more preferably from 0.66 g / ^{m 2,} and particularly preferably 0.61~0.65g / ^{m 2.}
C. in (iii) above. I. P. V. The content of 23 is indispensable to be 0.065 to 0.075 g / m ² in a dry film in which the colored curable composition is applied with a film thickness of 1 to 3 μm, and is 0.066 to 0.00. 074 g / m ² is more preferable, and 0.067 to 0.073 g / m ² is particularly preferable.

These pigments are preferably used as a dispersion. This dispersion can be prepared by adding and dispersing a composition obtained by previously mixing the pigment and the pigment dispersant in an organic solvent (or vehicle). The vehicle refers to a portion of the medium in which the pigment is dispersed when the paint is in a liquid state, and is a liquid portion that binds to the pigment and hardens the coating film (binder), which is dissolved and diluted. Component (organic solvent). The disperser used when dispersing the pigment is not particularly limited, and examples thereof include known dispersers such as a kneader, roll mill, atrider, super mill, dissolver, homomixer, and sand mill.
When the colorant (E) used in the present invention is a pigment, it is preferable that the particle diameter is 0.1 μm or less, particularly 0.08 μm or less.

The curable composition of the present invention can contain at least one metal fine particle and / or at least one carbon black as the colorant (E). By including metal fine particles and / or carbon black, for example, it can be suitably used for forming a light shielding layer of a color filter.
Any known carbon black can be used without particular limitation. As the metal fine particles, silver fine particles, gold fine particles, copper fine particles and the like can be used. As the metal fine particles, commercially available ones can be used, and they can be prepared by a chemical reduction method of metal ions, an electroless plating method, a metal evaporation method, or the like.

  For example, in the case of silver fine particles (colloidal silver), a conventionally known method, for example, a method of reducing a soluble silver salt with hydroquinone in an aqueous gelatin solution disclosed in US Pat. No. 2,688,601. , A method of reducing a sparingly soluble silver salt described in German Patent 1,096,193 with hydrazine, reduced to silver with tannic acid described in US Pat. No. 2,921,914 A method of chemically reducing silver ions in a solution, a method of forming silver particles by electroless plating described in JP-A-5-134358, and an inert gas such as helium as a bulk metal. It is possible to use a method such as a gas evaporation method in which the solvent is evaporated in the inside and cold trapped with a solvent.

  Moreover, when a light shielding layer is formed using the curable composition of this invention, it is preferable that the optical density per 1 micrometer of film thickness of a light shielding layer will be 1 or more. Further, in consideration of preventing the metal fine particles from fusing at the time of the heating process or the like when producing the color filter, the content of the metal fine particles in the curable composition is included in the light shielding layer to be formed. It is preferable to adjust so that the content of the metal fine particles is about 10 to 90% by mass, preferably about 10 to 80% by mass.

The average particle diameter of the metal fine particles used in the curable composition of the present invention is preferably 60 to 250 nm from the viewpoint of the optical density (OD) of the light shielding layer. More preferably, it is 70-200 nm.
The average particle size of the metal fine particles in the present invention is obtained by, for example, measuring 50 particle sizes by observation with a transmission electron microscope (TEM) and calculating the average value.

-Fine particles (F)-
The curable composition of the present invention preferably contains at least one kind of fine particles (F). By including the fine particles (F), for example, it can be suitably used for forming a photospacer.

  The fine particles (F) in the present invention are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] are preferable. Of these, colloidal silica is preferred from the viewpoint of obtaining a photospacer having good developability and mechanical strength.

  The average particle diameter of the fine particles (F) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and more preferably 15 to 30 nm from the viewpoint that a photospacer having high mechanical strength can be obtained. Is particularly preferred.

  In addition, the content of the fine particles (F) is 5 to 50% by mass with respect to the total solid content in the photosensitive composition in the present invention from the viewpoint that a photospacer having high mechanical strength is obtained. Is more preferable, 10 to 40% by mass is more preferable, and 15 to 30% by mass is particularly preferable.

[Patterning process]
In the present invention, a patterning step of exposing and developing the curable composition layer formed on the support can be further provided. In the manufacturing method of the cured film of this invention, it is preferable that the patterning process of exposing and developing a curable composition layer is further included from the point which can be patterned to a desired aspect.
Specific examples of the exposure / development processing include formation examples described in paragraphs [0071] to [0077] of JP-A-2006-64921, and paragraph numbers [0040] to [0051] of JP-A-2006-23696. The process described in the above is also a preferable example in the present invention.

<Curing film>
Since the cured film of the present invention is formed by curing the curable composition, it is a cured film having good surface characteristics. The cured film of the present invention is formed, for example, by forming a curable resin layer by the layer forming step and then curing it by irradiation with active energy rays. In addition to curing by irradiation of active energy rays, sufficient reaction progress at the reaction site and cross-linking when a polymer containing an epoxy unit whose reactive compound is represented by compound structure P-36 to P-42 is used. From the viewpoint of improving the curing characteristics by sufficiently proceeding the reaction, it is preferable to perform curing by heating. Moreover, it may be patterned by the patterning step.
Since the cured film of the present invention has good surface characteristics, it has good plastic deformation recovery against external force, and can be suitably applied to, for example, the formation of photo spacers, colored layers, protective layers, and the like.

  The cured film produced by the method for producing a cured film of the present invention is preferably any one of a colored layer of a color filter, a light shielding layer, a photospacer, and a protective film from the viewpoint of the surface characteristics of the cured film, and deformation recovery. Since it is excellent in property, it is more preferable that it is a photo spacer.

It is preferable that the curable composition forming the colored layer of the color filter further contains a colorant. Thereby, it can be set as the colored layer which has a desired hue.
The colored layer of the color filter can be formed by a known method such as a method in which a curable resin layer is formed on the support by the above-described method and the patterning step is repeated by the number of colors. If necessary, the boundary may be divided by a black matrix.

The curable composition for forming the light shielding layer preferably further contains a colorant, and more preferably further contains metal fine particles and / or carbon black as the colorant. Thereby, a light shielding layer having a desired optical density can be formed. For example, the black matrix can be formed as the light shielding layer.
The light shielding layer can be formed by, for example, forming a curable resin layer on the support by the above-described method, and exposing and developing through a black matrix photomask in the patterning step.

The curable composition forming the photospacer preferably contains a resin (A) having a reactive group, an acidic group, and a group having a branched and / or alicyclic structure. As a result, a photospacer having good deformation recovery can be formed.
The photospacer is preferably formed on a light shielding layer such as a black matrix formed on a support or a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a light shielding layer such as a black matrix, a driving element such as a TFT, and a photo spacer.

  For example, when the photo spacer is provided on the light shielding layer or the driving element, the light shielding layer (such as a black matrix) or the driving element previously disposed on the support is covered so as to cover the photosensitive resin transfer film, for example. The photosensitive resin layer can be laminated on the support surface, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment and the like to form a photospacer.

The curable composition for forming the protective film preferably has characteristics such as low refractive index, high heat resistance, and high adhesion from the viewpoint of display characteristics and reduction of manufacturing process load.
For example, the protective film is formed by forming a curable resin layer by the above-described method on a support on which a colored layer of a color filter and a black matrix are formed, and in the patterning step, exposure and development are performed through a desired photomask. Can be formed.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention is provided with at least one kind of cured film obtained by the method for producing a cured film of the present invention. The cured film used for the substrate for a liquid crystal display device of the present invention is preferably any one of a colored layer of a color filter, a light shielding layer, a photospacer, and a protective film from the viewpoint of surface characteristics of the cured film. It is more preferable that

The substrate for a liquid crystal display device of the present invention can be constituted, for example, by forming a color filter including a light shielding layer such as a black matrix and a colored layer such as a colored pixel and then forming a photo spacer.
The light shielding layer, the colored layer, and the photospacer are formed by arbitrarily combining a coating method for applying a curable composition and a transfer method using a transfer material having a curable resin layer made of the curable composition. It is possible.

The light-shielding layer, the colored layer, and the photospacer can each be formed from a curable composition. Specifically, for example, a curable resin can be formed by directly applying the liquid curable composition to a support (substrate). After forming the layer, exposure / development is performed to form the light shielding layer and the colored layer in a pattern, and then the curable composition of another liquid is applied onto a temporary support to form a curable resin layer. After using the curable resin transfer material produced by forming the curable resin transfer material, the curable resin transfer material is brought into close contact with the substrate on which the light shielding layer and the colored layer are formed, and then the curable resin layer is transferred. As a result, the photo spacer can be formed in a pattern.
In addition, after the curable resin transfer material is adhered to the substrate and the curable resin layer is transferred to the light shielding layer and the colored layer, exposure and development are performed to form the light shielding layer and the colored layer in a pattern, By using another curable resin transfer material, this curable resin transfer material is brought into close contact with the substrate on which the light shielding layer and the colored layer are formed, and the curable resin layer is transferred, followed by exposure and development. Photo spacers can be formed in a pattern.
In this manner, a substrate for a liquid crystal display device can be produced.

[Liquid crystal display element]
A liquid crystal display element can be formed by providing the substrate for a liquid crystal display device of the present invention. As one of the liquid crystal display elements, a liquid crystal layer and liquid crystal driving means (simple matrix driving method and active matrix driving method) are provided between a pair of supports (including the substrate for a liquid crystal display device of the present invention), at least one of which is transparent. Including at least).

  In this case, the substrate for a liquid crystal display device 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 being separated from each other by a black matrix. The color filter substrate is provided with a photo spacer having a uniform height and excellent deformation recovery property formed from the curable composition of the present invention, so that the liquid crystal display device provided with the color filter substrate faces the color filter substrate. Generation of cell gap unevenness (cell thickness fluctuation) between the substrate and the substrate can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

As another aspect of the liquid crystal display element, at least one of the liquid crystal display elements includes a liquid crystal layer and a liquid crystal driving unit between a pair of light transmissive supports (including the liquid crystal display device substrate of the present invention), The driving means has an active element (for example, TFT), and the height between the pair of substrates is uniform, and is regulated to a predetermined width by a photo spacer formed of the curable composition of the present invention and having excellent deformation recovery properties. It is configured.
Also in this case, the substrate for a liquid crystal display device of the present invention is configured as a color filter substrate having a plurality of RGB pixel groups, and each pixel constituting the pixel group is separated from each other by a black matrix.

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

<Liquid crystal display device>
The liquid crystal display device of the present invention comprises the liquid crystal display device substrate. Moreover, the liquid crystal display device of the present invention comprises the liquid crystal display element. That is, as described above, the space between a pair of substrates facing each other so as to face each other is regulated to a predetermined width by the photo spacer produced by the photo spacer production method of the present invention, and the liquid crystal material is placed in the regulated gap. The liquid crystal layer is configured to be sealed (the sealed portion is referred to as a liquid crystal layer), and the thickness (cell thickness) of the liquid crystal layer is maintained at a desired uniform thickness.

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

  The basic configuration of the liquid crystal display device of the present invention includes: (a) a driving side substrate in which driving elements such as thin film transistors (TFTs) and pixel electrodes (conductive layers) are arranged; and a counter electrode (conductive layer). And (b) a driving substrate and a counter substrate provided with a counter electrode (conductive layer); and a counter substrate provided with a counter electrode (conductive layer). The liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices, and the like. .

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

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

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example, unless the main point is exceeded. Unless otherwise specified, “part” and “%” are based on mass.

Synthesis of the resin (A) represented by the compound structure P-10 is shown in Synthesis Example 1 below.
(Synthesis Example 1)
In a reaction vessel, 8.57 parts of 1-methoxy-2-propanol (MFG, manufactured by Daicel Chemical Industries, Ltd.) was added in advance, and the temperature was raised to 90 ° C., 6.27 parts of cyclohexyl methacrylate, 5.15 parts of methacrylic acid, A mixed solution consisting of 1 part of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 8.57 parts of 1-methoxy-2-propanol was placed in a reaction vessel at 90 ° C. for 2 hours under a nitrogen gas atmosphere. It was dripped over. Reaction was performed for 4 hours after the dropwise addition to obtain an acrylic resin solution.
Next, 0.025 part of hydroquinone monomethyl ether and 0.084 part of tetraethylammonium bromide were added to the acrylic resin solution, and then 5.41 parts of glycidyl methacrylate was added dropwise over 2 hours. After dropping, the compound structure P-10 having an ethylenically unsaturated group and an alicyclic structure is obtained by reacting at 90 ° C. for 4 hours while blowing air and then adding a solvent so that the solid content concentration becomes 45%. A 1-methoxy-2-propanol solution (45%) of a resin represented by the formula (solid content acid value; 73 mg KOH / g, Mw; 10,000) was obtained.
The molecular weight Mw of the resin represented by the compound structure P-10 indicates a weight average molecular weight, and the molecular weight was measured using a gel permeation chromatograph (GPC).

(Example 1): Transfer Method—Preparation of Curable Resin Transfer Material for Photospacer—
On a polyethylene terephthalate film temporary support (PET temporary support) having a thickness of 75 μm, a thermoplastic resin layer coating solution having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 6.0 μm. Formed.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethyleneoxy) phenyl] propane 39.0 parts Surfactant 1 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51 .0 parts, methyl ethyl ketone ... 700 parts

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

Next, on the formed thermoplastic resin layer, an intermediate layer coating solution comprising the following formulation B is applied and dried, and an intermediate layer having a dry layer thickness of 1.5 μm is laminated, and a PET temporary support / thermoplastic resin A laminated structure composed of layers / intermediate layers was obtained.
[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by IS Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, a coating solution for a curable resin composition layer having the formulation-5 shown in Table 1 below is further applied onto the formed intermediate layer and dried to provide a curable resin composition layer having a dry layer thickness of 4.1 μm. Were laminated.

  As described above, after forming a laminated structure of PET temporary support / thermoplastic resin layer / intermediate layer / curable resin composition layer (total thickness of 3 layers is 11.6 μm), curable resin composition Further, a 12 μm-thick polypropylene film was applied to the surface of the layer by heating and pressing as a cover film to obtain a curable resin transfer material for photospacer (1).

-Fabrication of color filter substrate-
A color filter substrate having a black matrix, R pixel, G pixel, and B pixel was produced by the method described in paragraph Nos. [0084] to [0095] of JP-A-2005-3861. Next, a transparent electrode of ITO (Indium Tin Oxide) was further formed on the R pixel, G pixel, B pixel and black matrix of the color filter substrate by sputtering.

-Production of photo spacer-
The cover film of the curable resin transfer material for photospacer (1) obtained as described above is peeled off, and the surface of the exposed curable resin composition layer is formed on the color filter substrate on which the ITO film prepared above is sputtered. Overlaid on the ITO film and laminated using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.) under a linear pressure of 100 N / cm and a pressurization and heating condition of 130 ° C. at a conveyance speed of 2 m / min. . Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the curable resin composition layer was transferred together with the thermoplastic resin layer and the intermediate layer (layer forming step).

Next, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the mask (quartz exposure mask having an image pattern) and the mask and the thermoplastic resin layer face each other. The distance between the mask and the surface of the curable resin composition layer on the side in contact with the intermediate layer is set to 40 μm with the color filter substrate placed in a vertical position substantially parallel and perpendicular to the thermoplastic resin through the mask. Proximity exposure was performed at an exposure amount of 60 mJ / cm ² from the layer side.

Next, a triethanolamine developer (containing 30% triethanolamine, trade name: T-PD2 (manufactured by FUJIFILM Corporation) 12 times with pure water (1 part of T-PD2 and 11 parts of pure water). The mixture was diluted with a ratio at a flat nozzle pressure of 0.04 MPa for 30 seconds at 30 ° C. to remove the thermoplastic resin layer and the intermediate layer. Subsequently, after air was blown off on the upper surface of the glass substrate, pure water was sprayed for 10 seconds by a shower, pure water shower cleaning was performed, and air was blown to reduce a liquid pool on the substrate.
Subsequently, a sodium carbonate developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, anionic surfactant, antifoaming agent, and stabilizer Contained; trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) and shower-developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa, and a photo spacer Pattern image was obtained.
Subsequently, a solution obtained by diluting a cleaning agent (containing phosphate, silicate, nonionic surfactant, antifoaming agent, stabilizer; trade name: T-SD3 (manufactured by Fuji Film Co., Ltd.)) 10 times with pure water Then, it was sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa to remove residues around the formed pattern image, thereby obtaining a desired photospacer pattern.

Next, the color filter substrate provided with the photospacer pattern was subjected to heat treatment at 230 ° C. for 30 minutes (heat treatment step) to produce a photospacer.
The obtained photospacer was cylindrical with a diameter of 24 μm and an average height of 3.6 μm. In addition, average height is the highest position of the highest spacer from the transparent electrode formation surface of ITO using three-dimensional surface structure analysis microscopes (manufacturer: ZYGO Corporation, model: New View 5022) for the obtained photospacers. Was measured (n = 20).

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

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

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

(Examples 2-5, Comparative Examples 2-4, 6-7)
In Example 1, the photospacer and the liquid crystal were prepared in the same manner as in Example 1 except that each formulation shown in Table 1 was used instead of Formula-5 as the formulation of the coating liquid for the curable resin composition layer. A display device was produced. The obtained photospacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

(Example 7)
In Example 1, a photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that the exposure amount in proximity exposure was changed from 60 mJ / cm ² to 30 mJ / cm ² . The obtained photospacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

(Comparative Example 1)
In Example 1, the formulation -1 instead formulation -5 used as the formulation of the curable resin composition layer coating solution, further, changing the exposure amount in the proximity exposure from 60 mJ / cm ^2, in 30 mJ / cm ² A photo spacer and a liquid crystal display device were produced in the same manner as in Example 1 except that. The obtained photospacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

(Example 6): Coating method-Production of photo spacer (liquid register method)-
Table 1 below shows a glass substrate coater MH-1600 (manufactured by FS Asia Co., Ltd.) having a slit-like nozzle on the ITO film of the color filter substrate on which the ITO film produced above is formed by sputtering. The coating liquid for curable resin composition layer which consists of prescription-9 was apply | coated. Subsequently, part of the solvent was dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to remove the fluidity of the coating film, and then prebaked at 120 ° C. for 3 minutes to cure to a film thickness of 4.0 μm A functional resin composition layer was formed (layer forming step).

Subsequently, a photospacer was produced on the color filter substrate by the same patterning process and heat treatment process as in Example 1. However, the exposure amount was 300 mJ / cm ² , and the development with the KOH developer was 23 ° C. for 60 seconds. The obtained photospacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

  After the production of the photospacer, a PVA mode liquid crystal display device was produced in the same manner as in Example 1 using this color filter substrate.

(Comparative Example 5)
In Example 6, the photospacer and the liquid crystal were prepared in the same manner as in Example 6 except that Formula-4 described in Table 1 was used instead of Formula-9 as the formulation of the coating liquid for the curable resin composition layer. A display device was produced. The obtained photospacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

[Evaluation]
The following evaluation was performed about the photospacer and liquid crystal display device which were obtained above. The evaluation results are shown in Table 2.
-Deformation recovery rate-
Each of the photo spacers was measured and evaluated as follows using a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation). The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
(Formula) Deformation recovery rate (%) = (Recovery amount after weight release [μm] / Deformation amount by weight [μm]) × 100

<Evaluation criteria>
5: Deformation recovery rate was 90% or more.
4: The deformation recovery rate was 87% or more and less than 90%.
3: The deformation recovery rate was 85% or more and less than 87%.
2: Deformation recovery rate was 80% or more and less than 85%.
1: The deformation recovery rate was 75% or more and less than 80%.
0: Deformation recovery rate was less than 75%.

-Developability-
In the above-mentioned “-Production of Photo Spacer”, after proximity exposure, development was performed in the same manner as the development conditions of each Example, and SEM observation was performed on the periphery of the formed Photo Spacer to confirm whether there was a residue in the periphery. .

<Evaluation criteria>
5: No residue is seen at all.
4: Some residue was observed around the pattern.
3: Residue was observed around the pattern.
2: Residue was observed on the periphery of the pattern and on the substrate in the vicinity of the pattern.
1: Residue could be confirmed in some places on the substrate.

-Laminate suitability <Lami foam> evaluation-
About the state which transferred the curable resin layer to the color filter board | substrate using the curable resin transfer material, after peeling a temporary support body, the lamination state was observed with the optical microscope, and the presence or absence of the lami bubble was observed.

<Evaluation criteria>
3: No lami bubbles.
2: Lami bubbles were generated in places other than the pattern formation location.
1: Lami bubbles were generated in the pattern forming portion.

-Reticulation-
The surface of the curable resin transfer material after being allowed to stand in a 45 ° C./75% RH environment for 24 hours was observed with a microscope, and visually evaluated according to the following criteria.

<Evaluation criteria>
4: Occurrence of fine “wrinkles” was not recognized at all.
3: The occurrence of fine “wrinkles” was slightly observed, but was practically usable.
2: Occurrence of fine “wrinkles” was slightly observed.
1: Generation | occurrence | production of fine "wrinkles" etc. was recognized considerably.

-Display unevenness-
For each liquid crystal display device, the gray display when a gray test signal was input was observed visually and with a loupe, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.

<Evaluation criteria>
○: Display unevenness was not recognized at all.
Δ: Display unevenness was slightly recognized.
X: Display unevenness was recognized remarkably.

  From Table 2, it can be seen that the photospacer formed from the curable composition of the present invention has a good deformation recovery rate, and the liquid crystal display device having this has good display unevenness. Further, it can be seen that the photo spacer formed from the curable composition of the present invention can maintain the same performance even when the exposure amount is reduced.

(Example 8)
-Production of photosensitive black transfer material-
The black pigment composition having the composition shown in Table 3 below was dispersed with a motor mill M-50 (manufactured by Eiger Corp.) using zirconia beads having a diameter of 0.65 mm for 9 hours at a peripheral speed of 9 m / s. A liquid CB1 was obtained.

  Next, on the intermediate layer of the laminated structure composed of the PET temporary support / thermoplastic resin layer / intermediate layer obtained in the same manner as in the preparation of the curable resin transfer material for photospacer in Example 1, the following formulation- A curable resin composition layer coating solution consisting of 13 was applied and dried to provide a photosensitive black resin layer having a dry film thickness of 1.7 μm. Further, a polypropylene film having a thickness of 12 μm was stuck as a cover film on the surface of the photosensitive black resin layer to obtain a photosensitive black transfer material.

-Preparation of black matrix (light-shielding layer)-
The photosensitive black transfer material obtained above was laminated on a glass substrate by the following method.
A cleaned glass substrate (Corning # 1737) having a thickness of 0.7 mm and 400 mm × 300 mm is immersed in a 0.3% aqueous solution of a silane coupling agent (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) for 30 seconds, and then pure water for 30 seconds. Rinse and dry with an air knife.

  Next, while peeling the cover film of the photosensitive black transfer material, the photosensitive black resin layer surface is directed to a transparent glass substrate heated to 100 ° C., using a laminator (Automatic cut laminator ASL-24 manufactured by Somaru). , Pressurization (2 MPa), heating (130 ° C.) and bonding. After the glass substrate was at room temperature, the PET temporary support was peeled off while removing electricity from the peeling interface and the back surface of the substrate with an ionizer.

Next, pattern exposure was performed through a photomask at an exposure amount of 70 mJ / cm ² .
In order to remove the thermoplastic resin layer and the intermediate layer, development was performed at 30 ° C. for 30 seconds using a 10% diluted solution of T-PD-2 (Fujifilm Transer Developer). Subsequently, in order to remove the unexposed portion of the photosensitive black resin layer, development was performed at 30 ° C. for 30 seconds using a 20% diluted solution of T-CD-1 (Fujifilm Transer Developer). Shower development was performed at 33 ° C. for 30 seconds using a 10% dilution of T-SD-1 (Fujifilm Transer Developer) for removing residues as a third developer. Next, heat treatment was performed at 220 ° C. for 10 minutes to form a black matrix (light-shielding layer) having a film thickness of 1.5 μm on the glass substrate to obtain a glass substrate with a black matrix.

(Comparative Example 8)
In the production of the photosensitive black transfer material of Example 8, as in the case of Example 8, except that the prescription-12 was used instead of the prescription-13 as the prescription of the coating liquid for the curable resin composition layer. A photosensitive black transfer material was prepared, and a black matrix (light-shielding layer) having a film thickness of 1.5 μm was formed on the glass substrate using the photosensitive black transfer material to obtain a glass substrate with a black matrix.

Example 9
-Preparation of coating solution for photosensitive colored resin layer-
The coating liquid for red photosensitive coloring resin (R), the coating liquid for green photosensitive coloring resin (G), and the coating liquid for blue photosensitive coloring resin (G) comprising the composition of Formulation-17 to Formulation-19 shown in Table 5 below. B) was prepared respectively.

<Formation of color filter>
Next, the coating solution for red photosensitive resin layer was applied to the surface of the glass substrate with the black matrix obtained in Example 8 on which the black matrix was formed, and dried using a spinner (manufactured by Daitron), and dried. A red photosensitive resin layer having a thickness of 2.0 μm was provided.
Next, a photomask was placed thereon, and pattern exposure was performed through the photomask at an exposure amount of 100 mJ / cm ² . Next, a 20% diluted solution of T-CD-1 for removing the unexposed portion of the red photosensitive resin layer was shower-developed at 33 ° C. for 30 seconds. As the next developing solution, a 10% diluted solution of T-SD-1 for removing the residue was shower-developed at 33 ° C. for 30 seconds. Thereafter, a heat treatment was carried out at 220 ° C. for 10 minutes to form a red pixel pattern (red colored layer).
Next, except for using the green photosensitive resin layer coating solution and the blue photosensitive resin layer coating solution, respectively, the same process as the formation of the red pixel pattern is performed, and the green pixel pattern and the blue pixel pattern are respectively obtained. Formed.
Finally, heating was performed at 220 ° C. for 120 minutes to obtain a color filter substrate.

(Comparative Example 9)
In Example 9, a glass substrate with a black matrix obtained in Comparative Example 8 was used instead of the glass substrate with a black matrix obtained in Example 8, and a photosensitive resin having the composition of Formulas 17 to 19 was used. A color filter substrate was produced in the same manner as in Example 9 except that the photosensitive resin layer coating solution having the composition of Formulation-14 to Formulation-16 was used instead of the layer coating solution.

[Evaluation]
For the color filter substrate obtained above, the number of black matrix portion defects per 1 m ² (defects caused by the inclusion of agglomerated foreign matter having a size of 20 μm or more) was measured with an optical microscope (magnification: 300 times). ). The number of defects was determined as an average value for five color filter substrates.
In addition, the film thickness of the black matrix after the heat treatment at 220 ° C. for 10 minutes after the exposure / development treatment was measured using slice SEM observation.
Furthermore, the optical density OD of the black matrix was determined by measurement using a reflective Macbeth densitometer (RD-918, manufactured by Macbeth). The results are shown in Table 6.

About the pixel pattern (colored layer) of each color of the color filter substrate obtained above,
Using slice SEM observation, the film thickness of the colored layer after coating and drying and the film thickness of the colored layer after heat treatment at 220 ° C. for 10 minutes are measured, and further the difference in film thickness between the black matrix and the colored pixels Was measured.
Further, the number of defective portions of the colored layer was measured in the same manner as in the case of the black matrix.
In addition, the state of air contamination that may occur due to the influence of the defective portion of the black matrix portion or the defective portion of the colored layer during pixel formation was observed using an optical microscope.
Further, the optical density of the black matrix was measured using a reflection Macbeth densitometer (RD-918, manufactured by Macbeth Co.).

From Table 6 and Table 7, when a black matrix (light-shielding layer) and a colored layer were formed using the curable composition of the present invention, the coating thickness variation after heat treatment at 220 ° C. for 10 minutes was small and good. It can be seen that it shows excellent performance.
Moreover, it turns out that the air mixing which may generate | occur | produce at the time of pixel formation can be suppressed effectively by using the curable composition of this invention. Here, the last half of the pixel means that in the pixel surrounded by the black matrix, air mixing has occurred in the application downstream region during pixel formation.

(Example 10)
<Preparation of protective layer forming coating solution>
A coating solution 1 for forming a protective layer having the following composition was prepared.
-Coating liquid for forming protective layer 1-
Poly (benzyl methacrylate / acrylic acid) 10 parts by weight (molar ratio 7/3, weight average molecular weight 85000, Tg = 73 ° C., acid value = 110)
-Resin (Compound structure P-15, Mw = 10,000) 1-methoxy-2-propanol solution (45%) 7.5 parts by weight-Dipentaerythritol hexaacrylate 15 parts by weight-2,4-trichloromethyl ( Piperonyl) -6-triazine 0.5 parts by weight-Surfactant initiator (Exemplary Compound 30) 0.2 parts by weight-Methoxypropyl acetate 67 parts by weight

[Evaluation]
A protective layer was formed using the protective layer forming coating solution 1 as described below, and the properties of the formed protective layer were evaluated. The results are shown in Table 7.

-Developability and curability-
The protective layer-forming coating solution 1 was applied and dried on a glass substrate using a spin coater to form a protective layer-forming composition layer having a dry film thickness of 5 μm on the glass substrate. Next, using a mercury lamp, exposure was performed at an exposure amount of 50 mJ / cm ² through a protective layer baking mask. A protective layer was formed by developing with a 1% aqueous sodium carbonate solution at 30 ° C. for 60 seconds.
The surface of the obtained protective layer was observed with a microscope (magnification: 500 times). First, the unexposed part (masked part) was observed and the presence or absence of a residue was evaluated as developability. It shows that developability is so good that there is no residue. Further, the boundary between the exposed portion and the unexposed portion (masked portion) was observed, and the linearity of the boundary was evaluated as curability. Higher linearity indicates better developability.

-Board adhesion-
In the same manner as described above, a protective layer-forming composition layer having a dry film thickness of 3 μm was formed on a glass substrate. Next, the entire surface of the protective layer-forming composition layer was exposed (exposure amount: 200 mJ / cm ² ) and developed in the same manner as described above. After that, using a NT cutter, cross-cut (1 mm square lattice), and apply Mylar tape (Nichiban Co., Ltd., CT405AP-18). The adhesion was evaluated by counting whether peeling occurred. One having 100 pieces of crosscut portions with no peeling was regarded as having good adhesion, and one of 100 pieces of crosscuts having peeled even at one place was determined to have poor adhesion.

-Deformability-
In the same manner as described above, a protective layer-forming composition layer having a dry film thickness of 3 μm was formed on a glass substrate. Next, the entire surface of the protective layer-forming composition layer was exposed (200 mJ / cm ² ) and developed in the same manner as described above to form a protective layer.
Press a steel ball of 0.5mmφ against the surface of the formed protective layer with a load of 50g for 1 minute as a contact point, and observe the deformation after removing the steel ball and the damage of the surrounding area under a microscope (magnification: 300x) It was evaluated with.

−Scratch resistance−
The surface of the protective layer produced in the same manner as the evaluation of the deformability was subjected to a scratch test with a load of 50 g using a 0.1 mmR sapphire needle. The presence or absence of scratches was evaluated by microscopic observation (magnification: 300 times).

(Comparative Example 10)
In Example 10, instead of the protective layer forming coating solution 1, a protective layer was formed in the same manner as in Example 10 except that the protective layer forming coating solution 2 having the following composition was used. The results are shown in Table 8.

-Coating liquid for protective layer formation 2-
Poly (benzyl methacrylate / acrylic acid) 10 parts by weight (molar ratio 7/3, weight average molecular weight 85000, Tg = 73 ° C., acid value = 110)
-Resin (Compound structure P-15, Mw = 10,000) 1-methoxy-2-propanol solution (45%) 7.5 parts by weight-Dipentaerythritol hexaacrylate 15 parts by weight-2,4-trichloromethyl ( Piperonyl) -6-triazine 0.5 parts by weight / Methoxypropyl acetate 67 parts by weight

From Table 8, it can be seen that when the protective layer is formed using the curable composition of the present invention, excellent performance is obtained in all of developability, curability, adhesion, deformability, and scratch resistance.

Claims (19)

  A curable composition containing at least a resin (A) having a reactive group and an acidic group, a polymerizable compound (B), a photopolymerization initiator (C), and a surface active photopolymerization initiator (D). object.   The surface-active photopolymerization initiator (D) is selected from an optionally substituted alkyl group having 3 to 30 carbon atoms, an optionally substituted siloxane group, and an optionally substituted fluorinated alkyl group. The curable composition according to claim 1, which is a compound having at least one kind.   The said resin (A) further has group which has a branched and / or alicyclic structure, The curable composition of Claim 1 or Claim 2 characterized by the above-mentioned.   The curable composition according to claim 3, wherein the group having an alicyclic structure is a group derived from an optionally substituted cyclic compound having 6 to 25 carbon atoms.   The curable composition according to any one of claims 1 to 4, wherein the reactive group is an ethylenically unsaturated group.   The curable composition according to any one of claims 1 to 5, further comprising a colorant (E).   The curable composition according to any one of claims 1 to 6, further comprising fine particles (F).   The curable composition according to claim 7, wherein the fine particles (F) have an average particle diameter of 5 to 50 nm and a mass ratio of 5 to 50 mass% with respect to the total solid content.   The curable composition according to claim 7 or 8, wherein the fine particles (F) are colloidal silica.   A curable resin transfer material having at least a curable composition layer formed using the curable composition according to any one of claims 1 to 9 on a temporary support.   The curable resin transfer material according to claim 10, further comprising an oxygen barrier layer and / or a thermoplastic resin layer between the temporary support and the curable resin layer.   The cured film formed by exposing and developing the curable resin layer formed using the curable composition of any one of Claims 1-9.   The cured film according to claim 12, wherein the cured film is used for any of a colored layer, a light shielding layer, a photospacer, and a protective film of a color filter.   The manufacturing method of the cured film which has the process of forming a curable composition layer on a support body by apply | coating the curable composition of any one of Claims 1-9.   The process of forming a curable composition layer on a support body by transferring a curable composition layer by heating and / or pressurization using the curable resin transfer material according to claim 10 or 11. The manufacturing method of the cured film which has this.   15. The method further comprises a patterning step of forming a pattern by exposing and developing the curable composition layer to produce any one of a colored layer of a color filter, a light shielding layer, a photospacer, and a protective film. Or the manufacturing method of the cured film of Claim 15.   The said patterning process further includes heat processing, The manufacturing method of the cured film of any one of Claims 14-16 characterized by the above-mentioned.   The board | substrate for liquid crystal display devices provided with the cured film manufactured by the manufacturing method of the cured film of any one of Claims 14-17.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 18.