JP2009079140A - Curable composition, curable resin transfer film, method for manufacturing spacer, substrate for liquid crystal display and liquid crystal display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable composition and a curable resin transfer film, suppressing degradation in developing property of a curable resin layer formed on a substrate with lapse of time and degradation in display irregularity of a liquid crystal display when the composition is used as a spacer. <P>SOLUTION: The curable composition comprises at least: a resin (A) having a branched and/or alicyclic structure, an acidic group and a group having an ethylenically unsaturated bond, in a side chain; a polymerizable compound (B); and an initiator (C) having two or more polybenzene structures having a (4,6-bistrihalomethyl-S-triazin-2-yl) group or a 2-(5-trihalomethyl-1,3,4-oxadiazol-2-yl)ethenyl group and a group having a valence of n in the benzene ring. The curable resin transfer film has a curable resin layer formed by using the above composition, on a temporary support. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing a curable composition, a curable resin transfer film and a spacer, a substrate for a liquid crystal display device provided with the spacer produced by this method, and a liquid crystal display device.

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

  Conventionally, the spacer has been formed by bead dispersion, but in recent years, a spacer having high positional accuracy has been formed by proximity exposure using a curable resin composition. A spacer formed using such a curable resin composition is called a photospacer.

About the photo spacer produced through patterning, alkali development, and baking using the curable resin composition, the compressive strength of the spacer dots is weak, and the plastic deformation tends to increase 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. Moreover, it is also important that the alkali development residue of a curable resin composition does not arise in the point of the liquid stability of a curable resin composition, and the high precision of a liquid crystal display device.
Furthermore, in recent years, for production adjustment, after laminating a curable resin layer on a glass substrate using a curable resin composition and a curable resin transfer film, it is once stored in a rack or the like, and after a certain period of time, after exposure The process may be carried out. In such a case, developability, mechanical properties (deformation recovery rate, etc.), display properties, etc. may deteriorate due to the influence of storage time.

For spacers with high positional accuracy by proximity exposure, co-polymerization of ethylenically unsaturated carboxylic acid and / or ethylenically unsaturated carboxylic acid anhydride, epoxy group-containing ethylenically unsaturated compound and other ethylenically unsaturated compounds For display panels that can faithfully reproduce the mask pattern design size even with proximity exposure, and have excellent strength, heat resistance, etc., required for spacers, using a radiation-sensitive resin composition containing coalescence and trihalomethyltriazines A method for forming a spacer has been proposed. (For example, refer to Patent Document 1).
However, in the above method, a composition stored at a low temperature provides good performance, but the stability is poor, and when a composition stored at room temperature is applied, uneven coating may occur or coating may not be possible. It was.
In order to improve this, a segment consisting of a segment A having a carboxyl group in the side chain, a segment B in which a compound having a polymerizable double bond is bonded to the side chain via an ester bond, and a nonionic segment C A photocurable resin composition characterized by containing a polymer has been proposed. (For example, see Patent Document 2)

In addition, as a spacer forming technique for keeping the thickness (cell thickness) of the liquid crystal layer constant, it is disclosed that a resin having an allyl group is used for spacer formation (see, for example, Patent Document 3).
Although these proposals improve the liquid stability, developability, mechanical properties (deformation recovery rate, etc.), display properties, etc., when a curable resin layer is laminated on a glass substrate and after an elapse of a certain time, the exposure process is performed. Could get worse.
JP 2002-278064 A JP 2005-62620 A JP 2003-207787 A

  The object of the present invention is to solve the conventional problems and to solve the following problems. That is, the present invention provides a curable composition with good liquid stability, deterioration of display unevenness of a liquid crystal display device when applied as a spacer and a developing property over time after a curable resin layer is formed on a substrate. Curable composition and curable resin transfer film, method for producing spacer using curable composition or curable resin transfer film, and substrate for liquid crystal display device provided with the spacer produced by this method, An object of the present invention is to provide a liquid crystal display device capable of displaying a high-quality image.

As a result of intensive studies, the present inventors have found that the above problem can be achieved by combining a specific copolymer and an initiator.
That is, the present invention
<1> Resin (A), polymerizable compound (B) having the group having a branched and / or alicyclic structure, an acidic group, and a group having an ethylenically unsaturated bond in the side chain, and the following general formula (I) It is a curable composition characterized by including the initiator (C) represented at least.

  In the formula, T represents a (4,6-bistrihalomethyl-S-triazin-2-yl) group or a 2- (5-trihalomethyl-1,3,4-oxadiazol-2-yl) ethenyl group, Y represents an n-valent group, and n represents an integer of 2 or more. The benzene ring may have a substituent other than T.

  <2> The curable composition according to <1>, wherein the group having an alicyclic structure is a group having a cyclic structure having 6 or more carbon atoms which may have a substituent. .

  <3> The curable composition according to <1> or <2>, further comprising fine particles (D).

  <4> The average particle size of the fine particles (D) is 5 to 50 nm, and the mass ratio with respect to the total solid content in the curable composition is 5 to 50 mass%. It is a curable composition.

  <5> The curable composition according to <3> or <4>, wherein the fine particles (D) are colloidal silica.

  <6> A curable resin transfer film having at least a curable resin layer on a temporary support, wherein the curable resin layer is a curable composition according to any one of <1> to <5>. A curable resin transfer film formed using a product.

  <7> The curable resin transfer film according to <6>, further comprising an intermediate layer and / or a thermoplastic resin layer between the curable resin layer and the temporary support.

  <8> A spacer having a step of forming a curable resin layer on a support by coating with the curable composition according to any one of <1> to <5>. It is a manufacturing method.

  <9> A spacer having a step of transferring a curable resin layer onto a support by heating and / or pressurization using the curable resin transfer film according to <6> or <7>. It is a manufacturing method.

  <10> A substrate for a liquid crystal display device, comprising a spacer produced by the method for producing a spacer according to <8> or <9>.

  <11> A liquid crystal display device comprising the substrate for a liquid crystal display device according to <10>.

  According to the present invention, a curable composition with good liquid stability, deterioration of display unevenness of a liquid crystal display device when applied as a spacer, and developability over time after a curable resin layer is formed on a substrate. Curable composition and curable resin transfer film, method for producing spacer using curable composition or curable resin transfer film, and substrate for liquid crystal display device provided with the spacer produced by this method, In addition, a liquid crystal display device capable of displaying a high-quality image is provided.

  Hereinafter, the curable composition, the curable resin transfer film, the method for producing a spacer, the substrate for a liquid crystal display device and the liquid crystal display device of the present invention will be described in detail.

<Curable composition>
The curable composition of the present invention includes a resin (A) having a branched and / or alicyclic structure, an acidic group, and a group having an ethylenically unsaturated bond in the side chain (A), the polymerizable compound (B), and the following. It is characterized by comprising at least the initiator (C) represented by the general formula (I).

  In the formula, T represents a (4,6-bistrihalomethyl-S-triazin-2-yl) group or a 2- (5-trihalomethyl-1,3,4-oxadiazol-2-yl) ethenyl group, Y represents an n-valent group, and n represents an integer of 2 or more. The benzene ring may have a substituent other than T.

  According to the curable composition of the present invention, after forming a curable resin layer on a substrate using the curable composition of the present invention, the development of the liquid crystal display device when applied as a spacer over time. Deterioration of display unevenness can be suppressed. Moreover, when the curable composition of the present invention is used as a liquid, good liquid stability can be realized.

Hereinafter, each component which comprises the curable composition of this invention is demonstrated in detail.
-Resin (A)-
The resin (A) according to the present invention comprises a group having a branched and / or alicyclic structure: X (x mol%), an acidic group: Y (y mol%), and a group having an ethylenically unsaturated bond: Z ( z mol%) in the side chain, and may optionally have other groups: L (1 mol%). A group having a branched and / or alicyclic structure, an acidic group, and a group having an ethylenically unsaturated bond may be contained in different side chains, or a part of them may be combined in the same side chain. It may be contained, or all may be contained in the same side chain.

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

-Group having a branched and / or alicyclic structure: X-
The “group having a branched and / or alicyclic structure” will be described.
First, examples of the group having a branched structure include a branched alkyl group having 3 to 12 carbon atoms. Specifically, 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.

Examples of the group having an alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms. Specifically, for example, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group And a tricyclopentanyl group.
In the present invention, the group having an alicyclic structure is preferably a group having a cyclic structure having 6 or more carbon atoms which may have a substituent. Specifically, a cyclohexyl group, a norbornyl group, an isobornyl group, an adamantyl group, a tricyclodecyl group, a tricyclopentenyl group, a tricyclopentanyl group and the like are preferable, and a cyclohexyl group, a norbornyl group, an isobornyl group, and a tricyclopentenyl group are more preferable. Etc. are preferred.

  Examples of the monomer containing a group having a branched and / or alicyclic structure 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 the group having a branched structure include i-propyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and (meth) acrylic acid. t-butyl, i-amyl (meth) acrylate, t-amyl (meth) acrylate, sec-iso-amyl (meth) acrylate, 2-octyl (meth) acrylate, 3-octyl (meth) acrylate , (Meth) acrylic acid t-octyl, and the like. Among them, i-propyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl methacrylate and the like are preferable, and methacrylic acid is more preferable. i-propyl, t-butyl methacrylate and the like.

  Specific examples of the monomer containing a group having the alicyclic structure include (meth) acrylate having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Specific examples include (meth) acrylic acid (bicyclo [2.2.1] heptyl-2), (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2-adamantyl, (meth) acrylic. Acid-3-methyl-1-adamantyl, (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, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, oct (meth) acrylate Hydro-4,7-mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, (meth) acrylate-1-menthyl, tricyclo (meth) acrylate 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) acrylate, isobornyl (meth) acrylate, fuentyl (meth) acrylate, (meth) acrylic acid-2,2,5-trimethylcyclohexyl, (meth) And 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 preferable, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, ( Particularly preferred are isobornyl (meth) acrylate and 2-adamantyl (meth) acrylate.

  Specific examples of the monomer containing a group having an alicyclic structure further 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, 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.

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

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

  Specific examples of the monomer having an acidic group can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, Itaconic acid, crotonic acid, cinnamic acid, sorbic acid, α-cyanocinnamic acid, acrylic acid dimer, addition reaction product of hydroxyl group-containing monomer and cyclic acid anhydride, ω-carboxy-polycaprolactone mono (meth) acrylate Etc. 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 an ethylenically unsaturated bond: Z-
The “group having an ethylenically unsaturated bond” is not particularly limited, but is preferably a (meth) acryloyl group. The group having an ethylenically unsaturated bond is introduced into the side chain of the resin (A) via a divalent linking group such as an ester group, an amide group, or a carbamoyl group, but is particularly limited to the divalent linking group. There is no. The method of introducing a group having an ethylenically unsaturated bond into the side chain of the resin (A) can be appropriately selected from known ones. For example, (meth) acrylate having an epoxy group in a repeating unit having an acidic group , A method of adding a (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, a method of adding a (meth) acrylate having a hydroxy group to a repeating unit having an isocyanate group, and the like.
Among these, the method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group is most preferable because it is the easiest to produce and is low in cost.

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

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

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

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

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

-Other groups: L-
The resin (A) may have other groups as necessary, and the monomer for introducing the other groups into the resin (A) is not particularly limited. Or a (meth) acrylic acid ester having no alicyclic structure; styrene; a monomer having a vinyl ether group, a dibasic acid anhydride group, a vinyl ester group, or a hydrocarbon alkenyl group.
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 resin (A), it is preferable that it is 0-30 mol% by molar composition ratio, and it is more preferable that it is 0-20 mol%.

  Specific examples of the resin (A) include compounds represented by the following compounds P-1 to P-35.

-Manufacturing method of resin (A)-
Resin (A) is produced through two steps: a step of (co) polymerizing monomers to obtain a (co) polymer and a step of introducing an ethylenically unsaturated group into the (co) polymer. can do.
First, the (co) polymerization reaction is carried out using 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 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 the production suitability and developability of the resin (A). Further, it is preferable in that the shape formed by the decrease in melt viscosity is difficult to be crushed, the crosslinking is difficult to occur, and there is no spacer-shaped residue in development.

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

-Acid value-
The preferred range of 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. Particularly preferred is g. When the acid value is within the preferred range, a spacer having good developability and mechanical strength can be obtained.

The glass transition temperature (Tg) of the resin (A) is 40 to 180 ° C., and the weight average molecular weight is 10,000 to 100,000, whereby a spacer having good developability and mechanical strength can be obtained. Is preferable.
Furthermore, the preferable example of the said resin (A) has more preferable each combination of the said preferable molecular weight, glass transition temperature (Tg), and an acid value.

The resin (A) according to the present invention includes a group having a branched and / or alicyclic structure: X (x mol%), an acidic group: Y (y mol%), and a group having an ethylenically unsaturated bond: Z. From the viewpoint of deformation recovery rate, development residue, and reticulation, a copolymer of at least ternary copolymer having (z mol%) in different copolymer units is preferable. Specifically, a copolymer obtained by copolymerizing at least one of the respective monomers containing X, Y, and Z is preferable.
The copolymer composition ratio of the respective components of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally described. However, the group having a branched and / or alicyclic structure is 10 to 70. Mol% is preferable, 15 to 65 mol% is more preferable, and 20 to 60 mol% is particularly 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 acidic group is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, particularly preferably 20 to 50 mol%. When the acidic group is within the above range, good curability and developability can be obtained.
Further, the group having an ethylenically unsaturated bond is preferably from 10 to 70 mol%, more preferably from 20 to 70 mol%, particularly preferably from 30 to 70 mol%. When the group having an ethylenically unsaturated bond is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

  As content of resin (A), 5-70 mass% is preferable with respect to curable composition total solid of this invention, and 10-50 mass% is more preferable. Other resins described later can be contained in the curable composition of the present invention in combination with the resin (A), but only the resin (A) is preferable.

-Other resins-
The other resin that can be used in combination with the resin (A) is preferably a compound that shows swelling property with respect to the alkaline aqueous solution, and more preferably a compound that is soluble in the alkaline aqueous solution.
As the resin exhibiting swellability or solubility with respect to the 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 the 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 a mixture of maleamic acid and the like.
The acidic group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. Among these, the availability of raw materials, etc. From the viewpoint, a carboxyl group is preferable.

-Ratio of resin (A) to other resins-
The total content of the resin (A) and the other resin 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 of the present invention. 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.

-Polymerizable compound (B)-
In the present invention, a component constituting a known composition as the polymerizable compound (B) can be suitably used. For example, the monomer or oligomer described in paragraph [0011] of JP-A-2006-23696, Examples thereof include polymerizable monomers described in paragraph numbers [0040] to [0049] of JP-A No. 2006-64921.

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

-Initiator (C)-
The initiator (C) according to the present invention is represented by the following general formula (I).

  In the formula, T represents a (4,6-bistrihalomethyl-S-triazin-2-yl) group or a 2- (5-trihalomethyl-1,3,4-oxadiazol-2-yl) ethenyl group, Y represents an n-valent organic group, and n represents an integer of 2 or more. The benzene ring may have a substituent other than T. As n, 2-6 are preferable and 2-4 are still more preferable.

The n-valent group Y, is not particularly limited, for example, the terminal _{-COO -, - O -, -} N (CH 3) -, - N (C 2 H 5) -, - N ( _{CH 3 OCOCH 2) -, -} N (CH 3 OCO) -, - NH -, - N (CH 3) CO -, - N (C 2 H 5) CO- or aliphatic or aromatic having a -NHCO- A hydrocarbon etc. are mentioned. Among these, the terminal _{-COO -, - O -, -} N (C 2 H 5) -, - N (CH 3 OCOCH 2) -, - NH -, - N (C 2 H 5) CO- or - aliphatic or aromatic hydrocarbons are preferred having NHCO-, -COO terminated _{-, - O -, - N} (C 2 H 5) -, - NH-, or aliphatic or aromatic having a -NHCO- More preferred are hydrocarbons.

  Specific examples of the initiator (C) include the following compounds.

  In the above compound examples, T represents a (4,6-bistrihalomethyl-S-triazin-2-yl) group, and Ac represents an acetyl group.

  Compounds according to the above compound examples can be synthesized by the method of the following formula 1 or formula 2.

In the above formula, X represents a halogen atom, Y, Y ₁ represents a divalent group, U represents —O—, —NR— or —NHCO (C ₆ H ₄ ) O—, and Z represents a halogen atom or a substituent. In the sulfonyloxy group, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. That is, Formula 1 is a reaction of bisbenzonitrile and trihaloacetonitrile, and Formula 2 is a dimerization of a phenol or aniline derivative having a triazine skeleton using a bifunctional acid halide, active halide, or active sulfonate. To do. Similarly, those having a trimer or higher are synthesized according to a conventional method.

  As content of an initiator (C), 0.1-20 mass% is preferable with respect to resin (A), and 0.5-10 mass% is more preferable.

-Fine particles (D)-
The curable composition of the present invention preferably contains fine particles (D). The fine particles (D) are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A-2003-302539 [0035] to [0041] are preferable, and among them, good Colloidal silica is preferable from the viewpoint that a spacer having excellent developability and mechanical strength can be obtained.

  The average particle size of the fine particles (D) is preferably 5 to 50 nm, more preferably 10 to 40 nm, and particularly preferably 15 to 30 nm because a spacer having high mechanical strength can be obtained. .

  Further, the content of the fine particles (D) is preferably 5 to 50% by mass with respect to the total solid content in the curable composition in the present invention, since a spacer having high mechanical strength is obtained. It is more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass.

-Solvent-
In the curable composition of this invention, you may contain a solvent other than the said component. Examples of the solvent include, but are not limited to, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methyl isobutyl ketone, ethyl lactate, methyl lactate, and caprolactam. . The content of the solvent when the curable composition of the present invention is used as a liquid can be appropriately adjusted in consideration of the viscosity and the like. For example, the curable composition preferably contains 50 to 90% by mass, More preferably, it is contained in an amount of 60 to 85% by mass.

-Other ingredients-
The curable composition of this invention can use suitably the well-known component which comprises a composition as another component as needed. Specific examples of other components include, for example, the components described in paragraph numbers [0014] to [0020] of JP-A-2006-23696 and the paragraph numbers [0053] of JP-A-2006-64921. Ingredients.

<Curable resin transfer film>
The curable resin transfer film of the present invention is characterized by having a curable resin layer formed on the temporary support using at least the curable composition of the present invention. The film thickness of the curable resin layer is preferably about 0.2 to 2.0 μm, and more preferably 0.2 to 0.9 μm.
According to the curable resin transfer film of the present invention, after the curable resin layer is formed on the substrate using the curable resin transfer film of the present invention, the liquid crystal display device when applied as a developability with time and as a spacer It is possible to suppress the deterioration of display unevenness.

  The curable resin transfer film of the present invention has a curable resin layer formed using at least the curable composition of the present invention on a temporary support, and if necessary, a curable resin layer and An intermediate layer and / or a thermoplastic resin layer may be provided between the temporary support. Hereinafter, each component constituting the curable resin transfer film of the present invention will be described in detail.

(Temporary support)
In the present invention, the temporary support is required to be flexible and not to cause significant deformation, shrinkage or elongation even under pressure or pressure and heating. Examples of such a support include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film, and among them, a biaxially stretched polyethylene terephthalate film is particularly preferable. The thickness of the temporary support is suitably 5 to 300 μm, particularly preferably 20 to 150 μm.

(Thermoplastic resin layer)
As the component used for the thermoplastic resin layer, organic polymer substances described in JP-A-5-72724 are preferable, and the polymer softening point according to the Viker Vicat method (specifically, the American Material Testing Method ASTM D1 ASTM D1235). It is particularly preferable that the softening point by the measurement method is selected from organic polymer substances having a temperature of about 80 ° C. or less.

Specifically, polyolefins such as polyethylene and polypropylene, ethylene copolymers such as ethylene and vinyl acetate or saponified products thereof, ethylene and acrylic acid esters or saponified products thereof, polyvinyl chloride, vinyl chloride and vinyl acetate and saponified products thereof. Vinyl chloride copolymer such as fluoride, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer such as styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene, vinyl toluene and (meta ) Vinyl toluene copolymer such as acrylic ester or saponified product thereof, poly (meth) acrylic ester, (meth) acrylic ester copolymer such as butyl (meth) acrylate and vinyl acetate, vinyl acetate copolymer Combined nylon, copolymer nylon, N-alkoxyme Le nylon, and organic polymeric polyamide resins such as N- dimethylamino nylon.
The dry thickness of the thermoplastic resin layer is generally 2 to 30 μm, preferably 5 to 20 μm, and particularly preferably 7 to 16 μm.

(Middle layer)
In the curable resin transfer film of the present invention, it is preferable to provide an intermediate layer for the purpose of preventing mixing of components during application of a plurality of application layers and during storage after application. As the intermediate layer, it is preferable to use an oxygen-blocking film having an oxygen-blocking function, which is described as “separation layer” in JP-A-5-72724. This reduces the time load and improves productivity.
The oxygen barrier film is preferably one that exhibits low oxygen permeability and is dispersed or dissolved in water or an aqueous alkali solution, and can be appropriately selected from known ones. Among these, a combination of polyvinyl alcohol and polyvinyl pyrrolidone is particularly preferable. The dry thickness of the intermediate layer is generally 0.2 to 5 μm, preferably 0.5 to 3 μm, particularly preferably 1 to 2.5 μm.

(Protective film)
It is preferable to provide a thin protective film on the curable resin layer in order to protect it from contamination and damage during storage of the curable resin transfer film. The protective film may be made of the same or similar material as the temporary support, but it must be easily separated from the curable resin layer. For example, silicone paper, polyolefin or polytetrafluoroethylene sheet is suitable as the protective film material. The thickness of the protective film is generally 4 to 40 μm, preferably 5 to 30 μm, and particularly preferably 10 to 25 μm.

(Method for producing curable resin transfer film)
The curable resin transfer film of the present invention is a thermoplastic resin layer obtained by applying a coating solution (coating solution for a thermoplastic resin layer) in which a composition constituting the thermoplastic resin layer is dissolved on a temporary support and drying the coating solution. Then, apply and dry a solution of an intermediate layer material composed of a solvent that does not dissolve the thermoplastic resin layer on the thermoplastic resin layer, and then apply and dry the curable resin layer using a solvent that does not dissolve the intermediate layer. It can produce by providing.
In addition, a sheet provided with the thermoplastic resin layer and the intermediate layer on the temporary support and a sheet provided with the curable resin layer on the protective film are prepared, and the intermediate layer and the curable resin layer are in contact with each other. In addition, a sheet provided with a thermoplastic resin layer on the temporary support and a sheet provided with a curable resin layer and an intermediate layer on a protective film are prepared, and a thermoplastic resin layer is prepared. Can also be produced by bonding them so that the intermediate layer is in contact with each other.

  In addition, although application | coating in the said preparation method can be performed with a well-known coating apparatus etc., in this invention, it is preferable to perform with the coating apparatus (slit coater) using a slit-shaped nozzle. Preferred specific examples of the slit coater will be described later.

<Method for manufacturing spacer>
The manufacturing method of the 1st spacer of this invention has the process of forming a curable resin layer on a support body by apply | coating using the curable composition of this invention, It is characterized by the above-mentioned. The second spacer production method of the present invention includes a step of transferring a curable resin layer onto a support by heating and / or pressurization using the curable resin transfer film of the present invention. And

The curable composition can be applied by a known application method such as spin coating, curtain coating, slit coating, dip coating, air knife coating, roller coating, wire bar coating, gravure coating, or It can be carried out by 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-shaped nozzle or a slit coater described in JP-A No. 2001-310147 is suitable.
When a curable resin layer is formed by coating using the curable composition of the present invention, a suitable amount of solvent is added to the curable composition of the present invention, and the viscosity suitable for the coating method using the viscosity of the composition. It is prepared and used. After application of the curable composition, a curable resin layer is obtained by drying the coating film formed by application.

  When using a curable resin transfer film, after the curable composition formed in a film form on the temporary support is bonded to the surface of the support by pressing or heat pressing with a roller or flat plate heated and / or pressed The curable resin layer is formed on 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.

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

  After forming the curable resin layer, the curable resin layer formed on the support is exposed and developed to be patterned (patterning step). Specific examples of the patterning process include the formation examples described in paragraphs [0071] to [0077] of Japanese Patent Application Laid-Open No. 2006-64921 and the paragraph numbers [0040] to [0051] of Japanese Patent Application Laid-Open No. 2006-23696. The described steps and the like are also preferable examples in the present invention. Through the patterning step, a spacer having a desired shape is obtained.

The spacer of the present invention can be formed after forming a color filter including a black shielding portion such as a black matrix and a colored portion such as a colored pixel.
The black shielding part, the colored part, and the spacer are formed by arbitrarily combining an application method for applying a curable composition and a transfer method using a transfer material having a curable resin layer made of the curable composition. Is possible.
The black shielding part, the colored part, and the spacer can each be formed from a curable composition. Specifically, for example, after a curable resin layer is formed by directly applying a liquid curable composition to a substrate, exposure and development are performed to form the black shielding portion and the colored portion in a pattern. Then, using a curable resin transfer film produced by placing another liquid curable composition on another substrate (temporary support) different from the substrate to form a curable resin layer, After the curable resin transfer film is brought into close contact with the substrate on which the black shielding portion and the colored portion are formed and the curable resin layer is transferred, the spacer can be formed in a pattern by exposure and development. In this way, a color filter provided with a spacer can be produced.

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention is provided with the spacer manufactured by the spacer manufacturing method of the present invention. The spacer is preferably formed on a display light-shielding portion 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 be present between the display light-shielding portion such as a black matrix or a driving element such as TFT and the spacer.

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

<Liquid crystal display element>
A liquid crystal display element can be configured using 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. Since this color filter substrate is provided with a spacer having a uniform height and excellent deformation recovery property, a liquid crystal display element equipped with the color filter substrate has a cell gap unevenness between the color filter substrate and the counter substrate ( Occurrence of cell thickness fluctuations) can be suppressed, and display unevenness such as color unevenness can be effectively prevented. Thereby, the produced liquid crystal display element can display a vivid image.

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), and the liquid crystal The driving means includes an active element (for example, TFT), and a pair of substrates is configured to be regulated to a predetermined width by a spacer having a uniform height and excellent deformation recovery.
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 of the present invention. In addition, the liquid crystal display device of the present invention may be configured by providing the liquid crystal display element. In other words, as described above, the space between a pair of substrates arranged to face each other is regulated to a predetermined width by the spacer produced by the spacer production method of the present invention, and a liquid crystal material is sealed in the regulated gap ( The enclosing portion is referred to as a liquid crystal layer.), And the thickness (cell thickness) of the liquid crystal layer may be 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 drive substrate and a counter substrate provided with a counter electrode (conductive layer). For example, the liquid crystal display device of the present invention can be suitably applied to various liquid crystal display devices.

  The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, side industry research committee, published in 1994)”. The liquid crystal display device of the present invention is not particularly limited except that it includes the substrate for the liquid crystal display device of the present invention. Can do. 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 polarization film, a retardation film, a backlight, a viewing angle compensation film, an antireflection film, a light diffusion film, except that the liquid crystal display device of the present invention described above is provided. It can be generally constructed using various members such as an antiglare film. Regarding these members, for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima, CMC Co., Ltd., published in 1994)”, “Current Status and Future Prospects of the 2003 Liquid Crystal Related Market (Part 2)” (Fuji Chimera Research Institute, Inc., 2003, etc.) ”.

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

A synthesis method of the resin (A) represented by the compound structure P-1 is shown in Synthesis Example 1 below.
(Synthesis Example 1)
8.57 parts of 1-methoxy-2-propanol (manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel, and the temperature was raised to 90 ° C., 6.27 parts of isopropyl methacrylate, 5.15 parts of methacrylic acid, azo series A mixed solution consisting of 1 part of a polymerization initiator (manufactured by Wako Pure Chemical Industries, Ltd., V-601) and 8.57 parts of 1-methoxy-2-propanol was placed in a 90 ° C. reaction vessel over 2 hours in a nitrogen gas atmosphere. It was dripped. 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 the dropwise addition, the mixture was reacted at 90 ° C. for 4 hours while blowing air, and then prepared by adding 1-methoxy-2-propyl acetate (MMPGAC) so that the solid concentration was 45%. A resin solution represented by the compound structure P-1 was obtained. The molecular weight Mw of the resin was 30000.
In addition, the molecular weight Mw of the resin represented by the compound structure P-1 represents a weight average molecular weight, and the molecular weight was measured using a gel permeation chromatograph (GPC).

  Next, synthesis methods of resins represented by the compound structures P-25, P-29 to P-35, and P-21 are shown in Synthesis Examples 2 to 10 below.

(Synthesis Examples 2 to 10)
The synthesis of the resins represented by the compound structures P-25, P-29 to P-35 and P-21 was carried out using x: l in the compound structures P-25, P-29 to P-35 and P-21: The addition amount of each compound, methyl methacrylate, methacrylic acid, glycidyl methacrylate and the like described in the x unit of Table 1 is changed so that y: z becomes the molar ratio (mol%) described in Table 1, and the weight Resin solutions represented by the compound structures P-25, P-29 to P-35 and P-21 having unsaturated groups by the same method as in Synthesis Example 1 except that the average molecular weight was 30000. Got.

  In Table 1, [1] is the binder of Synthesis 1 used in Example 1 of JP-A-2002-278064, and [2] is Example 1 of JP-A-2003-207787 <Coating liquid H1 for thermoplastic resin layer > Methacrylic acid / allyl methacrylate copolymer (molar ratio) = 20/80 (weight average molecular weight = 40,000) described in [3] is a binder used in Example 1 of JP-A-2005-62620, [4] is IRUGACURE907 (manufactured by Ciba Specialty Chemicals), [5] is benzyl methacrylate / methacrylic acid copolymer ((molar ratio) = 76/24, weight average molecular weight 40,000), and ADMA is 2-adamantyl methacrylate. Represents.

(Example 1): Transfer Method—Preparation of Curable Resin Transfer Film—
On a 75 μm-thick polyethylene terephthalate film temporary support (PET temporary support), a coating solution for a thermoplastic resin layer having the following formulation A is applied and dried to form a thermoplastic resin layer having a dry layer thickness of 16.5 μm. did.

[Prescription A for Coating Solution for Thermoplastic Resin Layer]
Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer 25.0 parts (= 55 / 11.7 / 4.5 / 28.8 [molar ratio], weight average molecular weight 90,000)
-Styrene / acrylic acid copolymer: 58.4 parts (= 63/37 [molar ratio], weight average molecular weight 8,000)
2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane
39.0 parts-Surfactant 1 (Megafac F-780-F, manufactured by Dainippon Ink & Chemicals, Inc.)
... 10.0 parts · Methanol ... 90.0 parts · 1-methoxy-2-propanol ... 51.0 parts · Methyl ethyl ketone ... 700 parts

Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.6 μm.
[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205, saponification rate 88%, 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 liquid for a curable resin layer (curable composition) comprising the formulation 1 shown in Table 2 below is further applied onto the formed intermediate layer and dried to obtain a curable resin having a dry layer thickness of 3.5 μm. Layers were laminated.

  In Table 2, the molecular weight Mw in the compound structure P-1 (45%) solution * 2 is 30000; solvent ratio = MMPGAC / 1-methoxy-2-propanol (wt / wt) = 0.3664).

  In Table 2, Compound 1 is as follows.

  After forming the laminated structure of the PET temporary support / thermoplastic resin layer / intermediate layer / curable resin layer as described above, a polypropylene film having a thickness of 12 μm is further formed as a cover film on the surface of the curable resin layer. Affixed by heating and pressing to obtain a curable resin transfer film (1).

-Fabrication of color filter substrate-
A color filter having a black matrix, an R pixel, a G pixel, and a 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 spacer-
The cover film of the obtained curable resin transfer film (1) is peeled off, and the exposed surface of the curable resin layer is overlaid on the ITO film of the color filter substrate on which the ITO film prepared above is sputtered, Using a laminator Lamic II type (manufactured by Hitachi Industries, Ltd.), the films were bonded together at a conveyance speed of 2 m / min under pressure and heating conditions of a linear pressure of 100 N / cm and 130 ° C. Thereafter, the PET temporary support was peeled and removed at the interface with the thermoplastic resin layer, and the curable resin 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 surface and the surface of the curable resin layer on the side in contact with the intermediate layer is 100 μm with the color filter substrate placed in a vertical position substantially parallel and perpendicular to the thermoplastic resin layer through the mask. Proximity exposure was performed at an exposure amount of 90 mJ / cm ² from the side. The period from the transfer of the curable resin layer to the proximity exposure was set to within 20 minutes at 23 ° C. and 55% RH.

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 developed at 29 ° C. for 50 seconds at a cone type nozzle pressure of 0.15 MPa. A 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, spraying was performed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa, and the residue around the formed pattern image was removed to obtain a desired spacer pattern (patterning step).

Next, the color filter substrate provided with the spacer pattern was subjected to a heat treatment at 240 ° C. for 50 minutes (heat treatment step) to produce a spacer.
The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm. In addition, average height measured the highest position from the transparent electrode formation surface of ITO, using three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022). The average was taken as the average height of the spacer.

<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.

(Example 2)
In Example 1, instead of the compound structure P-1 of the formulation 1 of the coating liquid for curable resin layer, the compound structure P-25 of the synthesis example 2 was used, and the spacer and the spacer were formed in the same manner as in the example 1. A liquid crystal display device was created. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Examples 3 to 14)
In Example 2, a spacer and a liquid crystal display were prepared in the same manner as in Example 2 except that the compound 1 was changed to the following compounds 2 to 7 and 9 to 14 instead of the compound 1 in the formulation 1 of the coating solution for the curable resin layer. Created a device. All of the obtained spacer patterns were cylindrical with a diameter of 15 μm and an average height of 3.2 μm.

(Example 15): Coating method-Spacer production (liquid cash register method)-
The following is shown in Table 3 on a glass substrate coater MH-1600 (manufactured by FS Asia Co.) having a slit-shaped nozzle on the ITO film of the color filter substrate on which the ITO film produced above is formed by sputtering. The formulation was applied. Subsequently, using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.), part of the solvent was dried for 30 seconds to eliminate the fluidity of the coating film, and then pre-baked at 120 ° C. for 3 minutes to cure to a film thickness of 3.5 μm. A functional resin layer was formed (layer forming step).

  In Table 3, the molecular weight Mw in the compound structure P-25 (45%) solution * 2 is 30000; solvent ratio = MMPGAC / 1-methoxy-2-propanol (wt / wt) = 0.3664).

Subsequently, spacers were 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 development with a sodium carbonate-based developer was 23 ° C. for 60 seconds. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

  After producing the spacer, a liquid crystal display device was produced in the same manner as in Example 1 using this color filter substrate.

(Examples 16 to 23)
In Example 3, a spacer and a liquid crystal display device were produced in the same manner as in Example 3 except that the binders (P29 to 35, P21) shown in the table were used instead of P-25. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Comparative Example 1)
In Example 15, the resin (A) was changed from P-25 to the binder of Synthesis 1 used in Example 1 of JP-A-2002-278064, the initiator (C) was changed from Compound 2 to the following Compound 8 (2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine), except that the total solid content and the hydroquinone monomethyl ether concentration in the composition were combined. A spacer and a liquid crystal display device were prepared. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Comparative Example 2)
In Example 3, instead of the compound structure P-25, the methacrylic acid / allyl methacrylate copolymer (molar ratio) described in Example 1 <Coating liquid H1 for thermoplastic resin layer> in JP-A-2003-207787 = 20 / 80 (weight average molecular weight = 40,000), the initiator (C) was changed from compound 2 to the following compound 15 (2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonyl) Tilamino) -3-bromophenyl] -s-triazine) and the spacer and the liquid crystal display device were prepared in the same manner as in Example 3 except that the total solid content and the hydroquinone monomethyl ether concentration in the composition were combined. Created. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Comparative Example 3)
In Example 15, the resin (A) is changed from P-25 to the binder used in Example 1 of JP-A-2005-62620, and the initiator (C) is changed from Compound 2 to IRUGACURE907 (manufactured by Ciba Specialty Chemicals). A spacer and a liquid crystal display device were prepared in the same manner as in Example 15 except that the total solid content concentration and the hydroquinone monomethyl ether concentration in the composition were combined. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Comparative Example 4)
In Example 3, the initiator (C) was changed from compound 2 to compound-15 (2,4-bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonyltylamino) -3-bromo. A spacer and a liquid crystal display device were prepared in the same manner as in Example 3 except that the phenyl] -s-triazine) was used. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

(Comparative Example 5)
In Example 3, the resin (A) was changed from P-25 to benzyl methacrylate / methacrylic acid copolymer ((molar ratio) = 76/24, weight average molecular weight 40,000), and the solid content concentration and the solvent composition were combined. A spacer and a liquid crystal display device were prepared in the same manner as in Example 3 except that. The obtained spacer pattern was a cylindrical shape having a diameter of 15 μm and an average height of 3.2 μm.

[Evaluation]
The following evaluation was implemented with respect to the coating liquid for curable resin layers obtained by each Example and the comparative example, a spacer, and a liquid crystal display device. Table 4 shows the obtained results.

-Deformation recovery rate-
Each of the spacers was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
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-
At the stage of “--Production of the spacer”, after the proximity exposure, develop under the same conditions as the development conditions of each Example and Comparative Example, and observe the SEM observation of the peripheral part of the spacer, and whether there are residues in the periphery Confirmed no.

<Evaluation criteria>
5: No residue is seen at all.
4: A slight residue was observed around the pattern.
3: Some 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-
Regarding the state in which the curable resin layer of the curable resin transfer film is transferred to the color filter substrate, the laminate is observed with an optical microscope after the temporary support is peeled off, and air bubbles (between the color filter substrate and the curable resin layer ( The presence or absence of lami bubbles 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 curable resin transfer film was allowed to stand for 24 hours in an environment of 45 ° C./75% RH, and then the surface of the curable resin transfer film after being allowed to stand was observed using 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>
5: No display unevenness was observed at any part of the liquid crystal cell.
4: Slight display unevenness was observed only at the four corners of the liquid crystal cell.
3: Slight display unevenness was observed only at the edge portions of the four sides of the liquid crystal cell.
2: Display unevenness was also observed in the central portion of the liquid crystal cell.
1: Remarkable display unevenness was observed on the entire surface of the liquid crystal cell.

-Storage stability (liquid stability)-
After storing the coating solution for the curable resin layer at 25 ° C. for 1 week, it is applied to the temporary support under the same conditions as those of the examples and comparative examples, or is applied to the color filter substrate, and the above three-dimensional surface is applied. Ten thicknesses of unevenness were measured with a structural analysis microscope and evaluated according to evaluation criteria.

<Evaluation criteria>
5: Unevenness of curable resin layer is extremely good with less than ± 0.5%.
4: The unevenness of the curable resin layer is good with less than ± 1%.
3: Ordinary unevenness of curable resin layer is less than ± 3%.
2: Unevenness of curable resin layer is bad at ± 3% or more.
1: The viscosity increased remarkably and could not be applied.

-Preservability (developability)-
After a curable resin layer is laminated on the color filter substrate by coating or laminating, it is left for 24 hours at a temperature / humidity of 23 ° C./55% RH, and then subjected to proximity exposure, which is the same as the development conditions of each example or comparative example. Development was performed under conditions, and SEM observation of the peripheral portion of the formed spacer was performed to confirm whether or not a residue remained in the periphery, and evaluation was performed according to the evaluation criteria.

<Evaluation criteria>
5: No residue is seen at all.
4: A slight residue was observed around the pattern.
3: Some 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.

-Preservability (uneven display)-
A curable resin layer is laminated on the color filter substrate by coating or transfer, and left for 24 hours at a temperature / humidity of 23 ° C./55% RH, and then subjected to proximity exposure, which is the same as the development conditions of each example or comparative example. With respect to each of the liquid crystal display devices that were developed under conditions, the gray display when the gray test signal was input was observed visually and with a magnifying glass, and the presence or absence of display unevenness was evaluated according to the following evaluation criteria.

<Evaluation criteria>
5: No display unevenness was observed at any part of the liquid crystal cell.
4: Slight display unevenness was observed only at the four corners of the liquid crystal cell.
3: Slight display unevenness was observed only at the edge portions of the four sides of the liquid crystal cell.
2: Display unevenness was also observed in the central portion of the liquid crystal cell.
1: Remarkable display unevenness was observed on the entire surface of the liquid crystal cell.

-Preservability (deformation recovery rate)-
A curable resin layer is laminated on the color filter substrate by coating or transfer, and left for 24 hours at a temperature / humidity of 23 ° C./55% RH, and then subjected to proximity exposure, which is the same as the development conditions of each example or comparative example. Each of the spacers developed by developing under conditions was measured and evaluated by a micro hardness tester (DUH-W201, manufactured by Shimadzu Corporation) as follows. The measurement was performed by a load-unloading test method using a frustum-type indenter with a diameter of 50 μm, a maximum load of 50 mN, and a holding time of 5 seconds. From this measured value, the deformation recovery rate [%] was obtained by the following formula and evaluated according to the following criteria. The measurement was performed in an environment of 22 ± 1 ° C. and 50% RH.
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%.

Claims (11)

It is represented by the resin (A), the polymerizable compound (B), and the following general formula (I) having a group having a branched and / or alicyclic structure, an acidic group, and a group having an ethylenically unsaturated bond in the side chain. A curable composition comprising at least an initiator (C).

In the formula, T represents a (4,6-bistrihalomethyl-S-triazin-2-yl) group or a 2- (5-trihalomethyl-1,3,4-oxadiazol-2-yl) ethenyl group, Y represents an n-valent group, and n represents an integer of 2 or more. The benzene ring may have a substituent other than T.   The curable composition according to claim 1, wherein the group having an alicyclic structure is a group having a cyclic structure having 6 or more carbon atoms which may have a substituent.   The curable composition according to claim 1 or 2, further comprising fine particles (D).   4. The curable composition according to claim 3, wherein the fine particles (D) have an average particle diameter of 5 to 50 nm and a mass ratio to the total solid content in the curable composition of 5 to 50 mass%. object.   The curable composition according to claim 3 or 4, wherein the fine particles (D) are colloidal silica.   A curable resin transfer film having at least a curable resin layer on a temporary support, wherein the curable resin layer is formed using the curable composition according to any one of claims 1 to 5. A curable resin transfer film characterized by being made.   The curable resin transfer film according to claim 6, further comprising an intermediate layer and / or a thermoplastic resin layer between the curable resin layer and the temporary support.   A method for producing a spacer, comprising a step of forming a curable resin layer on a support by applying the curable composition according to any one of claims 1 to 5.   A method for producing a spacer, comprising using the curable resin transfer film according to claim 6 or 7 to transfer a curable resin layer onto a support by heating and / or pressing.   A substrate for a liquid crystal display device, comprising a spacer manufactured by the spacer manufacturing method according to claim 8.   A liquid crystal display device comprising the liquid crystal display device substrate according to claim 10.