JP5207837B2 - Curable composition, cured film, method for producing photospacer, substrate for liquid crystal display device and liquid crystal display device - Google Patents

Description

  The present invention relates to a curable composition, a cured film, a method for producing a photospacer, 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 has a liquid crystal layer disposed between a pair of substrates to enable image display with a predetermined orientation. Maintaining the distance between the substrates, that is, the thickness of the liquid crystal layer, is one of the factors that determine the image quality. For this purpose, a spacer is provided to keep the thickness of the liquid crystal layer constant. 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. .

  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 curable composition. A spacer formed using such a curable composition is called a photo spacer.

  About the photo spacer produced through patterning, alkali development, and baking using the curable composition, the compressive strength of the spacer dot 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. In addition, it is important that no alkali development residue of the curable 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 curable 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 curable composition containing the surface active photoinitiator which can improve the surface strength of the cured film formed as a curable 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

Originally, a photo spacer used in a liquid crystal cell is required to have high deformation recovery. In order to achieve this, the crosslinking reaction rate of monomers and the like is increased, and the deformation recovery rate can be increased to some extent, but the improvement effect tends to reach its peak, and further improvement is required. It was.
The present invention has been made in view of the above, and has a high degree of deformation recovery after curing, for example, a curable composition that can eliminate display unevenness when a liquid crystal display device is formed, a cured film, and a photospacer. It is an object of the present invention to provide a substrate for a liquid crystal display device and a liquid crystal display device capable of displaying a high-quality image by preventing display unevenness, and a liquid crystal display device.

Specific means for solving the above problems are as follows.
<1> A resin containing a group having a branched and / or alicyclic structure, a group having an acidic group, and a group having an epoxy group, a polymerizable compound, a photopolymerization initiator, and a carbon number of 9 or more and 30 A curable composition comprising at least a surfactant photopolymerization initiator having at least one selected from the following alkyl groups, siloxane groups, and fluorinated alkyl groups .
<2> The curable composition according to <1>, wherein the surfactant photopolymerization initiator is a compound having at least one selected from an alkyl group having 16 to 30 carbon atoms, a siloxane group, and a fluorinated alkyl group . Composition.
<3> The surfactant photopolymerization initiator includes a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or an oxime compound. The curable composition according to <1> or <2>, which is a compound.
<4> The group according to any one of <1> to <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> A cured film obtained by curing the curable composition according to any one of <1> to <4>.
<6> A method for producing a photospacer comprising a step of forming a curable composition layer on a support by applying the curable composition according to any one of <1> to <4>.
<7> A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to <6>.
<8> A liquid crystal display device comprising the substrate for a liquid crystal display device according to <7>.

  ADVANTAGE OF THE INVENTION According to this invention, it has a high deformation | transformation recovery property after hardening, for example, when a liquid crystal display device is formed, the curable composition which can eliminate display nonuniformity, a cured film, the manufacturing method of a photo spacer, and a display It is possible to provide a liquid crystal display device substrate and a liquid crystal display device that can display high-quality images while preventing unevenness.

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

<Method for producing curable composition and photospacer>
The curable composition of the present invention includes at least one resin (A) containing a group having a branched and / or alicyclic structure, a group having an acidic group, and a group having an epoxy group, and a polymerizable compound. It contains at least one of (B), at least one photopolymerization initiator (C), and at least one surface-active photopolymerization initiator (D). Since the photospacer produced from the curable composition of the present invention has a high degree of deformation recovery, display unevenness in the display device can be eliminated.

  In addition, the method for producing a photospacer according to the present invention includes at least two supports, a liquid crystal provided between the supports, two electrodes for applying an electric field to the liquid crystal, and a cell between the supports. A photospacer for regulating a thickness, and a method for producing the photospacer in a liquid crystal display device, and curing using the curable composition of the present invention on one of the two supports A layer forming step of forming a conductive composition layer.

  According to the method for producing a photospacer of the present invention, a photospacer having a high degree of deformation recovery can be easily produced.

  Hereinafter, the manufacturing method of the photospacer 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 layer forming step in the present invention is a step of forming a curable composition layer (hereinafter also simply referred to as “curable resin layer”) that is included by applying the curable composition of the present invention on a support.
This curable resin layer can constitute a photospacer that has a good deformation recovery property and can maintain a uniform cell thickness through a patterning step described later. By using the photospacer, display unevenness in an image in a display device in which display unevenness is likely to occur due to a change in cell thickness is effectively eliminated.

  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 composition layer on a temporary support is used, and a curable resin layer formed in a film shape on the temporary support is formed on the support surface. After laminating by pressing or thermocompression bonding with a heated and / or pressurized roller or flat plate, the curable resin composition 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 blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) may be provided between the curable resin layer and the temporary support. it can. Thereby, the exposure sensitivity can be increased. Moreover, in order to improve transferability, you may provide the thermoplastic resin layer which has cushioning properties.
Regarding the temporary support, the oxygen blocking layer, the thermoplastic resin layer, other layers and the method for producing the curable transfer film constituting the curable transfer film, paragraph Nos. [0024] to JP-A-2006-23696. This is the same as the configuration and the manufacturing method described in [0030].

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

  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 is a resin (A) containing a group having a branched and / or alicyclic structure, a group having an acidic group, and a group having an epoxy group (hereinafter also simply referred to as “resin (A)”). ), A polymerizable compound (B), a photopolymerization initiator (C), and a surface active photopolymerization initiator (D). Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.
The curable composition is particularly preferably used for a photospacer.

-Resin (A)-
The resin (A) contains, in the side chain, a group having a branched and / or alicyclic structure: X, a group having an acidic group: Y, and a group having an epoxy group: Z, as necessary. And may have other groups (L). A plurality of X, Y, and Z may be combined in one group in the resin (A).

-Group having a branched and / or alicyclic structure: X-
The “group having a branched and / or alicyclic structure” will be described.
First, as the group having a branch, a branched alkyl group having 3 to 12 carbon atoms is shown, for example, i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, Examples include neopentyl group, 2-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, i-amyl group, t-amyl group, 3-octyl, t-octyl and the like. 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 optionally substituted alicyclic hydrocarbon group having 5 to 25 carbon atoms. 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, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, 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, dicyclopentenyl 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, etc. ) 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, specific examples of the monomer containing a group having an alicyclic structure in the side chain have an alicyclic hydrocarbon group having 5 to 20 carbon atoms, preferably 6 to 20 carbon atoms ( (Meth) acrylate. 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) acrylates, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acrylic acid-1-adamantyl, (meth) acrylic acid-2 -Adamantyl, (meth) acrylic acid-2-methyl-2-adamantyl, (meth) acrylic acid-2-ethyl-2-adamantyl, (meth) acrylic acid-3-hydroxy-1-adamantyl, (meth) acrylic acid Fuentyl, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, etc. are preferable, cyclohexyl (meth) acrylate, (nor) bornyl (meth) acrylate, isobornyl (meth) acrylate, (meth ) Acrylate-2-adamantyl is particularly preferred.

  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 a hydrogen atom 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.

-Group having an 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 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.

  Specific examples of 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, monoalkyl maleate. 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 A mono (meth) acrylate etc. are 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, Toagosei 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 epoxy group: Z-
There is no restriction | limiting in particular as group which has an epoxy group, For example, the group derived from the (meth) acrylate compound represented by following Structural formula (1) or 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 a divalent linking group.

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

  The compound represented by the structural formula (1) or the monomer having an epoxy group in the side chain represented by the structural formula (2) is not particularly limited. For example, the following exemplary compounds (1) to (16).

  The monomer having an epoxy group in the side chain in the present invention is preferably glycidyl (meth) acrylate from the viewpoints of solubility and synthesis suitability. Moreover, you may use these monomers individually by 1 type or in combination of 2 or more types.

―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, hydrocarbon having no branched and / or alicyclic structure. And monomers having an 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 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-7. In the following structures, x, y, z, and l represent the respective constituent ratios (mol%).

-Manufacturing method-
The resin (A) can be produced by including at least the (co) polymerization reaction step of the monomer (monomer) described above.
The (co) polymerization reaction method is not particularly limited and may be appropriately selected from known methods. 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 cannot be crushed easily, it is hard to become a crosslinking defect, and the residue in image development can be suppressed.
In addition, a weight average molecular weight is measured using a gel permeation chromatograph (GPC), for example.

-Glass transition temperature-
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 photospacer having good developability and mechanical strength can be obtained.

-Acid value-
The preferred range of the acid value suitable for 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 that When the acid value is within the preferred range, a photospacer having good developability and mechanical strength can be obtained.

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, whereby a photospacer having good developability and mechanical strength can be obtained. This 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) in the present invention comprises a group having a branched and / or alicyclic structure in the side chain: X, a group having an acidic group: Y, and a group having an epoxy group: Z. From the viewpoint of deformation recovery rate, development residue, and reticulation, a copolymer having at least terpolymerization in the polymer unit is preferred. Specifically, a copolymer obtained by copolymerizing at least one of the respective monomers constituting X, Y, and Z is preferable.

The copolymer composition ratio of each component of the resin (A) is determined in consideration of the glass transition temperature and the acid value, and cannot be generally described. However, “group having a branched and / or alicyclic structure” is 10 -70 mol% is preferable, 15-65 mol% is still more preferable, and 20-60 mol% is especially preferable. When the composition ratio of the group having a branched and / or alicyclic structure in the side chain is within the above range, good developability is obtained and the resistance of the image area to the developer 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 composition ratio of the group having an acidic group in the side chain is within the above range, good curability and developability can be obtained.
Further, the “group having an epoxy group” is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, particularly preferably 30 to 70 mol%. When the composition ratio of the group having an epoxy group in the side chain is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.

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

-Resins other than resin (A)-
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 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.

-Total content of resin other than resin (A) and resin (A)-
As total content of resin other than the said resin (A) and resin (A), 5-70 mass% is preferable with respect to the said solid content of the said curable composition, and 10-50 mass% is more preferable. When the 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, and when it exceeds 70% by mass. The exposure sensitivity may decrease. In addition, the said content represents the 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. For example, at least a substituent having a surface active action can be used. 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, the surface of the cured film formed by the curable composition by further containing the surface active photopolymerization initiator (D) in addition to the photopolymerization initiator (C). The properties are improved and good development resistance can be exhibited. Thereby, for example, when a photo spacer constituting the display device is produced, a high degree of deformation recovery is exhibited.

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 group, 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.

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

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 is a fluorinated alkyl group having 3 to 12 carbon atoms. It is more preferable.
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 1-44 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 group having an alicyclic structure as the resin (A) is a cyclohexyl group, a tricyclopentenyl group or a dicyclopentenyl group, and an acidic group is Using a resin that is a carboxy group (for example, compound structures P-4, P-6, etc.), a group derived from a trihalomethyl-s-triazine compound as the surface active compound (D), and a fluorine having 1 to 16 carbon atoms. It is preferable to use a compound having an alkyl group, 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). A resin having a ring structure is a dicyclopentenyl group and an acidic group is a carboxy group (for example, compound structure P-6), and a surface active compound (D Compounds having a fluorinated alkyl group group and having 1 to 16 carbon atoms derived from trihalomethyl -s- triazine compound (e.g., Exemplary Compound 30, etc.) are more preferably used.

  In the curable composition of the present invention, 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 ratio (B) / (A) is within the preferred range, a photospacer 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), 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.

-Fine particles-
The curable composition of the present invention can further contain fine particles. The fine particles are not particularly limited and may be appropriately selected depending on the intended purpose. For example, extender pigments described in JP-A-2003-302039 [0035] to [0041] can be used. 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 is preferably 5 to 50 nm, more preferably 10 to 40 nm, and particularly preferably 15 to 30 nm from the viewpoint that a photospacer having high mechanical strength can be obtained. .

  The content of the fine particles is preferably 5 to 50% by mass with respect to the total solid content in the curable composition in the present invention, from the viewpoint that a photospacer having high mechanical strength is obtained. It is more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass.

[Patterning process]
In this invention, the patterning process of exposing and developing the curable resin layer formed on the support body and patterning can be further provided. 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.

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 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 with active energy rays, curing by heating may be performed. 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 photo spacer in the present invention can be formed after forming a color filter including a black shielding part such as a black matrix and a colored part such as a colored pixel.
The black shielding part and the colored part and the photo spacer are formed by arbitrarily combining an application method for applying a curable composition and a transfer method using a transfer material having a photosensitive resin layer made of the curable composition. It is possible.

  The black shielding part, the colored part, and the photospacer can each be formed from a curable composition. Specifically, for example, a curable resin layer is formed by directly applying the liquid curable composition to a substrate. Later, exposure / development is performed to form the black shielding portion and the colored portion in a pattern, and then the curable composition of another liquid is placed on another substrate (temporary support) different from the substrate. Then, the curable resin transfer material produced by forming the curable resin layer is used, and the curable resin transfer material is brought into close contact with the substrate on which the black shielding portion and the colored portion are formed. After transferring the photo spacer, the photo spacer can be formed in a pattern by exposure and development. In this manner, a color filter provided with a photospacer can be manufactured.

  In addition, the black shielding portion and the coloring portion are respectively exposed to and developed after the curable resin transfer material is brought into close contact with the substrate to transfer the curable resin layer, and the black shielding portion and the coloring portion are formed in a pattern. Thereafter, a liquid curable composition is directly applied to form a curable resin layer on the substrate on which the black shielding portion and the colored portion are formed, and then a photo spacer is formed by performing exposure and development. It can be formed in a pattern. In this manner, a color filter provided with a photospacer can be manufactured.

  In the method for producing a photospacer of the present invention, from the viewpoint of display quality, a curable resin layer (curable composition) is applied by applying the curable composition on a support on which a black shielding part and a colored part are formed. It is preferable to include a step of forming a physical layer).

<Liquid crystal display substrate>
The substrate for a liquid crystal display device of the present invention comprises a photospacer obtained by the method for producing a photospacer of the present invention. The photospacer is preferably formed on a display light-shielding portion such as a black matrix formed on a support or on a driving element such as a TFT. Further, a transparent conductive layer (transparent electrode) such as ITO or a liquid crystal alignment film such as polyimide may exist between a light shielding portion for display such as a black matrix, a driving element such as TFT and a photo spacer.

For example, when the photo spacer is provided on the display light-shielding portion or the driving element, the display light-shielding portion (black matrix or the like) or the driving element previously disposed on the support is covered with, for example, a photosensitive resin. The photosensitive resin layer of the transfer film is laminated on the surface of the support, peeled and transferred to form a photosensitive resin layer, and then subjected to exposure, development, heat treatment, etc. to form a photo spacer. A substrate for a liquid crystal display device 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 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 light transmissive. 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 photo 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 has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a photo spacer having a uniform height between a pair of substrates 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 is constituted by providing the liquid crystal display device substrate. The liquid crystal display device of the present invention is configured by providing 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.

As resin A in this invention, the synthesis example of the compound represented by compound structure P-1 to P-7 is shown below.
(Synthesis Example 1)
In the reaction vessel, 203.9 parts of 1-methoxy-2-propanol (MFG, manufactured by Daicel Chemical Industries, Ltd.) was heated to 70 ° C. in a nitrogen gas atmosphere in advance, and 12.5 parts of styrene and glycidyl methacrylate 76. 8 parts, 66.1 parts of dicyclopentenyl methacrylate, 46.5 parts of methacrylic acid, and 9.5 parts of azo polymerization initiator (V-65, manufactured by Wako Pure Chemical Industries, Ltd.) were dropped over 2 hours. . Reaction was performed for 4 hours after the dropwise addition to obtain a resin solution (28.6% solution) represented by the compound structure P-1.
It was 31,500 when the weight average molecular weight Mw of resin represented by the said compound structure P-1 was calculated | required by the gel permeation chromatograph.

(Synthesis Example 2)
In Synthesis Example 1, a resin solution (28.0% solution) represented by Compound Structure P-2 was obtained in the same manner as in Synthesis Example 1 except that 2-adamantyl methacrylate was used instead of dicyclopentenyl methacrylate. It was.
The weight average molecular weight Mw of the resin represented by the compound structure P-2 was 28,700.

(Synthesis Example 3)
In Synthesis Example 1, a resin solution (28.6% solution) represented by Compound Structure P-3 was obtained in the same manner as in Synthesis Example 1 except that isobornyl methacrylate was used instead of dicyclopentenyl methacrylate. It was.
The weight average molecular weight Mw of the resin represented by the compound structure P-3 was 34,200.

(Synthesis Example 4)
In Synthesis Example 1, a resin solution (28.2% solution) represented by Compound Structure P-4 was obtained in the same manner as in Synthesis Example 1 except that tricyclopentenyl methacrylate was used instead of dicyclopentenyl methacrylate. It was.
The weight average molecular weight Mw of the resin represented by the compound structure P-4 was 30,700.

(Synthesis Example 5)
In Synthesis Example 1, a resin solution (28.6% solution) represented by Compound Structure P-5 was obtained in the same manner as in Synthesis Example 1 except that cyclohexyl methacrylate was used instead of dicyclopentenyl methacrylate.
The weight average molecular weight Mw of the resin represented by the compound structure P-5 was 28,100.

(Synthesis Example 6)
In Synthesis Example 1, a compound structure P- was synthesized in the same manner as in Synthesis Example 1 except that dicyclopentenyloxyethyl methacrylate (Fanacryl FA-512M manufactured by Hitachi Chemical Co., Ltd.) was used instead of dicyclopentenyl methacrylate. A resin solution (28.2% solution) represented by 6 was obtained.
The weight average molecular weight Mw of the resin represented by the compound structure P-6 was 29,800.

(Synthesis Example 7)
In Synthesis Example 1, compound structure P-7 was obtained in the same manner as in Synthesis Example 1 except that tricyclopentenyloxyethyl methacrylate (TCPD-M manufactured by Hitachi Chemical Co., Ltd.) was used instead of dicyclopentanyl methacrylate. (28.5% solution) was obtained.
The weight average molecular weight Mw of the resin represented by the compound structure P-7 was 31,800.

-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.

Example 1
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. A coating solution for a curable resin layer consisting of formulation 5 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 prebaked at 120 ° C. for 3 minutes to cure to a film thickness of 3.8 μm. A functional resin layer was formed (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 curable resin layer face each other. The distance between the mask and the exposed surface of the curable resin layer is set to 40 μm with the color filter substrate placed on the color filter substrate standing substantially parallel and vertically, and the exposure amount is 300 mJ / mm from the curable resin layer side through the mask. Proximity exposure was performed at cm ² .

Next, a sodium carbonate-based developer (0.38 mol / liter sodium bicarbonate, 0.47 mol / liter sodium carbonate, 5% sodium dibutylnaphthalenesulfonate, an anionic surfactant, an antifoaming agent, and a stabilizer Agent-containing; Trade name: T-CD1 (manufactured by Fuji Film Co., Ltd.) diluted 10 times with pure water) at 29 ° C. for 30 seconds, with a cone type nozzle pressure of 0.15 MPa, shower developed, and photo A 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 Used, and sprayed with a shower at 33 ° C. for 20 seconds at a cone type nozzle pressure of 0.02 MPa, the residue around the formed pattern image was removed to obtain a desired spacer pattern.

Next, the color filter substrate provided with the spacer pattern was heat-treated 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, the average height is the highest of the highest photospacer from the transparent electrode forming surface of ITO using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) for 1000 obtained photospacers. The position 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.

(Example 2 to Example 4, Example 7 to Example 11, Comparative Example 2 to Comparative Example 4, Comparative Example 6, Comparative Example 7)
In Example 1, a color provided with a photospacer in the same manner as in Example 1 except that the formulations shown in Table 1 and Table 2 below were used instead of the coating solution for the curable resin layer of Formula 5 respectively. A filter substrate was produced. The obtained spacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

  Next, a liquid crystal display device was produced in the same manner as in Example 1 except that each of the color filter substrates obtained above was used instead of the color filter substrate obtained in Example 1.

(Example 5)
In Example 1, instead of the coating liquid for the curable resin layer of Formulation 5, the formulation 8 shown in Table 1 below was used, and the exposure amount was changed to 100 mJ / cm ² instead of 300 mJ / cm ^2. In the same manner as in Example 1, a color filter substrate provided with a photospacer was produced, and a liquid crystal display device was produced using the color filter substrate. The obtained spacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

(Example 6)
In Example 1, a color filter substrate provided with a photo spacer was prepared in the same manner as in Example 1 except that the exposure amount was changed to 100 mJ / cm ² instead of 300 mJ / cm ^2. A liquid crystal display device was produced. The obtained spacer 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, instead of the coating liquid for the curable resin layer of Formulation 5, the formulation 1 shown in Table 1 below was used, except that the exposure amount was changed to 100 mJ / cm ² instead of 300 mJ / cm ^2. In the same manner as in Example 1, a color filter substrate provided with a photospacer was produced, and a liquid crystal display device was produced using the color filter substrate. The obtained spacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm.

(Comparative Example 5)
In Example 1, instead of the coating liquid for the curable resin layer of Formulation 5, the formulation 4 shown in Table 1 below was used, and the exposure amount was changed to 100 mJ / cm ² instead of 300 mJ / cm ^2. In the same manner as in Example 1, a color filter substrate provided with a photospacer was produced, and a liquid crystal display device was produced using the color filter substrate. The obtained spacer 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 3.

-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 the 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 3, it can be seen that the photospacer produced from the curable composition of the present invention exhibits a high deformation recovery rate. Furthermore, even when a photospacer is produced with a low exposure amount, it shows a high deformation recovery rate, so that the influence of oxygen from the surface of the curable resin layer is reduced, and effective polymerization of the entire curable resin layer is achieved. It is assumed that is promoted.

Claims (8)

A resin containing a group having a branched and / or alicyclic structure, a group having an acidic group, and a group having an epoxy group, a polymerizable compound, a photopolymerization initiator, and an alkyl having 9 to 30 carbon atoms A curable composition comprising at least a surface active photopolymerization initiator having at least one selected from a group, a siloxane group, and a fluorinated alkyl group . The curable composition according to claim 1, wherein the surface-active photopolymerization initiator is a compound having at least one selected from an alkyl group having 16 to 30 carbon atoms, a siloxane group, and a fluorinated alkyl group .   The surfactant photopolymerization initiator is a compound containing a substituent derived from a trihalomethyl-s-triazine compound, a trihalomethyloxadiazole compound, an α-aminoketone compound, an α-hydroxyketone compound, or an oxime compound. The curable composition of Claim 1 or Claim 2.   The curable composition according to any one of claims 1 to 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 cured film formed by hardening the curable composition of any one of Claims 1-4.   The manufacturing method of the photo spacer 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 1-4.   A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to claim 6.   A liquid crystal display device comprising the substrate for a liquid crystal display device according to claim 7.