JP2009128487A - Photosensitive resin composition and manufacturing method for photo spacer, substrate for liquid crystal display device, liquid crystal display element and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition, having high elastic recovery in a formed photo spacer, uniform in height, and eliminating display unevenness in a liquid crystal display device, a method of manufacturing a photo spacer using it, a substrate for a liquid crystal display device, capable of restraining the occurrence of display unevenness, a liquid crystal display element and a liquid crystal display device. <P>SOLUTION: This photosensitive resin composition at least contains polymerizable compound, a binder and a photopolymerization initiator, wherein the polymerizable compound including a group having a bridging ring structure and a group having ethylenic unsaturated bond, and having a molecular weight of 2000 or less is contained. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a photosensitive resin composition, a method for producing a photospacer using the same, and a substrate for a liquid crystal display device, a liquid crystal display element and a liquid crystal display device provided with the photospacer.

  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 with high positional accuracy has been formed by photolithography using a photosensitive composition. A spacer formed using such a photosensitive composition is called a photospacer.

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

In relation to the above, as a highly sensitive spacer forming resin, it is disclosed to use a resin obtained by reacting an isocyanate compound with a copolymer containing a hydroxyl group-containing unsaturated compound (for example, see Patent Document 1). .
In addition, a photosensitive composition capable of forming a photospacer with high cell gap accuracy and capable of fine processing is disclosed (for example, see Patent Document 2).
JP 2007-84809 A JP 2004-12671 A

However, it is difficult to say that the photo spacers made of the resins described in Patent Document 1 and Patent Document 2 are sufficient in terms of elastic recovery and flatness.
The present invention has been made in view of the above problems, and has a high degree of elastic recovery when an external force is applied. For example, when a resin structure such as a photospacer is formed, the height of the resin structure is high. Photosensitive resin composition capable of eliminating display unevenness in liquid crystal display device with little variation, photospacer manufacturing method using the same, liquid crystal display device substrate capable of suppressing occurrence of display unevenness, and liquid crystal display element An object of the present invention is to provide a liquid crystal display device.

Specific means for solving the above problems are as follows.
<1> A photosensitive resin having at least a polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond, a molecular weight of 2000 or less, a binder, and a photopolymerization initiator. Composition.
<2> The group having a bridged ring structure includes at least one of alicyclic structures represented by any one of the following chemical formulas (1) to (3): Photosensitive resin composition.

<3> The photosensitive resin composition according to <1>, wherein the group having a bridged ring structure is a group containing 6 or more chemical bonds between silicon atoms and oxygen atoms.
<4> The binder according to any one of <1> to <3>, wherein the binder has a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in each side chain. The photosensitive resin composition as described in 2.
<5> The photosensitive resin composition according to any one of <1> to <4>, which is for producing a photospacer.

<6> Two support members, a liquid crystal provided between the support members, two electrodes for applying an electric field to the liquid crystal, and a photo spacer for regulating a cell thickness between the support members. It is a manufacturing method of the photospacer in the liquid crystal display device provided at least, wherein one of the surfaces facing each other in the two supports is described in any one of <1> to <5>. A method for producing a photospacer, comprising: a layer forming step of forming a photosensitive resin layer containing a photosensitive resin composition; and a patterning step of patterning by exposing and alkali developing the photosensitive resin layer.
<7> The layer forming step includes a photosensitive transfer material having a photosensitive resin layer composed of the photosensitive resin composition according to any one of <1> to <5> on a temporary support. The production of the photospacer according to <6>, further comprising a transfer step of forming the photosensitive resin layer by transferring the photosensitive resin layer so as to be in contact with one of the opposing surfaces of the two supports. Method.
<8> In the layer forming step, the solution containing the photosensitive resin composition according to any one of <1> to <5> is applied onto one of the surfaces facing each other in the two supports. The manufacturing method of the photospacer as described in said <6> including the process of apply | coating and drying and forming the photosensitive resin layer.

<9> A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to any one of <6> to <8>.
<10> A liquid crystal display device comprising the liquid crystal display device substrate according to <9>.
<11> A liquid crystal display device comprising the liquid crystal display element according to <10>.

  According to the present invention, it has a high degree of elastic recovery when an external force is applied. For example, when a resin structure such as a photospacer is formed, there is little variation in height, and the display in a liquid crystal display device To provide a photosensitive resin composition capable of eliminating unevenness, a method for producing a photospacer using the same, and a substrate for liquid crystal display device, a liquid crystal display element, and a liquid crystal display device capable of suppressing the occurrence of display unevenness. it can.

<Production method of photosensitive resin composition and photospacer>
The photosensitive resin composition of the present invention has at least one polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond and having a molecular weight of 2000 or less, and at least one binder. It contains at least a seed and at least one photopolymerization initiator. For example, a resin structure such as a photo spacer manufactured by the photosensitive resin composition of the present invention has a high degree of elastic recovery when subjected to an external force. Therefore, for example, when a photospacer is manufactured and used as a display device, occurrence of display unevenness in the display device can be suppressed.

  The method for producing a photospacer according to the present invention includes two supports, a liquid crystal provided between the supports, two electrodes for applying an electric field to the liquid crystal, and a cell thickness between the supports. And a photo spacer for regulating the photo spacer, wherein the photo spacer is produced on a liquid crystal display device having at least one surface facing each other in the liquid crystal display device. A layer forming step of forming a photosensitive resin layer containing an object.

According to the method for producing a photospacer of the present invention, a photospacer having a high degree of elastic recovery can be easily produced.
Hereinafter, the manufacturing method of the photospacer of this invention is demonstrated, and the detail of the photosensitive 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 photosensitive resin layer containing the photosensitive resin composition of the present invention (hereinafter also simply referred to as “photosensitive resin layer”) on the support.
This photosensitive resin layer constitutes a photospacer that has good elastic recovery and can maintain a uniform cell thickness through the manufacturing process 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 photosensitive resin layer on the support, (a) a method of applying a solution containing the photosensitive composition of the present invention by a known coating method, and (b) a photosensitive resin transfer material was used. A method of laminating by a transfer method is preferable. Each will be described below.

(A) Coating method The photosensitive composition is 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, using a photosensitive resin transfer material, a photosensitive resin layer formed in a film shape on a temporary support is pressure-bonded with a roller or flat plate heated and / or pressurized on the support surface. After bonding by thermocompression bonding, the photosensitive resin layer is transferred onto the support by peeling off the temporary support. Specific examples include laminators and laminating methods described in JP-A-7-110575, JP-A-11-77942, JP-A-2000-334836, and JP-A-2002-148794. From the viewpoint, it is preferable to use the method described in JP-A-7-110575.

When a photosensitive resin layer is formed on a temporary support, an oxygen blocking layer (hereinafter also referred to as “oxygen blocking film” or “intermediate layer”) is further provided between the photosensitive 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, and other layers constituting the photosensitive transfer film, and the method for producing the photosensitive transfer film, paragraph numbers [0024] to JP-A-2006-23696. This is the same as the configuration and the manufacturing method described in [0030].

  When the photosensitive resin layer is applied and formed by both (a) the coating method and (b) the transfer method, 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 photosensitive 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.

-Photosensitive resin composition-
Next, the photosensitive resin composition will be described.
The photosensitive resin composition of the present invention has a polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond and a molecular weight of 2000 or less (hereinafter referred to as “polymerizable compound (B)”. ”), A binder, and a photopolymerization initiator. Moreover, it can comprise using other components, such as a coloring agent and surfactant, as needed.
The photosensitive resin composition is particularly preferably used for preparing a photospacer.

-Polymerizable compound-
The polymerizable compound in the present invention includes at least one group having a bridged ring structure. The bridged ring structure is not particularly limited as long as it has a structure in which two non-adjacent atoms constituting the ring structure are bonded to each other via another atom, and an alicyclic structure composed of a hydrocarbon. It may have a ring structure including a chemical bond (siloxane bond) between a silicon atom and an oxygen atom.

  Specific examples of the bridged ring structure having an alicyclic structure include, for example, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentenyl group, tricyclopenta Nyl group, tricyclopentadiene group, dicyclopentadiene group and the like can be mentioned.

  Among these, from the viewpoint of elastic recovery, norbornyl group, isobornyl group, adamantyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group, tricyclopentadiene Group, dicyclopentadiene group and the like are preferable, and isobornyl group, adamantyl group, dicyclopentenyl group, dicyclopentanyl group, tricyclopentadiene group and dicyclopentadiene group are more preferable, and the following chemical formulas (1) to Particularly preferred is at least one alicyclic structure represented by any one of the chemical formulas (3).

  Here, the group having an alicyclic structure represented by any one of the above chemical formulas (1) to (3) is an alicyclic compound represented by any one of the chemical formulas (1) to (3). It means a group formed by removing at least one hydrogen atom.

  In the present invention, the group having a bridged ring structure is also preferably a group having a ring structure containing six or more chemical bonds (siloxane bonds) between a silicon atom and an oxygen atom. Examples of the polymerizable compound containing a group having a ring structure containing 6 or more chemical bonds between a silicon atom and an oxygen atom and a group having an ethylenically unsaturated bond include a cage shape represented by the following chemical formula (A). A polymerizable compound having a structure can be exemplified.

In the chemical formula (A), R ^{1 to} R ⁸ are an alkyl group, an aryl group, a (meth) acryloyl group, a (meth) acryloylalkyl group, or a (meth) acryloylaryl group, and at least one is a (meth) acryloyl group Represents a group, a (meth) acryloylalkyl group, or a (meth) acryloylaryl group, and R ^{1 to} R ⁸ may be the same group or different groups.

The polymerizable compound contains at least one group having an ethylenically unsaturated bond. There is no restriction | limiting in particular as group which has an ethylenically unsaturated bond, For example, a vinyl group, vinyl ether group, acryloyl group, a methacryloyl group etc. can be mentioned. Of these, an acryloyl group and a methacryloyl group are preferable.
In particular, when the group having a bridged ring structure is a group having a ring structure containing 6 or more siloxane bonds, from the viewpoint of elastic recovery, 4 or more groups having an ethylenically unsaturated bond are included. It is more preferable that 6 or more are included.

  The molecular weight of the polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond in the present invention is 2000 or less. From the viewpoint of the flatness of the resin film formed by the photosensitive resin composition, the molecular weight is preferably 100 to 2000, and more preferably 200 to 1500. When the molecular weight exceeds 2000, the flatness of the resin film formed by the photosensitive resin composition tends to be lowered, and when the photo spacer is formed, the height of the photo spacer may be uneven.

As the polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond and having a molecular weight of 2000 or less, an appropriately produced compound may be used, or a commercially available product may be used. May be.
Examples of commercially available polymerizable compounds having a bridged ring structure having an alicyclic structure include, for example, manufactured by Hitachi Chemical Co., Ltd .: FA-511A, FA-512A (S), FA-512M, FA-513A, FA- 513M, ADMA, and the like. Among these, FA-512A, FA-513A, and ADMA are preferable because they are excellent in the height distribution and deformation recovery rate of the photo spacer.

  Moreover, as a commercial item of the polymerizable compound in which the bridge ring structure includes a siloxane bond, the POSS series manufactured by Hybrid Plastics can be exemplified, and specifically, AcrylIsobutyl POSS MA0701 and Acrylo POSS Cage Mixture MA0736 are exemplified. .

  As the polymerizable compound in the present invention, as a bridged ring structure, an alicyclic structure represented by any one of the chemical formulas (1) to (3) and a (meth) acryloyl group having an ethylenically unsaturated bond. As a group having a group having a molecular weight of 100 to 2000, a ring structure containing a siloxane bond represented by the chemical formula (A) as a bridged ring structure, and an ethylenically unsaturated bond ( A polymerizable compound having a (meth) acryloyl group and a molecular weight of 200 to 2000 is particularly preferred.

The polymerizable compound in the present invention is a polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond and having a molecular weight of 2000 or less, but within a range not impairing the effects of the present invention. Other polymerizable compounds may be used in combination. Examples of the other polymerizable compound include monomers and oligomers described in paragraph No. [0011] of JP-A-2006-23696.
Moreover, the polymeric compound in this invention may be used individually by 1 type or in combination of 2 or more types.

In the photosensitive resin composition of the present invention, the total content of the polymerizable compound (B) and the other polymerizable compound is preferably 5 to 80% by mass with respect to the total solid content. More preferably, it is 50 mass%. When the content of the polymerizable compound is within the above range, good elastic recovery can be obtained, and a good planar photosensitive resin layer can be formed.
Further, the content ratio of the polymerizable compound (B) in the total polymerizable compound (polymerizable compound (B) / total polymerizable compound) is preferably 10% by mass or more, and more preferably 20% by mass or more. Is more preferable.

-Binder-
The photosensitive resin composition of the present invention contains at least one binder (polymer resin). As the binder in the present invention, a polymer having a polar group such as a carboxy group or a carboxylate group in the side chain, or the light described in paragraph numbers [0031] to [0054] of JP-A No. 2003-131379, which itself has polymerizability. A preferred example is a polymer resin having an allyl group that can be polymerized.
Among these, from the viewpoint of elastic recovery, a polymer resin (hereinafter referred to as “resin (A)”) having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in each side chain. ) Is preferable.

The binder may be either a homopolymer of a monomer appropriately selected according to the purpose or a copolymer composed of a plurality of monomers, and two or more types are used in combination other than one type alone. You may do it.
Examples of the polymer having a polar group such as a carboxy group or a carboxylate group in the side chain include JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54- No. 25957, JP-A-59-53836 and JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer Examples thereof include a polymer, a maleic acid copolymer, and a partially esterified maleic acid copolymer. Moreover, the cellulose derivative which has a carboxy group in a side chain can also be mentioned, In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. Particularly preferred examples include copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid, and other Mention may be made of multicomponent copolymers with monomers.

There is no restriction | limiting in particular as a monomer which comprises the polymer resin which has an allyl group, According to the objective, it can select suitably, For example, alkyl (meth) acrylate, allyl (meth) acrylate, hydroxyalkyl (meta ) Acrylate, vinyl compound, allyl group-containing (meth) acrylate, and the like. In the present specification, (meth) acrylate represents acrylate or methacrylate.
These monomers may be used in combination of two or more in addition to being used alone.

  Examples of the alkyl (meth) acrylate and allyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyisobutyl (meth) acrylate, hydroxypentyl ( And (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, and the like, among others, hydroxyethyl (meth) acrylate, hydroxy n-propyl (meth) acrylate, hydroxy n-butyl (meth) acrylate, etc. Is preferred.

  As the vinyl compound, for example, styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like are preferable. Can be mentioned.

  Examples of the allyl group-containing (meth) acrylate include allyl (meth) acrylate, 2-methylallyl acrylate, crotyl acrylate, chloroallyl acrylate, phenylallyl acrylate, and cyanoallyl acrylate. ) Acrylate is particularly preferred.

  Among the binders described above, a resin having at least an allyl group-containing (meth) acrylate as a monomer unit is preferable, and a monomer selected from allyl group-containing (meth) acrylate, (meth) acrylic acid, and allyl group-free (meth) acrylate. Are more preferable as monomer units.

A preferred specific example of the binder is a binary copolymer resin of (meth) acrylic acid (M ¹ ) and allyl (meth) acrylate (M ² ) [preferred copolymerization ratio [molar ratio] is M ¹ : M ² = 2-90: 10-98], and terpolymers of (meth) acrylic acid (M ³ ), allyl (meth) acrylate (M ⁴ ) and benzyl (meth) acrylate (M ⁵ ) [preferred Examples of the copolymerization ratio [molar ratio] include M ³ : M ⁴ : M ⁵ = 5 to 40:20 to 90: 5 to 70].

  When the binder has an allyl group, the content of the allyl group-containing monomer is preferably 10 mol% or more, preferably 10 to 100 mol%, more preferably 15 to 90 mol%, still more preferably 20 to 85 mol. %.

  The binder in the present invention is preferably a polymer resin (“resin (A)”) having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in each side chain. Moreover, the said resin (A) may further have another group in the side chain as needed.

(Branched and / or alicyclic structure)
The binder in the present invention preferably contains at least one of a branched and / or alicyclic structure in the side chain bonded to the main chain of the resin. A plurality of branched and / or alicyclic structures may be contained in the side chain of the binder. Moreover, the branched and / or alicyclic structure may be contained in the side chain of the binder together with an acidic group and / or an ethylenically unsaturated bond.
The branched and / or alicyclic structure may be directly bonded to the main chain of the binder to constitute the side chain of the binder only by the branched and / or alicyclic structure. The side chain of a binder may be comprised as a group which couple | bonds through an organic coupling group and has a branched and / or alicyclic structure.

  The divalent organic linking group is preferably one or a combination selected from an alkylene group, an arylene group, an ester group, an amide group, and an ether group. As said alkylene group, a C1-C20 alkylene group is preferable, More preferably, 1-10 are preferable. Specific examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, octylene, dodecylene, octadecylene, and the like, which may have a branched / cyclic structure or a functional group, and more preferably a methylene group. , Ethylene group and octylene group are preferable. As the arylene group, an arylene group having a total carbon number of 6 to 20 is preferable, and 6 to 12 is more preferable. Specific examples include a phenylene group, a biphenylene group, a naphthalene group, and an anthracene group, which may have a branched or functional group, and more preferably a phenylene group or a biphenylene group.

  The form in which the branched and / or alicyclic structure is bonded to the main chain of the binder via at least an ester group (—COO—) is preferable from the viewpoint of ease of synthesis. This form is not limited to the form in which the branched and / or alicyclic structure is bonded to the main chain of the binder only through the ester group (—COO—), and the branched and / or alicyclic structure is an ester group (—COO). The form couple | bonded with the principal chain of the binder through the bivalent coupling group containing-) may be sufficient. That is, other atoms and other linking groups may be included between the branched and / or alicyclic structure and the ester chain, and / or between the ester chain and the main chain of the binder.

  Examples of the branched structure include branched alkyl groups having 3 to 12 carbon atoms, such as i-propyl group, i-butyl group, s-butyl group, t-butyl group, isopentyl group, and 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 are preferable. Among these, i-propyl group, s-butyl group, t-butyl group, isopentyl group and the like are more preferable, and i-propyl group, s-butyl group, t-butyl group and the like are particularly preferable.

  Examples of the alicyclic structure include alicyclic hydrocarbon groups having 5 to 20 carbon atoms, such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, isobornyl group, adamantyl group, A tricyclodecyl group, a dicyclopentenyl group, a dicyclopentanyl group, a tricyclopentenyl group, a tricyclopentanyl group, and the like, and groups having these are preferable. Among these, dicyclopentenyl group, cyclohexyl group, norbornyl group, isobornyl group, adamantyl group, tricyclodecyl group, tricyclopentenyl group, tricyclopentanyl group and the like are more preferable, dicyclopentenyl group, cyclohexyl group, norbornyl Group, isobornyl group, tricyclopentenyl group and the like are more preferable, and dicyclopentenyl group is particularly preferable.

Furthermore, the form comprised by having group represented by following General formula (1) as a group which has a branched and / or alicyclic structure is preferable.

  In the general formula (1), x represents 1 or 2, and m and n each independently represents an integer of 0 to 15.

  Examples of the monomer for introducing a branched and / or alicyclic structure into the side chain of the binder 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 monomers for introducing a branched structure into the side chain of the binder 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. Propyl, t-butyl methacrylate and the like are more preferable.

  Examples of the monomer for introducing an alicyclic structure into the side chain of the binder include (meth) acrylates 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, 3,5-dimethyl-1-adamantyl (meth) acrylate, 3-ethyladamantyl (meth) acrylate, 3-methyl-5-ethyl-1-adamantyl (meth) acrylate, ( 3,5,8-triethyl-1-adamantyl (meth) acrylate, 3,5-dimethyl-8-ethyl-1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, (meth ) 2-ethyl-2-adamantyl acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, octahydro-4,7 (meth) acrylate Mentanoinden-5-yl, octahydro-4,7-mentanoinden-1-ylmethyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, (meth) acrylic acid 3-hydroxy-2,6,6-trimethyl-bicyclo [3.1.1] heptyl, 3,7,7-trimethyl-4-hydroxy-bicyclo [4.1.0] heptyl (meth) acrylate, ( (Meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid fuentyl, (meth) acrylic acid 2,2,5-trimethylcyclohexyl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid di Examples include cyclopentenyl and tricyclopentenyl (meth) acrylate.

  Among these (meth) acrylic acid esters, in terms of improved compression modulus and elastic recovery, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meta ) 1-adamantyl acrylate, 2-adamantyl (meth) acrylate, fuentyl (meth) acrylate, 1-menthyl (meth) acrylate, tricyclodecyl (meth) acrylate, dicyclopentenyl (meth) acrylate, (Meth) acrylic acid tricyclopentenyl etc. are preferable, (meth) acrylic acid cyclohexyl, (meth) acrylic acid (nor) bornyl, (meth) acrylic acid isobornyl, (meth) acrylic acid 2-adamantyl, (meth) acrylic acid Dicyclopentenyl, especially tricyclopentenyl (meth) acrylate Masui.

  Moreover, as a monomer for introduce | transducing an alicyclic structure into the side chain of a binder, the compound represented by following General formula (2) or (3) is mentioned. Here, in the general formulas (2) and (3), x represents 1 or 2, and R represents hydrogen or a methyl group. m and n each independently represent 0-15. Among general formulas (2) and (3), 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. Preferred specific examples of the compound represented by the general formula (2) or (3) include the following compounds D-1 to D-5 and T-1 to T-8.

As a monomer for introducing an alicyclic structure into the side chain of the binder, 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)
The binder preferably contains at least one acidic group in the side chain connected to the main chain. A plurality of acidic groups may be contained in the side chain. Moreover, the acidic group may be contained in the side chain of the binder together with the branched and / or alicyclic structure and the ethylenically unsaturated bond.
The acidic group may be directly bonded to the main chain of the binder to constitute the side chain of the binder only by the acidic group, or may be bonded to the main chain of the binder via a divalent organic linking group, You may comprise the side chain of a binder as a group to have. Here, examples of the divalent organic linking group include the divalent organic linking groups exemplified in the description of the branched and / or alicyclic structure, and preferred ranges thereof are also the same.

  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 for introducing the acidic group into the binder 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 for introducing the acidic group into the binder can be appropriately selected from known ones such as (meth) acrylic acid, vinyl benzoic acid, maleic acid, monoalkyl maleate. Esters, 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.

  Commercially available monomers for introducing the acidic group into the binder include Toa Gosei Chemical Co., Ltd .: Aronix M-5300, Aronix M-5400, Aronix M-5500, Aronix M-5600, Shin Nakamura Chemical Industry Co., Ltd .: NK Ester CB-1, NK Ester CBX-1, Kyoeisha Oil Chemical Co., Ltd .: HOA-MP, HOA-MS, Osaka Organic Chemical Industry Co., Ltd .: Biscote # 2100 Can be mentioned. Among these, (meth) acrylic acid and the like are preferable in terms of excellent developability and low cost.

(Ethylenically unsaturated group)
The binder in the present invention preferably contains at least one ethylenically unsaturated bond in the side chain linked to the main chain. A plurality of ethylenically unsaturated bonds may be contained in the side chain. Moreover, the ethylenically unsaturated bond may be contained in the side chain of the binder together with the branched and / or alicyclic structure and / or the acidic group.

  In addition, the ethylenically unsaturated bond is bonded to the main chain of the binder via at least one ester group (—COO—), and the ethylenically unsaturated bond and the ester group constitute a binder side chain. It may be. Further, a divalent organic linking group may be further provided between the main chain of the binder and the ester group and / or between the ester group and the ethylenically unsaturated bond. You may comprise the side chain of a binder as "group which has an ethylenically unsaturated bond." Here, the divalent organic linking group includes the divalent organic linking groups exemplified in the description of the branched and / or alicyclic structure, and the preferred range is also the same.

The ethylenically unsaturated bond is preferably arranged by introducing a (meth) acryloyl group.
The method of introducing the (meth) acryloyl group into the side chain of the binder can be appropriately selected from known methods, for example, a method of adding (meth) acrylate having an epoxy group to a repeating unit having an acidic group. And a method of adding (meth) acrylate having an isocyanate group to a repeating unit having a hydroxyl group, a method of adding (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.

  The (meth) acrylate having an ethylenically unsaturated bond and an epoxy group is not particularly limited as long as it has these. For example, in the compound represented by the following structural formula (1) and the following structural formula (2) The compounds represented are preferred.

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.

  The other group-containing monomer is not particularly limited. For example, (meth) acrylic acid ester having no branched and / or alicyclic structure, styrene, vinyl ether, dibasic acid anhydride group, vinyl ester group, And monomers having 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.

Specific examples of the binder include compounds represented by the following structures (Exemplary Compounds P-1 to P-35).
In addition, x, y, and z in the exemplified compound represent a composition ratio (mass ratio) of each repeating unit, and a form configured in a preferable range described later is preferable. Moreover, the form comprised also in the preferable range mentioned later of the weight average molecular weight of each exemplary compound is suitable.

<Synthesis method>
The resin (A) in the present invention can be synthesized from a two-step process including a monomer (co) polymerization reaction process and an ethylenically unsaturated group introduction process.
First, the (co) polymerization reaction is made by a (co) polymerization reaction of various monomers, and is not particularly limited and can be appropriately selected from known ones. For example, radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization and the like can be appropriately selected for the active species of polymerization. Among these, radical polymerization is preferable from the viewpoint of easy synthesis and low cost. Moreover, there is no restriction | limiting in particular also about the polymerization method, It can select suitably from well-known things. For example, a bulk polymerization method, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method and the like can be appropriately selected. Among these, the solution polymerization method is more desirable.

  The total number of carbon atoms of the resin (A) in the present invention is preferably 10 or more in terms of elastic modulus (hardness). Especially, as for total carbon number, 10-30 are more preferable, Most preferably, it is 10-15.

<Molecular weight>
The molecular weight of the resin (A) in the present invention is preferably 10,000 to 100,000, more preferably 12,000 to 60,000, and particularly preferably 15,000 to 45,000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, it is desirable from the viewpoint of production suitability and developability of a resin (preferably a copolymer). Further, it is preferable in that the shape formed by the decrease in melt viscosity is difficult to be crushed, in that it is difficult to cause crosslinking failure, and there is no spacer-shaped residue in development.
The weight average molecular weight is measured by gel permeation chromatography (GPC). GPC will be described in detail in the section of the examples described later.

<Glass transition temperature>
The glass transition temperature (Tg) of the resin (A) in the present invention 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 of the specific resin in the present invention 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 spacer having good developability and mechanical strength can be obtained.

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

Resin (A) in the present invention is a copolymer having a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond, each having a repeating unit (copolymerization unit) in a separate copolymer unit or higher. The combination is preferable from the viewpoint of deformation recovery rate, development residue, and reticulation when a pattern structure (for example, a spacer for a color filter) is formed.
Specifically, the resin (A) in the present invention comprises a repeating unit having a branched and / or alicyclic structure: X (x mol%), a repeating unit having an acidic group: Y (y mol%), and ethylene. It is preferable that the copolymer is a terpolymer or more copolymer having at least a repeating unit having a polymerizable unsaturated bond: Z (z mol%). Furthermore, you may have other repeating units: L (1 mol%) as needed.
Such a copolymer includes, for example, a monomer having a branched and / or alicyclic structure, a monomer having an acidic group, a monomer having an ethylenically unsaturated bond, and others as necessary. Can be obtained by copolymerizing the above monomer.

The copolymer composition ratio when the resin (A) in the present invention is a copolymer is determined in consideration of the glass transition temperature and the acid value. Although it cannot be generally stated, the following ranges can be adopted.
The composition ratio (x) of the repeating unit having a branched and / or alicyclic structure in the resin (A) in the present invention is preferably 10 to 70 mol%, more preferably 15 to 65 mol%, and more preferably 20 to 60 mol%. Is particularly preferred. When the composition ratio (x) is within the above range, good developability is obtained and the developer resistance of the image area is also good.
The composition ratio (y) of the repeating unit having an acidic group in the resin (A) in the present invention is preferably from 5 to 70 mol%, more preferably from 10 to 60 mol%, particularly preferably from 20 to 50 mol%. When the composition ratio (y) is within the above range, good curability and developability can be obtained.
In the resin (A) in the present invention, the composition ratio (z) of the repeating unit having an ethylenically unsaturated bond is preferably 10 to 70 mol%, more preferably 20 to 70 mol%, and particularly preferably 30 to 70 mol%. preferable. When the composition ratio (z) is within the above range, the pigment dispersibility is excellent, and the developability and curability are also good.
Furthermore, as specific resin in this invention, composition ratio (x) is 10-70 mol% (further 15-65 mol%, especially 20-50 mol%), Comprising: Composition ratio (y) is 5 ˜70 mol% (more preferably 10 to 60 mol%, especially 30 to 70 mol%), and the composition ratio (z) is 10 to 70 mol% (more preferably 20 to 70 mol%, particularly 30 to 70 mol%). Mol%) is preferred.

As content of resin (A) in the said this invention, 5-70 mass% is preferable with respect to the total solid of polymerizable resin composition, and 10-50 mass% is more preferable.
The resin (A) in the present invention can be used in combination with the other resins described above, but is preferably composed of only the resin (A) in the present invention.
In addition, the ratio (M / A) of the total amount (M) of the polymerizable compound (B) and other polymerizable compounds to the resin (A) is preferably 0.5 to 2.0, More preferably, it is 0.7-1.7.

-Photopolymerization initiator-
As the photopolymerization initiator, those containing at least one component having a molecular extinction coefficient of about 50 or more in a wavelength region of about 300 nm to 500 nm are preferable. For example, JP-A-2-48664 and JP-A-1 -152449 and JP-A-2-153353, aromatic ketones, lophine dimers, benzoin, benzoin ethers, polyhalogens, halogenated hydrocarbon derivatives, ketone compounds, ketoxime compounds, organic peroxides. Examples thereof include oxides, thio compounds, hexaarylbiimidazoles, aromatic onium salts, and ketoxime ethers.

  Among these, a combination of 4,4′-bis (diethylamino) benzophenone and 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2,4-bis- (trichloromethyl) -6- [ 4 ′-(N, N-bis (ethoxycarbonylmethyl) amino) -3′-bromophenyl] -s-triazine and the like are preferable.

  The above photopolymerization initiators may be used in combination of two or more, in addition to being used alone. As a content rate of the photoinitiator in the photosensitive resin composition of this invention, 0.1-20 mass% is preferable with respect to the solid content of the said polymeric compound, and 0.5-10 mass% is more. preferable.

  The photosensitive resin layer according to the present invention may contain a colorant such as a dye and a pigment in addition to the above-described polymer substance, polymerizable monomer, and photopolymerization initiator. About the kind, size, etc. of a preferable pigment, it can select suitably from description of Unexamined-Japanese-Patent No. 11-149008, for example. When a colorant such as a pigment is contained, a colored pixel can be formed. Moreover, additives, such as surfactant, can also be added as needed.

[Patterning process]
In the patterning step in the present invention, the photosensitive resin layer formed on the support is exposed and developed for patterning. 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.

The photospacer 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 and the colored part and the photo spacer are formed by arbitrarily combining a coating method for applying a photosensitive composition and a transfer method using a transfer material having a photosensitive resin layer made of the photosensitive composition. It is possible.
The black shielding part, the colored part, and the photospacer can each be formed from a photosensitive composition. Specifically, for example, a photosensitive resin layer is formed by directly applying the liquid photosensitive 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 photosensitive composition of another liquid is placed on another substrate (temporary support) different from the substrate. Then, after using the transfer material prepared by forming the photosensitive resin layer, the transfer material is brought into close contact with the substrate on which the black shielding portion and the colored portion are formed, and the photosensitive resin layer is transferred, and then exposed. -Photo spacers can be formed in a pattern by developing. In this manner, a color filter provided with a photospacer can be manufactured.

<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 drive element, the display light-shielding portion (black matrix or the like) or the drive 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 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 the color filter substrate is provided with a photo spacer having a uniform height and excellent elastic recovery, a liquid crystal display element including 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), The driving means has an active element (for example, TFT), and is configured to be regulated to a predetermined width by a photospacer having a uniform height between the pair of substrates and excellent in elastic 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 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “part” and “%” are based on mass.

As an example of the binder that can be used in the present invention, the resin P-1 and the resin P-29 whose structures are shown as the exemplary compounds P-1 and P-29, and the resin PH-1 and the resins MH-1 to MH- Synthesis of 3 is shown in Synthesis Examples 1 to 3.
(Synthesis Example 1)
-Synthesis of Resin P-1-
8.57 parts of 1-methoxy-2-propanol (MMPGAC, manufactured by Daicel Chemical Industries, Ltd.) was added in advance to the reaction vessel, the temperature was raised to 90 ° C., 6.27 parts of isopropyl methacrylate and 5.15 of methacrylic acid as monomers. A mixed solution consisting of 1 part of an azo polymerization initiator (V-601, manufactured by Wako Pure Chemical Industries, Ltd.) and 8.57 parts of 1-methoxy-2-propanol was placed in a 90 ° C. reaction vessel in a nitrogen gas atmosphere. It was dripped over 2 hours. 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 a solvent so that the solid concentration was 45%. A solution of the resin P-1 having an unsaturated group (solid acid Value: 73 mg KOH / g, Mw: 10,000, 1-methoxy-2-propanol 45% solution).
In addition, the molecular weight Mw of the resin P-1 indicates a weight average molecular weight, and the molecular weight was measured using a gel permeation chromatograph (GPC).

(Synthesis Example 2)
-Synthesis of Resin P-29-
In Synthesis Example 1, instead of isopropyl methacrylate and methacrylic acid, dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) and methacrylic acid were used as monomers, and resin P as shown in the above exemplary compound Resin represented by Exemplified Compound P-29, which was synthesized by the same method as in Synthesis Example 1 except that the addition amount of the monomer was changed so that the monomer composition ratio in -29 was 40:25:35. A solution of P-29 (solid concentration = 45%) was obtained.
Resin P-29 had an acid value; 73.9 mgKOH / g, Mw; 15,000.

(Synthesis Example 3)
-Synthesis of resin PH-1-
Charge 4 parts of 2,2'-azobisisobutyronitrile (AIBN) and 200 parts of diethylene glycol ethyl methyl ether, followed by 5 parts of 1,3-butadiene, 18 parts of methacrylic acid, 40 parts of benzyl methacrylate and n-methacrylic acid n- After charging 37 parts of butyl and substituting with nitrogen, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., maintained at this temperature for 5 hours, and then heated to 100 ° C. for further reaction for 1 hour. . Subsequently, the temperature of the reaction solution was lowered to room temperature to obtain a resin PH-1 solution (solid content concentration = 45%). Mw of this resin PH-1 was 27,000.

(Synthesis Example 4)
-Synthesis of Resin MH-1-
In Synthesis Example 2, synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of the azo polymerization initiator used was 2 parts, and a solution of resin MH-1 (solid content concentration = 45%) was obtained. .
Mw of this resin MH-1 was 3500.

(Synthesis Example 5)
-Synthesis of Resin MH-2-
In Synthesis Example 2, synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of the azo polymerization initiator used was 3 parts, and a solution of resin MH-2 (solid content concentration = 45%) was obtained. .
Mw of this resin MH-2 was 3000.

(Synthesis Example 6)
-Synthesis of Resin MH-3-
In Synthesis Example 2, synthesis was performed in the same manner as in Synthesis Example 2 except that the amount of the azo polymerization initiator used was 5 parts, and a solution of resin MH-3 (solid content concentration = 45%) was obtained. .
Mw of this resin MH-3 was 2500.

(Example 1)
-Production of photosensitive resin transfer material for photo spacer-
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 6.0 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 (structure 1 below) 10.0 parts methanol 90.0 parts 1-methoxy-2-propanol 51.0 parts methyl ethyl ketone 700 parts

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

  Next, on the formed thermoplastic resin layer, an intermediate layer coating solution having the following formulation B was applied and dried to laminate an intermediate layer having a dry layer thickness of 1.5 μm.

[Prescription B of coating solution for intermediate layer]
Polyvinyl alcohol: 3.22 parts (PVA-205, saponification rate 80%, manufactured by Kuraray Co., Ltd.)
-Polyvinylpyrrolidone: 1.49 parts (PVP K-30, manufactured by IS Japan Co., Ltd.)
・ Methanol: 42.3 parts ・ Distilled water: 524 parts

  Next, on the formed intermediate layer, a photosensitive resin layer-forming coating liquid having the formulation 1 shown in Table 1 below was further applied and dried to laminate a photosensitive resin layer having a dry layer thickness of 4.1 μm.

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

-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 photo spacer-
The cover film of the obtained photosensitive resin transfer material for photospacer (1) is peeled off, and the exposed surface of the photosensitive resin layer is placed on the ITO film of the color filter substrate on which the ITO film prepared above is sputtered. Lamination was performed using a laminator type Lamic II [manufactured by Hitachi Industries, Ltd.], and the film was bonded 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 photosensitive 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 photosensitive resin layer on the side in contact with the intermediate layer is set to 40 μm with the color filter substrate placed on the substrate in a state where the color filter substrate stands substantially parallel and vertically, and the thermoplastic resin layer is interposed through the mask. Proximity exposure was performed from the side with an exposure amount of 60 mJ / cm ² .

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-fold with pure water) and developed at 29 ° C. for 30 seconds at a cone type nozzle pressure of 0.15 MPa for shower development. 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 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 spacer pattern was a cylindrical shape having a diameter of 24 μm and an average height of 3.6 μm. In addition, the average height is the highest position of each photo spacer from the transparent electrode formation surface of ITO using a three-dimensional surface structure analysis microscope (manufacturer: ZYGO Corporation, model: New View 5022) for the obtained 1,000 photo spacers. Was calculated by measuring (n = 20).

<Production of liquid crystal display device>
Next, a TFT substrate was separately prepared as a counter substrate. An ITO film is formed on one surface of the TFT substrate by sputtering. Subsequently, the ITO film (transparent electrode) of the color filter substrate and the ITO film of the TFT substrate were respectively patterned for the PVA mode, and an alignment film made of polyimide was further provided thereon.

Thereafter, a sealant of UV curable resin is applied by a dispenser method to a seal portion having a width of 0.5 mm and a height of 40 μm corresponding to an outer frame of a black matrix provided around the pixel group of the color filter, A liquid crystal for PVA mode was dropped, and the color filter substrate and the TFT substrate were bonded together. Thereafter, the pressure was returned to normal pressure, and a load was applied to control the cell thickness to 4 μm. In this state, a metal halide lamp is used to filter out ultraviolet rays of less than 340 nm, and the sealant is exposed under a nitrogen atmosphere so that the integrated light amount of 340 to 390 nm is equivalent to 3,000 mJ / cm ^2. After light curing, the sealing agent was cured by heat treatment to obtain a liquid crystal cell. A polarizing plate (HLC2-2518, manufactured by Sanlitz Co., Ltd.) was attached to both surfaces of the liquid crystal cell thus obtained. Next, a CCFL backlight was constructed and installed on the back side of the liquid crystal cell to which the polarizing plate was attached, thereby producing the PVA mode liquid crystal display device of the present invention.

(Examples 2-14, Comparative Examples 1-6),
In Example 1, a photosensitive resin composition was used in the same manner as in Example 1 except that instead of the resin P-1 (binder) and the polymerizable compound FA-513A, the binder and the polymerizable compound shown in Table 2 below were used. Product, a photospacer, and a PVA mode liquid crystal display device were produced.

(Example 15)
-Production of photo spacer (liquid cash register method)-
A glass substrate coater MH-1600 (manufactured by FS Japan Co., Ltd.) having a slit-like nozzle on the ITO film on the color filter substrate on which the ITO film produced in the same manner as in Example 1 was formed by sputtering. Then, a coating solution for a photosensitive resin composition layer having the formulation 1 shown in Table 1 was applied. Subsequently, after a part of the solvent is dried for 30 seconds using a vacuum dryer VCD (manufactured by Tokyo Ohka Kogyo Co., Ltd.) to eliminate the fluidity of the coating film, unnecessary portions around the substrate are removed with an EBR (edge bead remover). The coating solution was removed and prebaked at 120 ° C. for 3 minutes to form a photosensitive resin composition layer having a thickness of 2.4 μm (layer forming step).
Subsequently, a photospacer was produced on the color filter substrate by the same patterning process and heat treatment process as in Example 1. However, the exposure amount was 300 mJ / cm ² , and development with a sodium carbonate-based developer was 23 ° C. for 60 seconds.

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

(Comparative Example 7)
In Example 15, in place of the coating solution for photosensitive resin composition layer consisting of the formulation 1, the coating solution for photosensitive resin composition layer consisting of the formulation 15 shown in Table 2 above was used. Similarly, a photo spacer and a liquid crystal display device were produced.

  The following evaluation was performed about the photospacer and liquid crystal display device which were obtained in the said Examples 1-15 and Comparative Examples 1-7. The results are shown in Table 3.

[Evaluation]
-1. Photo spacer height distribution measurement-
The highest position of the 20 photo spacers was measured in the plane of the color filter substrate on which the photo spacers were formed, and the average value of the standard deviation and the height was obtained. A value (standard deviation / average value) obtained by dividing the standard deviation of the height distribution by the average height was calculated. The height was measured using a surface roughness meter P-10 (manufactured by TENCOR).

-2. Deformation recovery rate
Each of the photo spacers was measured and evaluated as follows with 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.
Deformation recovery rate (%) = (Recovery amount after weight release [μm] / Deformation amount by weight [μm]) × 100

-3. Display unevenness
For each of the liquid crystal display devices, after turning on the backlight for 24 hours, the gray display when the 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. did.
<Evaluation criteria>
○: Display unevenness was not recognized at all.
Δ: Display unevenness was slightly recognized.
X: Display unevenness was recognized remarkably.

-4. Low temperature foaming
The liquid crystal display device was left to stand in a thermostatic layer at −30 ° C. for 6 to 12 hours and then taken out. The presence or absence of bubbles was visually evaluated according to the following evaluation criteria.
<Evaluation criteria>
○: No foaming was observed after standing for 12 hours.
Δ: No foaming was observed after standing for 6 hours.
X: Foaming was observed when left for 6 hours.

  From Table 3, it can be seen that the photosensitive resin layer formed by the photosensitive resin composition of the present invention has high uniformity in layer thickness. Moreover, it turns out that the photospacer formed with the photosensitive resin composition of this invention has a high elastic recovery property. Furthermore, it can be seen that the liquid crystal display device provided with the photo spacer suppresses the occurrence of display unevenness and low-temperature foaming.

Claims (11)

  A photosensitive resin composition comprising at least a polymerizable compound having a group having a bridged ring structure and a group having an ethylenically unsaturated bond, having a molecular weight of 2000 or less, a binder, and a photopolymerization initiator. 2. The photosensitive resin according to claim 1, wherein the group having a bridged ring structure includes at least one alicyclic structure represented by any one of the following chemical formulas (1) to (3). Composition.

  The photosensitive resin composition according to claim 1, wherein the group having a bridged ring structure is a group containing 6 or more chemical bonds between a silicon atom and an oxygen atom.   The photosensitive material according to any one of claims 1 to 3, wherein the binder has a branched and / or alicyclic structure, an acidic group, and an ethylenically unsaturated bond in each side chain. Resin composition.   The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition is used for producing a photospacer. Two supports, at least a liquid crystal provided between the supports, two electrodes for applying an electric field to the liquid crystal, and a photo spacer for regulating a cell thickness between the supports. A method of manufacturing the photospacer in a liquid crystal display device,
A layer forming step of forming a photosensitive resin layer containing the photosensitive resin composition according to any one of claims 1 to 5 on one of mutually opposing surfaces of the two supports. ,
A patterning step of patterning by exposing and alkali developing the photosensitive resin layer; and
The manufacturing method of the photospacer which has.   The layer forming step uses a photosensitive resin transfer material having a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 5 on a temporary support. The method for producing a photospacer according to claim 6, further comprising a transfer step of forming the photosensitive resin layer by transferring the photosensitive resin layer so as to be in contact with one of the opposing surfaces of the two supports.   In the layer forming step, a solution containing the photosensitive resin composition according to any one of claims 1 to 5 is applied onto one of the opposing surfaces of the two supports and dried. The method for producing a photospacer according to claim 6, further comprising a step of forming a photosensitive resin layer.   A substrate for a liquid crystal display device comprising a photospacer produced by the method for producing a photospacer according to any one of claims 6 to 8.   The liquid crystal display element provided with the board | substrate for liquid crystal display devices of Claim 9.   A liquid crystal display device comprising the liquid crystal display element according to claim 10.