JP6008152B2 - Resin composition, liquid crystal alignment material and retardation material - Google Patents

Description

  The present invention relates to a resin composition, a liquid crystal alignment material, and a retardation material.

  In general, in an optical device such as a liquid crystal display element, an organic EL (electroluminescence) element, and a solid-state imaging element, a protective film is provided to protect the element surface from a solvent and heat in a manufacturing process. This protective film is required not only to have high solvent resistance and heat resistance, but also to have high adhesion to the substrate to be protected and high transparency.

  The protective film is used, for example, as a protective film for color filters used in color liquid crystal display devices and solid-state imaging devices. In this case, the protective film is required to be formed with a film thickness of, for example, 1 μm or more in order to flatten the underlying color filter or black matrix. In particular, when manufacturing a color liquid crystal display element of STN method or TFT method, it is necessary to very closely bond the color filter substrate and the counter substrate, so that the cell gap between the substrates is made uniform. Is indispensable, and the protective film is required to have a high leveling ability with respect to the base. Furthermore, in order to maintain the transmittance of light passing through the color filter, the protective film also needs to have high transparency.

  In recent years, studies have been made to reduce cost and weight by introducing a phase difference material into a cell of a liquid crystal display.

  FIG. 2 is a schematic configuration diagram of a liquid crystal cell 200 in which a liquid crystal alignment film is formed by a conventional technique. In this figure, the liquid crystal layer 208 is sandwiched between two substrates 201 and 211. On the substrate 211, an ITO 210 and an alignment film 209 are formed. On the substrate 201, a color filter 202, a color filter (CF) overcoat (hereinafter referred to as a CF overcoat) 203, an alignment film 204, a phase difference material 205, an ITO 206, an alignment A film 207 is formed in this order.

  In the conventional liquid crystal cell, since the polymerizable liquid crystal for forming the retardation material described above is aligned before curing, it is necessary to separately provide a film capable of aligning the liquid crystal in the lower layer, that is, an alignment film. . The alignment film is formed through processes such as rubbing treatment and polarized light irradiation. That is, as shown in FIG. 2, conventionally, after the alignment film 204 is formed on the CF overcoat 203, a retardation material 205 obtained from a polymerizable liquid crystal such as a liquid crystal monomer is formed thereon. It was common. That is, after the color filter 202 is formed, it is necessary to further form two layers of the CF overcoat 203 and the alignment film 204, which complicates the manufacturing process.

  For these reasons, it is strongly desired to provide a film that satisfies a plurality of different required characteristics at the same time and a material for forming the film. Specifically, a film that doubles as an alignment film and a CF overcoat and a material for forming this film are required. Thereby, when manufacturing a liquid crystal display, it is possible to enjoy great advantages such as cost reduction, reduction in the number of processes, and improvement in throughput.

Generally, a highly transparent acrylic resin is used for the CF overcoat. These acrylic resins are made of glycol-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ester-based solvents such as ethyl lactate and butyl lactate, and ketone-based solvents such as cyclohexanone and methyl amyl ketone. Widely used from the viewpoint of sex. And heat resistance and solvent tolerance are expressed by hardening an acrylic resin with a heat | fever or light (for example, refer patent document 1 or 2).

  However, according to the study by the present inventors, a conventional CF overcoat made of a thermosetting or photocurable acrylic resin can provide transparency and flatness, but is subjected to a rubbing treatment. However, it has been found that sufficient liquid crystal orientation cannot be exhibited. Therefore, it is understood that the conventional CF overcoat cannot be applied as it is to a film serving as both the alignment film and the CF overcoat.

  On the other hand, as the alignment film, materials made of solvent-soluble polyimide or polyamic acid have been conventionally used. It has been reported that these materials can be completely imidized at the time of post-baking to obtain solvent resistance and also realize sufficient orientation by rubbing treatment (see Patent Document 3). However, when viewed as a CF overcoat, there is a problem in that the transparency is greatly reduced by increasing the film thickness. In addition, polyimide and polyamic acid are soluble in solvents such as N-methylpyrrolidone and γ-butyrolactone, but have low solubility in glycol solvents and ester solvents. There is also a problem that is difficult to apply.

JP 2000-103937 A JP 2000-119472 A JP 2005-037920 A

  The present invention has been made based on the above knowledge and examination results. That is, an object of the present invention is to provide a resin composition having excellent orientation, solvent resistance, heat resistance, and transparency, and capable of forming a cured film that can be applied as a CF overcoat. is there.

  Other objects and advantages of the present invention will become apparent from the following description.

  1st aspect of this invention is related with the resin composition characterized by including the polymer (component A) which has a cyclohexene ring in a side chain.

  1st aspect of this invention WHEREIN: It is preferable that the polymer principal chain which is A component is a polymer of the monomer which has an unsaturated double bond.

  1st aspect of this invention WHEREIN: It is preferable that the polymer principal chain which is A component is an acrylic polymer.

  In the first aspect of the present invention, the polymer as the component A is preferably derived from polyvinyl alcohol.

  1st aspect of this invention WHEREIN: It is preferable that the polymer principal chain which is A component contains a ring structure.

1st aspect of this invention WHEREIN: It is preferable that the polymer principal chain which is A component is a polyester resin.

  1st aspect of this invention WHEREIN: It is preferable that the polymer principal chain which is A component is a novolak resin.

  1st aspect of this invention WHEREIN: It is preferable that the polymer which is A component is a cycloolefin polymer.

  1st aspect of this invention WHEREIN: It is preferable that the polymer which is A component has a side chain used as a crosslinking group.

  In the first aspect of the present invention, the crosslinking group of the polymer as the component A is preferably at least one functional group selected from the group consisting of a hydroxy group, a carboxyl group, an epoxy group, and an acryloyl group.

  1st aspect of this invention WHEREIN: Furthermore, it is preferable to contain the crosslinking agent (C component) which reacts with a heat | fever.

  1st aspect of this invention WHEREIN: Furthermore, it is preferable to contain a crosslinking catalyst (E component).

According to a second aspect of the present invention, there is provided a compound (component B) having a cyclohexene ring at the terminal represented by the formula (1);
The present invention relates to a resin composition containing a binder polymer (component D).

［式（１）中、Ｒは炭素原子数１乃至２０の有機基を表し、Ｘは水素原子、メチル基又はハロゲン原子を表す。］

[In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. ]

  2nd aspect of this invention WHEREIN: It is preferable that (D) component is a polyester resin containing the structural unit represented by Formula (2).

［式（２）中、Ａは、脂環式骨格又は脂肪族骨格に４つの結合手が結合した４価の有機基を表し、Ｂは、脂環式骨格又は脂肪族骨格に２つの結合手が結合した２価の有機基を表す。］

[In Formula (2), A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B represents two bonds to an alicyclic skeleton or an aliphatic skeleton. Represents a divalent organic group to which is bonded. ]

  In the second aspect of the present invention, the component (D) is preferably an acrylic polymer.

In the second aspect of the present invention, it is preferable to further contain a crosslinking agent (component C) that reacts with heat.
In the 2nd aspect of this invention, it is preferable to contain a crosslinking catalyst (E component) further.

［式（１）中、Ｒは炭素原子数１乃至２０の有機基を表し、Ｘは水素原子、メチル基又はハロゲン原子を表す。］
According to a third aspect of the present invention, there is provided a liquid crystal alignment material obtained by using the resin composition of the first and second aspects of the present invention.
Moreover, this invention hardens the resin composition containing the compound (B component) which has a cyclohexene ring at the terminal represented by following formula (1), and a binder polymer (D component), and forms a cured film. Process, and
The present invention relates to a method for producing a liquid crystal alignment material, comprising a step of rubbing the cured film.

[In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. ]

［式（１）中、Ｒは炭素原子数１乃至２０の有機基を表し、Ｘは水素原子、メチル基又はハロゲン原子を表す。］ A fourth aspect of the present invention relates to a retardation material characterized by being formed using a cured film obtained from the resin composition of the first and second aspects of the present invention.
Moreover, this invention hardens the resin composition containing the compound (B component) which has a cyclohexene ring at the terminal represented by following formula (1), and a binder polymer (D component), and forms a cured film. Process,
Performing a rubbing treatment on the cured film; and
The present invention relates to a method for producing a retardation material, comprising a step of applying a retardation material on the rubbed cured film and curing.

[In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. ]

  According to the resin composition of the first aspect of the present invention, it is possible to form a cured film that has excellent orientation, solvent resistance, heat resistance and transparency and can be applied as a CF overcoat.

  According to the resin composition of the second aspect of the present invention, it is possible to form a cured film that has excellent orientation, solvent resistance, heat resistance and transparency and can be applied as a CF overcoat.

  The liquid crystal aligning material of the 3rd aspect of this invention is excellent in light transmittance, heat resistance, solvent tolerance, and orientation.

  The retardation material of the fourth aspect of the present invention can be arranged in a liquid crystal cell. In the liquid crystal cell using the retardation material, the contrast ratio can be improved.

It is a typical block diagram of the liquid crystal cell by embodiment of this invention. It is a typical block diagram of the conventional liquid crystal cell.

  The present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a retardation material formed using a cured film obtained from the resin composition. More specifically, a resin composition that has excellent orientation, solvent resistance, heat resistance, and transparency, and that can form a cured film that can be applied as a CF overcoat, and using this resin composition The present invention relates to a liquid crystal alignment material to be formed and a retardation material formed using the liquid crystal alignment material. The cured film formed from the resin composition of the present invention is suitable as a film having a function as a CF overcoat in a liquid crystal display, and has an alignment function with respect to a polymerizable liquid crystal for forming a retardation layer. Therefore, it is also suitable for forming a built-in retardation layer.

  That is, according to the resin composition of the present invention, it can be applied with a film thickness of, for example, 1 μm or more, and in addition to high transparency and high solvent resistance, a cured film having liquid crystal alignment ability can be formed. it can. Therefore, this resin composition can be used as a material for forming a liquid crystal alignment film or a planarization film. In particular, the liquid crystal alignment film and the overcoat layer of the color filter that have been conventionally formed independently can be provided in the liquid crystal cell as a “liquid crystal alignment layer (CF overcoat)” having both characteristics. Accordingly, it is possible to realize a reduction in cost by simplifying the manufacturing process and reducing the number of processes.

Furthermore, since the resin composition of the present invention is soluble in a glycol-based solvent and a lactic acid ester-based solvent, it is suitable for a production line for a planarized film mainly using these solvents.

  Hereinafter, the resin composition, the liquid crystal alignment material, and the retardation material of the present invention will be described in detail with specific examples.

The components that can be contained in the resin composition of the embodiment of the present invention are as follows.
(A) Component: Polymer having a cyclohexene ring in the side chain (B) Component: Compound having a cyclohexene ring at the terminal (C) Component: Crosslinking agent (D) Component: Other polymer (In this specification, a binder polymer is also used. say.)
Component (E): cross-linking catalyst

Moreover, in the resin composition of embodiment of this invention, the combination of a preferable component is as follows.
[1]: A resin composition containing 1 to 100 parts by mass of component (C) based on 100 parts by mass of component (A).
[2]: A resin composition containing 1 to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of component (B) and component (D).
[3]: A resin composition containing 1 to 100 parts by mass of component (C) and a solvent based on 100 parts by mass of component (A).
[4]: A resin composition containing 1 to 100 parts by mass of component (C) and a solvent based on 100 parts by mass of the total amount of component (B) and component (D).
[5]: A resin composition containing 1 to 100 parts by mass of component (C), 0.01 to 5 parts by mass of component (E), and a solvent based on 100 parts by mass of component (A).
[6]: Based on 100 parts by mass of the total amount of component (B) and component (D), 1 to 100 parts by mass of component (C), 0.01 to 5 parts by mass of component (E), and solvent A resin composition to contain.

  Below, the detail of each component which comprises the resin composition of this invention is described.

(A) component (A) component contained in the resin composition of embodiment of this invention is a polymer which has a cyclohexene ring in a side chain. The skeleton of the polymer main chain is not particularly limited. The polymer preferably has a reactive group that is self-reactive or crosslinks with a crosslinking agent by heat.

  Examples of the polymer as component (A) include acrylic polymers, vinyl polymers, polyester resins, novolac resins, and cycloolefin polymers.

  As a method of introducing a cyclohexene ring into a polymer, a method of adding cyclohexene carboxylic acid to a polymer having an epoxy group, a method of subjecting a polymer having a hydroxy group to a condensation reaction of cyclohexene dicarboxylic acid anhydride, a polymer having a hydroxy group or an amino group And a method of reacting with cyclohexene carboxylic acid chloride or a method of polymerizing using a monomer having a cyclohexene ring.

  Hereinafter, the specific example of the polymer which is (A) component is shown.

In the above formulas (A-1) to (A-7), X ₁ represents a hydrogen atom or a carboxyl group, Y ₁ represents a hydrogen atom or a methyl group, and R ₁ represents a hydrogen atom, an alkyl group or an acetyl group. R ₂ represents a hydrogen atom or a glycidyl group. The ratio of n to m is
n / m = 100/0 to 30/70. In the formula (A-7), A ₁ represents an alicyclic group,
Represents a group comprising an alicyclic group and an aliphatic group or a group containing a benzene ring structure, and B ₁ contains an alicyclic group, a group comprising an alicyclic group and an aliphatic group or a benzene ring structure Represents a group.

  The weight average molecular weight of the component (A) is preferably 1,000 to 50,000 in terms of polystyrene.

  A synthesis method of the acrylic (A) component will be described.

  The method for obtaining the acrylic polymer having a cyclohexene ring as described above is not particularly limited. For example, an acrylic polymer having a glycidyl group or a hydroxy group is previously generated by radical polymerization or the like, and then this is performed. Is reacted with cyclohexene carboxylic acid, cyclohexene carboxylic acid chloride, cyclohexene dicarboxylic acid anhydride, or the like to obtain an acrylic polymer as component (A).

Examples of the radical polymerizable monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 4-hydroxybutyl methacrylate glycidyl ether, and the like.

  Examples of the radical polymerizable monomer having a hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 2-hydroxyethyl acrylate, 2-hydroxy Propyl acrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxyl-6-lactone, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxyl-6 -Lactone etc. can be mentioned.

  In the resin composition of the embodiment of the present invention, a monomer that can be copolymerized with a monomer having a specific functional group when obtaining an acrylic polymer having a specific functional group effective for introduction of a cyclohexene ring such as a glycidyl group or a hydroxy group Can be used in combination. Specific examples of such monomers are given below, but are not limited thereto.

  Examples of monomers that can be copolymerized with a monomer having a specific functional group include acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

  Specific examples of the monomer include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl) maleimide. , N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2 -Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethyl Glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8 -Ethyl-8-tricyclodecyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert- Butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate Rate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8- Methyl-8-tricyclodecyl methacrylate and 8-ethyl-8-tricyclodecyl methacrylate, vinyl ether, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether, styrene , Methylstyrene, chlorostyrene, bromostyrene, maleimide, N-methyl Maleimide, may be mentioned N- phenylmaleimide and N- cyclohexyl maleimide.

The method for obtaining the acrylic polymer having a cyclohexene ring used in the resin composition of the embodiment of the present invention is not particularly limited. For example, a monomer having a specific functional group, another copolymerizable monomer, and polymerization initiation if desired It can be obtained by carrying out a polymerization reaction at a temperature of 50 to 110 ° C. in a solvent in which an agent or the like coexists. In that case, the solvent used will not be specifically limited if it dissolves the monomer which comprises the acrylic polymer which has a specific functional group, and the acrylic polymer which has a specific functional group. Specific examples include the solvents described below.

  The acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.

  Next, the resulting acrylic polymer having a specific functional group is reacted with a compound having a cyclohexene ring to obtain an acrylic polymer having a cyclohexene ring as the component (A) (hereinafter also referred to as a specific copolymer). be able to. At this time, a solution of an acrylic polymer having a specific functional group is usually used. Specifically, for example, there are synthesis methods shown below.

  A specific copolymer can be obtained by reacting cyclohexenecarboxylic acid with a solution of an acrylic polymer having a glycidyl group in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of 80 to 150 ° C. At this time, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described below.

  A specific copolymer can be obtained by reacting a solution of an acrylic polymer having a hydroxy group with cyclohexene dicarboxylic acid anhydride in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of 80 ° C. to 150 ° C. . In this case, the solvent to be used is preferably a solvent that dissolves the monomer constituting the specific copolymer and the specific copolymer and does not have a hydroxy group.

  A solution of an acrylic polymer having a hydroxy group is reacted with cyclohexene dicarboxylic acid chloride in the presence of a tertiary amine such as triethylamine at a temperature of 0 ° C. to 40 ° C., and then the generated salt and amine are removed. A specific copolymer can be obtained. In this case, the solvent to be used is preferably a solvent that dissolves the monomer constituting the specific copolymer and the specific copolymer and does not have a hydroxy group.

  The specific copolymer obtained as described above is usually in a solution state in which the specific copolymer is dissolved in a solvent.

  In addition, the solution of the specific copolymer obtained as described above is poured into diethyl ether or water with stirring to reprecipitate, and the generated precipitate is filtered and washed, and then is subjected to normal pressure or reduced pressure. Thus, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a purified powder of the specific copolymer can be obtained. In addition, when it cannot refine | purify enough by one operation | movement, what is necessary is just to redissolve the obtained powder in a solvent and to repeat said operation.

  In the resin composition of the embodiment of the present invention, the powder of the specific copolymer may be used as it is, or the powder may be used as a solution by re-dissolving in a solvent described later, for example.

  In the resin composition of the embodiment of the present invention, the acrylic polymer as the component (A) may be a mixture of a plurality of types of specific copolymers.

  Next, a method for synthesizing the phenol novolac type (A) component will be described.

  To obtain a polymer having a cyclohexene ring by reacting an epoxidized phenol novolak resin or an epoxidized cresol novolak resin with cyclohexene carboxylic acid in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of 80 ° C. to 150 ° C. Can do. At this time, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. Specific examples include the solvents described below.

  In the resin composition of the embodiment of the present invention, commercially available epoxidized phenol novolac resins usable as the component (A) include, for example, Epicoat 152, 154 (above, Yuka Shell Epoxy Co., Ltd. (current Japan Epoxy). Resin Co., Ltd.), EPPN 201 and 202 (Nippon Kayaku Co., Ltd.) and other phenol novolac type epoxy resins. Examples of commercially available cresol novolac epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.) and Epicoat Examples thereof include cresol novolac type epoxy resins such as 180S75 (Oilized Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)).

(B) component (B) component contained in the resin composition of embodiment of this invention is a compound which has a cyclohexene ring in the terminal represented by following formula (1).

  In formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group, or a halogen atom. The compound having a cyclohexene ring at the terminal, which is the component (B), is a method of reacting a polyfunctional epoxy compound with cyclohexene carboxylic acid, or a method of reacting a polyfunctional alcohol compound with cyclohexene carboxylic acid chloride or cyclohexene dicarboxylic acid anhydride. Is obtained.

  Examples of the compound (B) that has a cyclohexene ring at the terminal include the following.

(C) component (C) component contained in the resin composition of embodiment of this invention is a crosslinking agent. As this crosslinking agent, an epoxy compound, a methylol compound, an isocyanate compound, etc. are mentioned, for example.

  When the component (A) or the component (D) described later is a polymer having a hydroxy group, the component (C) is preferably a methylol compound or an isocyanate compound. Moreover, when (A) component or (D) component is a polymer which has a carboxyl group, (C) component has an preferable epoxy compound, a methylol compound, or an isocyanate compound.

Examples of the epoxy compound include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, and diethylene glycol diester. Glycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4 ′ -Methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether and And pentaerythritol polyglycidyl ether.

  As the epoxy compound, a commercially available compound may be used because it is easily available. Although the specific example (brand name) is given to the following, it is not limited to these. For example, epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.), Epolide GT-401, GT-403, GT-301, GT-302, Celoxide 2021, and Celoxide 3000 ( Epoxy resin having a cyclohexene oxide structure such as Daicel Chemical Industries, Ltd., Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (above, Yuka Shell Epoxy Co., Ltd.) Bisphenol A type epoxy resin such as (made by Japan Epoxy Resin Co., Ltd.), Bisphenol F type epoxy resin such as Epicoat 807 (made by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)), Denacol EX-252 (manufactured by Nagase ChemteX Corporation), Y175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (above, manufactured by CIBA-GEIGY AG (currently BASF)), Epicron 200, 400 (above, Dainippon Ink and Chemicals, Inc.) Co., Ltd. (currently DIC Corporation), Epicoat 871, 872 (above, Yuka Shell Epoxy Co., Ltd. (present Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5661 (above, Sera Needs coating Co., Ltd.) and other cycloaliphatic epoxy resins, Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, Aliphatic polyglycidyl ethers such as EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation) And the like can be given.

  In addition, as a compound having at least two epoxy groups, a polymer having an epoxy group can be used without particular limitation. Such a polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. As an example, an addition polymerization polymer such as a copolymer of polyglycidyl acrylate, glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, or a condensation polymerization polymer such as epoxy novolac, etc. Can be mentioned.

  Moreover, the polymer which has the said epoxy group can also be manufactured by reaction of the high molecular compound which has a hydroxyl group, and compounds which have epoxy groups, such as epichlorohydrin and glycidyl tosylate. The weight average molecular weight of such a polymer is, for example, 300 to 200,000 in terms of polystyrene.

Examples of methylol compounds that can be used as the component (C) include methoxymethylated glycoluril, methoxymethylated benzoguanamine, and methoxymethylated melamine. Specific examples include hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3 -Bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4, Examples include 5-dihydroxy-2-imidazolinone and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. Further, as commercially available products, methoxymethyl type melamine compounds (trade names Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade names My Coat 506, My Coat 508), Glycoluril compound (trade name Cymel 1170, Powder Link 1174), methylated urea resin (trade name UFR65), butylated urea resin (
UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin (high condensation type, trade name Beccamin J-300S, manufactured by Dainippon Ink & Chemicals, Inc. (currently DIC)), Becamine P-955, becamine N) and the like.

  Moreover, the following can be mentioned as an example of an isocyanate compound. For example, examples of the compound having two or more isocyanate groups in one molecule include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, methylene bis (4-cyclohexyl isocyanate), trimethylhexamethylene diisocyanate, etc. And a reaction product of these with diols, triols, diamines or triamines. In order to improve the storage stability in the solution, it is preferable to use those isocyanate compounds that are blocked with a blocking agent.

  Examples of the blocking agent include phenols such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol, lactams such as ε-caprolactam, acetone oxime, methyl ethyl ketone oxime, and methyl isobutyl ketone. Examples include oximes such as oxime, cyclohexanone oxime, acetophenone oxime, and benzophenone oxime, pyrazoles such as pyrazole, 3,5-dimethylpyrazole, and 3-methylpyrazole, and thiols such as dodecanethiol and benzenethiol.

  Specific examples of the compound (C) include the following.

  The following examples can be given as isocyanate compounds derived from isophorone diisocyanate.

［式（Ｃ−４）乃至式（Ｃ−６）中、Ｒはポリエーテル構造を表わす。］
ポリエーテル構造としては、例えば、ポリエチレングリコールやポリプロピレングリコール由来の２価の基等が挙げられる。

[In the formulas (C-4) to (C-6), R represents a polyether structure. ]
Examples of the polyether structure include divalent groups derived from polyethylene glycol and polypropylene glycol.

  The crosslinking agent may be a compound obtained by condensing a melamine compound, urea compound, glycoluril compound or benzoguanamine compound in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group. For example, the high molecular weight compound manufactured from the melamine compound (trade name Cymel 303) and the benzoguanamine compound (trade name Cymel 1123) described in US Pat. No. 6,323,310 can be mentioned.

  Furthermore, as the component (C), an acrylamide compound substituted with a hydroxymethyl group or alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or methacryl Polymers produced using amide compounds can also be used. Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethylmethacrylamide. And a copolymer of N-butoxymethylacrylamide, a copolymer of benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like. The weight average molecular weight of such a polymer is, for example, 1,000 to 500,000 in terms of polystyrene, preferably 2,000 to 200,000, more preferably 3,000 to 150,000, and 3,000 to 50,000 is more preferable.

  The cross-linking agents described above can be used alone or in combination of two or more.

  In the resin composition of the embodiment of the present invention, the content of the crosslinking agent as the component (C) is 1 to 100 parts by mass based on 100 parts by mass of the component (A) when the component (A) is used. Preferably there is. Moreover, when using (B) component, it is preferable that it is 1 thru | or 100 mass parts based on 100 mass parts of total amounts of (B) component and (D) component. When this ratio is too small, the solvent resistance of the cured film is lowered, whereby the orientation is lowered or the heat resistance is lowered. On the other hand, if the ratio is excessive, the orientation may be lowered, or the storage stability may be lowered.

(D) component (D) component contained in the resin composition of embodiment of this invention is a "other polymer", Comprising: It is a polymer (binder polymer) used as the binder for adding (B) component. is there. The type of the “other polymer” is not particularly limited. However, it is preferable that the “other polymer” be self-crosslinked by reacting with a crosslinking agent as the component (C) by having a thermal crosslinking group. Examples of the thermal crosslinking group include a carboxyl group, a hydroxy group, an epoxy group, an oxetanyl group, an acryloyl group, and a methacryloyl group. The weight average molecular weight of the component (D) is preferably 1,000 to 100,000 in terms of polystyrene.

  Preferable examples of other polymers include a polyester resin containing a structural unit represented by the following formula (2), an acrylic polymer having a crosslinking group, a polyester resin represented by the following formula (3), and the like. .

［式（２）中、Ａは、脂環式骨格又は脂肪族骨格に４つの結合手が結合した４価の有機基を表し、Ｂは、脂環式骨格又は脂肪族骨格に２つの結合手が結合した２価の有機基を表す。］

[In Formula (2), A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B represents two bonds to an alicyclic skeleton or an aliphatic skeleton. Represents a divalent organic group to which is bonded. ]

［式（３）中、Ａ’及びＢ’は、それぞれ独立して脂環式骨格、脂肪族骨格又は芳香環骨格に２つの結合手が結合した２価の有機基、または、これら骨格にエーテル結合、エステル結合又はアミド結合を結合させたものに２つの結合手が結合した２価の有機基を表す。］

[In Formula (3), A ′ and B ′ each independently represent a divalent organic group in which two bonds are bonded to an alicyclic skeleton, an aliphatic skeleton or an aromatic ring skeleton, or an ether to these skeletons. A divalent organic group in which two bonds are bonded to a bond, an ester bond or an amide bond. ]

  The polymer represented by the above formula (2) is obtained by a polymerization reaction of the following tetracarboxylic dianhydride (formula (i)) and a diol compound (formula (ii)).

  In the above formulas (i) and (ii), A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B represents an alicyclic skeleton or an aliphatic skeleton. Represents a divalent organic group in which two bonds are bonded.

  In the resin composition of the embodiment of the present invention, the mixing ratio of the component (B) and the component (D) is preferably 5:95 to 50:50. If the component (B) is less than this ratio, the orientation may be lowered. On the other hand, if it is excessive, the solvent resistance may be lowered, the orientation may be lowered, and the film formability may be lowered. In addition, you may mix (D) component with (A) component in the range which does not reduce a characteristic.

(E) component The resin composition of embodiment of this invention may contain a crosslinking catalyst as (E) component. (E) A component is effective at the point which accelerates | stimulates the thermosetting of a resin composition.

  For example, when a hydroxy group contained in the resin composition reacts with a methylol compound, an acid or thermal acid generator is useful for the crosslinking catalyst as the component (E). Examples of such an acid or thermal acid generator include a sulfonic acid group-containing compound, hydrochloric acid, or a salt thereof, and a compound that generates an acid by thermal decomposition during pre-baking or post-baking, that is, heat at 80 to 250 ° C. Any compound that decomposes to generate an acid is not particularly limited.

  Specific examples of the acid include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethane. Sulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H -Sulfonic acids such as perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid and dodecylbenzenesulfonic acid, or hydrates and salts thereof. Can be mentioned.

  Further, as the thermal acid generator, bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2,3-phenylene Tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluene Sulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl-p-toluenesulfonate, 2,2,2-trifluoroethyl-p-toluenesulfonate, 2-hydroxybutyl Besides p- tosylate and N- ethyl-4-toluenesulfonamide, and the like, it may also be mentioned compounds represented by the following formula.

  Content of (E) component in the resin composition of embodiment of this invention is preferable with respect to 100 mass parts of (A) component, or the total amount of 100 mass parts of (B) component and (D) component. Is 0.01 to 5 parts by mass. When the content of the component (E) is less than 0.01 parts by mass, the effect of promoting the thermosetting property of the resin composition may not be seen. On the other hand, if it exceeds 5 parts by mass, the storage stability of the resin composition may decrease.

<Solvent>
The resin composition of the embodiment of the present invention can be used in a solution state dissolved in a solvent. As a solvent to be used, it is necessary to dissolve the component (A) or dissolve the component (B) and the component (D). In addition, the component (C) is dissolved as needed, the component (E) is dissolved together with the component (C), or the component (E) is dissolved alone. is there. Furthermore, other additives described later are dissolved as necessary. The type and structure of the solvent are not particularly limited as long as the solvent has such dissolving ability.

Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene Glycolpropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxy acetate, ethyl hydroxyacetate 2-hydroxy-3-methylbutanoic acid Chill, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can be mentioned. These solvents can be used alone or in combination of two or more.

<Other additives>
Furthermore, the resin composition according to the embodiment of the present invention may contain a silane coupling agent, surfactant, rheology modifier, pigment, dye, storage stabilizer, A foaming agent, antioxidant, etc. can be contained.

<Resin composition>
The resin composition of the embodiment of the present invention contains either a polymer having a cyclohexene ring as the component (A) or a compound having a cyclohexene ring as the component (B) at the terminal.

  Moreover, the resin composition of embodiment of this invention contains the crosslinking agent which is (C) component depending on necessity.

  Moreover, when the resin composition of embodiment of this invention contains (B) component, it contains the other polymer which is (D) component.

  Furthermore, the resin composition of the embodiment of the present invention can contain a crosslinking catalyst as component (E), and can contain one or more of other additives.

  The resin composition of the embodiment of the present invention can be used as a solution by dissolving the above components in a solvent.

Preferred examples of the resin composition of the embodiment of the present invention are as follows.
[1]: A resin composition containing 1 to 100 parts by mass of component (C) based on 100 parts by mass of component (A).
[2]: A resin composition containing 1 to 100 parts by mass of component (C) based on 100 parts by mass of the total amount of component (B) and component (D).
[3]: A resin composition containing 1 to 100 parts by mass of component (C) and a solvent based on 100 parts by mass of component (A).
[4]: A resin composition containing 1 to 100 parts by mass of component (C) and a solvent based on 100 parts by mass of the total amount of component (B) and component (D).
[5]: A resin composition containing 1 to 100 parts by mass of component (C), 0.01 to 5 parts by mass of component (E), and a solvent based on 100 parts by mass of component (A).
[6]: Based on 100 parts by mass of the total amount of component (B) and component (D), 1 to 100 parts by mass of component (C), 0.01 to 5 parts by mass of component (E), and solvent A resin composition to contain.

  When using the resin composition of embodiment of this invention as a solution, the compounding ratio, the preparation method, etc. are as follows.

  The ratio of the solid content in the resin composition of the embodiment of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is preferably 1 to 80% by mass, more preferably Is 3 to 60% by mass, more preferably 5 to 40% by mass. Here, solid content means what remove | excluded the solvent from all the components of the resin composition.

The method for preparing the resin composition according to the embodiment of the present invention is not particularly limited. For example, the component (A) or the component (B) and the component (D) are dissolved in a solvent, and the component (C) is dissolved in this solution. , (E) component is mixed at a predetermined ratio to obtain a uniform solution. Further, at an appropriate stage of the preparation method, other additives can be further added and mixed as necessary.

  In preparing the resin composition of the embodiment of the present invention, a polymer solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, when the (A) component or the (B) component and the (D) component solution are mixed with the (C) component, the (E) component, etc., as described above, the concentration is adjusted. For the purpose, an additional solvent may be added. At this time, the solvent used in the production process of the polymer and the solvent used for concentration adjustment at the time of preparing the resin composition may be the same or different.

  The resin composition solution prepared as described above is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film, cured film and liquid crystal alignment layer>
A coating film can be formed by the following method using the resin composition of the embodiment of the present invention.
First, a resin composition is applied onto a substrate or a film by spin coating, flow coating, roll coating, slit coating, spin coating following the slit, ink jet coating, or printing. Subsequently, a coating film can be formed by predrying (prebaking) with a hot plate or oven. Then, a cured film is formed by heat-treating (post-baking) this coating film.

  As a substrate to which the resin composition is applied, for example, a silicon / silicon dioxide-coated substrate, a silicon nitride substrate, a glass substrate, a quartz substrate, an ITO substrate, or the like can be used. In addition, for example, a substrate coated with a metal such as aluminum, molybdenum, or chromium can be used. Furthermore, for example, a resin film such as a triacetyl cellulose film, a polyester film, and an acrylic film can be used as the substrate.

  As prebaking conditions for forming the coating film, for example, a heating temperature and a heating time appropriately selected from the range of a temperature of 70 to 160 ° C. and a time of 0.3 to 60 minutes are employed. The heating temperature and heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.

  As the post-bake, a heating temperature appropriately selected from a temperature range of 140 to 250 ° C. according to a heating method or the like can be adopted. The same applies to the heating time. For example, the heating time may be 5 to 30 minutes on the hot plate, and 30 to 90 minutes in the oven.

  By curing the resin composition of the embodiment of the present invention under the above conditions, it is possible to sufficiently cover and flatten the step of the substrate due to the color filter (CF) and the like. A cured film having high transparency can be formed. Note that the thickness of the cured film can be set to, for example, 0.1 to 30 μm, and can be appropriately selected in consideration of the level difference of the substrate to be used and the optical and electrical properties.

  The cured film obtained as described above can function as a liquid crystal alignment layer that aligns liquid crystal alignment materials, that is, molecules having liquid crystallinity, by performing a rubbing treatment.

  The rubbing process is generally performed under the conditions of a rotational speed of 300 to 1,000 rpm, a feed speed of 10 to 80 mm / second, and a push-in amount of 0.1 to 1 mm. After the rubbing treatment, residues generated by rubbing are removed by ultrasonic cleaning using pure water or the like.

  After coating the retardation material on the liquid crystal alignment layer thus formed, the retardation material is brought into a liquid crystal state by heating to the phase transition temperature of the liquid crystal. Then, when this is photocured, a retardation material as a layer having optical anisotropy can be formed.

  As the retardation material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same is used. When the substrate on which the liquid crystal alignment layer is formed is a film, it is useful as an optically anisotropic film. Such retardation materials include materials having orientation such as horizontal orientation, cholesteric orientation, vertical orientation, hybrid orientation, and biaxial orientation, and can be used properly according to the required retardation.

  Also, the two substrates having the liquid crystal alignment layer formed as described above are bonded so that the liquid crystal alignment layers face each other via a spacer, and then liquid crystal is injected between these substrates. Thus, a liquid crystal display element in which liquid crystal is aligned can be obtained.

  Thus, the resin composition of the embodiment of the present invention can be suitably used for constituting various optical anisotropic films and liquid crystal display elements.

  The resin composition of the embodiment of the present invention is also useful as a material for forming a cured film such as a protective film, a planarizing film, and an insulating film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element. It is. In particular, in addition to the overcoat material (CF overcoat) of the color filter (CF), it is also suitable as a material for forming an interlayer insulating film of a TFT type liquid crystal element, an insulating film of an organic EL element, and the like.

  When the resin composition of the embodiment of the present invention is used as a CF overcoat material, the obtained CF overcoat not only covers and flattens the steps of the color filter, but also functions as a liquid crystal alignment material. Therefore, it can be used as a CF overcoat having orientation.

  FIG. 1 is a schematic configuration diagram of a liquid crystal cell 100 according to an embodiment of the present invention. In this figure, the liquid crystal layer 108 is sandwiched between two substrates 101 and 111. An ITO 110 and an alignment film 109 are formed on the substrate 111. On the substrate 101, a color filter 102, a CF overcoat 103, a retardation material 105, an ITO 106, and an alignment film 107 are formed in this order. In this case, since the CF overcoat 103 also functions as an alignment film, a film corresponding to the alignment film 204 in FIG. 2 can be dispensed with.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in more detail, this invention is not limited to these Examples.

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Polymer raw material>
HEMA: 2-hydroxyethyl methacrylate MAA: methacrylic acid MMA: methyl methacrylate GMA: glycidyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: α, α′-azobisisobutyronitrile BGOP: 4,4′-bisglycidyloxyphenyl CHECA : Cyclohexene-4-carboxylic acid BA: Benzoic acid CHCA: Cyclohexanecarboxylic acid CHEDA: Cyclohexene-4,5-dicarboxylic anhydride BPAGE: Bisphenol A diglycidyl ether CHDCA: Cyclohexanedicarboxylic acid PVA: Polyvinyl alcohol HBPDA: 3, 3 ′ -4,4'-bicyclohexyltetracarboxylic dianhydride HBPA: hydrogenated bisphenol A
BTEAC: benzyltriethylammonium chloride GT4: Daicel Chemical Industries, Ltd. Epolide GT-401 (product name) (compound name: epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl) modified ε-caprolactone)
<Crosslinking agent>
CEL: Daicel Chemical Industries, Ltd. Celoxide P-2021 (product name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate)
TMGU: 1,3,4,6-tetrakis (methoxymethyl) glycoluril PWL: Powder link 1174 (Mitsui Cytec Co., Ltd.)
<Crosslinking catalyst>
PTSA: p-toluenesulfonic acid monohydrate <solvent>
CHN: cyclohexanone PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether NMP: N-methylpyrrolidone

  The number average molecular weight and the weight average molecular weight of the polymer obtained in accordance with the following synthesis example were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation and the elution solvent tetrahydrofuran at a flow rate of 1 mL / min. It was measured under the condition that it was eluted by flowing through (column temperature 40 ° C.). The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

<Synthesis Example 1>
GMA 18.4 g, HEMA 4.6 g, and AIBN 1.1 g were dissolved in PGMEA 65.1 g and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration 27 mass%) (P1). . Mn of the obtained acrylic polymer was 4,940 and Mw was 9,090.

<Synthesis Example 2>
By adding CHECA 4.34g, PGMEA 12.0g, and BTEAC 0.083g to 25.0g of the P1 solution and reacting at 120 ° C for 10 hours, a polymer having a cyclohexene ring (solid content concentration 27% by mass) (P2) Obtained. Mn of the obtained acrylic polymer was 8,240 and Mw was 19,440.

<Synthesis Example 3>
Commercially available PVA (Mw 31,000) 3.30 g of CHEDA 7.10 g, PGMEA 31.6 g, and BTEAC 0.125 g were added and reacted at 120 ° C. for 10 hours to give a polymer having a cyclohexene ring (solid content concentration 25% by mass) ) (P3) was obtained. Mn of the obtained vinyl polymer was 47,720 and Mw was 111,303.

<Synthesis Example 4>
7.69 g of CHOCA, 53.6 g of PGMEA, and 0.14 g of BTEAC were added to 12.0 g of BGOP and reacted at 120 ° C. for 10 hours to obtain a compound having a cyclohexene ring at the terminal (solid content concentration 27% by mass) (B1) Obtained.

<Synthesis Example 5>
CEL 10.0g, CHECA 9.62g, PGMEA 53.5g, BTEAC
0.18 g was added and reacted at 120 ° C. for 10 hours to obtain a compound having a cyclohexene ring at the terminal (solid content concentration 27% by mass) (B2).

<Synthesis Example 6>
A compound having a cyclohexene ring at the terminal (solid content concentration: 27% by mass) (B3) is added by adding 6.00 g of GTEC to 3.30 g of GTEC, 46.7 g of PGMEA and 0.06 g of BTEAC and reacting at 120 ° C. for 10 hours. Obtained.

<Synthesis Example 7>
By reacting 12.0 g of HBPDA, 10.2 g of HBPA and 0.22 g of BTEAC in 54.48 g of PGMEA at 125 ° C. for 19 hours, a polyester solution (solid content concentration: 30.0 mass%) (P4) is obtained. It was. Mn of the obtained polyester was 1,980 and Mw was 3,500.

<Synthesis Example 8>
MAA 2.5g, MMA 9.2g, HEMA 5.0g, AIBN as a polymerization catalyst
0.2 g was dissolved in 50.7 g of PGME and reacted at 70 ° C. for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25 mass%) (P5). Mn of the obtained acrylic copolymer was 19,600 and Mw was 45,200.

<Synthesis Example 9>
By adding 4.21 g of BA, 11.6 g of PGMEA and 0.083 g of BTEAC to 25.0 g of the P1 solution and reacting at 120 ° C. for 10 hours, an acrylic polymer (solid content concentration 27 mass%) (P6) was obtained. . Mn of the obtained acrylic polymer was 7,920 and Mw was 17,940.

<Synthesis Example 10>
P1 solution 25.0g, CHCA 4.41g, PGMEA 12.2g, BTEAC
0.083 g was added and reacted at 120 ° C. for 10 hours to obtain an acrylic polymer having a cyclohexene ring (solid content concentration 27% by mass) (P7). Mn of the obtained acrylic polymer was 7,620 and Mw was 17,860.

<Synthesis Example 11>
CEL 10.02 g, CHCA 9.62 g, PGMEA 53.5 g, and BTEAC 0.18 g were added and reacted at 120 ° C. for 10 hours to obtain a compound having a cyclohexane ring at the terminal (solid content concentration 27% by mass) (B4). Obtained.

<Synthesis Example 12>
4.0 g of CHMI, 6.0 g of HEMA, and 0.5 g of AIBN as a polymerization catalyst were dissolved in 24.5 g of PGMEA and reacted at 80 ° C. for 20 hours to react an acrylic copolymer solution (solid content concentration 30% by mass) (P8 ) Mn of the obtained acrylic copolymer is 3,
500 and Mw were 7,500.

<Synthesis Example 13>
CHEDA 7.87 g, PGMEA 22.9 g, and BTEAC 0.077 g were added to 50.0 g of the P8 solution and reacted at 120 ° C. for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration 30% by mass) (P9). Obtained. Mn of the obtained acrylic polymer was 8,243 and Mw was 24,990.

<Synthesis Example 14>
By reacting 15.0 g of PAGE, 8.35 g of CHDCA, and 0.10 g of BTEAC in 54.71 g of PGMEA at 120 ° C. for 20 hours, a polyester solution (solid content concentration: 30.0 mass%) (P10) is obtained. It was. Mn of the obtained polyester was 3,650 and Mw was 9,060.

<Synthesis Example 15>
6.86 g of CHEDA and 16.2 g of PGMEA were added to 50.0 g of a solution of P10 and reacted at 120 ° C. for 15 hours to obtain a polymer having a cyclohexene ring (obtained a solid content concentration of 30% by mass) (P11). . Mn of the obtained polyester was 6,960 and Mw was 44,000.

<Examples 1 to 8 and Comparative Examples 1 to 3>
Each composition of Example 1 thru | or Example 8 and Comparative Example 1 thru | or Comparative Example 3 was prepared with the composition shown in Table 1, and the solvent tolerance, the transmittance | permeability, and orientation were evaluated about each.

[Evaluation of solvent resistance]
After each composition of Examples 1 to 8 and Comparative Examples 1 to 3 was applied to a silicon wafer using a spin coater, it was pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 1 A 1 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 1.0 μm.
Next, this cured film was immersed in CHN or NMP for 60 seconds, and then dried at a temperature of 100 ° C. for 60 seconds, and the film thickness was measured. The case where there was no change in film thickness after immersion in CHN or NMP was marked with ○, and the case where the film thickness decreased after immersion was marked with x.

[Evaluation of transmittance (transparency)]
Each composition of Examples 1 to 8 and Comparative Examples 1 to 3 was applied on a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A 1.0 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C. for 30 minutes to form a cured film.
Next, the transmittance of the cured film at a wavelength of 400 nm was measured using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).

[Evaluation of orientation]
Each composition of Example 1 to Example 8 and Comparative Example 1 to Comparative Example 3 was applied on an ITO substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A 2.8 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, this film was post-baked in a hot air circulating oven at a temperature of 200 ° C. for 30 minutes to form a cured film.

Next, this cured film was rubbed at a rotational speed of 400 rpm, a feed speed of 30 mm / second, and an indentation amount of 0.4 mm. The rubbed substrate was ultrasonically cleaned with pure water for 5 minutes. Next, a retardation material composed of a liquid crystal monomer was applied onto the substrate using a spin coater, and then prebaked on a hot plate at 80 ° C. for 60 seconds to form a coating film having a thickness of 1.4 μm. Next, the coating film on the substrate was exposed to light of 1,000 mJ / cm ^{2 in} a nitrogen atmosphere to cure the retardation material. The substrate thus produced was sandwiched between deflection plates, and the orientation was confirmed with an optical microscope. In the crossed Nicol state, no light leakage was indicated by ○, and light leakage occurred by ×.

[Evaluation of heat resistance]
Each composition of Examples 1 to 8 and Comparative Examples 1 to 3 was applied on a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness. A 1.1 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, this coating film was post-baked at 230 ° C. for 30 minutes in a hot air circulating oven to form a cured film having a thickness of 1.0 μm.
Next, the cured film was irradiated perpendicularly with 313 nm linearly polarized light. Subsequently, this cured film was further baked in a hot air circulating oven at 230 ° C. for 3 hours, and the color difference Ea * b * from the post-baked state was measured.

[Evaluation results]
The results of the above evaluation are summarized and shown in Table 2 below.

In the cured films formed from the compositions of Examples 1 to 8, the liquid crystal alignment was excellent. Therefore, it was found that the compositions of Examples 1 to 8 can form excellent liquid crystal alignment materials. In addition, heat resistance and transparency were high, and resistance to both CHN and NMP was observed.

  On the other hand, in the cured films formed from the compositions of Comparative Examples 1 to 3, the liquid crystal was not aligned at all, or light leakage was observed with a polarizing microscope.

  As described above, it was found that the cured film obtained from the resin composition of the present invention has high liquid crystal alignment performance, and also has light transmittance, solvent resistance, and heat resistance. Therefore, according to the resin composition of the present invention, it is possible to provide a cured film having excellent properties as described above, that is, a liquid crystal alignment material, and further, it is possible to form a retardation material. It was.

  The resin composition according to the present invention is very useful as an optically anisotropic film or a liquid crystal alignment layer of a liquid crystal display element, and further, a protective film in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element, It is also suitable as a material for forming a cured film such as a flattening film and an insulating film, particularly as a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film for a color filter or an insulating film for an organic EL element.

100, 200 Liquid crystal cell 101, 111, 201, 211 Substrate 102, 202 Color filter 103, 203 CF overcoat 105, 205 Phase difference material 106, 110, 206, 210 ITO
107, 109, 204, 207, 209 Alignment film 108, 208 Liquid crystal layer

Claims (10)

Formula (1) compounds having a cyclohexene ring at the terminal represented by the component (B), the step of the tree fat composition you containing a binder polymer (D component) is cured to form a cured film and,
A method for producing a liquid crystal alignment material, comprising a step of rubbing the cured film.

[In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. ] The said (D) component is a polyester resin containing the structural unit represented by Formula (2), The manufacturing method of the liquid crystal aligning material of Claim 1 characterized by the above-mentioned.

[In Formula (2), A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B represents two bonds to an alicyclic skeleton or an aliphatic skeleton. Represents a divalent organic group to which is bonded. ] The method for producing a liquid crystal alignment material according to claim 1, wherein the component (D) is an acrylic polymer. The method for producing a liquid crystal alignment material according to any one of claims 1 to 3, wherein the resin composition further contains a crosslinking agent (C component) that reacts with heat. The method for producing a liquid crystal alignment material according to any one of claims 1 to 4, wherein the resin composition further contains a crosslinking catalyst (E component). A step of curing a resin composition containing a compound having a cyclohexene ring at the terminal represented by the following formula (1) (component B) and a binder polymer (component D) to form a cured film;
Performing a rubbing treatment on the cured film; and
A method for producing a retardation material, comprising a step of applying and curing a retardation material on the rubbed cured film.

[In the formula (1), R represents an organic group having 1 to 20 carbon atoms, and X represents a hydrogen atom, a methyl group or a halogen atom. ] The said (D) component is the polyester resin containing the structural unit represented by Formula (2), The manufacturing method of the phase difference material of Claim 6 characterized by the above-mentioned.

[In Formula (2), A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B represents two bonds to an alicyclic skeleton or an aliphatic skeleton. Represents a divalent organic group to which is bonded. ] The method for producing a retardation material according to claim 6, wherein the component (D) is an acrylic polymer. The method for producing a retardation material according to any one of claims 6 to 8, wherein the resin composition further contains a crosslinking agent (C component) that reacts with heat. The method for producing a retardation material according to claim 6, wherein the resin composition further contains a crosslinking catalyst (E component).

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