TWI613223B - Resin composition, liquid crystal alignment material and phase difference material - Google Patents

Description

Resin composition, liquid crystal alignment material and phase difference material

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

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

The protective film is used, for example, as a protective film for a color filter used in a color liquid crystal display device or a solid-state image sensor. At this time, in order to planarize the color filter or the black matrix of the substrate, for example, it is required to form a protective film with a film thickness of 1 μm or more. In particular, when manufacturing a color liquid crystal display device of an STN type or a TFT type, it is necessary to closely bond the color filter substrate and the counter substrate, and it is necessary to make the cell gap between the substrates uniform. Missing, the protective film is also required to be on the substrate High flattening ability. Furthermore, in order to maintain the transmittance of light penetrating through the color filter, high transparency is also required in the protective film.

In recent years, it has been reviewed to introduce a phase difference material into a cell of a liquid crystal display to reduce cost and weight.

Fig. 2 is a schematic view showing a liquid crystal cell 200 in which a liquid crystal alignment film is formed by a conventional technique. In the figure, the liquid crystal layer 208 is sandwiched between the two substrates 201, 211. An ITO 210 and an alignment film 209 are formed on the substrate 211. Further, on the substrate 201, a color filter 202, a color filter (CF) overcoat layer (hereinafter referred to as a CF overcoat layer) 203, an alignment film 204, a phase difference material 205, and an ITO 206 are sequentially formed. Alignment film 207.

In the conventional liquid crystal cell, in order to align the polymerizable liquid crystal for forming the phase difference material before the curing, it is necessary to separately provide a film which can align the liquid crystal, that is, an alignment film. The alignment film is formed through a step such as rubbing treatment or polarized light irradiation. In other words, as shown in FIG. 2, a phase difference material 205 obtained by forming a polymer film of a liquid crystal monomer or the like is formed on the CF overcoat layer 203. That is, after the color filter 202 is formed, it is necessary to form the CF overcoat layer 203 and the alignment film 204 in two layers, and the process is complicated.

Therefore, it is strongly desired to simultaneously satisfy the provision of a plurality of different desired characteristics of the film and the material from which it is formed. Specifically, it is required to serve both the film of the alignment film and the CF overcoat layer and the material for forming the film. As a result, in the manufacture of a liquid crystal display, it is possible to enjoy the advantages of low cost, reduction in the number of processes, and improvement in throughput.

Generally, an acrylic resin having high transparency is used in the CF overcoat layer. Among these acrylic resins, a glycol solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ethyl acetate, ethyl lactate or butyl lactate is widely used from the viewpoint of handleability and coatability. A ketone solvent such as an ester solvent such as cyclohexanone or methyl amyl ketone. Further, the acrylic resin is cured by heat or light to exhibit heat resistance or solvent resistance (for example, refer to Patent Document 1 or 2).

However, according to the review by the present inventors, in the CF overcoat layer composed of the conventional thermosetting or photocurable acrylic resin, although transparency or flatness is obtained, it is clear that even if it is administered Friction treatment does not exhibit sufficient liquid crystal alignment. Therefore, it can be seen that the conventional CF overcoat layer cannot be directly applied to the above-mentioned film which is also an alignment film and a CF overcoat layer.

On the other hand, as the alignment film, a material made of a solvent-soluble polyimine or a polyamic acid has conventionally been used. It has been reported that these materials are completely imidized by post-baking to obtain solvent resistance, and at the same time, sufficient alignment property can be exhibited by rubbing treatment (see Patent Document 3). However, when it is regarded as a CF overcoat layer, there is a problem that transparency is largely lowered due to thick film formation. Further, although polyimine or polylysine is soluble in a solvent such as N-methylpyrrolidone or γ-butyrolactone, solubility in a solvent of a glycol type or an ester type solvent It is low, but there are also problems in the production line that is difficult to apply to the CF overcoat.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] JP-A-2000-103937

[Patent Document 2] JP-A-2000-119472

[Patent Document 3] JP-A-2005-037920

The present invention has been completed on the basis of the above knowledge or review results. That is, an object of the present invention is to provide a resin composition which has excellent alignment property, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.

Other objects and advantages of the present invention will be made clear from the description below.

A first aspect of the invention relates to a resin composition comprising a polymer (component A) having a cyclohexene ring in a side chain.

In the first aspect of the invention, the main chain of the polymer of the component A is preferably a polymer of a monomer having an unsaturated double bond.

In the first aspect of the invention, the main chain of the polymer of the component A is preferably an acrylic polymer.

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

In the first aspect of the invention, the main chain of the polymer of the component A preferably has a ring structure.

In the first aspect of the invention, the main chain of the polymer of the component A is preferably It is a polyester resin.

In the first aspect of the invention, the main chain of the polymer of the component A is preferably a novolak resin.

In the first aspect of the invention, the polymer of the component A is preferably a cycloolefin polymer.

In the first aspect of the invention, the polymer of the component A preferably has a side chain which becomes a crosslinking group.

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

In the first aspect of the invention, it is preferred to further contain a crosslinking agent (component C) which reacts with heat.

In the first aspect of the invention, it is preferred to further contain a crosslinking catalyst (component E).

[式(1)中，R表示碳原子數1至20的有機基，X表示氫原子、甲基或鹵素原子]。 A second aspect of the present invention relates to a resin composition comprising a compound (B component) having a cyclohexene ring at a terminal represented by the formula (1) and a binder polymer (component D).

[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(2)中，A表示以4個結合鍵鍵結於脂環式骨架或脂肪族骨架的4價有機基，B表示以2個結合鍵鍵結於脂環式骨架或脂肪族骨架的2價有機基]。 In the second aspect of the invention, the component (D) is preferably a polyester resin containing a structural unit represented by the formula (2).

[In the formula (2), A represents a tetravalent organic group bonded to an alicyclic skeleton or an aliphatic skeleton by four bonding bonds, and B represents a bonding bond bonded to an alicyclic skeleton or an aliphatic skeleton by two bonding bonds. 2-valent organic group].

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

In the second aspect of the invention, it is preferred to further contain a crosslinking agent (component C) which reacts with heat.

In the second aspect of the invention, it is preferred to further contain a crosslinking catalyst (component E).

A third aspect of the invention relates to a liquid crystal alignment material which is obtained by using the resin compositions of the first and second aspects of the invention.

A fourth aspect of the present invention relates to a phase difference material characterized by using the resin composition of the first and second aspects of the present invention. The film is formed.

The resin composition according to the first aspect of the present invention has excellent alignment properties, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.

The resin composition according to the second aspect of the present invention has excellent alignment properties, solvent resistance, heat resistance and transparency, and can form a cured film which is suitable as a CF overcoat layer.

The liquid crystal alignment material according to the third aspect of the present invention is excellent in light transmittance, heat resistance, solvent resistance, and alignment.

The phase difference material of the fourth aspect of the present invention can be disposed in the liquid crystal cell. The use of this phase difference material of the liquid crystal cell line can improve the contrast.

100,200‧‧‧ liquid crystal cell

101, 111, 201, 211‧‧‧ substrates

102, 202‧‧‧ color filters

103, 203‧‧‧CF overcoat

105, 205‧‧‧ phase difference materials

106, 110, 206, 210‧‧‧ ITO

107, 109, 204, 207, 209‧‧ ‧ alignment film

108, 208‧‧‧ liquid crystal layer

Fig. 1 is a schematic configuration diagram of a liquid crystal cell according to an embodiment of the present invention.

Fig. 2 is a schematic configuration diagram of a conventional liquid crystal cell.

[Formation of the Invention]

The present invention relates to a resin composition, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed using the cured film obtained from the resin composition. In more detail, with respect to having excellent alignment, solvent resistance, heat resistance and transparency, it can be suitably used as a CF overcoat layer. A resin composition of a cured film, a liquid crystal alignment material formed using the resin composition, and a phase difference material formed using the liquid crystal alignment material. The cured film formed of the resin composition of the present invention is suitable as a film which also functions as a CF overcoat layer in a liquid crystal display, and also has an alignment function for a polymerizable liquid crystal for forming a phase difference layer. It is suitable for the formation of phase difference layers in the built-in phase.

That is, the resin composition according to the present invention can be applied, for example, at a film thickness of 1 μm or more, and can form a possible cured film which has liquid crystal alignment ability in addition to high transparency and high solvent resistance. Therefore, this resin composition can be used as a material for forming a liquid crystal alignment film or a planarization film. In particular, a liquid crystal alignment film (CF overcoat layer) having both characteristics of the liquid crystal alignment film and the color filter which have been independently formed in the past can be provided in the liquid crystal cell. Therefore, the simplification of the process and the cost reduction due to the reduction in the number of processes can be achieved.

In addition, 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 use in a production line for using a planarizing film mainly composed of such a solvent.

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

The components which can be contained in the resin composition of the embodiment of the present invention are as follows.

(A) component: a polymer having a cyclohexene ring in its side chain

(B) component: a compound having a cyclohexene ring at the terminal

(C) Component: Crosslinker

(D) Ingredients: Other polymers (also referred to as binder polymers in this specification)

(E) component: cross-linking catalyst

Further, in the resin composition of the embodiment of the present invention, preferred component combinations are as follows.

[1]: A resin composition containing 1 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A).

[2]: The resin composition of the component (C) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D).

[3]: a resin composition containing 1 to 100 parts by mass of the component (C) and a solvent based on 100 parts by mass of the component (A).

[4]: A resin composition containing 1 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the components (B) and (D).

[5]: A resin composition containing 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent, based on 100 parts by mass of the component (A).

[6]: Based on 100 parts by mass of the total of the components (B) and (D), the resin composition contains 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent. Things.

The details of each component constituting the resin composition of the present invention will be described in detail below.

(A) component

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

Examples of the polymer of the component (A) include an acrylic polymer, a vinyl polymer, a polyester resin, a novolak resin, and a cycloolefin polymer.

As a method of introducing a cyclohexene ring into a polymer, a method of adding a cyclohexene carboxylic acid to a polymer having an epoxy group, and a method of condensing a polymer having a hydroxyl group with cyclohexene dicarboxylic anhydride A method of reacting a polymer having a hydroxyl group or an amine group with cyclohexene carboxyfluorene chloride, a method of polymerizing using a monomer having a cyclohexene ring, and the like.

Specific examples of the polymer of the component (A) are shown below.

In the above formulae (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, R ₁ represents a hydrogen atom, an alkyl group or an ethyl fluorenyl group, and R ₂ represents a hydrogen atom. Or epoxy propyl. Further, 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, a group derived from an alicyclic group and an aliphatic group, or a group having a benzene ring structure, and B ₁ represents an alicyclic group and an alicyclic group. a group formed with an aliphatic group or a group having a benzene ring structure.

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

A method for synthesizing the acrylic (A) component will be described.

The method for obtaining an acrylic polymer having a cyclohexene ring as described above is not particularly limited, and for example, an acrylic polymer having a glycidyl group or a hydroxyl group is formed by radical polymerization or the like in advance, and this is followed by a cyclohexene carboxyl group. An acrylic polymer which is reacted with an acid, cyclohexene carboxy fluorene chloride or cyclohexene dicarboxylic anhydride to form (A).

Examples of the radically polymerizable monomer having a glycidyl group include glycidyl methacrylate, glycidyl acrylate, 4-hydroxybutyl acrylate epoxypropyl ether, and 4-hydroxy methacrylate. Butyl ester epoxypropyl ether and the like.

Examples of the radical polymerizable monomer having a hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, and N-(hydroxyphenyl). Maleimide, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, 2-hydroxy methacrylate Ethyl ester, 2-hydroxypropyl methacrylate and 5-methylpropenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone.

In the resin composition of the embodiment of the present invention, when an acrylic polymer having a specific functional group which is effective for introduction of a cyclohexene ring such as a glycidyl group or a hydroxyl group is obtained, a combination of a specific functional group and a specific functional group can be obtained. Monomer copolymerized monomer. Specific examples of the monomer are given below, but are not limited thereto.

Examples of the monomer copolymerizable with a monomer having a specific functional group include an acrylate compound, a methacrylate compound, a maleimide compound, acrylonitrile, maleic anhydride, a styrene compound, and a vinyl group. Compounds, etc.

Specific examples of the monomer include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloxy)ethyl)phthalate, and mono-(2-(methacryloxime). Oxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)propenamide, acrylic acid Methyl ester, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, decyl acrylate, decyl methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, third butyl acrylate Ester, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methyl acrylate Oxybutyl butyl ester, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-acrylic acid Tricyclononyl ester, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, decyl methacrylate, methacrylic acid methacrylate Ester, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methyl methacrylate Oxyethyl ester, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, methacrylic acid 2-methyl-2-adamantyl ester, 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 hydrazine, vinyl carbazole, 2-hydroxyethyl vinyl ether, phenyl vinyl ether and propyl vinyl ether, styrene, methyl styrene, chlorostyrene, bromostyrene, malayan Amine, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The method of obtaining the cyclohexene ring-containing acrylic polymer used in the resin composition of the embodiment of the present invention is not particularly limited, and examples thereof include a monomer having a specific functional group, and a copolymerizable monomer other than The polymerization initiator or the like is obtained by a polymerization reaction at a temperature of 50 to 110 ° C in a solvent which is coexistent. The solvent to be used at the time is not particularly limited as long as it is a monomer which dissolves an acrylic polymer having a specific functional group and an acrylic polymer having a specific functional group. As a specific example, the solvent mentioned later is mentioned.

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

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

The specific copolymerization can be obtained by reacting a solution of a propylene group-containing acrylic polymer with cyclohexene carboxylic acid in the presence of a catalyst such as benzyltriethylammonium chloride at a temperature of from 80 ° C to 150 ° C. Things. At this time, the solution used The agent is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. As a specific example, the solvent mentioned later is mentioned.

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

The solution of the acrylic polymer having a hydroxyl group is reacted with cyclohexene dicarboxyfluorene chloride in the presence of a tertiary amine such as triethylamine at a temperature of from 0 ° C to 40 ° C to remove the formed salt and amine. , a specific copolymer can be obtained. In this case, the solvent to be used is a solvent which dissolves a monomer constituting a specific copolymer and a specific copolymer, and preferably a solvent which does not have a hydroxyl group.

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

Further, a solution of the specific copolymer obtained as described above is placed in diethyl ether or water under stirring to reprecipitate, and the resulting precipitate is washed and washed, and then taken under normal pressure or reduced pressure. It can be a powder of a specific copolymer by drying at room temperature or by heating. By such an operation, the polymerization initiator or the unreacted monomer which coexists with the specific copolymer can be removed, and as a result, the powder of the purified specific copolymer can be obtained. Further, when the primary operation cannot be sufficiently purified, the obtained powder can be redissolved in a solvent, and the above operation can be repeated.

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 redissolved in a solvent to be described later, for example, and used as a solution.

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

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

The epoxidized phenol novolak resin or the epoxidized cresol novolac resin and the cyclohexene carboxylic acid are reacted at a temperature of 80 ° C to 150 ° C in the presence of a catalyst such as benzyltriethylammonium chloride. A polymer having a cyclohexene ring can be obtained. In this case, the solvent to be used is not particularly limited as long as it dissolves the monomer constituting the specific copolymer and the specific copolymer. As a specific example, the solvent mentioned later is mentioned.

In the resin composition of the embodiment of the present invention, commercially available epoxidized phenol novolac resin which can be used as the component (A), for example, Epikote 152, and 154 (above, oiled Shell Epoxy) It is a phenol novolak type epoxy resin etc. which are made by Japan Epoxy Resin Co., Ltd., EPPN201, and 202 (above, Nippon Chemical Co., Ltd.). Further, examples of commercially available cresol novolac type epoxy resins include EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (the above are Japanese chemical drugs ( A cresol novolac type epoxy resin such as Epikote 180S75 (oiled Shell Epoxy (now manufactured by Japan Epoxy Resin Co., Ltd.)).

(B) component

The component (B) contained in the resin composition of the embodiment of the present invention is a compound having a cyclohexene ring at the terminal represented by the following formula (1).

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. a compound having a cyclohexene ring at the terminal of the component (B), which is a method of reacting a polyfunctional epoxy compound with a cyclohexene carboxylic acid, or a polyfunctional alcohol compound with cyclohexene carboxy fluorene or a cyclohexane Obtained by a method in which an enedicarboxylic anhydride is reacted.

Examples of the compound having a cyclohexene ring at the terminal of the component (B) include the following.

(C) component

The component (C) which is contained in the resin composition of the embodiment of the present invention is a crosslinking agent. Examples of the crosslinking agent include an epoxy compound, a methylol compound, and an isocyanate compound.

When the component (A) or the component (D) described later is a polymer having a hydroxyl group, the component (C) is preferably a methylol compound or an isocyanate compound. Further, when the component (A) or the component (D) is a polymer having a carboxyl group, the component (C) is preferably an epoxy compound, a methylol compound or an isocyanate compound.

Examples of the epoxy compound include tris(2,3-epoxypropyl)isocyanate, 1,4-butanediol diepoxypropyl ether, and 1,2-epoxy- 4-(epoxyethyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl ether, 2,6-diepoxypropyl phenylepoxypropyl ether, 1 , 1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diepoxy Propyl ester, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylic acid Ester, trimethylolethane triepoxypropyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyepoxypropyl ether, and the like.

From the point of view of ease of use, a compound of a commercially available product can also be used as the epoxy compound. The specific examples (trade names) are given below, but are not limited by these. For example, an epoxy group having an amine group such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.), Epolead GT-401, GT-403, GT-301, GT-302, and Celloxide 2021 may be mentioned. And an epoxy resin having a structure of cyclohexene oxide, such as Celloxide 3000 (manufactured by DAICEL Chemical Industry Co., Ltd.), Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 ( The above is a bisphenol A type epoxy resin such as oiled Shell Epoxy (now manufactured by Japan Epoxy Co., Ltd.), and Epikote 807 (oiled Shell Epoxy (now) (now Japanese epoxy resin ( )))) bisphenol F type epoxy resin, Denacol EX-252 (made by Nagase Chemtex), CY175, CY177, CY179, Araldite CY-182, same CY-192, same as CY-184 (above) It is CIBA-GEIGY AG (now BASF), Epiclon 200, 400 (above is Dainippon Ink Chemical Industry Co., Ltd. (now DIC)), Epikote 871, and 872 (above is Oiled Shell) Epoxy (currently manufactured by Nippon Epoxy Resin Co., Ltd.), ED-5661, ED-5662 (above: Celanese Coating Co., Ltd.), alicyclic epoxy resin, Denacol EX-611, same EX-612, same as EX-614, with EX-622, with EX-411 With EX-512, with EX-522, with EX-421, with EX-313, with EX-314, with EX- An aliphatic polyepoxypropyl ether such as 321 (manufactured by Nagase Chemtex Co., Ltd.).

Further, the compound having at least two epoxy groups is not particularly limited, and a polymer having an epoxy group can be used. The polymer having such an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. As an example, a copolymer of polyacrylic acid glycidyl acrylate, glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate may be mentioned. An addition polymerization polymer of a copolymer or a polycondensation polymer such as an epoxy novolac.

Further, the polymer having an epoxy group may be produced by a reaction of a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or a epoxypropyl tosylate. The weight average molecular weight of such a polymer is, for example, 300 to 200,000 in terms of polystyrene.

Examples of the methylol compound which can be used as the component (C) include methoxymethylated glycoluril, methoxymethylated benzoguanamine, and methoxymethylated melamine. Specific examples thereof include hexamethoxymethyl melamine, tetramethoxymethylbenzoguanamine, 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)-4,5-dihydroxy-2-imidazolidone and 1,3-bis(methoxymethyl)-4,5- Dimethoxy-2-imidazolidone and the like. Further, as a commercially available product, a methoxymethyl type melamine compound (trade name: Cymel 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Mitsui CYTEC Co., Ltd., and a butoxymethyl melamine compound are mentioned. (trade name Mycoat 506, Mycoat 508), glycoluril compound (trade name) Cymel 1170, Powder link 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Dainippon Ink Chemical Industry Co., Ltd. (current DIC (share)) urea/formaldehyde resin (high condensation type, trade name Beckamine J-300S, Beckamine P-955, Beckamine N).

Moreover, as an example of an isocyanate compound, the following are mentioned. 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 or the like, or a dimer, a trimer, or a reactant thereof with a glycol, a triol, a diamine or a triamine. These isocyanate compounds are preferably used by blocking with a blocking agent in order to improve storage stability in a solution.

Examples of the terminal blocking agent include phenol such as phenol, o-nitrophenol, p-chlorophenol, o-, m- or p-cresol, acrylamide such as ε-hexylamine, and acetone oxime. , methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, acetophenone oxime and diphenyl ketone oxime and the like, pyrazole, 3,5-dimethylpyrazole, 3 a thiol such as pyrazole such as methylpyrazole, dodecanethiol or benzenethiol.

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

Examples of the isocyanate compound derived from isophorone diisocyanate include the following examples.

[式(C-4)至式(C-6)中，R表示聚醚構造]。

[In the formula (C-4) to the formula (C-6), R represents a polyether structure].

The polyether structure may, for example, be a divalent group derived from polyethylene glycol or polypropylene glycol.

The crosslinking agent may be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound or a benzoguanamine compound in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group. For example, the US patent A high molecular weight compound produced by a melamine compound (trade name Cymel 303) and a benzoguanamine compound (trade name Cymel 1123) as described in No. 6323310.

Further, as the component (C), N-methylol acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, N-butoxy can also be used. A polymer produced by a hydroxymethyl or alkoxymethyl group-substituted acrylamide compound or a methacrylamide compound such as methyl methacrylamide. Examples of the polymer include poly(N-butoxymethyl acrylamide), a copolymer of N-butoxymethyl acrylamide and styrene, and N-methylol methacrylamide. Copolymer with methyl methacrylate, copolymer of N-ethoxymethyl methacrylamide and benzyl methacrylate, and N-butoxymethyl acrylamide and benzyl methacrylate a copolymer of 2-hydroxypropyl methacrylate or 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, particularly preferably 3,000 to 50,000.

The above-mentioned crosslinking agents may be used singly or in combination of two or more kinds.

In the resin composition of the embodiment of the present invention, the content of the crosslinking agent of the component (C) is preferably from 1 to 100 based on 100 parts by mass of the component (A) when the component (A) is used. Share. In addition, when the component (B) is used, it is preferably from 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D). When the ratio is too small, the solvent resistance of the cured film is lowered, the alignment property is lowered, or the heat resistance is lowered. On the other hand, on If the ratio is too large, the alignment will be lowered, or the preservation stability will be lowered.

(D) component

The component (D) contained in the resin composition of the embodiment of the present invention is a polymer (adhesive polymer) which is a binder for adding the component (B). The type of the "other polymer" is not particularly limited, but is preferably self-crosslinking or reacting with a crosslinking agent of the component (C) by having a thermal crosslinking group. Examples of the thermal crosslinking group include a carboxyl group, a hydroxyl group, an epoxy group, an oxetanyl group, an acryloyl group, and a methacryl group. Further, the weight average molecular weight of the component (D) is preferably from 1,000 to 100,000 in terms of polystyrene.

Preferable examples of the other polymer include a polyester resin having a structural unit represented by the following formula (2), an acrylic polymer having a crosslinking group, or a polyester represented by the following formula (3). Resin, etc.

[式(2)中，A表示以4個結合鍵鍵結於脂環式骨架或脂肪族骨架的4價有機基，B表示以2個結合鍵鍵結於脂環式骨架或脂肪族骨架的2價有機基]。

[In the formula (2), A represents a tetravalent organic group bonded to an alicyclic skeleton or an aliphatic skeleton by four bonding bonds, and B represents a bonding bond bonded to an alicyclic skeleton or an aliphatic skeleton by two bonding bonds. 2-valent organic group].

[式(3)中，A’及B’各自獨立地表示以2個結合鍵鍵結於脂環式骨架、脂肪族骨架或芳香環骨架的2價有機基，或以2個結合鍵鍵結於在此等骨架鍵結有醚鍵、酯鍵或醯胺鍵者的2價有機基]。

[In the formula (3), A' and B' each independently represent a divalent organic group bonded to an alicyclic skeleton, an aliphatic skeleton or an aromatic ring skeleton by two bonding bonds, or bonded by two bonding bonds. A divalent organic group in which an ether bond, an ester bond or a guanamine bond is bonded to the skeleton.

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

In the above formulas (i) and (ii), A represents a tetravalent organic group bonded to an alicyclic skeleton or an aliphatic skeleton by four bonding bonds, and B represents an alicyclic skeleton bonded by two bonding bonds. Or a divalent organic group of an aliphatic skeleton.

In the resin composition of the embodiment of the present invention, the mixing of the component (B) and the component (D) is preferably from 5:95 to 50:50. If the component (B) is less than this ratio, the alignment property is lowered. On the other hand, if it is too large, solvent resistance will The reduction, or the alignment, is lowered, and the film formability is also lowered. Further, the component (D) may be mixed in the component (A) insofar as the properties are not lowered.

(E) component

The resin composition of the embodiment of the present invention may contain a crosslinking catalyst as the component (E). The component (E) is effective in promoting the thermosetting property of the resin composition.

For example, when a hydroxyl group contained in the resin composition is reacted with a methylol compound, an acid or a thermal acid generator is useful in the crosslinking catalyst of the component (E). Examples of such an acid or thermal acid generator include a compound containing a sulfonic acid group, hydrochloric acid or a salt thereof, as long as it is a compound which can be thermally decomposed to generate an acid during prebaking or postbaking, that is, at 80 to 250. The compound which thermally decomposes to generate an acid at ° C is not particularly limited.

Specific examples of the acid include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, valeric acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, and the like. Fluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, trimethylbenzenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H , 2H, 2H-perfluorooctane sulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Sulfonic acid or a hydrate or salt thereof.

Further, examples of the thermal acid generator include bis(toluenesulfonyloxy)ethane, bis(toluenesulfonyloxy)propane, bis(toluenesulfonyloxy)butane, and p-nitrobenzyltoluene. Sulfonate, o-nitrobenzyl tosylate, 1,2,3-phenylphenyl tris(methylsulfonate), pyridinium p-toluenesulfonate, morpholinium p-toluenesulfonate, Ethyl tosylate, propyl p-toluenesulfonate, p-toluene Butyl acrylate, isobutyl p-toluenesulfonate, methyl p-toluenesulfonate, phenylethyl p-toluenesulfonate, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonic acid Examples of the ester, 2-hydroxybutyl p-toluenesulfonate, and N-ethyl-4-toluenesulfonamide include compounds represented by the following formulas.

The content of the component (E) in the resin composition of the embodiment of the present invention is 100 parts by mass of the component (A) or 100 parts by mass based on the total amount of the component (B) and the component (D). It is preferably from 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 is not observed. On the other hand, when it exceeds 5 mass parts, the storage stability of a resin composition will fall.

<solvent>

The resin composition of the embodiment of the present invention can be used in the form of a solution dissolved in a solvent. As the solvent to be used, it is necessary to dissolve the component (A) or dissolve the component (B) and the component (D). Further, if necessary, those in which the component (C) is dissolved, or the component (C) is dissolved together with the component (E), or the component (E) is dissolved alone. Further, if necessary, those which dissolve other additives described later may be used. The type and structure of the solvent having such a dissolving ability are not particularly limited.

Examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, and diethylene glycol monomethyl ether. , diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, Cyclohexanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropanoate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2- Methyl hydroxy-3-methylbutanoate, 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 and N - methyl pyrrolidone or the like. These solvents may be used singly or in combination of two or more kinds.

<Other additives>

In addition, the resin composition of the embodiment of the present invention may contain a decane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage stabilizer, and an antifoaming agent, as needed, as long as the effects of the present invention are not impaired. and Antioxidants, etc.

<Resin composition>

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

Further, the resin composition of the embodiment of the present invention contains a crosslinking agent of the component (C) as desired.

Further, when the resin composition of the embodiment of the present invention contains the component (B), it is another polymer containing the component (D).

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

In the resin composition of the embodiment of the present invention, the above components can be dissolved in a solvent and used as a solution.

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 the component (C) based on 100 parts by mass of the component (A).

[2]: The resin composition of the component (C) is contained in an amount of 1 to 100 parts by mass based on 100 parts by mass of the total of the components (B) and (D).

[3]: a resin composition containing 1 to 100 parts by mass of the component (C) and a solvent based on 100 parts by mass of the component (A).

[4]: A resin composition containing 1 to 100 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the total of the components (B) and (D).

[5]: A resin composition containing 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent, based on 100 parts by mass of the component (A).

[6]: Based on 100 parts by mass of the total of the components (B) and (D), the resin composition contains 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (E), and a solvent. Things.

When the resin composition of the embodiment of the present invention is used as a solution, the mixing ratio, the preparation method, and the like 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 the respective components are uniformly dissolved in the solvent, and is preferably from 1 to 80% by mass, more preferably from 3 to 60% by mass, particularly Good is 5 to 40% by mass. The solid component referred to herein is one in which the solvent is removed from all the components of the resin composition.

The preparation method of the resin composition of the embodiment of the present invention is not particularly limited, and examples thereof include the component (A) or the component (B) and the component (D) dissolved in a solvent, and the solution is specified in the solution. A method in which a component (C) and a component (E) are mixed in proportion to form a uniform solution. Further, in an appropriate stage of the preparation method, other additives may be further added and mixed as needed.

In the preparation of the resin composition of the embodiment of the present invention, a solution of a polymer obtained by polymerization in a solvent can be used as it is. In this case, in the solution of the component (A) or the component (B) and the component (D), in the same manner as described above, when the component (C) or the component (E) is placed to form a uniform solution, the concentration is adjusted. For the purpose, an additional solvent can be added. In this case, it can be used to adjust the concentration of the solvent and the resin composition used in the formation of the polymer. The agents are the same or different.

The solution of the resin composition prepared as described above is preferably used after being filtered with a filter having a pore diameter of about 0.2 μm or the like.

<Coating film, cured film, and liquid crystal alignment layer>

The resin film of the embodiment of the present invention can be used to form a coating film by the following method.

First, a resin composition is applied onto a substrate, a film, or the like by spin coating, flow coating, roll coating, slit coating, spin coating after slit, inkjet coating, printing, or the like. . Next, preliminary drying (prebaking) can be performed by a hot plate or an oven to form a coating film. Then, this coating film is heat-treated (post-baking) to form a cured film.

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

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

The post-baking is carried out according to a heating method or the like, and a heating temperature suitably selected from the range of temperature 140 to 250 ° C is employed. Also, the heating time is the same, for example, 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. Clock and so on.

When the resin composition of the embodiment of the present invention is cured under the above-described conditions, the step of the substrate due to the color filter (CF) or the like can be sufficiently covered to be flattened, and hardening with high transparency can be formed. membrane. Further, the film thickness of the cured film may be, for example, 0.1 to 30 μm, and may be appropriately selected in consideration of the step difference of the substrate to be used or the optical or electrical properties.

The cured film obtained as described above can be used as a function of aligning a liquid crystal alignment material by rubbing treatment, that is, a liquid crystal alignment layer in which molecules having liquid crystallinity are aligned.

The conditions of the rubbing treatment are generally those using a rotation speed of 300 to 1,000 rpm, a conveying speed of 10 to 80 mm/sec, and a press-in amount of 0.1 to 1 mm. After the rubbing treatment, the residue generated by the friction is removed by washing with ultrasonic waves such as pure water.

After the phase difference material is applied onto the liquid crystal alignment layer thus formed, the phase difference material is heated to the phase transition temperature of the liquid crystal, and the phase difference material is brought into a liquid crystal state. Next, if the light is hardened, a phase difference material which is a layer having optical anisotropy can be formed.

As the phase difference material, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, or the like is used. When the substrate on which the liquid crystal alignment layer is formed is a film, it is suitably used as an optical anisotropic film. As such a phase difference material, there is an alignment having a horizontal alignment, a cholesterol alignment, a vertical alignment, a mixed alignment, a biaxial alignment, and the like, and each of them may be used in accordance with a desired phase difference.

Moreover, the two substrates having the liquid crystal alignment layer formed as described above, After the spacers are bonded to each other such that the liquid crystal alignment layers face each other, liquid crystal is injected between the substrates, and the liquid crystal display elements in which the liquid crystals are aligned may be used.

As described above, the resin composition of the embodiment of the present invention can be suitably used for constituting various optical anisotropic films or liquid crystal display elements.

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

When the resin composition of the embodiment of the present invention is used as a CF cover material, the obtained CF overcoat layer can be planarized not only by covering the step of the color filter but also as a function of the liquid crystal alignment material. Therefore, it can be used as an oriented CF overcoat layer.

Fig. 1 is a schematic configuration diagram of a liquid crystal cell 100 according to an embodiment of the present invention. In the figure, the liquid crystal layer 108 is sandwiched between the two substrates 101, 111. An ITO 110 and an alignment film 109 are formed on the substrate 111. Further, on the substrate 101, a color filter 102, a CF overcoat layer 103, a phase difference material 105, an ITO 106, and an alignment film 107 are formed in this order. At this time, since the CF overcoat layer 103 also functions as an alignment film, a film corresponding to the alignment film 204 of FIG. 2 may not be required.

[Examples]

The invention is illustrated in more detail below by the examples, but the invention is not limited by the examples.

[Abbreviation symbols used in the examples]

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'-diglycidoxyphenyl

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'-dicyclohexyltetracarboxylic dianhydride

HBPA: hydrogenated bisphenol A

BTEAC: benzyltriethylammonium chloride

GT4: Epolead GT-401 (product name) manufactured by DAICEL Chemical Industry Co., Ltd. (Compound name: epoxidized butane tetracarboxylic acid tetrakis(3-cyclohexenylmethyl) modified ε-caprolactone)

<crosslinker>

CEL: Celloxide P-2021 (product name) manufactured by DAICEL Chemical Industry Co., Ltd. (Compound name: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate )

TMGU: 1,3,4,6-tetrakis(methoxymethyl)glycoluril

PWL; Powder link 1174 (Mitsui CYTEC (share) system)

<crosslinking catalyst>

PTSA: p-toluenesulfonic acid monohydrate

<solvent>

CHN: cyclohexanone

PGMEA: propylene glycol monomethyl ether acetate

PGME: propylene glycol monomethyl ether

NMP: N-methylpyrrolidone

According to the number average molecular weight and the weight average molecular weight of the polymer obtained in the following synthesis examples, a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation was used, and a flow rate of 1 mL/min in a solvent of tetrahydrofuran was used. It was measured under the dissolution conditions in which the column was flowed (column temperature 40 ° C). Furthermore, the following number average molecular weight (below The weight average molecular weight (hereinafter referred to as Mw) and the weight average molecular weight (hereinafter referred to as Mw) are 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 the reaction was allowed to proceed at 80 ° C for 20 hours to obtain an acrylic polymer solution (solid content concentration: 27% by mass) (P1). The obtained acrylic polymer had an Mn of 4,940 and a Mw of 9,090.

<Synthesis Example 2>

To 25.0 g of a solution of P1, 4.34 g of CHECA, 12.0 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 27% by mass) (P2). . The obtained acrylic polymer had an Mn of 8,240 and a Mw of 19,440.

<Synthesis Example 3>

To a commercially available PVA (Mw31,000) 3.30 g, CHEDA 7.10 g, PGMEA 31.6 g, and BTEAC 0.125 g were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration 25). Mass%) (P3). The obtained vinyl polymer had an Mn of 47,720 and a Mw of 111,303.

<Synthesis Example 4>

In BGOP 12.0g, add CHECA 7.69g, PGMEA 53.6 g and BTEAC 0.14 g were reacted at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B1).

<Synthesis Example 5>

In a CEL 10.0 g, 9.62 g of CHECA, 53.5 g of PGMEA, and 0.18 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B2).

<Synthesis Example 6>

In GT4 6.0g, CHECA 3.30 g, PGMEA 46.7 g, and BTEAC 0.06 g were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexene ring at the end (solid content concentration: 27% by mass) (B3).

<Synthesis Example 7>

12.0 g of HBPDA, 10.2 g of HBPA, and 0.22 g of BTEAC were reacted in PGMEA 54.48 g at 125 ° C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P4). The obtained polyester had an Mn of 1,980 and a Mw of 3,500.

<Synthesis Example 8>

MAA 2.5g, MMA 9.2g, HEMA 5.0g, as a polymerization touch 0.2 g of AIBN of the medium was dissolved in 50.7 g of PGME, and the reaction was allowed to proceed at 70 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 25% by mass) (P5). The obtained acrylic copolymer had an Mn of 19,600 and a Mw of 45,200.

<Synthesis Example 9>

To 25.0 g of a solution of P1, 4.21 g of BA, 11.6 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain an acrylic polymer (solid content concentration: 27% by mass) (P6). The obtained acrylic polymer had an Mn of 7,920 and a Mw of 17,940.

<Synthesis Example 10>

To 25.0 g of a solution of P1, 4.41 g of CHCA, 12.2 g of PGMEA, and 0.083 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain an acrylic polymer having a cyclohexene ring (solid content concentration: 27% by mass) (P7). ). The obtained acrylic polymer had an Mn of 7,620 and a Mw of 17,860.

<Synthesis Example 11>

Into CEL 10.0 g, 9.62 g of CHCA, 53.5 g of PGMEA, and 0.18 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a compound having a cyclohexane ring at the terminal (solid content concentration: 27% by mass) (B4).

<Synthesis Example 12>

5.0 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 the reaction was allowed to proceed at 80 ° C for 20 hours to obtain an acrylic copolymer solution (solid content concentration: 30% by mass) (P8). The obtained acrylic copolymer had an Mn of 3,500 and a Mw of 7,500.

<Synthesis Example 13>

To 50.0 g of a solution of P8, 7.87 g of CHEDA, 22.9 g of PGMEA, and 0.077 g of BTEAC were added, and the reaction was carried out at 120 ° C for 10 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 30% by mass) (P9) . The obtained acrylic polymer had an Mn of 8,243 and a Mw of 24,990.

<Synthesis Example 14>

15.0 g of BPAGE, 8.35 g of CHDCA, and 0.10 g of BTEAC were dissolved in 54.71 g of PGMEA, and the reaction was carried out at 120 ° C for 20 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P10). The obtained polyester had an Mn of 3,650 and a Mw of 9,060.

<Synthesis Example 15>

To 50.0 g of a solution of P10, 6.86 g of CHEDA and 16.2 g of PGMEA were added, and the reaction was carried out at 120 ° C for 15 hours to obtain a polymer having a cyclohexene ring (solid content concentration: 30% by mass) (P11). The obtained polyester had an Mn of 6,960 and a Mw of 44,000.

<Example 1 to Example 8 and Comparative Example 1 to Comparative Example 3>

Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was prepared in the compositions shown in Table 1, and the composition was evaluated for solvent resistance, transmittance, and alignment.

[Evaluation of solvent resistance]

Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a ruthenium wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 1.1 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a film. A cured film having a thickness of 1.0 μm.

Next, the 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 change in the film thickness after immersion in CHN or NMP was regarded as ○, and the decrease in film thickness after immersion was regarded as ×.

[Evaluation of transmittance (transparency)]

Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. A coating film having a film thickness of 1.0 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The 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 was measured using a UV-visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation) at a wavelength of 400 nm.

[Evaluation of alignment]

Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto an ITO substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. A coating film having a film thickness of 2.8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Then, the 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, the cured film was rubbed at a rotation speed of 400 rpm, a conveyance speed of 30 mm/sec, and a press-in amount of 0.4 mm. The rubbed substrate was washed with pure water for 5 minutes with pure water. Next, a phase difference material made of a liquid crystal monomer was applied onto the substrate by a spin coater, and then prebaked on a hot plate at 80 ° C for 60 seconds to form a coating film having a film thickness of 1.4 μm. Next, the coating film on the substrate was exposed to light of 1,000 mJ/cm ² under a nitrogen atmosphere to harden the phase difference material. The prepared substrate was sandwiched by a deflecting plate, and the alignment was confirmed by an optical microscope. The person who has no light leakage in the crossed Nicols is regarded as ○, and the person who has light leakage is regarded as ×.

[Evaluation of heat resistance]

Each of the compositions of Examples 1 to 8 and Comparative Examples 1 to 3 was applied onto a ruthenium wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 1.1 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Then, this 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 film thickness of 1.0 μm.

Next, this cured film was vertically irradiated with linearly polarized light of 313 nm. Next, the cured film was fired in a hot air circulating oven at a temperature of 230 ° C for 3 hours, and the color difference Ea*b* in the state after post-baking was measured.

[Results of evaluation]

The above evaluations are summarized and shown in Table 2 below.

The cured film formed of the compositions of Examples 1 to 8 is excellent in the alignment property of the liquid crystal. Therefore, it is understood that the compositions of Examples 1 to 8 can form an excellent liquid crystal alignment material. Further, heat resistance and transparency are high, and resistance is also observed for any of CHN and NMP.

On the other hand, in the cured film formed of the compositions of Comparative Example 1 to Comparative Example 3, the liquid crystal was completely unaligned, or light leakage was observed by a polarizing microscope.

As described above, it is understood that the cured film obtained from the resin composition of the present invention has high liquid crystal alignment properties and has light transmissivity, solvent resistance, and heat resistance. Therefore, it is understood that the resin composition of the present invention can provide a cured film having excellent properties as described above, that is, a liquid crystal alignment material, and can further form a phase difference material.

[Industry use possibility]

The resin composition of the present invention is very suitable as a liquid crystal alignment layer for an optically anisotropic film or a liquid crystal display element, and is also suitable as a display for forming a thin film transistor (TFT) type liquid crystal display element or an organic EL element. A material of a cured film such as a protective film, a planarizing film, or an insulating film, in particular, an interlayer insulating film of a TFT liquid crystal element, a protective film of a color filter, or an insulating film of an organic EL element.

Claims (12)

A resin composition comprising a polymer having a cyclohexene ring in a side chain (component A) and a crosslinking agent (component C) reacted by heat, wherein the polymer has a property Side chain of the joint. The resin composition of claim 1, wherein the main chain of the polymer is a polymer of a monomer having an unsaturated double bond. The resin composition of claim 2, wherein the main chain of the polymer is an acrylic polymer. The resin composition of claim 1, wherein the polymer is derived from polyvinyl alcohol. The resin composition of claim 1, wherein the main chain of the polymer contains a ring structure. The resin composition of claim 1, wherein the main chain of the polymer is a polyester resin. The resin composition of claim 1, wherein the main chain of the polymer is a phenolic acid varnish resin. The resin composition of claim 1, wherein the polymer is a cycloolefin polymer. The resin composition of claim 1, wherein the crosslinking group is at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, and an acryl group. The resin composition of claim 1 further contains a crosslinking catalyst (component E). Liquid crystal alignment material characterized by use as a patent application A resin composition of any one of items 1 to 10. A phase difference material characterized by being formed using a cured film obtained by the resin composition according to any one of claims 1 to 10.