KR101736902B1 - Polyester composite for forming thermoset films - Google Patents

Abstract

[PROBLEMS] To provide a cured film which exhibits high solvent resistance, liquid crystal orientation, heat resistance, high transparency and high planarization property after the cured film is formed, but also can be applied to a production line of a planarizing film of a color filter, Provide materials that can be dissolved in the solvent. [MEANS FOR SOLVING PROBLEMS] A polyester composition for forming a thermosetting film, which comprises a component (A), a component (B) and a component (C): Component (A): a polyester obtained by reacting a tetracarboxylic dianhydride with a diol compound, Component (B): an epoxy compound having two or more epoxy groups, component (C): an amino group-containing carboxylic acid compound obtained by reacting a diamine compound, dicarboxylic anhydride and tetracarboxylic dianhydride.

Description

POLYESTER COMPOSITE FOR FORMING THERMOSET FILMS [0002]

The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained therefrom. More specifically, the present invention relates to a polyester composition for forming a thermosetting film having high transparency and planarizing property, a liquid crystal aligning ability, a high solvent resistance and a heat resistance, a cured film thereof, and a cured film thereof. The polyester composition for forming a thermosetting film is particularly suitable for a color filter overcoating agent having a liquid crystal aligning function in a liquid crystal display.

Generally, in an optical device such as a liquid crystal display device, an organic EL (electroluminescent) device, or a solid-state image pickup device, a protective film is provided to prevent the surface of the device from being exposed to solvent or heat during the manufacturing process. The protective film has high adhesion with the substrate to be protected, has high solvent resistance, and is required to have properties such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state image pickup device, the protective film generally has a capability of flattening the color filter or the black matrix resin of the base substrate, that is, . Particularly, when manufacturing a color liquid crystal display device of the STN type or TFT type, it is necessary to precisely align the color filter substrate and the counter substrate with each other, and it is essential to make the cell gap between the substrates uniform. In addition, in order to maintain the transmittance of light transmitted through the color filter, high transparency is required for the planarizing film as the protective film.

On the other hand, in recent years, lower cost and lighter weight have been studied by introducing retardation materials into the cells of a liquid crystal display, and a material obtained by applying and orienting a liquid crystal monomer and then photo-curing is generally used for such retardation. In order to orient the phase difference material, the lower layer film needs to be a material having orientation after rubbing treatment. Therefore, after the liquid crystal alignment layer is formed on the overcoat of the color filter, a phase difference material is formed (see Fig. 2 (a)). (See Fig. 2 (b)) that can also serve as an overcoat of the liquid crystal alignment layer and the color filter can be formed, it is required that such a material is strongly required in view of achieving a great merit such as reduction in cost and reduction in the number of processes have.

Generally, acrylic resin having high transparency is used for overcoating of the color filter. These acrylic resins include glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, ester solvents such as ethyl lactate and butyl lactate, and are widely used from the viewpoints of safety and handling. Such an acrylic resin imparts heat resistance and solvent resistance by thermally curing or photo-curing (Patent Literatures 1 and 2). However, conventional thermosetting or photo-curing acrylic resins show appropriate transparency and planarization property, but even if such a planarizing film is subjected to rubbing treatment, sufficient orientation can not be obtained.

On the other hand, a material composed of a solvent-soluble polyimide or polyamic acid is usually used for the liquid crystal alignment layer. It has been reported that these materials impart a solvent resistance by imidizing completely during post-baking, and exhibit sufficient orientation properties by rubbing treatment (Patent Document 3). However, in the case of the planarizing film of the color filter in this case, there is a problem that the flatness and transparency are largely lowered. Polyimide and polyamic acid are soluble in solvents such as N-methyl-2-pyrrolidone and? -Butyrolactone. However, they have low solubility in glycol solvents and ester solvents and can be applied to flattening film production lines Was difficult.

Japanese Patent Application Laid-Open No. 2000-103937 Japanese Patent Application Laid-Open No. 2000-119472 Japanese Patent Application Laid-Open No. 2005-037920

The present invention has been made based on the above-described circumstances. It is an object of the present invention to provide a cured film which exhibits high solvent resistance, liquid crystal alignability, heat resistance, high transparency and high planarization property after cured film formation, And a material that can be dissolved in a glycol-based solvent or an estersester-type solvent applicable to a production line of a planarizing film of a color filter.

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found the present invention.

That is, the first aspect relates to a polyester composition for forming a thermosetting film containing the component (A), the component (B) and the component (C).

(A): a polyester obtained by reacting a tetracarboxylic dianhydride with a diol compound,

Component (B): an epoxy compound having two or more epoxy groups,

Component (C): An amino group-containing carboxylic acid compound obtained by reacting a diamine compound, dicarboxylic anhydride and tetracarboxylic dianhydride.

As a second aspect, the present invention relates to a polyester composition for forming a thermosetting film according to the first aspect, wherein the component (A) is a polyester comprising a structural unit represented by the following formula (1).

(Wherein A represents a tetravalent organic group having four aliphatic groups or four aliphatic groups bonded to each other and B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group).

As a third aspect, there is provided a polyester obtained by reacting the component (A) with a tetracarboxylic dianhydride represented by the following formula (i) and a diol compound represented by the formula (ii) The present invention relates to a polyester composition for forming a thermosetting film.

(Wherein A represents a tetravalent organic group having four aliphatic groups or four aliphatic groups bonded to each other and B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group).

In a fourth aspect, in the formula (1), A represents at least one kind of group selected from the groups represented by the following formulas (A-1) to (A-8) To (B-5). The polyester composition for forming a thermosetting film according to the second aspect or the third aspect is a polyester composition for forming a thermosetting film.

As a fifth aspect, the present invention relates to a polyester composition for forming a thermosetting film according to any one of the first to fourth aspects, wherein the weight average molecular weight of the polyester as the component (A) is 1,000 to 30,000 in terms of polystyrene.

As a sixth aspect, there is provided a process for producing a carboxylic acid compound (C), wherein the component (C) is an amino group-containing carboxylic acid compound obtained by reacting 2 moles of a diamine compound and 2 moles of a dicarboxylic anhydride per 1 mole of a tetracarboxylic dianhydride, The present invention relates to a polyester composition for forming a thermosetting film described in any one of the above aspects.

As a seventh aspect, there is provided an amino group-containing carboxylic acid compound obtained by reacting the component (C) with a compound represented by the following formula (iii), (iv) or (v) To a polyester composition for forming a thermosetting film.

(In the formulas (iii) and (iv), P and Q each independently represent a divalent organic group, and in the formula (v), Z represents a tetravalent organic group.)

As an eighth aspect, any one of the first to seventh aspects, which contains from 3 to 50 parts by mass of the component (B) and from 5 to 80 parts by mass of the component (C) based on 100 parts by mass of the component (A) To a polyester composition for forming a thermosetting film.

As a ninth aspect, the present invention relates to a polyester composition for forming a thermosetting film according to any one of the first to eighth aspects, further comprising a bismaleimide compound as the component (D).

The tenth aspect relates to a polyester composition for forming a thermosetting film according to the ninth aspect, which contains 0.5 to 50 parts by mass of a component (D) based on 100 parts by mass of the component (A).

As an eleventh aspect, the present invention relates to a cured film obtained by using the polyester composition for forming a thermosetting film described in any one of the first to tenth aspects.

As a twelfth aspect, the present invention relates to a liquid crystal alignment layer obtained by using the polyester composition for forming a thermosetting film described in any one of the first to tenth aspects.

The polyester composition for forming a thermosetting film of the present invention can form a cured film having liquid crystal aligning ability together with high planarization property, high transparency, high solvent resistance and high heat resistance, and therefore can be used as a material for forming a liquid crystal alignment film or a planarizing film . In particular, since the liquid crystal alignment layer and the overcoat layer of the color filter, which have conventionally been formed independently, can be simultaneously formed as a " liquid crystal alignment layer " having both characteristics, the manufacturing process can be simplified and the number of processes can be reduced. Can be realized.

The polyester composition for forming a thermosetting film of the present invention can be suitably used for a production line of a planarizing film mainly using these solvents because of being soluble in glycol solvents and esters ester solvents.

1 is a model diagram showing a cured film formed when the polyester composition for forming a thermosetting film of the present invention is applied to a stepped substrate.
2 is a model diagram showing a comparison between a liquid crystal cell (a) having a liquid crystal alignment film formed by a conventional technique and a liquid crystal cell (b) having a planarized film formed using the polyester composition for forming a thermosetting film of the present invention .

As described above, conventionally proposed acrylic resin-based and polyimide-based cured films do not sufficiently satisfy all the performances such as flatness, transparency, and orientation required for a liquid crystal alignment film or a planarizing film.

Although there have been so far been proposed proposals for the use of polyester as an alignment material for a liquid crystal display element (see Japanese Patent Application Laid-Open No. H5-158055 and Japanese Patent Application Laid-Open No. 2002-229039), they were not all thermosetting, The solvent resistance of the formed membrane was not good.

The present invention is characterized in that the above-described performance improvement is achieved by using a thermosetting polyester. That is, the polyester of the component (A), the epoxy compound having two or more epoxy groups in the component (B) Is a polyester composition for forming a thermosetting film containing an amino group-containing carboxylic acid compound as the component (C). In addition to the components (A), (B) and (C), it is a polyester composition for forming a thermosetting film which can contain up to bismaleimide compounds as the component (D).

Hereinafter, each component will be described in detail.

[Component (A)] [

The polyester of the component (A) is preferably a polyester comprising a structural unit represented by the following formula (1), more preferably a polyester comprising a structural unit represented by the formula (1).

In the above formula, A represents a tetravalent organic group having four aliphatic groups bonded to an alicyclic group or aliphatic group, and B represents a divalent organic group having two aliphatic groups bonded to alicyclic or aliphatic groups.

The above A is preferably a group represented by the following formula (1A1), (1A2) or (1A3).

In the formula, A ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the group A ¹ may be independently substituted with an aliphatic group, and two of these substituents may be bonded to each other to form a 4- to 6-membered ring.

Here, the aliphatic group as the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantane group, or a condensed polycyclic hydrocarbon group in which a part or whole is hydrogenated is obtained.

R ¹ represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms and substituted with a fluorine atom. Preferably a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom.

R ² represents a saturated hydrocarbon group having 1 to 8 carbon atoms, preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

Preferable specific examples of A as a quadrivalent organic group in the formula (1) are shown in the following formulas (A-1) to (A-8). Among the groups represented by the following formulas (A-1) to (A-8), it is particularly preferable that A is a group selected from the formula (A-1) or (A-2).

In the formula (1), B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group, and is preferably a group represented by the following formula (1B1) or (1B2).

In the formula, B ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Any hydrogen atom contained in the group B ¹ may be independently substituted with an aliphatic group.

Here, the aliphatic group as the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantane group, or a condensed polycyclic hydrocarbon group in which a part or whole is hydrogenated is obtained.

B ² represents a phenylene group.

In the formulas, R ³ represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms and substituted with a fluorine atom, , An ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom.

R ⁴ and R ⁵ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms and a single bond.

R ⁶ and R ⁷ each independently represent an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.

K represents 0 or 1;

Preferable specific examples of B which is a bivalent organic group in the formula (1) are shown in the following formulas (B-1) to (B-5). Among the groups represented by the following formulas (B-1) to (B-5), B is preferably a group selected from among (B-1) to (B-4).

The polyester of the component (A) preferably contains at least one structure selected from the group consisting of the groups represented by the formulas (1A1) to (1A3) among the structural units represented by the formula (1) However, it may contain a structure other than the groups represented by the formulas (1A1) to (1A3). At this time, the structure is not particularly limited as far as the structure of the polyester is formed, but it is preferably at least one structure selected from the group consisting of the groups represented by the following formulas (1A4) to (1A5).

R ⁸ , R ⁹ and R ¹⁰ each independently represent a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms and substituted with a fluorine atom And preferably represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms and substituted with a fluorine atom.

Particularly, R ⁸ is preferably a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom, R ⁹ is preferably an ether group, A saturated hydrocarbon group of 1 to 5 in embroidery number or a saturated hydrocarbon group of 1 to 5 in carbon number substituted with fluorine atom and R ¹⁰ is preferably a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms, And is preferably a substituted hydrocarbon group having 1 to 5 carbon atoms.

Also, h represents 0 or 1.

Preferable examples of the formulas (1A4) to (1A5) are shown in the following formulas (a1) to (a7).

In the polyester of the component (A) used in the present invention, in the structural unit represented by the above formula (1), when A is at least 1 selected from the group consisting of the groups represented by the above formulas (1A1) to (1A3) It is preferable that the structural unit of the species contains at least 60 mol% or more.

The weight average molecular weight of the polyester of component (A) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000. When the weight average molecular weight of the polyester of the component (A) is smaller than the above-mentioned range, the orientation property and the solvent resistance tend to be lowered. If the weight average molecular weight exceeds the above range, the planarizing property may be lowered.

≪ Production method of component (A) >

In the present invention, the polyester (A) may be obtained by, for example, polymerizing a tetracarboxylic dianhydride and a diol compound. More preferably, a tetracarboxylic dianhydride (hereinafter also referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol containing a diol compound represented by the following formula (ii) (Hereinafter also referred to as a diol component).

In the above formulas, A and B are the same as defined in the above-mentioned formula (1), and the preferable form is also the same as that described above.

In the present invention, the tetracarboxylic dianhydride represented by the formula (i) and the diol compound represented by the formula (ii) may be used singly or in a combination of two or more.

The polyester as the component (A) is obtained by using not only the tetracarboxylic dianhydride represented by the above formula (i) but also other tetracarboxylic dianhydrides (hereinafter also referred to as other acid dianhydrides) as an acid component . At this time, the other acid dianhydride is not particularly limited so long as it does not deteriorate the effect of the present invention. And is preferably a tetracarboxylic dianhydride represented by the following formula (i2).

Here, in the formula (i2) W, at least the structure of one selected from the group consisting of groups represented by the formula (1A4) and the equation (1A5) defined by the above formula (1), R ^8, R ^9, R ¹⁰ , h are also the same as defined above.

In addition, preferable examples of the formulas (1A4) and (1A5) are also represented by the formulas (al) to (a7) described above.

In the present invention, it is preferable that the tetracarboxylic dianhydride represented by the formula (i) contains at least 60 mol% or more of the acid component.

In the polyester of the component (A), the blending ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) and the total amount of the diol compounds (total amount of the diol components), that is, <total mole number of the diol compound> / < The total number of moles of the dianhydride compound > is preferably 0.5 to 1.5. As in the case of the ordinary polycondensation reaction, the closer the molar ratio is to 1, the larger the degree of polymerization of the resulting polyester increases and the molecular weight increases.

The polyester of the component (A) is preferably an acid anhydride terminal at the terminal thereof in order to avoid a decrease in storage stability.

The end of the polyester varies depending on the blending ratio of the acid component and the diol component. For example, when an acid component is over-reacted, the terminal tends to become an acid anhydride.

Further, when the diol component is polymerized in excess, the terminal tends to be a hydroxyl group. In this case, the terminal hydroxyl group may be reacted with a carboxylic acid anhydride, and the terminal hydroxyl group may be blocked with an acid anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride, methyltetra Hydrophthalic anhydride, and bicyclo [2.2.2.] Octene-2,3-dicarboxylic anhydride.

In the production of the polyester of component (A), the reaction temperature of the acid component and the diol component may be selected from any temperature of 50 to 200 ° C, preferably 80 to 170 ° C. For example, the polyester may be obtained at a reaction temperature of 100 ° C to 140 ° C and a reaction time of 2 to 48 hours.

The reaction temperature in the case of protecting the terminal hydroxyl group with an acid anhydride may be selected from any temperature of 50 to 200 ° C, preferably 80 to 170 ° C.

The reaction of the acid component and the diol component is usually carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not contain a functional group reactive with an acid anhydride such as a hydroxyl group or an amino group. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, , Dimethyl sulfone, hexamethyl sulfoxide, m-cresol, gamma -butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol Propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate .

These solvents may be used singly or in admixture, but propylene glycol monomethyl ether acetate is more preferable in view of safety and applicability of the color filter to the overcoat line.

Further, even if the solvent does not dissolve the polyester, it may be mixed with the above-mentioned solvent within the range that the polyester produced by the polymerization reaction does not precipitate.

Further, a catalyst may be used in the reaction of the acid component (the formula (i) and the formula (i2))) with the diol component (the formula (ii)).

Specific examples of the catalyst used in the polymerization of the polyester include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetra Quaternary ammonium salts such as methylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride and tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, And a quaternary phosphonium salt such as ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and the like.

The thus obtained solution containing the polyester of the component (A) can be used as it is for the preparation of the polyester composition for forming a thermosetting film. The obtained polyester may be recovered by isolation in a poor solvent such as water, methanol, ethanol, diethyl ether, or hexane, and recovered.

&Lt; Component (B) >

Examples of the epoxy compound having two or more epoxy groups as the component (B) of the present invention include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, Glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [(2-hydroxyethyl) phenylenepropane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N-diglycidyl aniline), 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylol ethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

In addition, commercially available compounds can be used because they are readily available. Specific examples (trade names) include, but are not limited to, epoxy resins having amino groups such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.); Epoxy resins having a cyclohexene oxide structure such as Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Ceroxide 2021 and Ceroxide 3000 (Daicel Chemical Industries, (Manufactured by Japan Epoxy Resin Co. Ltd.), such as Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 Type epoxy resin; Bisphenol F type epoxy resins such as Epikote 807 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently, Japan Epoxy Resin Co. Ltd.)); Epikote 152, Epikote 154 (manufactured by Yuka Shell Epoxy Co., Ltd. (formerly Japan Epoxy Resin Co. Ltd.), EPPN 201 and EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.) Novolak type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (available from Yuka Shell Epoxy Co., Japan Epoxy Resin Co. Ltd.); (Manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (manufactured by CIBA- GEIGYA.G.), Epiclon 200, Epiclon 400 (Manufactured by Dainippon Ink and Chemicals, Inc. (DIC), Epikote 871, Epikote 872 (manufactured by Yuka Shell Epoxy Co., Ltd., Japan Epoxy Resin Co. Ltd.) ED-5662 (manufactured by Celanese Coating Co.), and other alicyclic epoxy resins; Denacol EX-311, Denacol EX-314, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, Denacol EX- And aliphatic polyglycidyl ethers such as Denacol EX-321 (manufactured by Nagase ChemteX Corporation).

As the compound having at least two epoxy groups, a polymer having an epoxy group can be used. As such a polymer, any polymer having an epoxy group can be used without any particular limitation.

The above-mentioned polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerization monomer having an epoxy group. For example, polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, an addition polymer of glycidyl methacrylate and a copolymer of styrene and 2-hydroxyethyl methacrylate And polycondensation polymers such as epoxy novolac.

Alternatively, the polymer having an epoxy group can be produced by a reaction between a polymer compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

The weight average molecular weight of such a polymer is, for example, 300 to 200,000.

These epoxy compounds having two or more epoxy groups may be used alone or in combination of two or more.

The content of the epoxy compound having two or more epoxy groups in the component (B) in the polyester composition for forming a thermosetting film of the present invention is preferably 3 to 50 parts by mass based on 100 parts by mass of the polyester of the component (A) More preferably 5 to 40 parts by mass, and particularly preferably 10 to 30 parts by mass. When the ratio is too small, the solvent resistance and heat resistance of the cured film obtained from the polyester composition for thermosetting film formation are lowered. On the other hand, when the ratio is too large, the solvent resistance may be lowered or the storage stability may be lowered.

&Lt; Component (C) >

(C) is an amino group-containing carboxylic acid compound obtained by reacting a diamine compound, dicarboxylic anhydride, or tetracarboxylic dianhydride. Specifically, it is an amino group-containing carboxylic acid compound obtained by reacting 2 moles of a diamine compound and 2 moles of a dicarboxylic anhydride per mole of tetracarboxylic dianhydride.

Examples of the diamine compound, dicarboxylic anhydride and tetracarboxylic dianhydride include compounds represented by the following formulas (iii) to (v).

In the formulas (iii) and (iv), P and Q each independently represent a divalent organic group, and in formula (v), Z represents a tetravalent organic group.

Therefore, by reacting the diamine compound represented by the formula (iii), the dicarboxylic anhydride represented by the formula (iv) and the tetracarboxylic dianhydride represented by the formula (v), the compound represented by the formula (2) .

In the formula (2), P, Q and Z are the same as defined in the formulas (iii), (iv) and (v).

In the present invention, only one kind of diamine compound, dicarboxylic anhydride, and tetracarboxylic dianhydride may be used respectively, or plural kinds may be used. Therefore, as the amino group-containing carboxylic acid compound of the component (C) of the present invention, not only one kind of compound represented by the formula (2) but also a plurality of kinds can be used.

It is preferable that P and Q are each independently a divalent organic group having a ring structure. Here, examples of the ring structure include a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon.

As the ring structure of P in formula (iii), a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, and a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms are preferable.

Thus, specific examples of the diamine compound having such a cyclic structure include the following: p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-dimethyl-1,3-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl-1,4 Diaminobenzene, 2,4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, N, N Diaryl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2- (4-aminophenyl) ethylamine, Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,6-naphthalene diamine, Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dihydroxy Diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 2, 2'-trifluoromethyl-4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3 , 3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodi Phenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4 (3, 4'-diaminodiphenyl) amine, N-methyl (3,4'-diamine) Aminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzanilide, 1,2- Bis (4-aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, Bis (3-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, Bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2- Bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis Bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis Bis (4-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) decane, 1,10- Bis (4-aminophenyl) pentanedioate, bis (4-aminophenyl) hexanedioate, bis (4-aminophenyl) pentanedioate, bis (4-amino (4-aminophenyl) decanedioate, 1,4-bis (4-aminophenyl) heptanedioate, bis (4-aminophenyl) octanedioate, bis Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, Bis (4-aminobenzyl) benzene, bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) methane], 1,3-phenylenebis [(4-aminophenyl) methanone] Phenanthrene], 1,4-phenylenebis (4-aminophenyl) methanone], 1,3-phenylenebis [ Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis - (1,4-phenylene) bis (4-aminobenzamide), N, N ' Aminobenzamide), bis (3-aminophenyl) terephthalamide, bis (3-aminobenzamide), bis Bis (4-aminophenoxy) phenyl] propane, 2,2-bis (4-aminophenyl) isophthalamide, (4-aminophenoxy) phenyl] hexafluoropropane, 4,4'-bis (4-aminophenoxy) diphenyl sulfone, 2,6- diaminopyridine, 2,4-diaminopyridine , 2,4-diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, 3,6-diaminodibenzofurane, 2,6 Diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole, 1,4-diaminocyclohexane, 1, 3-diaminocyclohexane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane and the like.

In the formula (iv), the ring structure of Q is preferably a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms. More preferably an alicyclic ring.

Specific examples of the dicarboxylic anhydride having such a cyclic structure include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride , Itaconic anhydride, tetrahydrophthalic anhydride and the like.

In the above formula (v), Z is preferably a tetravalent organic group having a cyclic structure. Here, examples of the ring structure include a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon. (Z-1), (Z-2) or (Z-3), more preferably a tetravalent organic group having four aliphatic groups or four aliphatic groups bonded to each other, .

In the formulas, Z ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, any hydrogen atom contained in the Z ¹ group may be independently substituted with an aliphatic group, and two of these substituents may be bonded to each other to form a 4- to 6-membered ring.

Here, the aliphatic group as the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, a bridged cyclic hydrocarbon group such as a norbornene group or an adamantane group, or a condensed polycyclic hydrocarbon group in which a part or whole is hydrogenated is obtained.

Y ¹ represents a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms and substituted with a fluorine atom. Preferably a single bond, a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom.

Y ² represents a saturated hydrocarbon group of 1 to 8 carbon atoms, preferably a saturated hydrocarbon group of 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group of 1 to 3 carbon atoms.

Specific preferred examples of Z include the above-mentioned formulas (A-1) to (A-8). Among them, particularly preferred is a group selected from the formula (A-1) or (A-2).

Examples of the tetracarboxylic dianhydride represented by the formula (v) include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride , 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,5,6-anthracene tetracarboxylic dianhydride, 3,3 ' , 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,5-dicarboxy methylene Phthalic acid dianhydride, 4,6-dicarboxymethylisophthalic acid dianhydride, 4- (2,5-dioxotetrahydro-3-furanyl) phthalic anhydride, 1,4-bis (2,5-dioxotetrahydro (2,6-dioxotetrahydro-4-pyranyl) benzene, 1,4-bis (2,5-dioxotetrahydro- (2,6-dioxotetrahydro-4-methyl-4-pyranyl) benzene, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 , 3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo Butane tetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic acid dianhydride, 4- (2,5-dioxotetrahydro-3-furanyl) -cyclohexane-1,2-dicarboxylic anhydride, 5- (2,5-dioxotetrahydro- Cyclohexene-1,2-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 3, 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalenesuccinic acid dianhydride Water, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ', 4,4'-bicyclohexyltetracarboxylic dianhydride, 2,3,5, 6-norbornenetetracarboxylic dianhydride, 3,5,6-tricarboxynorbomene-2-acetic acid dianhydride, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid dianhydride, tetracyclo [4.4.1.0 ^2,5 .0 ^7,10] undecane -3,4,8,9- tetracarboxylic dianhydride, bicyclo hexahydro [6.6.0.1 ^2,7 .0 ^3,6. 1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- Te (2,5-dioxotetrahydro-3-furanyl) hexane, and 4-bis (2,6-dioxotetrahydro-4-pyranyl) hexane. .

In the production of the compound of the component (C), the reaction temperature of the tetracarboxylic dianhydride, the diamine compound and the dicarboxylic anhydride may be selected at any temperature of 5 to 50 ° C, preferably 10 to 35 ° C . In order to avoid polymerization during the reaction, tetracarboxylic dianhydride and dicarboxylic anhydride are added in a state of being cooled to 23 deg. C to dissolve the diamine compound in an arbitrary solvent and then to avoid polymerization due to exothermic reaction during the reaction More preferably added.

The above reaction is usually carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not contain a functional group reactive with an acid anhydride such as a hydroxyl group or an amino group. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylimidazole, But are not limited to, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propyleneglycol monomethyl &lt; RTI ID = 0.0 & Ethyl acetate, propyleneglycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate , Methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propyleneglycol monomethyl ether, propyleneglycol propyl ether, ethyl lactate, butyl lactate, cyclohexanol, ethyl acetate , Butyl acetate, ethyl lactate, and butyl lactate.

These solvents may be used alone or in admixture. From the viewpoint of solubility, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl- Dimethylimidazole is preferred.

Further, even a solvent which does not dissolve the amino group-containing carboxylic acid compound, it may be mixed with the above-mentioned solvent within the range that the amino group-containing carboxylic acid compound produced by the polymerization reaction does not precipitate.

The content of the component (C) in the polyester resin composition for forming a thermosetting film of the present invention is preferably 5 to 80 parts by mass based on 100 parts by mass of the polyester polymer of the component (A), more preferably 5 To 60 parts by mass. When the ratio is too small, the orientation property of the cured film obtained from the polyester resin composition for forming a thermosetting film is lowered, while when it is too large, the transmittance may be lowered or the flatness may be lowered.

&Lt; Component (D) >

In the present invention, the bismaleimide compound represented by the following formula (3) may be contained as the component (D).

The bismaleimide compound which is the component (D) is effective in further improving the planarization property.

Wherein X is an organic group selected from the group consisting of an aliphatic group, an aliphatic group having a cyclic structure and an aromatic group, or a combination of a plurality of organic groups selected from these groups. Further, X may contain a bond such as an ester bond, an ether bond, an amide bond, a urethane bond or the like.

Examples of such bismaleimide compounds include N, N'-3,3-diphenylmethane bismaleimide, N, N '- (3,3-diethyl-5,5- , 4-diphenylmethane bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, 4,4-diphenylsulfone bismaleimide, N , N'-p-benzophenone bismaleimide, N, N'-diphenyl ethane bismaleimide, N, N'-diphenyl ether bismaleimide, N, N '- (methylenedio-ditetrahydrophenyl) N, N '- (3,3-dimethyl) -4,4-diphenylmethane bismaleimide, N, N' - (3-ethyl) -4,4-diphenylmethane bismaleimide, N, N '- (3,3-dichloro) -4,4-diphenylmethane bismaleimide, N, N' , N'-isophorone bismaleimide, N, N'-toluidine bismaleimide, N, N'-diphenylpropane bismaleimide, N, N'-naphthalene bismaleimide, Phenylene bismaleimide, N, N'-5-methoxy-1, 3-phenylene bismaleimide, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2- Propane, 2,2-bis (3-bromo-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Bis (3-propyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Propane, 2,2-bis (3-butyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Bis (3-methyl-4- (4-maleimidophenoxy) phenyl) ethane, 1,1-bis (3 (3-bromo-4- (4-maleimidophenoxy) phenyl) ethane, 3,3-bis (4- (4-maleimidophenoxy) phenyl) pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- 1,1,3 , 3,3-hexafluoro-2,2-bis (3,5-dimethyl-4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro Bis (3,5-dibromo-4- (4-maleimidophenoxy) phenyl) propane, N, N'-ethylene dimaleimide, N, N'-hexamethylene bismaleimide, N, N'-p-xylenebismaleimide, N, N'-1,3-bismethylene cyclohexane bis, and N, N'-dodecamethylene bismaleimide. Maleimide, N, N'-2,4-tolylene bismaleimide and N, N'-2,6-tolylene bismaleimide. These bismaleimide compounds are not particularly limited to those described above. These may be used alone or in combination of two or more components.

Among these bismaleimides, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, N, N'-4,4-diphenylmethane bismaleimide, N, N ' -Diethyl-5,5-dimethyl) -4,4-diphenyl-methane bismaleimide, and the like.

Among these aromatic bismaleimides, those having a molecular weight of 1,000 or less are preferable in order to obtain a higher leveling property.

In the present invention, the ratio of the bismaleimide compound of the component (D) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the polyester of the component (A) And preferably 2 to 20 parts by mass. When the ratio is too small, the planarizing property of the cured film obtained from the polyester composition for forming a thermosetting film is deteriorated, and when it is too large, the transmittance of the cured film may be lowered or the film may be roughened.

<Solvent>

The polyester composition for forming a thermosetting film of the present invention is often used in a solution state dissolved in a solvent. The solvent used here is a solvent which dissolves the components (A) to (C) and, if necessary, the component (D) and / or other additives to be described later. When the solvent has such a solubility ability, Is not particularly limited.

Examples of such a solvent include the solvent used for the polymerization of the component (A) and the following solvents. For example, there may be mentioned methylcellosolve acetate, ethylcellosolve acetate, methylcellosolve, ethylcellosolve, butylcellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, cyclohexanol, Ethyl, butyl acetate, ethyl lactate, and butyl lactate.

These solvents may be used singly or in combination of two or more.

<Other additives>

The polyester composition for forming a thermosetting film of the present invention may further contain additives such as a surfactant, a rheology modifier and a silane coupling agent, a pigment, a dye, a storage stabilizer , Antifoaming agents, dissolution accelerators such as polyhydric phenols and polyvalent carboxylic acids, antioxidants, and the like.

As the antioxidant, phenols are particularly preferable, and specific examples thereof include 2,6-di-t-butyl-4-cresol, 2,6-di-t-butylphenol, 2,4,6- (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) mercapto, 4,4'-methylenebis Butyl-4-hydroxyphenyl) propionate, 4,4'-thiodi (2,6-di-t-butylphenol), tris (3,5- 4-hydroxybenzyl) isocyanuric acid, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide and the like.

&Lt; Polyester composition for forming thermosetting film &

The polyester composition for forming a thermosetting film of the present invention contains a polyester of component (A), an epoxy compound having two or more epoxy groups in component (B), and an amino group-containing carboxylic acid compound of component (C) Is a composition capable of containing at least one of bismaleimide compounds of component (D) and other additives. Usually, they are often used as a solution in a solvent.

Among them, preferred examples of the polyester composition for forming a thermosetting film of the present invention are as follows.

[1] A polyester composition for forming a thermosetting film, which comprises 3 to 50 parts by mass of the component (B) and 5 to 80 parts by mass of the component (C) based on 100 parts by mass of the component (A).

[2] A polyester composition for forming a thermosetting film, which comprises 3 to 50 parts by mass of the component (B), 5 to 80 parts by mass of the component (C), and a solvent based on 100 parts by mass of the component (A).

[3] A thermosetting resin composition comprising: 3 to 50 parts by mass of a component (B), 5 to 80 parts by mass of a component (C), and 0.5 to 50 parts by mass of a component (D) / RTI &gt;

[4] A thermosetting resin composition comprising: 3 to 50 parts by mass of a component (B), 5 to 80 parts by mass of a component (C), 0.5 to 50 parts by mass of a component (D) Polyester composition for forming a cured film.

The mixing ratio, preparation method and the like when the polyester composition for forming a thermosetting film of the present invention is in the form of a solution will be described in detail below.

The proportion of the solid content in the thermosetting film-forming polyester composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but it is preferably 1 to 80 mass%, more preferably 5 to 60 mass% %, More preferably from 10 to 50 mass%. Here, the solid content means that the solvent is excluded from the entire components of the polyester composition for forming a thermosetting film.

The preparation method of the polyester composition for forming a thermosetting film of the present invention is not particularly limited. For example, the component (A) is dissolved in a solvent and the component (B), (C (D) are mixed in a predetermined ratio to prepare a homogeneous solution, or a method in which other additives are added, if necessary, at an appropriate stage of this preparation method and mixed .

In the preparation of the polyester composition for forming a thermosetting film of the present invention, a solution of a polyester obtained by a polymerization reaction in a solvent can be used as it is. In this case, when a homogeneous solution is prepared by adding the component (B), the component (C), the component (D) and the like to the solution of the component (A), the solvent is further added It can also be injected. At this time, the solvent used in the polyester production process and the solvent used for the concentration adjustment at the time of preparing the polyester composition for forming a thermosetting film may be the same or different.

The prepared solution of the polyester composition for thermosetting film formation is preferably filtered after using a filter having a pore size of about 0.2 탆 or the like.

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

The polyester composition for forming a thermosetting film of the present invention can be applied to a substrate (e.g., a substrate coated with a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum, A spin coating, a roll coating, a slit coating, a rotation after the slit, and the like (for example, a quartz substrate, an ITO substrate or the like) or a film (for example, a resin film such as a triacetyl cellulose film, a polyester film, Coating, inkjet coating, printing or the like, and then preliminarily drying (prebaking) with a hot plate or an oven to form a coating film. Thereafter, this coating film is heat-treated to form a coating film.

As the conditions of the heat treatment, for example, a heating temperature and a heating time appropriately selected from a temperature range of 70 to 160 DEG C and a time of 0.3 to 60 minutes are employed. The heating temperature and the heating time are preferably 80 占 폚 to 140 占 폚 for 0.5 to 10 minutes.

The film thickness of the film formed of the thermosetting film-forming polyester composition is, for example, 0.1 to 30 占 퐉 and can be appropriately selected in consideration of the step difference of the substrate to be used and the optical and electrical properties.

As the post bake, a method of treating at a heating temperature selected from the range of 140 ° C to 250 ° C, for 5 to 30 minutes in the case of the hot plate, and for 30 to 90 minutes in the case of the oven is adopted as the post bake.

By curing the polyester composition for forming a thermosetting film of the present invention based on the above-described conditions, it is possible to sufficiently planarize the steps of the substrate, and to form a cured film having high transparency.

The cured film thus formed can function as a liquid crystal aligning layer, that is, a layer for aligning a compound having liquid crystallinity by performing a rubbing treatment.

Conditions for the rubbing treatment are generally a condition of a rotational speed of 300 to 1,000 rpm, a conveying speed of 3 to 200 mm / sec, and an indentation amount of 0.1 to 1 mm.

Thereafter, the residue produced through rubbing is removed by ultrasonic cleaning using pure water or the like.

After the phase difference material is applied on the liquid crystal alignment layer thus formed, the phase difference material is made into a liquid crystal state and photo-cured, whereby a layer having optically anisotropy can be formed.

As the retardation material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the liquid crystal monomer is used.

When the material forming the liquid crystal alignment layer is a film, it is useful as an optically anisotropic film.

Further, two substrates having the liquid crystal alignment layer formed as described above were bonded together with the spacers interposed therebetween so as to face the liquid crystal alignment layers. Then, liquid crystal was injected between these substrates to form liquid crystal display elements .

Therefore, the polyester composition for forming a thermosetting film of the present invention can be suitably used for various optically anisotropic films and liquid crystal display elements.

In addition, since the polyester composition for forming a thermosetting film of the present invention has at least a necessary level of planarizing property, a protective film, a flattening film, an insulating film, and the like in various displays such as a thin film transistor (TFT) type liquid crystal display element, And is particularly suitable as a material for forming an overcoat material of a color filter, an interlayer insulating film of a TFT type liquid crystal device, an insulating film of an organic EL device, and the like.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Abbreviations used in the examples]

The meanings of the weak symbols used in the following examples are as follows.

&Lt; Polyester polymer raw material &

HBPDA: 3,3'-4,4'-bicyclohexyltetracarboxylic dianhydride

THPA: 1,2,5,6-tetrahydrophthalic anhydride

BPDA: biphenyltetracarboxylic dianhydride

HBPA: hydrogenated bisphenol A

BTEAC: Benzyltriethylammonium chloride

&Lt; Amino group-containing carboxylic acid compound raw material &

HBPDA: 3,3'-4,4'-bicyclohexyltetracarboxylic dianhydride

CBDA: 1,2,4,5-cyclohexane tetracarboxylic dianhydride

THPA: 1,2,5,6-tetrahydrophthalic anhydride

DA-4P: 1,3-bis (4-aminophenyl) benzene

DDS: 4,4'-diaminodiphenyl sulfone

<Material for polyimide precursor>

CBDA: 1,2,4,5-cyclohexane tetracarboxylic dianhydride

pDA: p-phenylenediamine

&Lt; Acrylic copolymer raw material &

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<Epoxy Compound>

CEL: Daicel Chemical Industries, Ltd .; (Product name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate)

<Bismaleimide compound>

BMI 1: N, N '- (3,3-diethyl-5,5-dimethyl) -4,4-diphenyl-methane bismaleimide

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

DMAc: N, N-dimethylacetamide

NMP: N-methyl-2-pyrrolidone

The number average molecular weight and the weight average molecular weight of the polyester polymer, the polyimide precursor and the acrylic copolymer obtained according to the following Synthesis Examples were measured using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L, manufactured by JASCO Corporation) Hydrofuran was measured under the conditions of eluting by flowing in a column (column temperature: 40 DEG C) at a flow rate of 1 ml / min. On the other hand, the following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed as polystyrene conversion values.

&Lt; Synthesis Example 1 &

(Solid concentration: 30.0 mass%) was obtained by reacting 12.0 g of HBPDA, 10.2 g of HBPA, 0.95 g of THPA and 0.22 g of BTEAC in 54.48 g of PGMEA at 120 캜 for 19 hours (P1 concentration). The obtained polyester polymer had Mn of 2,280 and Mw of 4,200.

&Lt; Synthesis Example 2 &

14.6 g of DA-4P was dissolved in 40.68 g of DMAc and then water-cooled and maintained at 23 占 폚. To this solution, 4.90 g of CBDA and 7.60 g of THPA were reacted at 23 占 폚 for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid concentration: 40.0% by mass). (A1)

&Lt; Synthesis Example 3 &

4.97 g of DDS was dissolved in 14.95 g of DMAc and then water-cooled and maintained at 23 占 폚. To this solution, 1.96 g of CBDA and 3.04 g of THPA were reacted at 23 占 폚 for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid concentration: 40.0% by mass). (A2)

&Lt; Synthesis Example 4 &

14.61 g of DA-4P was dissolved in 41.82 g of DMAc, then water-cooled and maintained at 23 占 폚. 7.66 g of HBPDA and 7.60 g of THPA were reacted with this solution at 23 占 폚 for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration: 40.0% by mass). (A3)

&Lt; Synthesis Example 5 &

A polyester polymer solution (solid concentration: 30.0 mass%) was obtained by reacting 40.0 g of BPDA, 35.3 g of HBPA, 3.31 g of THPA and 0.77 g of BTEAC in 175.7 g of PGMEA at 120 캜 for 19 hours (P2). The obtained polyester polymer had 1,100 Mn and 2,580 Mw.

&Lt; Synthesis Example 6 &

A polyimide precursor solution (solid concentration: 30.0 mass%) was obtained by reacting 17.7 g of CBDA and 10.2 g of pDA in 66.4 g of NMP at 23 占 폚 for 24 hours (P3). The obtained polyimide precursor had Mn of 5,800 and Mw of 12,500.

&Lt; Synthesis Example 7 &

10.9 g of MAA, 35.3 g of CHEMA, 25.5 g of HEMA and 28.3 g of MMA were used as monomer components and 5 g of AIBN was used as a radical polymerization initiator. These were polymerized in 150 g of solvent PGMEA at a temperature of 60 to 100 캜, Acrylic copolymer solution (solid concentration: 40.0 mass%) was obtained (P4). The obtained acrylic copolymer solution had Mn of 3,800 and Mw of 6,700.

&Lt; Examples 1 to 6 and Comparative Examples 1 to 4 >

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was prepared with the composition shown in Table 1, and the flatness, the solvent resistance, the transmittance and the orientation were evaluated for each of the compositions.

※ P1 ~ P2: Polyester polymer solution

P3: polyimide precursor solution

P4: Acrylic copolymer solution

[Evaluation of planarization property]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied to a stepped substrate (glass) having a height of 0.5 m, a line width of 10 m and a laminar space of 50 m using a spin coater, Baked on a hot plate at a temperature of 100 DEG C for 120 seconds to form a coat film having a thickness of 2.8 mu m. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was heated at 230 캜 for 30 minutes to perform post-baking to form a cured film having a film thickness of 2.5 탆.

The difference in film thickness between the coating film on the stepped substrate line and the coating film on the space was measured (refer to Fig. 1), and the flatness ratio (DOP) = 100 x [1- (film thickness difference )}] Was used to obtain the flatness ratio.

[Evaluation of Solvent Resistance]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied to a silicon wafer using a spin coater and then pre-baked on a hot plate at a temperature of 100 DEG C for 120 seconds to obtain a film having a thickness of 2.8 mu m Thereby forming a coating film. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was subjected to post-baking on a hot plate at 230 캜 for 30 minutes to form a cured film having a thickness of 2.5 탆.

The cured film was immersed in PGMEA or NMP for 60 seconds, and then dried at a temperature of 100 DEG C for 60 seconds to measure the film thickness. &Amp; cir &amp;, &amp; cir &amp; and &amp; cir &amp;

[Evaluation of light transmittance (transparency)] [

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was coated on a quartz substrate using a spin coater and prebaked on a hot plate at a temperature of 100 DEG C for 120 seconds to form a film having a thickness of 2.8 mu m Was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was subjected to post-baking on a hot plate at a temperature of 230 캜 for 30 minutes to form a cured film.

The cured film was measured for transmittance at a wavelength of 400 nm using an ultraviolet visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).

[Evaluation of orientation]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was coated on an ITO substrate using a spin coater and then prebaked on a hot plate at a temperature of 100 캜 for 120 seconds to form a film having a thickness of 2.8 탆 Was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This film was post-baked on a hot plate at a temperature of 230 캜 for 30 minutes to form a cured film.

This cured film was subjected to rubbing treatment at a rotating speed of 300 rpm, a conveying speed of 10 mm / sec, and an indentation amount of 0.45 mm. The rubbed substrate was ultrasonically cleaned with pure water for 5 minutes. A retardation material made of a liquid crystal monomer was coated on the substrate using a spin coater and then prebaked on a hot plate at 100 占 폚 for 40 seconds and at 55 占 폚 for 30 seconds to form a coating film having a thickness of 1.1 占 퐉. The substrate was exposed at 2,000 mJ under a nitrogen atmosphere. The prepared substrate was sandwiched between the polarizing plates, and the orientation was visually confirmed. The substrate was markedly changed in transparency when the substrate was tilted at 45 degrees and when it was not tilted.

[Evaluation of heat resistance]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was coated on a quartz substrate by using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C for 120 seconds, For 30 minutes on a hot plate to form a cured film, and the film thickness was measured using F20 manufactured by FILMETRICS Co., Ltd. Thereafter, the cured film was further baked on a hot plate at 230 캜 for 60 minutes to measure the film thickness again, and the amount of change in the film thickness after post-baking was calculated.

[Results of evaluation]

The results of the above evaluation are shown in Table 2 below.

In Examples 1 to 6, the planarization ratio and heat resistance were high, and resistance to both PGMEA and NMP was shown. In addition, all of them exhibited good alignment properties and achieved high transmittance (transparency) even after high-temperature firing.

On the other hand, Comparative Example 1 showed good resistance to solvent resistance, orientation, and flatness, but showed a very low heat resistance.

In Comparative Example 2, no cured film was formed.

In Comparative Example 3, the solvent resistance, the heat resistance and the orientation were good, but the planarization rate was very low.

In Comparative Example 4, the flatness, the heat resistance, the solvent resistance, and the transmittance were satisfactory but the orientation was deteriorated.

As described above, in the polyester resin composition for forming a thermosetting film of the present invention, it is possible to use a glycol solvent such as propylene glycol monomethyl ether acetate at the time of forming a cured film. In addition, the obtained cured film has excellent light transmittance , Solvent resistance, flattening property and orientation were obtained.

Claims (12)

A polyester composition for forming a thermosetting film, which comprises a component (A), a component (B) and a component (C).
(A): a polyester obtained by reacting a tetracarboxylic dianhydride with a diol compound,
Component (B): an epoxy compound having two or more epoxy groups,
Component (C): An amino group-containing carboxylic acid compound obtained by reacting a diamine compound, dicarboxylic anhydride and tetracarboxylic dianhydride. The method according to claim 1,
Wherein the component (A) is a polyester comprising a structural unit represented by the following formula (1).
[Chemical Formula 1]

(Wherein A represents a tetravalent organic group having four aliphatic groups or four aliphatic groups bonded to each other and B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group). The method according to claim 1,
Wherein the component (A) is a polyester obtained by reacting a tetracarboxylic dianhydride represented by the following formula (i) with a diol compound represented by the formula (ii).
(2)

(Wherein A represents a tetravalent organic group having four aliphatic groups or four aliphatic groups bonded to each other and B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group). 3. The method of claim 2,
In the above formula (1), A represents at least one kind of group selected from the groups represented by the following formulas (A-1) to (A-8) -5). &Lt; / RTI &gt;
(3)

[Chemical Formula 4]

The method according to claim 1,
Wherein the polyester as the component (A) has a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene. The method according to claim 1,
Wherein the component (C) is an amino group-containing carboxylic acid compound obtained by reacting 2 moles of a diamine compound and 2 moles of a dicarboxylic anhydride with respect to 1 mole of a tetracarboxylic dianhydride. The method according to claim 1,
Wherein the component (C) is an amino group-containing carboxylic acid compound obtained by reacting a compound represented by the following formula (iii), (iv) or (v).
[Chemical Formula 5]

(In the formulas (iii) and (iv), P and Q each independently represent a divalent organic group, and in the formula (v), Z represents a tetravalent organic group.) The method according to claim 1,
3 to 50 parts by mass of the component (B) and 5 to 80 parts by mass of the component (C) based on 100 parts by mass of the component (A). The method according to claim 1,
The polyester composition for forming a thermosetting film further contains a bismaleimide compound as the component (D). 10. The method of claim 9,
0.5 to 50 parts by mass of the component (D) based on 100 parts by mass of the component (A). A cured film obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 10. A liquid crystal alignment layer obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 10.

Images