KR20120000095A - Polyester composite for forming thermoset films - Google Patents

Abstract

[PROBLEMS] After the cured film is formed, not only does it exhibit high solvent resistance, liquid crystal alignment property, heat resistance, high transparency and high flattening property, but also when the cured film is formed, a glycol-based solvent or lactic acid ester applicable to the production line of the flattening film of the color filter. Provide materials that are soluble in solvents. SOLUTION: The polyester composition for thermosetting film formation containing (A) component, (B) component, and (C) component: (A) component: Polyester obtained by making tetracarboxylic dianhydride and a diol compound react, (B) component: The epoxy compound which has two or more epoxy groups, (C) component: The amino-group containing carboxylic compound obtained by making a diamine compound, a dicarboxylic acid anhydride, and tetracarboxylic dianhydride react.

Description

Polyester composition for thermosetting film formation {POLYESTER COMPOSITE FOR FORMING THERMOSET FILMS}

This invention relates to the polyester composition for thermosetting film formation, and the cured film obtained from this. More specifically, it relates to the application of the polyester composition for thermosetting film formation, its cured film, and its cured film which have high transparency, planarization property, and has liquid crystal aligning ability, high solvent resistance, and heat resistance. This polyester composition for thermosetting film formation is especially suitable for the color filter overcoat agent which has the liquid crystal aligning function in a liquid crystal display.

Generally, in optical devices, such as a liquid crystal display element, an organic electroluminescent (EL) element, and a solid-state image sensor, a protective film is provided in order to prevent that an element surface is exposed to a solvent or heat during a manufacturing process. This protective film has high adhesion to the substrate to be protected, high solvent resistance, and also requires performance such as transparency and heat resistance.

When such a protective film is used as a protective film of a color filter used in a color liquid crystal display device or a solid-state image sensor, generally, the performance of flattening the color filter or the black matrix resin of the underlying substrate, that is, the performance as a flattening film To be required. In particular, when manufacturing a color liquid crystal display device of the STN method or the TFT method, it is necessary to perform a very precise bonding accuracy of the color filter substrate and the counter substrate, and it is essential to make the cell gap between the substrates uniform. In addition, in order to maintain the transmittance of light passing through the color filter, high transparency is required for these planarization films, which are protective films.

On the other hand, cost reduction and weight reduction are examined by introducing a phase difference material into the cell of a liquid crystal display recently, The material which photocured after apply | coating and orienting a liquid crystal monomer to such a phase difference material is generally used. In order to orient this retardation material, the underlayer film needs to be a material having an orientation after rubbing treatment. Therefore, after forming a liquid crystal aligning layer on the overcoat of a color filter, a phase difference material is formed (refer FIG. 2 (a)). If it is possible to form a film (see Fig. 2 (b)) which also serves as an overcoat of the liquid crystal alignment layer and the color filter, such a material is strongly required in that a large merit such as low cost and reduced number of processes can be obtained. have.

Generally, the acrylic resin with high transparency is used for the overcoat of this color filter. For these acrylic resins, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and ester solvents such as ethyl lactate and butyl lactate are widely used from the viewpoint of safety and handling properties. Such acrylic resin is providing heat resistance and solvent resistance by thermosetting or photocuring (patent document 1, 2). However, in the conventional thermosetting and photocurable acrylic resins, proper transparency and flatness are exhibited, but even when such a flattening film is rubbed, sufficient orientation cannot be exhibited.

On the other hand, the material which consists of solvent-soluble polyimide and a polyamic acid is used normally for a liquid crystal aligning layer. It is reported that these materials impart solvent resistance by completely imidating at the time of post-baking and exhibit sufficient orientation by rubbing treatment (Patent Document 3). However, when viewed as a flattening film of a color filter, there existed a problem that planarization and transparency fell significantly. In addition, polyimide and polyamic acid are soluble in solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone, but have low solubility in glycol solvents and ester solvents, and thus are applicable to flattening film production lines. Was difficult.

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

The present invention has been made on the basis of the above circumstances, and the problem to be solved is not only exhibiting high solvent resistance, liquid crystal alignment, heat resistance, high transparency and high flattening property after the cured film is formed, The present invention provides a material which can be dissolved in a glycol solvent or a lactic acid ester solvent applicable to a production line of a flattening film of a color filter.

MEANS TO SOLVE THE PROBLEM This inventor discovered this invention as a result of earnestly researching in order to solve the said subject.

That is, as a 1st viewpoint, it is related with the polyester composition for thermosetting film formation containing (A) component, (B) component, and (C) component.

(A) component: Polyester obtained by making tetracarboxylic dianhydride and a diol compound react,

(B) component: The epoxy compound which has 2 or more of epoxy groups,

(C) component: The amino group containing carboxylic acid compound obtained by making a diamine compound, dicarboxylic anhydride, and tetracarboxylic dianhydride react.

As a 2nd viewpoint, it is related with the polyester composition for thermosetting film formation as described in a 1st viewpoint whose said (A) component is polyester containing the structural unit represented by following formula (1).

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

As a 3rd viewpoint, the said (A) component is polyester obtained by making tetracarboxylic dianhydride represented by following formula (i) and the diol compound represented by formula (ii) react to a 1st viewpoint or a 2nd viewpoint. It relates to the polyester composition for thermosetting film formation described.

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

As a 4th viewpoint, in said Formula (1), A represents at least 1 sort (s) of group chosen from group represented by following formula (A-1)-formula (A-8), B is a following formula (B-1) The polyester composition for thermosetting film formation as described in a 2nd viewpoint or a 3rd viewpoint which shows at least 1 sort (s) of group chosen from group represented by the formula (I)-(B-5).

As a 5th viewpoint, the weight average molecular weight of polyester which is (A) component is related with the polyester composition for thermosetting film formation in any one of 1st viewpoint to 4th viewpoint which is 1,000-30,000 in polystyrene conversion.

As a 6th viewpoint, (C) component is the amino group containing carboxylic acid compound obtained by making 2 mol of diamine compounds and 2 mol of dicarboxylic anhydrides react with respect to 1 mol of tetracarboxylic dianhydrides, 1st viewpoint thru | or 5th It relates to the polyester composition for thermosetting film formation in any one of a viewpoint.

As a 7th viewpoint, (C) component is any of 1st viewpoint thru | or 5th viewpoint which is an amino-group containing carboxylic acid compound obtained by making the compound represented by following formula (iii), (iv) and (v) react. It relates to the polyester composition for thermosetting film formation of description.

(In said Formula (iii) and (iv), P and Q respectively independently represent a divalent organic group, and in Formula (v), Z represents a tetravalent organic group.)

As an 8th viewpoint, Any of the 1st viewpoint thru | or a 7th viewpoint which contains 3-50 mass parts (B) component and 5-80 mass parts (C) component based on 100 mass parts of (A) component. It relates to the polyester composition for thermosetting film formation of description.

As a 9th viewpoint, it further relates to the polyester composition for thermosetting film formation as described in any one of 1st viewpoint thru | or 8 viewpoint which contains a bismaleimide compound as (D) component.

As a 10th viewpoint, it is related with the polyester composition for thermosetting film formation as described in a 9th viewpoint containing 0.5-50 mass parts (D) component based on 100 mass parts of (A) component.

As a 11th viewpoint, it is related with the cured film obtained using the polyester composition for thermosetting film formation in any one of a 1st viewpoint thru | or a 10th viewpoint.

As a 12th viewpoint, it is related with the liquid crystal aligning layer obtained using the polyester composition for thermosetting film formation in any one of a 1st viewpoint thru | or a 10th viewpoint.

Since the polyester composition for thermosetting film formation of this invention can form the cured film which has liquid crystal aligning ability with high planarization property, high transparency, high solvent resistance, and high heat resistance, it can be used as a formation material of a liquid crystal aligning film or a planarization film. Can be. In particular, since the liquid crystal aligning film and the overcoat layer of the color filter which were formed independently independently can be simultaneously formed as a "liquid crystal aligning layer" which has both the characteristics, the low cost by simplifying a manufacturing process and reducing the number of processes It can realize the sum.

Moreover, since the polyester composition for thermosetting film formation of this invention is soluble in a glycol type solvent and a lactic acid ester solvent, it can be used suitably for the production line of the planarization film which mainly uses these solvents.

1 is a model diagram showing a cured film formed when the polyester composition for thermosetting film formation of the present invention is applied to a stepped substrate.
Fig. 2 is a model diagram showing a comparison between a liquid crystal cell (a) in which a liquid crystal alignment film is formed according to the prior art and a liquid crystal cell (b) in which a flattening film is formed using the polyester composition for thermosetting film formation of the present invention. .

As mentioned above, in the cured film of the acrylic resin system and polyimide system proposed conventionally, there was no thing which fully satisfy | fills all the performances, such as planarization property, transparency, orientation property, which are required for a liquid crystal aligning film and a planarization film.

Moreover, although proposals for the use of polyesters (see Japanese Patent Application Laid-Open No. H5-158055 and Japanese Patent Application Laid-Open No. 2002-229039) have been made until now, they have not all had thermosetting properties. Solvent resistance of the formed film was not good.

This invention has the characteristics that the performance improvement mentioned above was aimed at using the thermosetting polyester, ie, the epoxy compound which has polyester of (A) component and two or more epoxy groups of (B) component, It is a polyester composition for thermosetting film formation containing the amino-group containing carboxylic acid compound of (C) component. And in addition to (A) component, (B) component, and (C) component, it is the polyester composition for thermosetting film formation which can contain even a bismaleimide compound as (D) component.

Hereinafter, each component is explained in full detail.

[(A) component]

Polyester of (A) component becomes like this. Preferably it is polyester containing the structural unit represented by following formula (1), More preferably, it is polyester which consists of a structural unit represented by Formula (1).

In the above formula, A represents a tetravalent organic group in which four bonds are bonded to an alicyclic or aliphatic group, and B represents a divalent organic group in which two bonds are bonded to an alicyclic or aliphatic group.

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

In the formula, A ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, and more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, the arbitrary hydrogen atoms contained in the A ¹ group may be each 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.

Herein, 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 combine to form a ring, a temporary exchangeable hydrocarbon group, such as a norbornene group and an adamantane group, or a part or all becomes hydrogenated condensed polycyclic hydrocarbon group, for example.

In the above formula, 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 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 is represented.

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

The preferable specific example of A which is a tetravalent organic group in Formula (1) is shown to following formula (A-1)-formula (A-8). Among groups represented by the following (A-1) to formula (A-8), A is particularly preferably a group selected from formula (A-1) or (A-2).

In said formula (1), B represents the bivalent organic group which two bond water couple | bonded with an alicyclic group or an aliphatic group, Preferably it is group represented by following formula (1B1) or formula (1B2).

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

Herein, 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 combine to form a ring, a temporary exchangeable hydrocarbon group, such as a norbornene group and an adamantane group, or a part or all becomes hydrogenated condensed polycyclic hydrocarbon group, for example.

In addition, B ² represents a phenylene group.

In the formula, 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 substituted with a fluorine atom, and preferably, a single bond or carbonyl group And 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, and preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

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.

In addition, k represents 0 or 1.

The preferable specific example of B which is a divalent organic group in Formula (1) is shown to following formula (B-1)-formula (B-5). Among the groups represented by the following (B-1) to formula (B-5), it is particularly preferable that B is a group selected from (B-1) to (B-4).

It is preferable that the polyester of (A) component contains at least 1 sort (s) of structure chosen from the group which A has from group represented by Formula (1A1)-formula (1A3) among the structural units represented by Formula (1). However, it may contain structures other than the group represented by Formula (1A1)-Formula (1A3). Under the present circumstances, if the structure of polyester is formed, the structure will not be specifically limited, It is preferable that it is at least 1 sort (s) of structure chosen from the group which consists of group represented by following formula (1A4)-formula (1A5).

Wherein 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 substituted with a fluorine atom And 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.

In particular, 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, and R ⁹ is an ether group, a carbon source It is preferably 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, and R ¹⁰ is a carbonyl group, an ether group, a sulfonyl group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a fluorine atom It is preferably a substituted hydrocarbon group of 1 to 5 carbon atoms.

H represents 0 or 1;

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

In the polyester of (A) component used by this invention, in the structural unit represented by the said Formula (1), at least 1 selected from the group which consists of group represented by said Formula (1A1)-formula (1A3). It is preferable to contain at least 60 mol% or more of a structural unit of a species.

The weight average molecular weight of the polyester of (A) component becomes like this. Preferably it is 1,000-30,000, More preferably, it is 1,500-10,000. When the weight average molecular weight of the polyester of (A) component is smaller than the said range, there exists a tendency for orientation and solvent tolerance to fall, and when it exceeds the said range, planarization property may fall.

<Production Method of (A) Component>

In this invention, polyester which is (A) component can be obtained by polymerizing tetracarboxylic dianhydride and a diol compound, for example. More preferably, the diol containing the tetracarboxylic dianhydride (henceforth an acid component) containing the tetracarboxylic dianhydride represented by following formula (i), and the diol compound represented by following formula (ii). It is obtained by making a compound (henceforth a diol component) react.

In said formula, A and B are the same as the definition demonstrated by Formula (1) mentioned above, and a preferable aspect is also the same as that mentioned above.

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

The polyester which is the said (A) component can use not only tetracarboxylic dianhydride represented by said formula (i) as an acid component, but also tetracarboxylic dianhydride (henceforth another acid dianhydride) other than that. Can be. Under the present circumstances, another acid dianhydride is not specifically limited unless the effect of this invention is reduced. Preferably, it is tetracarboxylic dianhydride represented by following formula (i2).

Here, W of said Formula (i2) is at least 1 sort (s) of structure chosen from the group which consists of group represented by Formula (1A4) and Formula (1A5) defined by Formula (1) mentioned above, R <^8> , R <^9> , R ¹⁰ and h are also the same as defined above.

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

In this invention, it is preferable that the tetracarboxylic dianhydride represented by Formula (i) contains at least 60 mol% or more in an acid component.

In the polyester of the said (A) component, the compounding ratio of the total amount (the total amount of an acid component) and the total amount (the total amount of a diol component) of a tetracarboxylic dianhydride, ie, <the total mole number of a diol compound> / <tetracarboxylic acid The total number of moles of the dianhydride compound> is preferably 0.5 to 1.5. As in the normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the resulting polyester and the higher the molecular weight.

In order to avoid the fall of storage stability, it is preferable that the polyester of (A) component makes the terminal into an acid anhydride terminal.

The terminal of the polyester changes depending on the blending ratio of the acid component and the diol component. For example, when an acid component is made to overreact, the terminal becomes an acid anhydride easily.

In addition, when superposing | polymerizing using a diol component excessively, a terminal becomes a hydroxyl group easily. In this case, the carboxylic acid anhydride can be reacted with the terminal hydroxyl group, and the terminal hydroxyl group can be sealed 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, and 4-methyl anhydride. -1,2-cyclohexanedicarboxylic anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid anhydride, tetrahydrophthalic anhydride, methyltetra Hydrophthalic anhydride, bicyclo [2.2.2.] Octene-2,3-dicarboxylic acid anhydride, and the like.

In manufacture of the polyester of the said (A) component, the reaction temperature of an acid component and a diol component can select arbitrary temperature of 50-200 degreeC, Preferably it is 80-170 degreeC. For example, polyester can be obtained by reaction temperature 100 to 140 degreeC and reaction time 2 to 48 hours.

In addition, the reaction temperature at the time of protecting a terminal hydroxyl group by an acid anhydride can select arbitrary temperature of 50-200 degreeC, Preferably it is 80-170 degreeC.

The reaction between the acid component and the diol component is usually carried out in a solvent. As a solvent which can be used at this time, if it does not contain the functional group reacting with an acid anhydride, such as a hydroxyl group and an amino group, it will not specifically limit. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea , Dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-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, ethyl 2-ethoxypropionate, and the like. .

These solvents may be used alone or in combination, but propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and applicability of the color filter to the overcoat agent line.

Moreover, even if it is a solvent which does not melt | dissolve polyester, it can also mix and use for the said solvent in the range which does not precipitate the polyester produced | generated by the polymerization reaction.

In addition, a catalyst can also be used at the time of reaction of the said acid component (formula (i and formula (i2))) with a diol component (formula (ii)).

As a specific example of the catalyst used at the time of superposition | polymerization of polyester, benzyl trimethyl ammonium chloride, benzyl trimethyl ammonium bromide, benzyl triethyl ammonium chloride, benzyl triethyl ammonium bromide, benzyl tripropyl ammonium chloride, benzyl tripropyl ammonium bromide, tetra Quaternary ammonium salts such as methyl ammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, And quaternary phosphonium salts such as ethyltriphenylphosphonium chloride and ethyltriphenylphosphonium bromide.

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

<(B) component>

As an epoxy compound which has two or more epoxy groups which are (B) component of this invention, For example, tris (2, 3- epoxypropyl) isocyanurate, 1, 4- butanediol diglycidyl ether, 1, 2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenylglycidyl ether, 1,1,3-tris [ p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N- diglycidylaniline), 3, 4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimetholethane triglycidyl ether, bisphenol-A- diglycidyl ether, pentaerythritol polyglycidyl ether, etc. are mentioned.

Moreover, since it is easy to obtain, you may use a compound which is a commercial item. Although the specific example (brand name) is given to the following, it is not limited to these: Epoxy resin which has amino groups, such as YH-434 and YH434L (made 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, Ceroxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Bisphenol A, such as Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote1009, Epikote 1010, Epikote 828 (above, Yuka Shell Epoxy Co., Ltd. (current, Japan Epoxy Resin Co. Ltd.)) Type epoxy resins; Bisphenol F-type epoxy resins such as Epikote 807 (manufactured by Yuka Shell Epoxy Co., Ltd. (present, Japan Epoxy Resin Co. Ltd.)); Phenolic, such as Epikote 152, Epikote 154 (above, Yuka Shell Epoxy Co., Ltd. (present, Japan Epoxy Resin Co. Ltd.), EPPN 201, EPPN 202 (above, Nippon Kayaku Co., Ltd.) Novolac type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Yuka Shell Epoxy Co., Ltd. (present, Cresol novolak-type epoxy resins such as those produced by Japan Epoxy Resin Co. Ltd.); Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, made by CIBA-GEIGYA.G), Epiclon 200, Epiclon 400 (or above, Dainippon Ink and Chemicals, Inc. (currently manufactured by DIC Corporation), Epikote 871, Epikote 872 (above, manufactured by Yuka Shell Epoxy Co., Ltd. (currently manufactured by Japan Epoxy Resin Co. Ltd.), ED-5661, Alicyclic epoxy resins such as ED-5662 (above, manufactured by Celanese Coating Co.); Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421, Denacol EX-313, Denacol EX-314, 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, if it has an epoxy group, it can use without a restriction | limiting in particular.

The polymer which has the said epoxy group can be manufactured by addition polymerization using the addition polymerization monomer which has an epoxy group, for example. As an example, an addition polymer such as polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and the like And polycondensation polymers, such as an epoxy novolak, are mentioned.

Or the polymer which has the said epoxy group can also be manufactured by reaction of the high molecular compound which has a hydroxyl group, and the compound which has epoxy groups, such as epichlorohydrin and glycidyl tosylate.

As a weight average molecular weight of such a polymer, it is 300-200,000, for example.

The epoxy compound which has 2 or more of these epoxy groups can be used individually or in combination of 2 or more types.

It is preferable that content of the epoxy compound which has two or more epoxy groups of (B) component in the polyester composition for thermosetting film formation of this invention is 3-50 mass parts based on 100 mass parts of polyester of (A) component. More preferably, it is 5-40 mass parts, Especially preferably, it is 10-30 mass parts. When this ratio is too small, the solvent resistance and heat resistance of the cured film obtained from the polyester composition for thermosetting film formation fall, and when too large, solvent resistance may fall or storage stability may fall.

&Lt; Component (C) >

(C) component is an amino-group containing carboxylic compound obtained by making a diamine compound, a dicarboxylic anhydride, and tetracarboxylic dianhydride react. Specifically, it is an amino group containing carboxylic compound obtained by making 2 mol of diamine compounds and 2 mol of dicarboxylic anhydrides react with respect to 1 mol of tetracarboxylic dianhydrides.

As said diamine compound, dicarboxylic anhydride, tetracarboxylic dianhydride, the compound represented by following formula (iii)-(v) is mentioned, for example.

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, the compound represented by following formula (2) is made by making the diamine compound represented by said Formula (iii), the dicarboxylic anhydride represented by Formula (iv), and the tetracarboxylic dianhydride represented by Formula (v) react. Is obtained.

In Formula (2), P, Q, and Z are the same as the definition demonstrated by said Formula (iii), Formula (iv), and Formula (v).

In this invention, only 1 type may be used for a diamine compound, dicarboxylic acid anhydride, and tetracarboxylic dianhydride, respectively, and multiple types may be used for it. Therefore, as an amino-group containing carboxylic acid compound of (C) component of this invention, not only 1 type but multiple types of compounds represented by Formula (2) can be used.

Especially, it is preferable that said P and Q are bivalent organic groups which have ring structure each independently. Here, as a ring structure, a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon are mentioned.

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

Accordingly, specific examples of the diamine compound having such a ring structure include the following: p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-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 -Diallyl-2,4-diaminoaniline, N, N-diallyl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2- (4-aminophenyl) ethylamine, 2- (3-aminophenyl) ethylamine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'- Diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dihydroxy -4,4'-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'-diaminodiphenylether 3,3'-diaminodiphenylether, 3,4'-diaminodi Phenylether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4 '-Diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) amine, N-methyl (3,4'-dia Minodiphenyl) 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, 4,4'-diaminotran, 1,3-bis (4- Minophenyl) propane, 1,3-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis ( 3-amino-4-methylphenyl) propane, 2,2-bis (4-aminophenyl) hexafuluropropane, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3 -Amino-4-methylphenyl) hexafuluropropane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4-aminophenoxy) butane, 1,5-bis (4-amino Phenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9 -Bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy Dodecane, bis (4-aminophenyl) propanedioate, bis (4-aminophenyl) butanedioate, bis (4-aminophenyl) pentanedioate, bis (4-aminophenyl) hexanedioate, bis (4- Army Phenyl) heptanedioate, bis (4-aminophenyl) octanedioate, bis (4-aminophenyl) nonanddioate, bis (4-aminophenyl) decanedioate, 1,4-bis (4-aminophenyl) Benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4 -Aminobenzyl) benzene, 1,3-bis (4-aminobenzyl) benzene, bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenyl Lenbis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4- Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), N, N ' -(1,4-phenylene) bis (4-aminobenzamide), N, N '-(1,3-phenylene) bis (4-aminobenzamide), N, N'-(1,4- Phenylene) bis (3-aminobenzamide), N, N '-(1,3-phenylene) bis (3-aminobenzamide), bis (4-aminophenyl) terephthalamide, bis (3-aminophenyl ) Terephthalamide, bis (4-aminophenyl) isophthalamide, bis (3-aminophenyl) isophthalamide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafuluropropane, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,6-diaminopyridine, 2,4-diaminopyridine , 2,4-diamino-1,3,5-triazine, 2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, 3,6-diaminodibenzofuran, 2,6 -Diaminocarbazole, 2,7-diaminocarbazole, 3,6-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.

Moreover, as said ring structure which Q has in said formula (iv), a benzene ring, the alicyclic ring of 4-8 carbon atoms, and the condensed polycyclic hydrocarbon of 7-16 carbon atoms are preferable. More preferably, it is alicyclic.

Specific examples of the dicarboxylic acid anhydride having such a ring structure include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride And itaconic anhydride, tetrahydrophthalic anhydride, etc. are mentioned.

In the formula (v), Z is preferably a tetravalent organic group having a ring structure. Here, as a ring structure, a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon are mentioned. More preferably, it is a tetravalent organic group which four bond water couple | bonded with an alicyclic group or an aliphatic group, More preferably, it is represented by a following formula (Z-1), a formula (Z-2), or a formula (Z-3). Qi.

In the formula, Z ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, and more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Here, arbitrary hydrogen atoms contained in the Z ¹ group may be each 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.

Herein, 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 combine to form a ring, a temporary exchangeable hydrocarbon group, such as a norbornene group and an adamantane group, or a part or all becomes hydrogenated condensed polycyclic hydrocarbon group, for example.

In the above formula, 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 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 is represented.

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

Preferred specific examples of Z include the above formulas (A-1) to (A-8). Among these, it is especially preferable that it is group chosen from Formula (A-1) or (A-2).

Examples of the tetracarboxylic dianhydride represented by the formula (v) include pyromellitic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride and 1,2,5,6-naphthalene tetracarboxylic dianhydride. , 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-anthracenetetracarboxylic 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) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,5-dicarboxymethylte Phthalic dianhydride, 4,6-dicarboxymethylisophthalic dianhydride, 4- (2,5-dioxotetrahydro-3-furanyl) phthalic anhydride, 1,4-bis (2,5-dioxotetrahydro -3-furanyl) benzene, 1,4-bis (2,6-dioxotetrahydro-4-pyranyl) benzene, 1,4-bis (2,5-dioxotetrahydro-3-methyl-3 -Furanyl) benzene, 1,4-bis (2,6-dioxotetrahydro-4-methyl-4-pyranyl) benzene, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclo Butanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,2,4,5-cyclohexanetetra Carboxylic dianhydride, 4- (2,5-dioxotetrahydro-3-furanyl) -cyclohexane-1,2-dicarboxylic acid anhydride, 5- (2,5-dioxotetrahydro-3-fura Yl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid 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 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-tricarboxynorbornene-2-acetic acid dianhydride, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid Dianhydrides, tetracyclo [4.4.1.0 ^2,5 .0 ^7,10 ] undecane-3,4,8,9-tetracarboxylic dianhydride, hexahexa [6.6.0.1 ^2,7 .0 ^3,6 . 1 ^9,14 .0 ^10,13] hexadecane -4,5,11,12- Te Lacarboxylic dianhydride, 1,4-bis (2,5-dioxotetrahydro-3-furanyl) hexane, 4-bis (2,6-dioxotetrahydro-4-pyranyl) hexane and the like Can be.

In the preparation of the compound of the component (C), the reaction temperature of the tetracarboxylic dianhydride, the diamine compound and the dicarboxylic anhydride may be selected from 5 to 50 ° C, preferably 10 to 35 ° C. . In order to avoid polymerisation during the reaction, first, the diamine compound is dissolved in an arbitrary solvent, and then tetracarboxylic dianhydride and dicarboxylic anhydride are dissolved in a water-cooled state at 23 ° C in order to avoid polymerization by exothermic heat during the reaction. It is more preferable to add.

The said reaction is normally performed in a solvent. As a solvent which can be used at this time, if it does not contain the functional group reacting with an acid anhydride, such as a hydroxyl group and an amino group, it will not specifically limit. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylimidazole, dimethyl sulfoxide Said, tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-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, ethyl 2-ethoxypropionate , Methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, cyclohexanol, ethyl acetate Butyl acetate, ethyl lactate, butyl lactate, and the like.

These solvents may be used alone or may be used after mixing, but from the viewpoint of solubility, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, Dimethylimidazole is preferred.

Moreover, even if it is a solvent which does not melt | dissolve an amino-group containing carboxylic acid compound, it can also be mixed and used for the said solvent in the range which does not precipitate the amino-group-containing carboxylic acid compound produced by a polymerization reaction.

It is preferable that content of (C) component in the polyester resin composition for thermosetting film formation of this invention is 5-80 mass parts based on 100 mass parts of polyester polymers of (A) component, More preferably, it is 5 To 60 parts by mass. When this ratio is too small, the orientation of the cured film obtained from the polyester resin composition for thermosetting film formation falls, while when too large, the transmittance | permeability may fall or planarization property may fall.

<(D) component>

In this invention, you may contain the bismaleimide compound represented by following formula (3) as (D) component.

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

In the formula, X is an organic group consisting of an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure and an aromatic group, or a combination of a plurality of organic groups selected from these groups. And X may also contain bonds, such as an ester bond, an ether bond, an amide bond, and a urethane bond.

As such a bismaleimide compound, For example, N, N'-3,3-diphenylmethanebismaleimide, N, N '-(3,3-diethyl-5,5-dimethyl) -4 , 4-diphenyl-methanebismaleimide, N, N'-4,4-diphenylmethanebismaleimide, 3,3-diphenylsulfonbismaleimide, 4,4-diphenylsulfonbismaleimide, N , N'-p-benzophenonebismaleimide, N, N'-diphenylethanebismaleimide, N, N'-diphenyletherbismaleimide, N, N '-(methylenedi-ditetrahydrophenyl) Bismaleimide, N, N '-(3-ethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3, 3-dimethyl) -4,4-diphenylmethanebismaleimide, N, N '-(3,3-diethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3,3-dichloro) -4,4-diphenylmethanebismaleimide, N , N'-isophoronebismaleimide, N, N'-tolidine bismaleimide, N, N'-diphenylpropanebismaleimide, N, N'-naphthalenebismaleimide, N, N'-m- Phenylenebismaleimide, N, N'-5-methoxy-1, 3-phenylenebismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-chloro-4- (4-maleimidephenoxy) phenyl) Propane, 2,2-bis (3-bromo-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-ethyl-4- (4-maleimidephenoxy) phenyl) propane , 2,2-bis (3-propyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-isopropyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-butyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-methoxy-4- (4-maleimidephenoxy) phenyl) propane, 1 , 1-bis (4- (4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3-methyl-4- (4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3 -Chloro-4- (4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3-bromo-4- (4-maleimidephenoxy) phenyl) ethane, 3,3-bis (4- (4-maleimidephenoxy) phenyl) pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 1, 1,1,3 , 3,3-hexafluoro-2,2-bis (3,5-dimethyl-4- (4-maleimidephenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro -2,2-bis (3,5-dibromo-4- (4-maleimidephenoxy) phenyl) propane, N, N'-ethylenedimaleimide, N, N'-hexamethylenebismaleimide, N, N'-dodecamethylenebismaleimide, N, N'-m-xylenebismaleimide, N, N'-p-xylenebismaleimide, N, N'-1,3-bismethylenecyclohexanebis Maleimide, N, N'-2,4- toylene bismaleimide, N, N'-2,6- toylene bismaleimide, etc. are mentioned. These bismaleimide compounds are not specifically limited to what was mentioned above. These can use together single or 2 types or more of components.

Of these bismaleimides, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, N, N'-4,4-diphenylmethanebismaleimide, N, N '-(3,3 Aromatic bismaleimides such as -diethyl-5,5-dimethyl) -4,4-diphenyl-methanebismaleimide are preferred.

Moreover, in order to obtain higher planarity among these aromatic bismaleimide, it is preferable that it is molecular weight 1,000 or less.

In this invention, it is preferable that the use ratio of the bismaleimide compound of (D) component is 0.5-50 mass parts with respect to 100 mass parts of polyester of (A) component, More preferably, it is 1-30 mass parts, Especially Preferably it is 2-20 mass parts. When this ratio is too small, the flattening property of the cured film obtained from the polyester composition for thermosetting film formation falls, and when too large, the transmittance | permeability of a cured film may fall or a coating film may become rough.

<Solvent>

The polyester composition for thermosetting film formation of this invention is used in the solution state melt | dissolved in the solvent in many cases. The solvent used at this time melt | dissolves (A) component-(C) component, if needed, (D) component and / or the other additive mentioned later, if it is a solvent which has such a solubility, the kind, structure, etc. Is not specifically limited.

As such a solvent, the solvent used for superposition | polymerization of (A) component, and the following solvent are mentioned. For example, methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, butyl lactate, cyclohexanol, acetic acid Ethyl, butyl acetate, ethyl lactate, butyl lactate, etc. are mentioned.

These solvents can be used individually by 1 type or in combination of 2 or more type.

<Other additives>

In addition, the polyester composition for thermosetting film formation of this invention is an adhesive adjuvant, such as surfactant, a rheology regulator, and a silane coupling agent, a pigment, dye, a storage stabilizer, as needed, unless the effect of this invention is reduced. , Antifoaming agents, dissolution accelerators such as polyhydric phenol and polycarboxylic acid, 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-butyl-phenol, 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- (3', 5'-di-t-butyl-4'-hydroxyphenyl) propio Nate], acetone bis (3,5-di-t-butyl-4-hydroxyphenyl) mercaptor, 4,4'-methylenebis (2,6-di-t-butylphenol), 3- (3 , 5-di-t-butyl-4-hydroxyphenyl) methyl propionate, 4,4'-thiodi (2,6-di-t-butylphenol), tris (3,5-di-t-butyl- 4-hydroxybenzyl) isocyanuric acid, bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide, etc. are mentioned.

<Polyester composition for thermosetting film formation>

The polyester composition for thermosetting film formation of this invention contains the polyester of (A) component, the epoxy compound which has two or more epoxy groups of (B) component, and the amino-group containing carboxylic acid compound of (C) component, and wants The bismaleimide compound of the case (D) component, and also a composition which can contain 1 or more types of other additives. And these are usually used as a solution which melt | dissolved in the solvent.

Especially, the preferable example of the polyester composition for thermosetting film formation of this invention is as follows.

[1]: Polyester composition for thermosetting film formation containing 3-50 mass parts (B) component and 5-80 mass parts (C) component based on 100 mass parts of (A) component.

[2]: Polyester composition for thermosetting film formation containing 3-50 mass parts (B) component, 5-80 mass parts (C) component, and a solvent based on 100 mass parts of (A) component.

[3]: Thermosetting film containing 3 to 50 parts by mass of (B) component, 5 to 80 parts by mass of (C) component and 0.5 to 50 parts by mass of (D) component based on 100 parts by mass of (A) component. Polyester composition for formation.

[4]: heat containing 3 to 50 parts by mass of (B) component, 5 to 80 parts by mass of (C) component, 0.5 to 50 parts by mass of (D) component and solvent based on 100 parts by mass of (A) component Polyester composition for cured film formation.

The mixing | blending ratio, preparation method, etc. when the polyester composition for thermosetting film formation of this invention is a form of a solution are demonstrated in detail below.

Although the ratio of solid content in the polyester composition for thermosetting film formation of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, it is 1-80 mass%, Preferably it is 5-60 mass %, More preferably, it is 10-50 mass%. Here, solid content means what remove | excluding the solvent from the all components of the polyester composition for thermosetting film formation.

Although the preparation method of the polyester composition for thermosetting film formation of this invention is not specifically limited, As the preparation method, (A) component is melt | dissolved in a solvent, for example, (B) component, (C) in this solution. ), The method of mixing (D) component in a predetermined ratio and making it into a uniform solution, or the method of adding and adding another additive further as needed at the suitable stage of this preparation method. Can be.

In preparing the polyester composition for thermosetting film formation of this invention, the solution of the polyester obtained by the polymerization reaction in a solvent can be used as it is. In this case, when (B) component, (C) component, (D) component, etc. are put into the solution of this (A) component, and it is set as a uniform solution, a solvent is further added for the purpose of concentration adjustment. You can also put in. At this time, the solvent used in the production | generation process of polyester and the solvent used for density | concentration adjustment at the time of preparation of the polyester composition for thermosetting film formation may be the same, and may differ.

And it is preferable to use, after filtering the prepared solution of the polyester composition for thermosetting film formation using a filter etc. which have a pore size of about 0.2 micrometer.

<Film, Cured Film, and Liquid Crystal Alignment Layer>

The polyester composition for forming a thermosetting film of the present invention may be a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, etc., a glass substrate, Rotational coating, flow coating, roll coating, slit coating, slit followed by rotation on a quartz substrate, an ITO substrate, or the like) or a film (for example, a resin film such as a triacetylcellulose film, a polyester film, an acrylic film, etc.) It is apply | coated by application | coating, inkjet coating, printing, etc., and then preliminary drying (prebaking) with a hotplate or oven etc. can form a coating film. Then, a film is formed by heat-processing this coating film.

As conditions of this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70 degreeC-160 degreeC, and time for 0.3 to 60 minutes are employ | adopted, for example. Heating temperature and a heat time become like this. Preferably they are 80 degreeC-140 degreeC, and 0.5 to 10 minutes.

In addition, the film thickness of the film formed from the polyester composition for thermosetting film formation is 0.1-30 micrometers, for example, and can select suitably in consideration of the level | step difference of the board | substrate to be used, and the optical and electrical property.

The postbaking is generally carried out at a heating temperature selected from the range of 140 ° C. to 250 ° C. for 5 to 30 minutes in the case of a hot plate and 30 to 90 minutes in the oven.

By hardening the polyester composition for thermosetting film formation of this invention based on conditions mentioned above, the level | step difference of a board | substrate can fully be planarized and the cured film which has high transparency can be formed.

Thus formed cured film can function as a layer which orientates a liquid-crystal material orientation layer, ie, a compound which has liquid crystallinity, by performing a rubbing process.

Generally as conditions of a rubbing process, the conditions of 300 to 1,000 rpm of rotation speeds, 3 to 200 mm / sec of feed rates, and 0.1-1 mm of indentation amount are used.

Thereafter, residues generated through rubbing are removed by ultrasonic cleaning using pure water or the like.

After apply | coating a phase difference material on the liquid crystal aligning layer formed in this way, it can photocure by making a phase difference material into a liquid crystal state, and can form the layer which has optical anisotropy.

As a retardation material, the liquid crystal monomer which has a polymeric group, the composition containing this, etc. are used, for example.

And when the material which forms a liquid crystal aligning layer is a film, it is useful as an optically anisotropic film.

In addition, after bonding two board | substrates which have the liquid crystal aligning layer formed as mentioned above so that a liquid crystal aligning layer may face through a spacer, the liquid crystal is inject | poured between these board | substrates, and the liquid crystal display element in which the liquid crystal was orientated You can do

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

In addition, the polyester composition for forming a thermosetting film of the present invention has at least the required level of flattening properties, so that a protective film, a flattening film, an insulating film, or the like in various displays such as a thin film transistor (TFT) type liquid crystal display device, an organic EL device, and the like. It is also useful as a material for forming a cured film of the present invention, 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 element, an insulating film of an organic EL element, and the like.

[Example]

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

[Weak symbol used in the Example]

The meaning of the abbreviation used in the following Example is as follows.

<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

<Amino group-containing carboxylic acid compound raw material>

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

CBDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

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

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

DDS: 4,4'-diaminodiphenylsulfone

<Polyimide precursor raw material>

CBDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride

pDA: p-phenylenediamine

<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 .. Ceroxide P-2021 (Product Name) (Compound name: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate)

<Bismaleimide compound>

BMI1: N, N '-(3,3-diethyl-5,5-dimethyl) -4,4-diphenyl-methanebismaleimide

<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 obtained by using the GPC apparatus (Shodex® column KF803L and KF804L) manufactured by JASCO Corporation. Hydrofuran was measured under conditions such that the flow rate was eluted by flowing the column (column temperature 40 ° C.) at a flow rate of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn) and weight average molecular weight (henceforth Mw) were shown by polystyrene conversion value.

Synthesis Example 1

The polyester polymer solution (solid content concentration: 30.0 mass%) was obtained by making HBPDA 12.0g, HBPA 10.2g, THPA 0.95g, and BTEAC0.22g react at 120 degreeC in 54.48g of PGMEA for 19 hours (P1). Mn of the obtained polyester polymer was 2,280 and Mw was 4,200.

&Lt; Synthesis Example 2 &

14.6 g of DA-4P was dissolved in 40.68 g of DMAc, followed by water cooling and holding at 23 ° C. The amino group containing carboxylic acid compound solution (solid content concentration 40.0 mass%) was obtained by making CBDA 4.90g and THPA7.60g react with this solution for 24 hours at 23 degreeC. (A1)

&Lt; Synthesis Example 3 &

4.97 g of DDS was dissolved in 14.95 g of DMAc, followed by water cooling and kept at 23 ° C. The amino group containing carboxylic acid compound solution (solid content concentration 40.0 mass%) was obtained by making CBDA 1.96g and THPA3.04g react at this solution for 24 hours at 23 degreeC. (A2)

&Lt; Synthesis Example 4 &

14.61 g of DA-4P was dissolved in 41.82 g of DMAc, followed by water cooling and holding at 23 ° C. 7.66 g of HBPDA and 7.60 g of THPA were reacted with the solution at 23 ° C. for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration of 40.0% by mass). (A3)

&Lt; Synthesis Example 5 &

The polyester polymer solution (solid content concentration: 30.0 mass%) was obtained by making BPDA40.0g, HBPA 35.3g, THPA3.31g, and BTEAC0.77g react at 120 degreeC in 175.7g of PGMEA for 19 hours (P2). Mn of the obtained polyester polymer was 1,100 and Mw was 2,580.

&Lt; Synthesis Example 6 &

Polyimide precursor solution (solid content concentration: 30.0 mass%) was obtained by making CBDA17.7g and pDA10.2g react in NMP66.4g for 24 hours at 23 degreeC (P3). Mn of the obtained polyimide precursor was 5,800 and Mw was 12,500.

&Lt; Synthesis Example 7 &

As the monomer component, 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, and 28.3 g of MMA were used, and 5 g of AIBN was used as a radical polymerization initiator, and these were polymerized at 150 ° C. solvent PGMEA at a temperature of 60 ° C. to 100 ° C., An acrylic copolymer solution (solid content concentration: 40.0 mass%) was obtained (P4). Mn of the obtained acrylic copolymer solution was 3,800 and Mw was 6,700.

<Examples 1 to 6 and Comparative Examples 1 to 4>

Each composition of Examples 1-6 and Comparative Examples 1-4 was prepared with the composition shown in Table 1, and planarization, solvent tolerance, transmittance | permeability, and orientation property were evaluated about each.

※ P1-P2: Polyester polymer solution

P3: polyimide precursor solution

P4: acrylic copolymer solution

[Evaluation of Flatness]

Each composition of Examples 1 to 6 and Comparative Examples 1 to 4 was applied on a stepped substrate (made of glass) with a height of 0.5 μm, a line width of 10 μm, and an interline space of 50 μm using a spin coater. It prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and formed the coating film of 2.8 micrometers in film thickness. The film thickness was measured using F20 by FILMETRICS. This coating film was heated at the temperature of 230 degreeC for 30 minutes, post-baking was carried out, and the cured film with a film thickness of 2.5 micrometers was formed.

The film thickness difference between the coating film on the stepped substrate line and the coating film on the space is measured (see Fig. 1). )}] Was used to determine the planarization rate.

[Evaluation of Solvent Tolerance]

Each composition of Examples 1 to 6 and Comparative Examples 1 to 4 was applied to a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. A coating film was formed. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film with a film thickness of 2.5 micrometers was formed.

After immersing this cured film in PGMEA or NMP for 60 second, it dried at the temperature of 100 degreeC for 60 second, respectively, and measured the film thickness. (Circle) and thing which showed the decrease of the film thickness after dipping were made into (circle) that there was no change in film thickness after PGMEA or NMP immersion.

[Evaluation of Light Transmittance (Transparency)]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. The coating film of was formed. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

The transmittance | permeability at the wavelength of 400 nm was measured for this cured film using the ultraviolet-visible spectrophotometer (The SHIMADSU UV-2550 model number by Shimadzu Corporation).

[Evaluation of Orientation]

Each of the compositions of Examples 1 to 6 and Comparative Examples 1 to 4 was applied onto an ITO substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds for a film thickness of 2.8 μm. The coating film of was formed. The film thickness was measured using F20 by FILMETRICS. This film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

The cured film was subjected to a rubbing treatment at a rotational speed of 300 rpm, a feed rate of 10 mm / sec, and an indentation amount of 0.45 mm. The rubbed substrate was ultrasonically cleaned for 5 minutes with pure water. After apply | coating the phase difference material which consists of liquid crystal monomers on this board | substrate using a spin coater, it prebaked on the hotplate for 40 second at 100 degreeC, and 30 second at 55 degreeC, and formed the coating film of 1.1 micrometers in thickness. This substrate was exposed to 2,000 mJ in a nitrogen atmosphere. The produced board | substrate was inserted into the deflection plate, and the orientation was visually confirmed. When the board | substrate was inclined at 45 degree | times, and when it did not incline, the thing which remarkably changed the light was made (circle) and the thing which did not change was made into x.

[Evaluation of Heat Resistance]

Each composition of Examples 1 to 6 and Comparative Examples 1 to 4 was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds, followed by a temperature of 230 ° C. Post-baking was performed on the hotplate for 30 minutes at and the cured film was formed, and the film thickness was measured using F20 by FILMETRICS. Thereafter, the cured film was further baked at a temperature of 230 ° C. for 60 minutes on a hot plate to measure the film thickness again, and the amount of change in the film thickness after postbaking was calculated.

[Evaluation result]

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

Examples 1 to 6 had high planarization rate and high heat resistance, and showed resistance to any of PGMEA and NMP. Moreover, all showed the favorable orientation and achieved high transmittance | permeability (transparency) even after high temperature baking.

On the other hand, Comparative Example 1 showed good solvent resistance, orientation, and planarization rate, but very low heat resistance.

In addition, in the comparative example 2, the cured film was not formed.

In addition, Comparative Example 3 showed good solvent resistance, heat resistance, and orientation, but had a very low planarization rate.

In Comparative Example 4, although the results of good flatness, heat resistance, solvent resistance, and transmittance were obtained, the orientation was deteriorated.

As mentioned above, the polyester resin composition for thermosetting film formation of this invention was able to use glycol-type solvents, such as propylene glycol monomethyl ether acetate at the time of cured film formation, Furthermore, the obtained cured film was excellent in light transmittance. Good results were obtained with any performance of solvent resistance, planarization and orientation.

Claims (12)

The polyester composition for thermosetting film formation containing (A) component, (B) component, and (C) component.
(A) component: Polyester obtained by making tetracarboxylic dianhydride and a diol compound react,
(B) component: The epoxy compound which has 2 or more of epoxy groups,
(C) component: The amino group containing carboxylic acid compound obtained by making a diamine compound, dicarboxylic anhydride, and tetracarboxylic dianhydride react. The method of claim 1,
The polyester composition for thermosetting film formation whose said (A) component is polyester containing the structural unit represented by following formula (1).
[Formula 1]

(Wherein A represents a tetravalent organic group having four bonds bonded to an alicyclic group or an aliphatic group, and B represents a divalent organic group having two bonds bonded to an alicyclic or aliphatic group.) The method according to claim 1 or 2,
The polyester composition for thermosetting film formation whose said (A) component is polyester obtained by making tetracarboxylic dianhydride represented by following formula (i) react with the diol compound represented by Formula (ii).
(2)

(Wherein A represents a tetravalent organic group having four bonds bonded to an alicyclic group or an aliphatic group, and B represents a divalent organic group having two bonds bonded to an alicyclic or aliphatic group.) The method according to claim 2 or 3,
In said formula (1), A represents at least 1 sort (s) of group chosen from group represented by following formula (A-1)-formula (A-8), B is following formula (B-1)-formula (B The polyester composition for thermosetting film formation which shows at least 1 sort (s) of group chosen from group represented by -5).
(3)

[Chemical Formula 4]

5. The method according to any one of claims 1 to 4,
The polyester composition for thermosetting film formation whose weight average molecular weight of polyester which is (A) component is 1,000-30,000 in conversion of polystyrene. The method according to any one of claims 1 to 5,
The polyester composition for thermosetting film formation whose (C) component is an amino-group containing carboxylic acid compound obtained by making 2 mol of diamine compounds and 2 mol of dicarboxylic anhydrides react with 1 mol of tetracarboxylic dianhydrides. The method according to any one of claims 1 to 5,
The polyester composition for thermosetting film formation whose (C) component is an amino-group containing carboxylic acid compound obtained by making the compound represented by following formula (iii), (iv), and (v) react.
[Chemical Formula 5]

(In said Formula (iii) and (iv), P and Q respectively independently represent a divalent organic group, and in Formula (v), Z represents a tetravalent organic group.) The method according to any one of claims 1 to 7,
The polyester composition for thermosetting film formation containing 3-50 mass parts (B) component and 5-80 mass parts (C) component based on 100 mass parts of (A) component. The method according to any one of claims 1 to 8,
Furthermore, the polyester composition for thermosetting film formation containing a bismaleimide compound as (D) component. 10. The method of claim 9,
The polyester composition for thermosetting film formation containing 0.5-50 mass parts (D) component based on 100 mass parts of (A) component. The cured film obtained using the polyester composition for thermosetting film formation in any one of Claims 1-10. The liquid crystal aligning layer obtained using the polyester composition for thermosetting film formation in any one of Claims 1-10.

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