KR20120007498A - Polyester composition for forming heat-cured film - Google Patents

Abstract

After the cured film is formed, it exhibits high solvent resistance, liquid crystal alignment, heat resistance, high transparency, and high flattening property, and at the time of forming the cured film, it provides a material that is dissolved in various solvents applicable to manufacturing lines such as flattening films of color filters. Is in.
The polyester composition for thermosetting film formation containing the polyester which is (A) component, the crosslinking agent which is (B) component, and at least 1 sort (s) of diester compound represented by following formula (1) which is (C) component. P represents an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by formula (2), and Q represents an alicyclic group or an alicyclic group or an aliphatic group.

Description

Polyester composition for forming heat-cured film

The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained therefrom. More specifically, it is related with the application of the polyester composition for thermosetting film formation which has high transparency and planarization property, and has liquid crystal aligning ability, high solvent resistance, and heat resistance, this cured film, and this cured film. 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 the element surface from being 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 for a color filter used in a color liquid crystal display device or a solid-state image pickup device, the protective film generally has the capability of flattening the color filter or the black matrix resin of the base substrate, that is, the performance as a flattening film. Required. In particular, when manufacturing a color liquid crystal display device of the STN method or the TFT method, the bonding accuracy between the color filter substrate and the counter substrate must be very precise and the cell gap between the substrates must be uniform. Moreover, in order to maintain the transmittance | permeability of the light which permeate | transmits a color filter, these planarization films which are this protective films require high transparency.

On the other hand, in recent years, cost reduction and weight reduction have been examined by introducing a phase difference material into a cell of a liquid crystal display, and a material obtained by applying and orienting a liquid crystal monomer and orienting such a phase difference material is generally used. In order to orient this retardation material, the underlayer film needs to be a material having orientation after rubbing treatment. For this reason, a phase difference material is formed after forming a liquid crystal aligning layer on the overcoat of a color filter (refer FIG. 2 (a)). If it is possible to form a layer (see Fig. 2 (b)) that combines the liquid crystal alignment layer and the overcoat of the color filter, such a material is strongly demanded because it can bring about great advantages such as low cost and reduced number of processors.

Generally, high transparency acrylic resin 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 in view of safety and handling properties. Such acrylic resins have given heat resistance and solvent resistance by thermosetting or photocuring (Patent Documents 1 and 2). However, in conventional thermosetting or photocurable acrylic resins, proper transparency and flatness are exhibited, but rubbing treatment of such a planarization film does not show sufficient orientation.

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 has been reported that these materials impart solvent resistance by completely imidating during post-baking and exhibit sufficient orientation by rubbing treatment (Patent Document 3). However, in the case of the flattening film of the color filter, there is a problem that the flatness and transparency are greatly reduced. In addition, polyimide and polyamic acid are soluble in solvents such as N-methylpyrrolidone and γ-butyrolactone, but have low solubility in glycol-based solvents and ester-based solvents and are difficult to apply to flattening film production lines. .

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 on the basis of the above circumstances, and the problem to be solved is high solvent resistance, liquid crystal alignment, heat resistance, high transparency, and high flattening property after the cured film is formed, and at the time of forming the cured film, the production line of the flattening film of the color filter It is to provide a material that is dissolved in a glycol-based solvent applicable to the.

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, the polyester for thermosetting film formation containing the polyester which is (A) component, the crosslinking agent which is (B) component, and at least 1 sort (s) of diester compound represented by following formula (1) which is (C) component from a 1st viewpoint. It relates to a composition.

(In formula, P represents a structure which consists of an alicyclic group, an alicyclic group, and an aliphatic group, or a structure represented by Formula (2), and Q shows the group containing the group which consists of an alicyclic group or an alicyclic group and an aliphatic group. In formula (2), R represents an alkylene group.)

From a 2nd viewpoint, in the 1st viewpoint, the diester compound which (1) mol of the diol compound represented by following formula (iii) and 1.7-2 mol of dicarboxylic anhydride represented by following formula (iv) reacted. It relates to a polyester composition for phosphorus thermosetting film formation.

(Wherein P represents an alicyclic group, a group consisting of an alicyclic group and an aliphatic group or a structure represented by formula (2), Q represents a group consisting of an alicyclic group or an alicyclic group and an aliphatic group, and P and Q are each included in each group) Any hydrogen atom to be substituted may be substituted with an aliphatic group, in which R represents an alkylene group.)

From a 3rd viewpoint, in 2nd viewpoint, it is related with the polyester composition for thermosetting film formation in which P represents group represented by a following formula (1P1).

In the formula, P ¹ represents a cyclic saturated hydrocarbon group, and any hydrogen atom in the P ¹ group may be independently substituted with an aliphatic group. R ¹¹ is a single bond, a carbonyl group, an ether group, a sulfonic acid group, or 1 to 1 carbon atoms. A saturated hydrocarbon group of 8 or a saturated hydrocarbon group of 1 to 8 carbon atoms substituted with a fluorine atom, R ¹² and R ¹³ each independently represent a single bond or an alkylene group of 1 to 5 carbon atoms, and h represents 0 or 1 Indicates.)

As a 4th viewpoint, in a 2nd viewpoint or a 3rd viewpoint, it is related with the polyester composition for thermosetting film formation in which Q represents group represented by following formula (1Q1).

(In the formula, Q ¹ represents a carbon atom number of 4 to 8, a cycloalkylene group or a cycloalkyl alkenylene, any hydrogen atom in the group Q ¹ may be substituted with an aliphatic group or a phenyl group. X represents a single bond or a carbon atom number 1 To alkylene groups of 3).

From a 5th viewpoint, in a 1st viewpoint, (C) component relates to the polyester composition for thermosetting film formation containing at least 1 sort (s) of polyhydric ester compound represented by a following formula (1-a).

(In formula, Pa represents the alicyclic group or aliphatic alkyl group which may be interrupted by the oxygen atom or the nitrogen atom, or the structure represented by Formula (2-a), Qa represents an alicyclic group, t represents the integer of 1-5. Ra in formula (2-a) represents an alkylene group.)

As a 6th viewpoint, in any one of a 1st viewpoint thru | or a 5th viewpoint, (A) component relates to the polyester composition for thermosetting film formation which is polyester containing the structural unit represented by following formula (3). .

(In formula, A represents the tetravalent organic group which the 4 bond number couple | bonded with an alicyclic group or an aliphatic group, B shows the bivalent organic group which the 2 bond number couple | bonded with an alicyclic group or an aliphatic group.)

In a seventh aspect, in any one of the first to sixth aspects, the polya (A) component is obtained by reacting a tetracarboxylic dianhydride represented by the following formula (i) with a diol compound represented by the formula (ii): It is related with the polyester composition for thermosetting film formation which is ester.

(In formula, A represents the tetravalent organic group which the 4 bond number couple | bonded with an alicyclic group or an aliphatic group, B shows the bivalent organic group which the 2 bond number couple | bonded with an alicyclic group or an aliphatic group.)

In the eighth aspect, in the sixth or seventh aspect, A in the formula (3) represents at least one group selected from the group represented by the following formulas (A-1) to (A-8), B is related with the polyester composition for thermosetting film formation which shows at least 1 sort (s) of group chosen from group represented by following formula (B-1)-formula (B-5).

As a ninth viewpoint, the weight average molecular weight of the polyester which is (A) component in any one of a 1st viewpoint thru | or 8 viewpoint is related with the polyester composition for thermosetting film formation whose polystyrene conversion is 1,000-30,000.

From a 10th viewpoint, in any one of a 1st viewpoint thru | or a ninth viewpoint, it further relates to the polyester composition for thermosetting film formation containing the phenol compound which is antioxidant as (D) component.

From an 11th viewpoint, in any one of a 1st viewpoint thru | or a 10th viewpoint, it is related with the polyester composition for thermosetting film formation containing a silane coupling agent as (E) component further.

From a 12th viewpoint, it is related with the polyester composition for thermosetting film formation containing the bismaleimide compound as (F) component further in any one of a 1st viewpoint thru | or 11th viewpoint.

From a 13th viewpoint, in any one of a 1st viewpoint thru | or a 12th viewpoint, 3-50 mass parts (B) component and 1-100 mass parts (C) component are based on 100 mass parts of (A) component. It relates to a polyester composition for forming a thermosetting film to contain.

From a 14th viewpoint, in a 10th viewpoint, it is related with the polyester composition for thermosetting film formation containing 0.01-5 mass parts (D) component based on 100 mass parts of (A) component.

In a fifteenth aspect, the eleventh aspect relates to a polyester composition for forming a thermosetting film containing 0.5 to 30 parts by mass (E) component based on 100 parts by mass of the component (A).

From a 16th viewpoint, it is related with the polyester composition for thermosetting film formation containing 0.5-50 mass parts (F) component based on 100 mass parts of (A) component.

From a 17th 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 16th viewpoint.

It relates to the liquid crystal aligning layer obtained using the polyester composition for thermosetting film formation as described in any one of a 1st viewpoint thru | or a 16th viewpoint from a 18th viewpoint.

Since the polyester composition for thermosetting film formation of this invention can form the cured film which has liquid crystal aligning ability in addition to 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. have. In particular, the liquid crystal aligning film and the overcoat layer of the color filter which were formed independently independently can be formed at once in a "liquid crystal aligning layer" having both characteristics, thereby simplifying the manufacturing process and reducing costs by reducing the number of processes. Can be realized.

Moreover, since the polyester composition for thermosetting film formation of this invention melt | dissolves in a glycol type solvent, it can be used suitably for the production line of the planarization film which mainly uses these solvents.

1 is a schematic diagram showing a cured film formed when a thermosetting polyester composition is applied to a stepped substrate.
Fig. 2 is a schematic 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 by using the polyester composition for thermosetting film formation of the present invention.

As described above, in the conventionally proposed cured films of acrylic resins and polyimides, none of the performances such as flatness, transparency, and orientation required for the liquid crystal alignment film and the planarization film are sufficiently satisfied.

In addition, although the use of polyester (see Japanese Patent Application Laid-Open Nos. 5-158055 and 2002-229039) has been proposed up to now, they do not all have thermosetting properties. Solvent resistance of the cured film was also deteriorated.

The present invention is characterized by using a thermosetting polyester to improve performance such as flattening, transparency, and orientation described above. That is, this invention is a diester compound represented by following formula (1) as polyester (A) component, a crosslinking agent as (B) component, and (C) component

(In formula, P represents the group represented by the group which consists of an alicyclic group, an alicyclic group, and an aliphatic group, or a structure represented by Formula (2), and Q represents the group which consists of an alicyclic group or an alicyclic group and an aliphatic group. Moreover, Formula (2) R represents an alkylene group.) Is a polyester composition for forming a thermosetting film.

Furthermore, in addition to the said (A)-(C) component, it can contain a phenol compound which is antioxidant as (D) component, a silane coupling agent as (E) component, and a bismaleimide compound as (F) component as needed. It is a polyester composition for thermosetting film formation.

Hereinafter, each component is explained in full detail.

[(A) component]

Polyester which is (A) component becomes like this. Preferably it is polyester containing the structural unit represented by following formula (3), More preferably, it is polyester which consists of a structural unit represented by Formula (3).

In the 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 (3A1), formula (3A2) or formula (3A3).

A ¹ in the formula 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. The arbitrary hydrogen atoms contained in A <^1> here may each independently be substituted by the aliphatic group, and two substituents among these may combine with each other, and may form the 4-6 membered ring.

Herein, the aliphatic group serving 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 and form a ring, it becomes a condensed polycyclic hydrocarbon group in which some or all hydrogenated is bridge | crosslinked cyclic hydrocarbon groups, such as a norbornene group and an adamantane group, for example.

In the formula, R ¹ represents a single bond, a carbonyl group, an ether group, a sulfonic acid 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 sulfonic acid 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.

Or 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 (3) 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 (3), 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 (3B1) or formula (3B2).

B ¹ in the formula 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, contained in the B ¹ group Arbitrary hydrogen atoms may be respectively independently substituted by aliphatic groups.

Here, the aliphatic group which is this substituent is preferably an aliphatic group having 1 to 5 carbon atoms, and more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents combine to form a ring, it becomes a condensed polycyclic hydrocarbon group in which some or all hydrogenated, such as a norbornene group and an adamantane group, are partially or fully hydrogenated, 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 sulfonic acid 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 or a carbonyl group , An ether group, a sulfonic acid 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, and preferably an alkylene group having 1 to 3 carbon atoms.

In addition, k represents 0 or 1.

Preferable specific examples of B which is a divalent organic group in Formula (3) are shown to following formula (B-1)-formula (B-5). Among the groups represented by the following (B-1) to formula (B-5), B is preferably a group selected from (B-1) to (B-4).

The polyester as the component (A) preferably contains at least one kind of structure selected from the group consisting of groups represented by formulas (3A1) to (3A3) among the structural units represented by formula (3), The structures other than the group represented by (3A1) to formula (3A3) may be included. At this time, if the structure of polyester is formed, the structure is not 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 (3A4)-formula (3A5).

Wherein R ⁸ , R ⁹ , and R ¹⁰ each independently represent a single bond, a carbonyl group, an ether group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a saturated carbon group having 1 to 8 carbon atoms substituted with a fluorine atom Hydrocarbon group is shown, Preferably a single bond, a carbonyl group, an ether group, a sulfonic acid group, the C1-C5 saturated hydrocarbon group, or the C1-C5 saturated hydrocarbon group substituted by the fluorine atom is shown.

In particular, R ⁸ is preferably a single bond, a carbonyl group, an ether group, a sulfonic acid 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 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 ¹⁰ is a carbonyl group, an ether group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms It is preferable that it is a C1-C5 saturated hydrocarbon group substituted by the group or the fluorine atom.

H represents 0 or 1;

Preferable specific examples of the formulas (3A4) to (3A5) are shown in the following formulas (a1) to (a7).

In the polyester which is (A) component used for this invention, in the structural unit represented by the said Formula (3), at least 1 type of structure chosen from the group which A consists of group represented by said Formula (3A1)-Formula (3A3). It is preferable to contain at least 60 mol% or more of a unit.

The weight average molecular weight of polyester which is (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 which is (A) component is smaller than the said range, there exists a tendency for orientation or solvent tolerance to fall, and when it exceeds the said range, planarization property may fall.

<The manufacturing method of (A) component>

Polyester which is (A) component in this invention can be obtained by superposing | polymerizing a tetracarboxylic dianhydride and a diol compound, for example. More preferably, the diol compound 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) (henceforth, Obtained by reacting the diol component).

In said formula, A and B are the same as the definition in Formula (3) mentioned above, and a preferable aspect is also the same as that mentioned above.

In the polyester which is 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 dianhydride The total mole number of the water compounds> is preferably 0.5 to 1.5. As in the conventional 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 which is (A) component is made into the acid anhydride terminal.

The terminal of the said polyester changes depending on the compounding ratio of an acid component and a diol component. For example, when the acid component is overreacted, the terminal tends to be an acid anhydride.

Moreover, when superposing | polymerizing using an diol component excessively, a terminal becomes a hydroxyl group easily. In this case, carboxylic anhydride can be made to react with this terminal hydroxyl group, and a terminal hydroxyl group can be sealed by acid anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrophthalic 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 the production of polyester as the 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 reaction temperature is 100 ℃ to 140 ℃, the reaction time can be obtained a polyester in 2 to 48 hours.

In addition, the reaction temperature in the case of protecting a terminal hydroxyl group with 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. The solvent which can be used at this time will not be specifically limited if it does not contain the functional group which reacts with acid anhydrides, such as a hydroxyl group and an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, 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.

Although these solvents may be used independently or may be mixed and used, propylene glycol monomethyl ether acetate is more preferable from a viewpoint of safety and applicability to the line of the overcoat agent of a color filter.

Moreover, even if the solvent which does not melt | dissolve polyester, you may mix and use with 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 a diol component (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, tetramethyl Quaternary ammonium salts such as ammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyl And quaternary phosphonium salts such as triphenylphosphonium chloride and ethyltriphenylphosphonium bromide.

The solution containing polyester which is thus obtained (A) component 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 poor solvents such as water, methanol, ethanol, diethyl ether and hexane.

<(B) component>

(B) component of this invention is a crosslinking agent. Although a compound, such as an epoxy compound and a methylol compound, is mentioned as a crosslinking agent, Preferably, it is an epoxy compound which has two or more epoxy groups.

Examples of such compounds include 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 And trimethylol ethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

Moreover, you may use a commercially available compound from the point which is easy to acquire. Although the specific example (brand name) is given to the following, it is not limited to this: 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, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000, CELLOXIDE P-2021 (manufactured by Daicel Chemical Industries Limited); Bisphenol A type epoxy resin such as Epikote 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, made by YUKA SHELL EPOXY KK (currently Japan Epoxy Resins Co., Ltd.)) ; Bisphenol F type epoxy resins such as Epikote 807 (YUKA SHELL EPOXY KK (now manufactured by Japan Epoxy Resins Co., Ltd.)); Phenol novolak type epoxy resins such as Epikote 152, 154 (above, manufactured by YUKA SHELL EPOXY KK (currently Japan Epoxy Resins Co., Ltd.)), EPPN201, 202 (above, manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (YUKA SHELL EPOXY KK (now Japan Epoxy Resins Co. Cresol novolac epoxy resins; Denacol EX-252 (manufactured by Negase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, copper CY-192, copper CY-184 (above, made by CIBA-GEIGY AG), Epiclon 200, copper 400 (or above, DIC Corporation), Epikote 871, copper 872 (above, YUKA SHELL EPOXY KK (now made by Japan Epoxy Resins Co., Ltd.), ED-5661, ED-5662 (above, manufactured by Celanese Coating Company) Suzy; Denacol EX-611, Copper EX-612, Copper EX-614, Copper EX-622, Copper EX-411, Copper EX-512, Copper EX-522, Copper EX-421, Copper EX-313, Copper EX-314, Aliphatic polyglycidyl ethers such as EX-321 (manufactured by Negase ChemteX Corporation).

As the compound having at least two epoxy groups, a polymer having an epoxy group can be used. Such a polymer can be used without particular limitation as long as it has an epoxy group.

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. Examples include polypolymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, Polycondensation polymers, such as an epoxy novolak, are mentioned.

Or the polymer which has the said epoxy group can also be manufactured by reaction with 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 two 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 crosslinking agent which is (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 which is (A) component, More preferably, it is 5- It is 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.

<(C) component>

(C) component is a diester compound represented by following formula (1). As the diester compound which is (C) component in this invention, not only one type but the multiple types of compound represented by Formula (1) can be used.

In the formula, P represents an alicyclic group, a group consisting of an alicyclic group and an aliphatic group or a structure represented by formula (2), Q represents a group consisting of an alicyclic group or an alicyclic group and an aliphatic group, and P and Q each represent any hydrogen in the group. The atom may be substituted with an aliphatic group.

In the formula (2), R represents an alkylene group, preferably R represents an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and more preferably Represents an alkylene group having 1 to 3 carbon atoms.

In said formula, preferable structure of P is represented by said Formula (2) or following formula (1P1).

In the formula, P 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. The arbitrary hydrogen atoms in the P ¹ group may be each independently substituted with an aliphatic group.

The aliphatic group which is this substituent is preferably an aliphatic group having 1 to 5 carbon atoms, and more preferably an aliphatic group having 1 to 3 carbon atoms.

In the formula, R ¹¹ represents a single bond, a carbonyl group, an ether group, a sulfonic acid 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 sulfonic acid 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 ¹² and R ¹³ 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.

H represents 0 or 1;

Preferable specific examples of P in the formula (1) are shown in the following formulas (P-1) to (P-5).

In said formula (2), Q represents group which consists of an alicyclic group or an alicyclic group, and an aliphatic group, Preferably it is group represented by following formula (1Q1).

In the formula, Q ¹ represents a cycloalkylene group or cycloalkenylene group having 4 to 8 carbon atoms, and preferably a cycloalkylene group or cycloalkenylene group having 4 to 6 carbon atoms. Q ¹ Any hydrogen atom in group may be substituted by the aliphatic group.

The aliphatic group which is this substituent is preferably an aliphatic group having 1 to 5 carbon atoms, and more preferably an aliphatic group having 1 to 3 carbon atoms.

In addition, X represents a single bond or an alkylene group having 1 to 3 carbon atoms.

Specific examples of preferred Q ¹ include cyclobutane group, methylcyclobutane group, dimethylcyclobutane group, cyclopentyl group, cyclohexylene group, methylcyclohexylene group, tetrahydrophthaloyl group, methyltetrahydrophthaloyl group and the like. Can be mentioned.

The diester compound which is (C) component of this invention can be obtained by making 1 mol of diols represented by following formula (iii), and 1.7-2 mol, preferably 1.8-2 mol of dicarboxylic anhydrides represented by formula (iv) react. have.

In the formulas (iii) and (iv), P represents an alicyclic group, a group consisting of an alicyclic group and an aliphatic group or a structure represented by formula (2), Q represents a group consisting of an alicyclic group or an alicyclic group and an aliphatic group, and R in (2) represents an alkylene group. In addition, P, Q, and R are the same as the definition of Formula (1) and Formula (2) mentioned above, and their preferable form is also the same as that mentioned above.

In this invention, only one type may be used for the diol compound represented by said Formula (iii), and the dicarboxylic acid anhydride represented by Formula (iv) may be used, respectively.

As a specific example of the diol compound represented by said Formula (iii), for example, hydrogenated bisphenol A, 4,4'-bicyclohexanol, 1, 4- cyclohexanediol, 1, 3- cyclohexanediol, 1,4 -Cyclohexane dimethanol, 1, 3- cyclohexane dimethanol, p-xylene glycol, m-xylene glycol, etc. are mentioned.

(C) component can be a polyhydric ester compound represented by a following formula (1-a). In this invention, not only one type but the multiple types of compound represented by Formula (1-a) can be used as this polyhydric ester compound.

In the formula, Pa represents an alicyclic group or an aliphatic alkyl group which may be interrupted by an oxygen atom or a nitrogen atom, or a structure represented by formula (2-a), Qa represents an alicyclic group, t represents an integer of 1 to 5, and Pa And Qa may be each substituted with an aliphatic group at any hydrogen atom. In the formula (2-a), Ra represents an alkylene group, preferably Ra represents an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, More preferably, an alkylene group having 1 to 3 carbon atoms is shown.

The said polyhydric ester compound can be obtained by making the diol represented by a following formula (iii-a), and the dicarboxylic anhydride represented by a formula (iv-a) react.

In the formulas (iii-a) and (iv-a), Pa represents a structure represented by an alicyclic group or an aliphatic alkyl group or a formula (2-a) which may be interrupted by an oxygen atom or a nitrogen atom, and t is 1 to 5 In the following formulae, Qa represents an alicyclic group, and Ra in formula (2-a) represents an alkylene group. In addition, Pa, Qa, and Ra are the same as that of the definition of Formula (1-a) and Formula (2-a) mentioned above, and their preferable form is also the same as that mentioned above.

In the present invention, the polyhydric alcohol compound represented by the formula (iii-a) and the dicarboxylic acid anhydride represented by the formula (iv-a) may each use only one kind or a plurality of kinds thereof.

Examples of the polyhydric alcohol compound represented by the formula (iii-a) include compounds such as 1,3,5-cyclohexanetriol and pentaerythritol.

The specific example of the polyhydric alcohol compound represented by said formula (iii-a) is shown below.

As a specific example of the dicarboxylic acid anhydride represented by said Formula (iv), a 1, 2- cyclohexane dicarboxylic acid anhydride, 4-methyl- 1, 2- cyclohexane dicarboxylic acid anhydride, tetrahydrophthalic anhydride, Methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc. are mentioned.

In the preparation of the diester compound (or polyhydric ester compound) as the component (C), the reaction temperature of the diol compound (or polyhydric alcohol compound) and the dicarboxylic anhydride is 50 to 200 ° C, preferably 80 to 170 ° C. Any temperature can be selected. For example, the reaction temperature can obtain a diester compound (or a polyhydric ester compound) by 100 to 140 degreeC, and reaction time 2 to 48 hours.

The reaction of the diol compound (or polyalcohol compound) and dicarboxylic anhydride is usually carried out in a solvent. The solvent which can be used at this time is not specifically limited if it does not contain the functional group reacting with an acid anhydride, such as a hydroxyl group and an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, 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.

Although these solvents may be used independently or may be used in mixture, propylene glycol monomethyl ether acetate is more preferable from a viewpoint of safety and applicability to the line of the overcoat agent of a color filter.

Moreover, even if it is a solvent which does not melt a diester compound, you may mix and use this solvent with the said solvent in the range which does not precipitate the diester compound produced | generated by the polymerization reaction.

Alternatively, a catalyst may be used in the reaction of the diol compound (formula (iii)) (or polyhydric alcohol compound (formula (iii-a))) with dicarboxylic acid anhydride (formula (iv) or formula (iv-a)). have.

Specific examples of the catalyst used at this time include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetra Quaternary ammonium salts such as ethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium And quaternary phosphonium salts such as chloride and ethyltriphenylphosphonium bromide.

It is preferable that content of (C) component in the polyester composition for thermosetting film formation of this invention is 1-100 mass parts based on 100 mass parts of polyester which is (A) component, More preferably, it is 5-60 It is a mass part. When this ratio is too small, the orientation of the cured film obtained from the polyester composition for thermosetting film formation falls, or planarization property falls, and when too large, the transmittance | permeability may fall.

<(D) component>

In this invention, you may contain antioxidant as (D) component. This component (D) is effective for preventing discoloration of the film due to high temperature firing assumed in the process after the thermosetting film formation of the present invention.

Especially as a antioxidant of (D) component, a phenolic compound is preferable, As a specific example, 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'-hydroxy Phenyl) propionate], acetone bis (3,5-di-t-butyl-4-hydroxyphenyl) mercaptole, 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 and the like.

Phenolic compounds which are these antioxidants are not specifically limited to the above. In addition, these can use together single or 2 types or more of components.

Of these antioxidants 2,6-di-t-butyl-4-cresol, 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, 4, 4'-methylenebis (2,6-di-t-butylphenol) and the like are particularly preferable in that the heat resistance is high without lowering the orientation.

In this invention, it is preferable that it is 0.01-5 mass parts with respect to 100 mass parts of polyester which is (A) component, and, as for the usage ratio of the phenolic compound which is antioxidant of (D) component, it is 0.1-3 mass parts. When this ratio is too small, the effect as an antioxidant may not be fully acquired, and when too large, orientation may fall or a coating film may become rough.

<(E) component>

In this invention, you may contain a silane coupling agent as (E) component.

The silane coupling agent which is (E) component is effective in improving adhesiveness with the retardation material which consists of a polymeric liquid crystal.

Specific examples of such a silane coupling agent include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane; trimethylmethoxysilane, dimethyldiethoxysilane and methyldimethoxysilane. Alkoxysilanes such as dimethylvinylethoxysilane, diphenyldimethoxysilane and phenyltriethoxysilane; hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilyl Silazanes such as midazole, vinyl trichlorosilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, and γ-glycidoxypropyltri Silanes such as ethoxysilane and γ- (N-piperidinyl) propyltriethoxysilane; benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzo Thiazole, 2-meth Heterocyclic compounds, such as captobenzoxazole, urasol, tauracil, mercaptoimidazole, and mercaptopyrimidine, urea or thiourea compounds, such as 1,1-dimethylurea and 1,3-dimethylurea, are mentioned. One kind or two or more kinds of these silane coupling agents can be used in combination.

Of these silane coupling agents, γ-methacryloxypropyltriethoxysilane is particularly preferable in view of adhesion to a retardation material made of a polymerizable liquid crystal and storage stability.

The said silane coupling agent can use the compound of commercial items, such as the Shin-Etsu Chemical Co., Ltd. make, the MOMENTIVE agent, and the Dow Corning Toray Co., Ltd., For example, These commercial items can be obtained easily.

The addition amount of these silane coupling agents is 0.5-30 mass parts normally with respect to 100 mass parts of (A) component, More preferably, it is 0.8-20 mass parts. When 20 mass parts or more are used, the solvent resistance of a coating film may fall, and when less than 0.5 mass part, sufficient effect of a silane coupling agent may not be acquired.

<(F) component>

In this invention, you may contain a bismaleimide compound as (F) component. The bismaleimide compound which is (F) component is effective in further improving planarization property, For example, the compound represented by following formula (4) is mentioned. These bismaleimide compounds are not specifically limited to said thing. These can use together single or 2 types or more of components.

In the above formula, Y is an organic group consisting of an organic group selected from the group consisting of an aliphatic group, an aliphatic group including a cyclic structure and an aromatic group, or a combination of a plurality of organic groups selected from these groups. And Y may include bonds such as ester bonds, ether bonds, amide bonds, urethane bonds and the like.

As a bismaleimide compound represented by said Formula (4), for example, N, N'-3,3- diphenylmethane bismaleimide, N, N '-(3,3-diethyl-5,5-dimethyl ) -4,4-diphenyl-methanebismaleimide, N, N'-4,4-diphenylmethanebismaleimide, 3,3-diphenylsulfonbismaleimide, 4,4-diphenylsulfonbismaleimide Mead, N, N'-p-benzophenonebismaleimide, N, N'-diphenylethanebismaleimide, N, N'-diphenyletherbismaleimide, N, N '-(methylenedi-ditetra Hydrophenyl) bismaleimide, N, N '-(3-ethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3, 3-dimethyl) -4,4-diphenylmethanebis Maleimide, N, N '-(3,3-diethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3,3-dichloro) -4,4-diphenylmethanebismaleimide Mid, N, N'-isophorone bismaleimide, N, N'- tolidine bismaleimide, N, N'- diphenyl propane bismaleimide, N, N'- naphthalene bismaleimide, N, N ' -m-phenylenebismaleimide, N, N'-5- Oxy-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) Pro , 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-bismethylenecyclohexanebismaleimide, N, N'-2,4-tolylene bismaleimide, N, N'-2,6-tolylene bismaleimide, etc. are mentioned, It is limited to what was mentioned above. It doesn't happen. 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 acquire higher planarity among these aromatic bismaleimide, the thing of molecular weight 1,000 or less is preferable.

In this invention, it is preferable that the use ratio of the bismaleimide compound which is (F) component is 0.5-50 mass parts with respect to 100 mass parts of polyester which is (A) component, More preferably, it is 1-30 mass parts, Especially preferably Preferably it is 2-20 mass parts. When this ratio is too small, the effect of improving the planarization property of the cured film obtained from the polyester composition for thermosetting film formation may be difficult to be acquired, 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 melt | dissolved in a solvent, and is used in a solution state in many cases. The solvent used at this time melt | dissolves (A) component-(C) component, (D) component-(F) component, and / or the other additives mentioned later as needed, and if it is a solvent which has such a solubility, the kind And structures are not particularly 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, ethyl acetate Butyl acetate, ethyl lactate, butyl lactate, and the like.

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

<Other additives>

Further, the polyester composition for forming a thermosetting film of the present invention may be used as the co-adjuvant, pigment, dye, preservative stabilizer, antifoaming agent, polyhydric phenol, etc., if necessary, so long as the effect of the present invention is not impaired. Dissolution accelerators, such as polyhydric carboxylic acid, etc. can be contained.

<Polyester composition for thermosetting film formation>

The polyester composition for thermosetting film formation of this invention contains the polyester which is (A) component, the crosslinking agent which is (B) component, and the diester (or polyhydric ester) which is (C) component, and if necessary, It is a composition which can contain 1 or more types of antioxidant (phenol compound), the silane coupling agent which is (E) component, the bismaleimide compound which is (F) component, and other additives. And usually, they are often used as a solution dissolved in a solvent.

Among these, 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 1-100 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, 1-100 mass parts (C) component, and a solvent based on 100 mass parts of (A) component.

[3]: 3 to 50 parts by mass of (B) component, 1 to 100 parts by mass of (C) component, 0.01 to 5 parts by mass of (D) component and 0.5 to 30 parts by mass based on 100 parts by mass of (A) component ( E) A component, the polyester composition for thermosetting film formation containing 0.5-50 mass parts (F) component.

[4]: 3 to 50 parts by mass of (B) component, 3 to 50 parts by mass of (C) component, 0.01 to 5 parts by mass of (D) component and 0.5 to 30 parts by mass based on 100 parts by mass of (A) component ( The polyester composition for thermosetting film formation containing E) component, 0.5-50 mass parts (F) component, and a solvent.

The compounding ratio, preparation method, etc. at the time of using the polyester composition for thermosetting film formation of this invention as a solution are explained in full 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) component, A method of mixing the component (D), the component (E), and the component (F) in a predetermined ratio to form a uniform solution, or a method of additionally adding and mixing other additives as necessary in a suitable step of the preparation method. Can be mentioned.

In preparation of 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, (E) component, (F) component, etc. are put into the solution of this (A) component, and it makes a uniform solution, concentration adjustment is carried out. You may add an additional solvent for the purpose. At this time, the solvent used for preparation of the polyester and the solvent used for concentration adjustment at the time of preparation of the polyester composition for thermosetting film formation may be same or different.

And the solution of the prepared polyester composition for thermosetting film formation is preferable to use, after filtering using a filter etc. of about 0.2 micrometer in diameter.

<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, or a quartz substrate). , ITO substrate, etc.) or a film (for example, a resin film such as a triacetyl cellulose film, a polyester film, an acrylic film), and the like, a rotary coating, a spill coating, a roll coating, a slit coating, and a slit, followed by a rotary coating and an inkjet coating. After coating by printing or the like, the coating film can be formed by pre-drying (pre-baking) with a hot plate or an oven. Thereafter, a coating is formed by heat treatment of the 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 0.3 to 60 minutes of hours are employ | adopted, for example. The heating temperature and the heating time are preferably 80 ° C to 140 ° C 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 optical and electrical characteristics.

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

By hardening the polyester composition for thermosetting film formation of this invention on condition 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.

The cured film formed in this way can function as a layer which orientates a liquid crystal aligning layer, ie, a compound which has liquid crystallinity, by performing a rubbing process.

As conditions of a rubbing process, the conditions of a rotational speed of 300-1000 rpm, a feed rate of 3-200 mm / sec, and an indentation amount of 0.1-1 mm are generally used.

Thereafter, pure water or the like is used to remove residues generated by rubbing by ultrasonic cleaning.

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.

In addition, two substrates having the liquid crystal alignment layer formed as described above may be bonded to each other so that the liquid crystal alignment layers face each other through spacers, and then liquid crystal is injected between these substrates to form a liquid crystal display device in which the liquid crystal is aligned.

Moreover, when using the base material which forms a liquid crystal aligning layer as a film, it becomes a material useful as an optically anisotropic film.

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

Further, the polyester composition for forming a thermosetting film of the present invention has at least the required level of flattening properties, so that protective films, planarizing films, insulating films, etc. in various displays such as thin film transistor (TFT) type liquid crystal display elements, organic EL elements, etc. It is also useful as a material for forming a cured film, and particularly useful 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, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

[Weak symbol used in the Example]

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

Polyester and diester compound raw materials

HBPDA: 3,3'-4,4'-bicyclohexyl tetracarboxylic dianhydride

BPDA: biphenyltetracarboxylic dianhydride

BPADA: 4,4 '-(4,4'-isopropylidenediphenoxy) bisphthalic anhydride

HPA: Hexahydrophthalic anhydride

CHDO: 1,4-cyclohexanediol

CHTO: 1,3,5-cyclohexanetriol

PE: Pentaerythritol

HBPA: Hydrogenated Bisphenol A

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

<Polyester and Polyester Compound Polymerization Catalyst>

BTEAC: benzyltriethylammonium chloride

<Polyimide precursor raw material>

CBDA: 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: CELLOXIDE P-2021 (product name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate) manufactured by Daicel Chemical Industries Limited.

Antioxidant

TBHBM: 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene

MBP: 4,4'-methylenebis (2,6-di-t-butylphenol)

<Silane coupling agent>

MPS: γ-methacryloxypropyl trimethoxysilane

Bismaleimide Compounds

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

NMP: N-methylpyrrolidone

The number average molecular weight and weight average molecular weight of the polyester, polyimide precursor, and acrylic copolymer obtained according to the synthesis examples described below were obtained by using the GPC apparatus (Shodex® columns KF803L and KF804L) manufactured by JASCO Corporation. Was measured on the conditions which put in a column (column temperature 40 degreeC), and elute at a flow volume 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

Polyester solution (solid content: 30.0 mass%) was obtained by making HBPDA 18.0g, BPDA 4.54g, HBPA 15.9g, THPA 2.01g, and BTEAC0.19g react at 125 degreeC for 19 hours in 95.1g of PGMEA (P1). Mn of obtained polyester was 1,310 and Mw was 3,270.

Synthesis Example 2

The polyester 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 125 degreeC in 54.48g of PGMEA for 19 hours (P2). Mn of obtained polyester was 1,980 and Mw was 3,500.

&Lt; Synthesis Example 3 &

Polyester solution (solid content: 30.0 mass%) was obtained by making HBPDA 18.0g, BPADA 7.37g, HBPA 17.0g, THPA 2.15g, and BTEAC0.10g react at 125 degreeC in 104.2g of PGMEA for 19 hours (P3). Mn of obtained polyester was 1,440 and Mw was 3,080.

&Lt; Synthesis Example 4 &

16.82 g (0.070 mol) of HBPA, 20.85 g (0.137 mol) of THPA, and 0.096 g of BTEAC were reacted for 16 hours at 130 ° C. in 88.13 g of PGMEA to obtain a diester solution (solid content concentration of 30.0% by mass) (A1).

&Lt; Synthesis Example 5 &

8.13 g (0.070 mol) of CHDO, 20.85 g (0.137 mol) of THPA, and 0.096 g of BTEAC were reacted for 16 hours at 130 ° C. in 67.86 g of PGMEA to obtain a diester solution (solid content concentration of 30.0% by mass) (A2).

&Lt; Synthesis Example 6 &

16.82 g (0.070 mol) of HBPA, 21.13 g (0.137 mol) of HPA, and 0.096 g of BTEAC were reacted for 16 hours at 130 ° C. in 88.77 g of PGMEA to obtain a diester solution (solid content concentration of 30.0% by mass) (A3).

Synthesis Example 7

5.50 g (0.042 mol) of CHTO, 17.08 g (0.112 mol) of THPA, and 0.057 g of BTEAC were reacted for 16 hours at 130 ° C. in 52.83 g of PGMEA to obtain a diester solution (solid content concentration of 30.0% by mass) (A4).

Synthesis Example 8

PE 5.00 g (0.037 mol), THPA 20.10 g (0.132 mol), and BTEAC 0.050 g were reacted for 16 hours at 130 ° C. in 58.69 g of PGMEA to obtain a diester solution (solid content concentration of 30.0% by mass) (A5).

Synthesis Example 9

The 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 (P4). Mn of the obtained polyimide precursor was 5,800 and Mw was 12,500.

Synthesis Example 10

Acrylic copolymer solution was prepared by using 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, 28.3 g of MMA as the monomer component, and 5 g of AIBN as the radical polymerization initiator, and polymerizing them at a temperature of 60 to 100 ° C. in 150 g of solvent PGMEA. Solid content concentration: 40.0 mass%) was obtained (P5). Mn of the obtained acrylic copolymer solution was 3,800 and Mw was 6,700.

<Examples 1 to 9 and Comparative Examples 1 to 3>

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 was prepared with the composition shown in Table 1, and the flattening property, solvent resistance, orientation, adhesiveness and transparency of the cured film obtained by the composition for each, respectively. And evaluation about heat resistance (transmittance) was performed.

(A) solution of component (A) (B) Component (g) (C) component (g) (D) component (g) (E) component (g) (F) Component (g) Solvent (g) Example 1 P1
14 CEL
1.5 A1
6.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 2 P2
14 CEL
1.5 A1
6.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 3 P3
14 CEL
1.5 A1
6.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 4 P2
10 CEL
1.5 A1
10 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 5 P2
14 CEL
1.5 A1
6.0 MBP
0.036 MPS
0.48 - PGME
4.0 Example 6 P2
16 CEL
1.5 A2
4.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 7 P3
14 CEL
1.5 A3
6.0 TBHBM
0.036 MPS
0.48 BM11
0.6 PGME
5.8 Example 8 P1
14 CEL
1.5 A4
6.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Example 9 P1
14 CEL
1.5 A5
6.0 TBHBM
0.036 MPS
0.48 - PGME
4.0 Comparative Example 1 P2
20 - - - PGMEA
2.22 Comparative Example 2 P4
20 CEL
1.2 - - NMP
2.97 Comparative Example 3 P5
20 CEL
1.2 - - PGMEA
2.80

* P1-P3: Polyester solution P4: Polyimide precursor solution P5: Acrylic copolymer solution

[Evaluation of Flatness]

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 was applied on a stepped substrate (made of glass) with a height of 1.0 μm, a line width of 100 μm, and an interline space of 40 μm using a spin coater, followed by a temperature of 100 Prebaking was performed on the hotplate at 120 degreeC for 120 second, and the coating film of 2.5 micrometers in thickness was formed. The film thickness was measured using F20 made from FILMETRICS. The coating film was heated in a hot air circulation oven at a temperature of 230 ° C. for 30 minutes to post-bake to form a cured film having a thickness of 2.0 μm.

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

In addition, in order to be recognized as a planarization film, it is required to have a planarization rate of at least 60% or more.

[Evaluation of Solvent Tolerance]

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 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 achieve 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 in the hot-air circulation type oven 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) that there was no film thickness change after PGMEA or NMP immersion, and (x) that the decrease of film thickness is found after immersion are shown.

[Evaluation of Orientation]

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 was applied on a ITO 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. Formed a coating film. The film thickness was measured using F20 by FILMETRICS. The film was post-baked in a hot air circulation oven at a temperature of 230 ° C. for 30 minutes to form a cured film.

The cured film was subjected to a rubbing treatment at a rotational speed of 400 rpm, a feed rate of 30 mm / sec, and an indentation amount of 0.4 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 60 second at 80 degreeC, and formed the coating film of 1.4 micrometer in thickness. This substrate was exposed at 1,000 mJ under a nitrogen atmosphere. The produced board | substrate was interposed in the polarizing plate, and the orientation was visually confirmed. When the board | substrate was inclined at 45 degree | times, and when it was not inclined, it marked with (circle) that the light transmittance changed remarkably and (x).

[Evaluation of Adhesiveness]

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 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 at a temperature of 230 ° C. Post-baking was performed in the hot air circulation oven for 30 minutes, and the cured film was formed.

The cured film was subjected to a rubbing treatment at a rotational speed of 400 rpm, a feed rate of 30 mm / sec, and an indentation amount of 0.4 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 60 second at 80 degreeC, and formed the coating film of 1.4 micrometer in film thickness. This substrate was exposed at 1,000 mJ under a nitrogen atmosphere. After making 25 grids of 1 mm X 1 mm in the produced coating film, an adhesive tape peeling test (used tape: Cello Tape (registered trademark)) was performed. (Circle) and the thing which peeled off at least one of 25 grid | grids were shown by x.

[Evaluation of Transparency (Transmittance)]

Each composition of Examples 1 to 9 and Comparative Examples 1 to 3 was applied on 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. Formed a coating film. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked in the hot-air circulation type oven 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 (SHIMADSUUV-2550 model number by Shimadzu Corporation).

[Evaluation of Heat Resistance (Transmittance)]

The cured film which evaluated the transparency mentioned above was further heated in the hot-air circulation type oven for 3 hours at the temperature of 230 degreeC, and the transmittance | permeability at the wavelength of 400 nm was measured using the ultraviolet-visible spectrophotometer (Shimadzu Corporation SHIMADSUUV-2550 model number).

[Evaluation result]

As mentioned above, the result of having evaluated is shown in following Table 2.

Planarization rate (%) Solvent resistance Orientation
Adhesion
Transparency (%)
Heat resistance (%)
PGMEA NMP Example 1 61

98 93 Example 2 61

99 97 Example 3 63

97 92 Example 4 64

99 97 Example 5 61

99 94 Example 6 60

99 96 Example 7 64

98 95 Example 8 63

99 97 Example 9 60

97 95 Comparative Example 1 - × × - - - - Comparative Example 2 20

× 85 84 Comparative Example 3 65

× × 96 95

Examples 1 to 9 were resistant to all planarization rates, PGMEA, and NMP. In addition, all exhibited good orientation, and even after high-temperature baking after high-temperature baking, high transmittance (transparency) was achieved and heat resistance was also provided. And all the Examples had good adhesiveness with retardation material.

On the other hand, in the comparative example 1, the cured film was not formed.

Moreover, although the solvent resistance, heat resistance, and orientation were favorable in Comparative Example 2, the problem remained in transparency, the planarization rate was very low, and the adhesiveness deteriorated.

And although the flattening rate, solvent resistance, and transparency of Comparative Example 3 were favorable, the orientation and adhesiveness deteriorated.

As mentioned above, the polyester composition for thermosetting film formation of this invention can use glycol solvent, such as propylene glycol monomethyl ether acetate, at the time of cured film formation, and the obtained cured film is excellent in light transmittance, solvent resistance, heat resistance, and flatness. Chemical performance, adhesiveness and orientation All the performances were good.

[Industrial Availability]

The polyester composition for thermosetting film formation by this invention is very useful as a liquid crystal aligning layer of an optically anisotropic film or a liquid crystal display element, and also has a protective film in various displays, such as a thin-film transistor (TFT) type liquid crystal display element and an organic electroluminescent element. And a material for forming a cured film such as a flattening film or an insulating film, in particular, an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, or the like.

Claims (18)

The polyester composition for thermosetting film formation containing the polyester which is (A) component, the crosslinking agent which is (B) component, and at least 1 sort (s) of diester compound represented by following formula (1) which is (C) component.
[Formula 1]

(Wherein P represents an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by formula (2), and Q represents an alicyclic group or an alicyclic group or an aliphatic group. R in the formula (2) represents alkylene) Group.)
The method of claim 1,
The polyester composition for thermosetting film formation whose (C) component is a diester compound by which 1 mol of the diol compounds represented by following formula (iii), and 1.7-2 mol of dicarboxylic anhydrides represented by following formula (iv) react.
(2)

(In formula, P represents an alicyclic group, a group consisting of an alicyclic group and an aliphatic group, or the structure represented by Formula (2). Any hydrogen atom to be substituted may be substituted with an aliphatic group, in which R represents an alkylene group.)
The method of claim 2,
The polyester composition for thermosetting film formation in which P represents group represented by a following formula (1P1).
(3)

In the formula, P ¹ represents a cyclic saturated hydrocarbon group, and any hydrogen atom in the P ¹ group may be independently substituted with an aliphatic group. R ¹¹ represents a single bond, a carbonyl group, an ether group, a sulfonic acid group, or 1 carbon atom. A saturated hydrocarbon group having from 1 to 8 carbon atoms or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom, R ¹² and R ¹³ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and H is 0 Or 1).
4. The method according to claim 2 or 3,
Polyester composition for thermosetting film formation in which Q represents group represented by a following formula (1Q1).
[Chemical Formula 4]

(In the formula, Q ¹ represents 4 to 8, a cycloalkylene group or an cycloalkyl alkenylene carbon atoms, and optionally any hydrogen atom in the group Q ¹ is substituted with an aliphatic. X 1 to be a single bond or a carbon atom 3 represents an alkylene group.)
The method of claim 1,
(C) The polyester composition for thermosetting film formation containing at least 1 sort (s) of polyhydric ester compound represented by a following formula (1-a).
[Chemical Formula 5]

(In formula, Pa shows the structure represented by the alicyclic group or aliphatic alkyl group which may be interrupted by an oxygen atom or a nitrogen atom, or a formula (2-a), Qa shows an alicyclic group, t shows the integer of 1-5. Ra in formula (2-a) represents an alkylene group.)
The method according to any one of claims 1 to 5,
The polyester composition for thermosetting film formation whose (A) component is polyester containing the structural unit represented by following formula (3).
[Formula 6]

(In formula, A represents the tetravalent organic group which the 4 bond number couple | bonded with an alicyclic group or an aliphatic group, B shows the bivalent organic group which the 2 bond number couple | bonded with an alicyclic group or an aliphatic group.)
The method according to any one of claims 1 to 6,
The polyester composition for thermosetting film formation which is polyester obtained by making (A) component react with tetracarboxylic dianhydride represented by following formula (i), and the diol compound represented by formula (ii).
[Formula 7]

(In formula, A represents the tetravalent organic group which the 4 bond number couple | bonded with an alicyclic group or an aliphatic group, B shows the bivalent organic group which the 2 bond number couple | bonded with an alicyclic group or an aliphatic group.)
The method according to claim 6 or 7,
In said Formula (3), 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-5) Polyester composition for thermosetting film formation which shows at least 1 sort (s) of group chosen from group represented by the following.
[Chemical Formula 8]

[Formula 9]

The method according to any one of claims 1 to 8,
The polyester composition for thermosetting film formation whose weight average molecular weight of polyester which is (A) component is 1,000-30,000 in polystyrene conversion.
The method according to any one of claims 1 to 9,
Furthermore, the polyester composition for thermosetting film formation containing the phenol compound which is antioxidant as (D) component.
The method according to any one of claims 1 to 10,
Furthermore, the polyester composition for thermosetting film formation containing a silane coupling agent as (E) component.
12. The method according to any one of claims 1 to 11,
Furthermore, the polyester composition for thermosetting film formation containing a bismaleimide compound as (F) component.
The method according to any one of claims 1 to 12,
The polyester composition for thermosetting film formation containing 3-50 mass parts (B) component and 1-100 mass parts (C) component based on 100 mass parts of (A) component.
The method of claim 10,
The polyester composition for thermosetting film formation containing 0.01-5 mass parts (D) component based on 100 mass parts of (A) component.
12. The method of claim 11,
The polyester composition for thermosetting film formation containing 0.5-30 mass parts (E) component based on 100 mass parts of (A) component.
The method of claim 12,
The polyester composition for thermosetting film formation containing 0.5-50 mass parts (F) component based on 100 mass parts of (A) component.
The cured film obtained using the polyester composition for thermosetting film formation of any one of Claims 1-16.
The liquid crystal aligning layer obtained using the polyester composition for thermosetting film formation of any one of Claims 1-17.

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