KR101706177B1 - Polyester Composition for Forming Heat-cured Film - Google Patents

Abstract

There is provided a material which exhibits high solvent resistance, liquid crystal alignment property, heat resistance, high transparency and high planarization property after the formation of a cured film, and which is soluble in various solvents applicable to a production line of a color filter film for forming a cured film It is on.
A polyester composition for forming a thermosetting film, which comprises a polyester as a component (A), a crosslinking agent as a component (B), and at least one diester compound represented by the following formula (1) as a component (C) P represents a group consisting of an alicyclic group, an alicyclic group and an aliphatic group or a structure represented by the formula (2), and Q represents an alicyclic group or a group consisting of an alicyclic group and an aliphatic group.

Description

[0002] Polyester Composition for Forming Heat-cured Film [0003]

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

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

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 pickup device, the protective film generally has a capability of flattening a color filter or a black matrix resin of the base substrate, Is required. Particularly, in manufacturing a color liquid crystal display device of the STN type or TFT type, the alignment accuracy between the color filter substrate and the counter substrate must be very strict and the cell gap between the substrates must be uniform. In order to maintain the transmittance of light transmitted through the color filter, these planarizing films as the protective film are required to have high transparency.

On the other hand, in recent years, low cost and light weight have been studied by introducing a retardation material into a cell of a liquid crystal display. A material obtained by applying and orienting a liquid crystal monomer and then photo-cured is generally used for such retardation material. In order to orient this phase difference material, the lower layer film needs to be a material having orientation after rubbing treatment. Therefore, a phase difference material is formed after the liquid crystal alignment layer is formed on the overcoat of the color filter (see Fig. 2 (a)). If the layer (see Fig. 2 (b)) having both the liquid crystal alignment layer and the color filter in an overcoat can be formed, such a material is strongly required because it can achieve great advantages such as low cost and reduction in the number of processors.

Generally, acrylic resin having high transparency is used for overcoat of the color filter. These acrylic resins include glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate, and ester solvents such as ethyl lactate and butyl lactate, which are widely used in view of safety and handling. Such an acrylic resin imparts heat resistance and solvent resistance by thermally curing or photo-curing (Patent Documents 1 and 2). However, conventional thermosetting or photo-curable acrylic resins show appropriate transparency and planarization property, but when such a planarizing film is rubbed, sufficient orientation is not exhibited.

On the other hand, a material composed of solvent-soluble polyimide or polyamic acid is usually used for the liquid crystal alignment layer. It has been reported that these materials are imparted with solvent resistance by imidizing completely during post-baking, and exhibit sufficient orientation by rubbing treatment (Patent Document 3). However, in the case of a planarizing film of a color filter, flatness and transparency are greatly reduced. Polyimide and polyamic acid are soluble in solvents such as N-methylpyrrolidone and? -Butyrolactone but have low solubility in glycol solvents and ester solvents and are difficult to apply to planarizing 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 based on the above-described circumstances, and an object to be solved by the present invention is to provide a process for producing a planarizing film of a color filter, which exhibits high solvent resistance, liquid crystal alignability, heat resistance, high transparency and high planarization property after the formation of a cured film, Which is soluble in an applicable glycol-based solvent.

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems and found the present invention.

That is, in the first aspect, there is provided a thermosetting film-forming polyester comprising a polyester as the component (A), a crosslinking agent as the component (B), and at least one diester compound represented by the following formula (1) ≪ / RTI >

(Wherein P represents an alicyclic group, a group comprising an alicyclic group and an aliphatic group, or a structure represented by the formula (2), Q represents an alicyclic group, or a group including a group consisting of an alicyclic group and an aliphatic group. And R represents an alkylene group.

According to a second aspect, in the first aspect, there is provided a diester compound obtained by reacting 1 mol of a diol compound represented by the following formula (iii) with 1.7 to 2 mol of a dicarboxylic anhydride represented by the following formula (iv) To a polyester composition for forming a thermosetting film.

(Wherein P represents an alicyclic group, a group comprising an alicyclic group and an aliphatic group or a structure represented by the formula (2), Q represents an alicyclic group or a group comprising an alicyclic group and an aliphatic group, and P and Q are included in the respective groups May be substituted with an aliphatic group. In the formula (2), R represents an alkylene group.)

In a third aspect, the present invention relates to a polyester composition for forming a thermosetting film, wherein P represents a group represented by the following formula (1P1).

(In the formula, P ¹ represents a cyclic saturated hydrocarbon group, P is even ^one random hydrogen atom in the group may be substituted each independently with an aliphatic. R ¹¹ is a single bond, a carbonyl group, an ether group, a sulfonic acid group, a carbon atom number of 1 to 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, and R represents a hydrogen atom or an alkyl group of 1 to 5 carbon atoms, .

According to a fourth aspect, in the second or third aspect, the present invention relates to a polyester composition for forming a thermosetting film, wherein Q represents a group represented by the 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 3 < / RTI >

In a fifth aspect, the present invention relates to a polyester composition for forming a thermosetting film, wherein the component (C) contains at least one polyvalent ester compound represented by the following formula (1-a).

(Wherein 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 the formula (2-a), Qa represents an alicyclic group, and t represents an integer of 1 to 5. Ra in the formula (2-a) represents an alkylene group.

In a sixth aspect, the present invention relates to a polyester composition for forming a thermosetting film, wherein the component (A) is a polyester comprising a structural unit represented by the following formula (3) in any one of the first to fifth aspects .

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

According to a seventh aspect, in any one of the first aspect to the sixth aspect, there is provided a method for producing a poly (arylene ether) copolymer, which comprises reacting a tetracarboxylic dianhydride represented by the following formula (i) with a diol compound represented by the formula (ii) To a polyester composition for forming a thermosetting film.

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

In an eighth aspect, in the sixth or seventh aspect, A in the formula (3) represents at least one kind of group selected from the groups represented by the following formulas (A-1) to (A-8) B is a polyester composition for forming a thermosetting film which exhibits at least one kind of group selected from groups represented by the following formulas (B-1) to (B-5).

In a ninth aspect, the polyester composition for forming a thermosetting film according to any one of the first to eighth aspects has a weight average molecular weight of the polyester (A) of 1,000 to 30,000 in terms of polystyrene.

In a tenth aspect, the present invention relates to a polyester composition for forming a thermosetting film, which further comprises a phenol compound as an antioxidant as the component (D) in any one of the first to ninth aspects.

According to an eleventh aspect, in any one of the first to tenth aspects, the present invention relates to a polyester composition for forming a thermosetting film further containing a silane coupling agent as the component (E).

In a twelfth aspect, the polyester composition for forming a thermosetting film according to any one of the first to eleventh aspects further comprises a bismaleimide compound as the component (F).

According to a thirteenth aspect, in any one of the first to twelfth aspects, 3 to 50 parts by mass of the component (B) and 1 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A) To a polyester composition for forming a thermosetting film.

In a fourteenth aspect, the tenth aspect relates to a polyester composition for forming a thermosetting film, which contains 0.01 to 5 parts by mass of component (D) based on 100 parts by mass of the component (A).

According to a fifteenth aspect, in the eleventh aspect, the present invention relates to a polyester composition for forming a thermosetting film, which contains 0.5 to 30 parts by mass of component (E) based on 100 parts by mass of the component (A).

According to a 16th aspect, in a twelfth aspect, the present invention relates to a polyester composition for forming a thermosetting film, which contains 0.5 to 50 parts by mass of component (F) based on 100 parts by mass of the component (A).

In a seventeenth aspect, the present invention relates to a cured film obtained by using the polyester composition for forming a thermosetting film according to any one of the first to sixteenth aspects.

And a liquid crystal alignment layer obtained by using the polyester composition for forming a thermosetting film according to any one of the first to sixteenth aspects from the 18th viewpoint.

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

Further, since the polyester composition for forming a thermosetting film of the present invention is soluble in a glycol-based solvent, it can be suitably used in a production line of a planarizing film mainly using these solvents.

1 is a schematic view showing a cured film formed when a thermosetting polyester composition is applied to a stepped substrate.
2 is a schematic view showing a liquid crystal cell (a) in which a liquid crystal alignment film is formed by a conventional technique and a liquid crystal cell (b) in which a planarization film is formed by using a polyester composition for forming a thermosetting film of the present invention.

As described above, in the acrylic resin-based and polyimide-based cured films proposed in the related art, all the performances such as flatness, transparency, and orientation required for a liquid crystal alignment film and a planarizing film are not sufficiently satisfied.

Although the use of polyester as an alignment material for a liquid crystal display element has been proposed (see JP-A-5-158055 and JP-A-2002-229039) And the solvent resistance of the cured film also deteriorated.

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

(2), Q represents an alicyclic group or a group consisting of an alicyclic group and an aliphatic group, and P represents an alicyclic group, a group comprising a group consisting of an alicyclic group and an aliphatic group or a structure represented by the formula (2) And R represents an alkylene group).

Further, in addition to the above components (A) to (C), if necessary, a phenol compound which is an antioxidant as the component (D), a silane coupling agent as the component (E) and a bismaleimide compound Is a polyester composition for forming a thermosetting film.

Hereinafter, each component will be described in detail.

[Component (A)] [

The polyester as the component (A) is preferably a polyester comprising a structural unit represented by the following formula (3), more preferably a polyester comprising a structural unit represented by the formula (3).

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

The above A is preferably a group represented by the following formula (3A1), (3A2) or (3A3).

A 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. Herein, any hydrogen atom contained in the group A ¹ may be independently substituted with an aliphatic group, and two of these substituents may be bonded to each other to form a 4- to 6-membered ring.

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

R ¹ represents a single bond, a carbonyl group, an ether group, a 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.

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

Preferable specific examples of A which is a tetravalent organic group in the formula (3) are shown in the following formulas (A-1) to (A-8). Among the groups represented by the following formulas (A-1) to (A-8), A is particularly preferably a group selected from the formula (A-1) or (A-2).

In the formula (3), B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group, and is preferably a group represented by the following formula (3B1) or (3B2).

B ¹ in the formula represents a cyclic saturated hydrocarbon, preferably carbon atoms represents a group of 4 to 8 cyclic saturated hydrocarbon, more preferably a carbon number represents a cyclic saturated hydrocarbon group of 4 to 6, which is included in B ¹ Air Any hydrogen atom may be independently substituted with an aliphatic group.

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

B ² represents a phenylene group.

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, , 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, 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.

K represents 0 or 1;

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

The polyester as the component (A) preferably contains at least one kind of structure selected from the group consisting of the groups represented by the formulas (3A1) to (3A3) among the structural units represented by the formula (3) (3A1) to (3A3). At this time, if the polyester structure is formed, its structure is not particularly limited, but is preferably at least one structure selected from the group consisting of the groups represented by the following formulas (3A4) to (3A5).

R ⁸ , R ⁹ and R ¹⁰ each independently 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 A hydrocarbon group, and 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.

In particular, R ⁸ is a single bond, a carbonyl group, an ether group, a sulfonic acid group, a carbon atom number of 1 to 5 saturated hydrocarbon group or a fluorine atom-substituted carbon atom number 1-5 saturated hydrocarbon group of preferably 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, and R ¹⁰ is preferably a carbonyl group, an ether group, a sulfonic acid group, a saturated hydrocarbon having 1 to 5 carbon atoms Or a saturated hydrocarbon group of 1 to 5 carbon atoms substituted with a fluorine atom.

Also, h represents 0 or 1.

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

In the polyester used as the component (A) used in the present invention, in the structural unit represented by the formula (3), at least one kind of structure selected from the group consisting of the groups represented by the formulas (3A1) to (3A3) Unit is preferably at least 60 mol% or more.

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

≪ Production method of component (A) >

In the present invention, the polyester (A) is obtained, for example, by polymerizing tetracarboxylic dianhydride and a diol compound. More preferred is a diol compound comprising a tetracarboxylic dianhydride (hereinafter also referred to as acid component) containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol compound represented by the following formula (ii) Also referred to as a diol component).

In the above formula, A and B are the same as defined in the above-mentioned formula (3), and their preferred forms are also the same as described above.

In the polyester as the component (A), the blending ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) and the total amount of the diol compounds (total amount of the diol components), that is, <total mole number of the diol compound> / <tetracarboxylic acid dianhydride The total molar number of water compounds > is preferably 0.5 to 1.5. As with this 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.

The polyester as the component (A) is preferably an acid anhydride terminal at its terminal in order to avoid deterioration of storage stability.

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

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

In the production of the 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 polyester can be obtained at a reaction temperature of 100 ° C to 140 ° C and a reaction time of 2 to 48 hours.

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

The reaction of the acid component with the diol component is usually carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not contain a functional group reactive with an acid anhydride such as a hydroxyl group or an amino group. For example, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, dimethylsulfone, Propyleneglycol monomethyl ether acetate, propyleneglycol propyl ether acetate, propyleneglycol monomethyl ether acetate, propyleneglycol monomethyl ether acetate, propyleneglycol monomethyl ether acetate, ethyleneglycol monomethyl ether acetate, Methyl 2-methoxypropionate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate.

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

Further, a solvent that does not dissolve the polyester may be used in combination with the above-described solvent within a range in which the polyester produced by the polymerization reaction does not precipitate.

A catalyst may also be used in the reaction of the acid component (formula (i)) with the 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 and 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 the polyester (A) thus obtained can be used as it is for the preparation of the polyester composition for forming a thermosetting film. The obtained polyester may be recovered by isolation by precipitation in a poor solvent such as water, methanol, ethanol, diethyl ether, or hexane, and then recovered.

&Lt; Component (B) >

The component (B) of the present invention is a crosslinking agent. As the crosslinking agent, compounds such as epoxy compounds and methylol compounds can be mentioned, but epoxy compounds having two or more epoxy groups are preferred.

Examples of such compounds are tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, glycerol triglycidyl 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,1,3,3-tetramethylpiperidine, 2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate , Trimethylol ethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

In addition, commercially available compounds may be used because they are readily available. Specific examples (trade names) include, but are not limited to, epoxy resins having amino groups such as YH-434 and YH434L (manufactured by Tohto Kasei Co., Ltd.); An epoxy resin having a cyclohexene oxide structure such as EPOLEAD GT-401, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000 and CELLOXIDE P-2021 (Daicel Chemical Industries Limited); Bisphenol A type epoxy resins such as Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010 and 828 (manufactured by YUKA SHELL EPOXY KK (now Japan Epoxy Resins Co., Ltd.) ; Epoxy resins such as Epikote 807 (manufactured by Japan Epoxy Resins Co., Ltd., YUKA SHELL EPOXY KK); Phenolic novolak type epoxy resins such as Epikote 152 and 154 (manufactured by YUKA SHELL EPOXY KK (currently available from Japan Epoxy Resins Co., Ltd.) and EPPN201 and 202 (manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (YUKA SHELL EPOXY KK; Cresol novolak type epoxy resins such as Nippon Kayaku Co., Ltd .; CY-184 (manufactured by CIBA-GEIGY AG), Epiclon 200, Copper 400 (above, DIC), CY-184 Epicote 871, Epoxy 872 (available from YUKA SHELL EPOXY KK (currently available from Japan Epoxy Resins Co., Ltd.), ED-5661 and ED-5662 (manufactured by Celanese Coating Company) Suzy; Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX- And 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 is not particularly limited as long as it has an epoxy group.

The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, addition polymerized polymers such as glycidyl methacrylate and copolymers of styrene and 2-hydroxyethyl methacrylate Epoxy novolak, and the like.

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

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

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

The content of the crosslinking agent as the component (B) in the polyester composition for forming a thermosetting film of the present invention is preferably 3 to 50 parts by mass, more preferably 5 to 20 parts by mass based on 100 parts by mass of the polyester (A) 40 parts by mass, particularly preferably 10 to 30 parts by mass. When the ratio is too small, the solvent resistance and heat resistance of the cured film obtained from the polyester composition for forming a thermosetting film are deteriorated. When the ratio is too large, the solvent resistance may be lowered and the storage stability may be lowered.

&Lt; Component (C) >

(C) is a diester compound represented by the following formula (1). In the present invention, as the diester compound as the component (C), not only one kind of compound represented by the formula (1) but also plural kinds can be used.

Wherein P represents a group comprising an alicyclic group, an alicyclic group and an aliphatic group or a structure represented by the formula (2), Q represents an alicyclic group or a group comprising an alicyclic group and an aliphatic group, and P and Q each represent any hydrogen 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, Represents an alkylene group having 1 to 3 carbon atoms.

In the above formula, the preferable structure of P is represented by the formula (2) or the formula (1P1) shown below.

In the formulas, P ¹ represents a cyclic saturated hydrocarbon group, preferably a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. Any hydrogen atom in the group P &^lt; ¹ &gt; may be independently substituted with an aliphatic group.

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

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, , 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, preferably a single bond or an alkylene group having 1 to 3 carbon atoms.

And h represents 0 or 1.

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

Q in the formula (2) represents an alicyclic group or a group comprising an alicyclic group and an aliphatic group, and is preferably a group represented by the following formula (1Q1).

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

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

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

Specific examples of preferable Q ¹ include a cyclobutane group, a methylcyclobutane group, a dimethylcyclobutane group, a cyclopentyl group, a cyclohexylene group, a methylcyclohexylene group, a tetrahydrophthalyl group, a methyltetrahydrophthalyl group and the like .

The diester compound as the component (C) of the present invention is obtained by reacting 1 mole of the diol represented by the following formula (iii) with 1.7 to 2 moles, preferably 1.8 to 2 moles of the dicarboxylic anhydride represented by the formula (iv) have.

In the formulas (iii) and (iv), P represents a group comprising an alicyclic group, an alicyclic group and an aliphatic group or a structure represented by the formula (2), Q represents an alicyclic group or a group comprising an alicyclic group and an aliphatic group, (2), R represents an alkylene group. P, Q and R are the same as the definitions of the above-mentioned formulas (1) and (2), and preferable forms are the same as those described above.

In the present invention, the diol compound represented by the formula (iii) and the dicarboxylic anhydride represented by the formula (iv) may be used alone or in combination.

Specific examples of the diol compound represented by the formula (iii) include, for example, hydrogenated bisphenol A, 4,4'-bicyclohexanol, 1,4-cyclohexanediol, 1,3-cyclohexanediol, 1,4 -Cyclohexanedimethanol, 1,3-cyclohexanedimethanol, p-xylylene glycol, m-xylylene glycol and the like.

(C) may be a polyvalent ester compound represented by the following formula (1-a). As the polyvalent ester compound in the present invention, not only one kind of compound represented by the formula (1-a), but also plural kinds can be used.

Pa represents an alicyclic group or aliphatic alkyl group which may be interrupted by an oxygen atom or a nitrogen atom or a structure represented by the formula (2-a), Qa represents an alicyclic group, t represents an integer of 1 to 5, Pa And Qa each may be an arbitrary hydrogen atom in the group substituted by an aliphatic group. 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.

The polyvalent ester compound can be obtained by reacting a diol represented by the following formula (iii-a) with a dicarboxylic anhydride represented by the formula (iv-a).

In the formulas (iii-a) and (iv-a), Pa represents an alicyclic group or 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, and Ra in the formula (2-a) represents an alkylene group. Pa, Qa and Ra are the same as the definitions of the above-mentioned formulas (1-a) and (2-a), and preferable forms are the same as those described 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 be used alone or plural types may be used.

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

Specific examples of the polyhydric alcohol compound represented by the above formula (iii-a) are shown below.

Specific examples of the dicarboxylic anhydride represented by the formula (iv) include 1,2-cyclohexanedicarboxylic anhydride, 4-methyl-1,2-cyclohexanedicarboxylic anhydride, tetrahydrophthalic anhydride, Methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and the like.

In the production of the diester compound (or the polyvalent 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, a diester compound (or a polyvalent ester compound) can be obtained at a reaction temperature of 100 ° C to 140 ° C and a reaction time of 2 to 48 hours.

The reaction of the diol compound (or polyhydric alcohol compound) with the dicarboxylic anhydride is usually carried out in a solvent. The solvent that can be used at this time is not particularly limited as long as it does not contain a functional group reactive with an acid anhydride such as a hydroxyl group or an amino group. For example, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, dimethylsulfone, Propyleneglycol monomethyl ether acetate, propyleneglycol propyl ether acetate, propyleneglycol monomethyl ether acetate, propyleneglycol monomethyl ether acetate, propyleneglycol monomethyl ether acetate, ethyleneglycol monomethyl ether acetate, Methyl 2-methoxypropionate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate and ethyl 2-ethoxypropionate.

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

Further, even if the solvent does not dissolve the diester compound, the solvent may be mixed with the solvent within the range in which the diester compound produced by the polymerization reaction does not precipitate.

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

Specific examples of the catalyst used in this case 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 and tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium And quaternary phosphonium salts such as chloride, ethyltriphenylphosphonium bromide and the like.

The content of the component (C) in the polyester composition for forming a thermosetting film of the present invention is preferably 1 to 100 parts by mass, more preferably 5 to 60 parts by mass based on 100 parts by mass of the polyester (A) Mass part. If the ratio is too small, the orientation property of the cured film obtained from the polyester composition for thermosetting film formation is lowered and the planarization property is lowered, and when it is too large, the transmittance may be lowered.

&Lt; Component (D) >

In the present invention, the antioxidant may be contained as the component (D). The component (D) is effective for preventing the discoloration of the film due to the high temperature baking which is assumed in the process after the formation of the thermosetting film of the present invention.

The antioxidant of the component (D) is preferably a phenol compound, and specific examples thereof include 2,6-di-t-butyl-4-cresol, 2,6- (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol tetrakis [3- Phenyl) propionate], acetone bis (3,5-di-t-butyl-4-hydroxyphenyl) mercaptole, 4,4'-methylenebis (2,6- Methyl) propionate, 4,4'-thiodi (2,6-di-t-butylphenol), tris (3,5- Di-t-butyl-4-hydroxybenzyl) isocyanuric acid, and bis (3,5-di-t-butyl-4-hydroxybenzyl) sulfide.

These phenolic compounds which are antioxidants are not particularly limited to those mentioned above. These may be used alone or in combination of two or more components.

Among these antioxidants, 2,4,6-tris (3 ', 5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, 2,4,6- 4'-methylenebis (2,6-di-t-butylphenol) and the like are particularly preferred because they do not deteriorate the orientation property and have high heat resistance.

In the present invention, the use ratio of the phenolic compound as the antioxidant of the component (D) is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, per 100 parts by mass of the polyester (A). When the ratio is too small, the effect as an antioxidant may not be sufficiently obtained. When the ratio is too large, the orientation may be deteriorated or the coating film may be roughened.

&Lt; Component (E) >

In the present invention, the silane coupling agent may be contained as the component (E).

The silane coupling agent, which is the component (E), is effective for improving adhesion with a retardation material comprising a polymerizable liquid crystal.

Specific examples of such a silane coupling agent include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane , Dimethylvinylethoxysilane, diphenyldimethoxysilane, and phenyltriethoxysilane; alkoxysilanes such as hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilylamine, trimethylsilyl Silane residues such as vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylidene fluoride, vinylcyclohexanecarbazole, vinylcyclohexylcyclohexylcyclohexylcyclohexyl, vinylcyclohexylcyclohexylcyclohexylcyclohexyl, Silanes such as ethoxysilane,? - (N-piperidinyl) propyltriethoxysilane, and the like; aromatic hydrocarbons such as benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, Thiazole, 2-me A heterocyclic compound such as mercaptobenzoxazole, ureasol, thaouracil, mercaptoimidazole and mercaptopyrimidine, or an urea or thiourea compound such as 1,1-dimethylurea or 1,3-dimethylurea These silane coupling agents may be used alone or in combination of two or more.

Among these silane coupling agents,? -Methacryloxypropyltriethoxysilane is particularly preferable from the viewpoint of adhesion strength with a retardation material comprising a polymerizable liquid crystal and storage stability.

As the silane coupling agent, for example, commercially available compounds such as those available from Shin-Etsu Chemical Co., Ltd., MOMENTIVE agent and Dow Corning Toray Co., Ltd. can be used, and these commercially available products are readily available.

These silane coupling agents are added in an amount of usually 0.5 to 30 parts by mass, more preferably 0.8 to 20 parts by mass based on 100 parts by mass of the component (A). When the amount is more than 20 parts by mass, the solvent resistance of the coating film may be lowered. When the amount is less than 0.5 parts by mass, sufficient effect of the silane coupling agent may not be obtained.

&Lt; Component (F) >

In the present invention, the bismaleimide compound may be contained as the component (F). The bismaleimide compound as the component (F) is effective for further improving the planarization property, and includes, for example, a compound represented by the following formula (4). These bismaleimide compounds are not particularly limited to those mentioned above. These may be used alone or in combination of two or more components.

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

Examples of the bismaleimide compound represented by the formula (4) include N, N'-3,3-diphenylmethane bismaleimide, N, N '- (3,3-diethyl- ) -4,4-diphenyl-methane bismaleimide, N, N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, N, N'-p-benzophenone bismaleimide, N, N'-diphenyl ethane bismaleimide, N, N'-diphenyl ether bismaleimide, N, N '- (3,3-dimethyl) -4,4-diphenylmethanebis (triphenylphosphine) bismaleimide, N, N '- (3,3-dichloro) -4,4-diphenylmethane bismaleimide, maleimide, N, N' N, N'-diphenylpropane bismaleimide, N, N'-naphthalene bismaleimide, N, N'-toluidine bismaleimide, -m-phenylenebismaleimide, N, N'-5- Bis (3-chloro-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Bis (3-ethyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Bis (3-propyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Phenyl) propane, 2,2-bis (3-butyl-4- (4-maleimidophenoxy) ) Propane, 1,1-bis (4- (4-maleimidophenoxy) phenyl) ethane, 1,1-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) ethane, 1,1-bis Bis (4- (4-maleimidophenoxy) phenyl) pentane, 1,1,1,3,3,3-hexafluoro-2,2- Pro , 1,1,1,3,3,3-hexafluoro-2,2-bis (3,5-dimethyl-4- (4-maleimidophenoxy) phenyl) propane, 1,1,1,3 , 3,3-hexafluoro-2,2-bis (3,5-dibromo-4- (4-maleimidophenoxy) phenyl) propane, N, N'-ethylene dimaleimide, N, N N, N'-p-xylenebismaleimide, N, N'-1-methylenebisimaleimide, N, N'- , 3-bismethylene cyclohexane bismaleimide, N, N'-2,4-tolylene bismaleimide and N, N'-2,6-tolylene bismaleimide. It is not. These may be used alone or in combination of two or more components.

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

In order to obtain higher planarization properties among these aromatic bismaleimides, those having a molecular weight of 1,000 or less are preferred.

In the present invention, the ratio of the bismaleimide compound as the component (F) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass, particularly preferably 100 to 50 parts by mass based on 100 parts by mass of the polyester (A) Is 2 to 20 parts by mass. When the ratio is too small, it may be difficult to obtain the effect of improving the planarizing property of the cured film obtained from the polyester composition for forming a thermosetting film. When the proportion is too large, the transmittance of the cured film may decrease or the film may become rough.

<Solvent>

The polyester composition for forming a thermosetting film of the present invention is often dissolved in a solvent and used in a solution state. The solvent used herein is one which dissolves the components (A) to (C), and optionally the components (D) to (F) and / or other additives described below. If the solvent has such a solubility, And the like are not particularly limited.

Such a solvent includes the solvent used for the polymerization of the component (A) and the following solvents. 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, and butyl lactate.

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

<Other additives>

In addition, the polyester composition for forming a thermosetting film of the present invention may contain, if necessary, additives such as a surfactant, a rheology modifier and the like, a pigment, a dye, a storage stabilizer, a defoamer, A dissolution accelerator such as a polyglycolic acid, and the like.

&Lt; Polyester composition for forming thermosetting film &

The polyester composition for forming a thermosetting film of the present invention contains a polyester as the component (A), a crosslinking agent as the component (B), a diester (or polyvalent ester) as the component (C) An antioxidant (phenol compound), a silane coupling agent as the component (E), a bismaleimide compound as the component (F), and further additives. And they are usually used as a solution in a solvent.

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

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

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

[3] The positive resist composition as described in [1] or [2], which comprises 3 to 50 parts by mass of the component (B), 1 to 100 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (D) E) component and 0.5 to 50 parts by mass of the component (F).

[4] A pressure-sensitive adhesive composition comprising: (B) 3 to 50 parts by mass of a component (C), 0.01 to 5 parts by mass of a component (D), and 0.5 to 30 parts by mass of E) component, 0.5 to 50 parts by mass of the component (F), and a solvent.

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

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

The preparation method of the polyester composition for forming a thermosetting film of the present invention is not particularly limited. For example, the preparation method thereof includes a method of dissolving the component (A) in a solvent, adding the component (B) (D), (E) and (F) in a predetermined ratio to prepare a homogeneous solution, or a method in which additional additives are further added and mixed in an appropriate step of the preparation method as required .

In the preparation of the polyester composition for forming a thermosetting film of the present invention, a solution of a polyester obtained by a polymerization reaction in a solvent may be used as it is. In this case, when the solution of the component (A) is made into a homogeneous solution by adding the component (B), the component (C), the component (D), the component (E) A solvent may be further added for the purpose. At this time, the solvent used in the production of the polyester and the solvent used for adjusting the concentration at the time of preparing the polyester composition for forming a thermosetting film may be the same or different.

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

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

The polyester composition for forming a thermosetting film of the present invention can be applied to a substrate (e.g., a substrate coated with a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal such as aluminum, molybdenum or chromium, , An ITO substrate, etc.) or a film (for example, a resin film such as a triacetylcellulose film, a polyester film, or an acrylic film), or the like is applied on the substrate by spin coating, roll coating, slit coating, , Printing or the like, and then pre-dried (pre-baked) with a hot plate or an oven to form a coating film. Thereafter, the coating film is formed by heating the coating film.

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

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

The post bake 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 hot plate and for 30 to 90 minutes in the oven.

By curing the polyester composition for forming a thermosetting film of the present invention under the above-described conditions, the step of the substrate can be sufficiently planarized, and a cured film having high transparency can be formed.

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

Conditions for the rubbing treatment are generally a condition of a rotational speed of 300 to 1000 rpm, a conveying speed of 3 to 200 mm / sec, and an indentation amount of 0.1 to 1 mm.

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

After applying the retardation material on the liquid crystal alignment layer thus formed, the retardation material may be in a liquid crystal state and photo-cured to form a layer having optically anisotropy.

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

Further, the 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 are opposed to each other through the spacer, and liquid crystal is injected between these substrates to form a liquid crystal display element in which liquid crystals are aligned.

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

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

Since the polyester composition for forming a thermosetting film of the present invention has at least a necessary level of planarizing property, the polyester composition for forming a protective film, a flattening film, an insulating film and the like in various displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL element It is also useful as a material for forming a cured film and can be used as a material for forming an overcoat material of a color filter, an interlayer insulating film of a TFT liquid crystal device, an insulating film of an organic EL device, and the like.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Abbreviations used in the examples]

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

&Lt; Polyester and diester compound raw materials >

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

BPDA: biphenyltetracarboxylic acid anhydride

BPADA: 4,4 '- (4,4'-isopropylidene diphenoxy) 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

&Lt; Polyester and diester compound polymerization catalyst >

BTEAC: Benzyltriethylammonium chloride

<Material for polyimide precursor>

CBDA: Cyclohexanetetracarboxylic acid dianhydride

pDA: p-phenylenediamine

&Lt; Acrylic copolymer raw material &

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<Epoxy Compound>

CEL: Daicel Chemical Industries Limited CELLOXIDE P-2021 (trade name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate)

<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:? -Methacryloxypropyltrimethoxysilane

<Bismaleimide compound>

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

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene glycol monomethyl ether

NMP: N-methylpyrrolidone

The number average molecular weight and the weight average molecular weight of the polyester, polyimide precursor and acrylic copolymer obtained according to the following Synthesis Examples were measured using a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation and eluting solvent tetrahydrofuran At a flow rate of 1 ml / min in a column (column temperature: 40 占 폚). The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are shown in terms of polystyrene conversion.

&Lt; Synthesis Example 1 &

A polyester solution (solid concentration: 30.0 mass%) was obtained by reacting 18.0 g of HBPDA, 4.54 g of BPDA, 15.9 g of HBPA, 2.01 g of THPA and 0.19 g of BTEAC in 95.1 g of PGMEA at 125 DEG C for 19 hours. The obtained polyester had Mn of 1,310 and Mw of 3,270.

&Lt; Synthesis Example 2 &

A polyester solution (solid concentration: 30.0 mass%) was obtained by reacting 12.0 g of HBPDA, 10.2 g of HBPA, 0.95 g of THPA and 0.22 g of BTEAC in 54.48 g of PGMEA at 125 DEG C for 19 hours (P2). The obtained polyester had 1,980 Mn and Mw 3,500.

&Lt; Synthesis Example 3 &

A polyester solution (solid content concentration: 30.0 mass%) was obtained by reacting 18.0 g of HBPDA, 7.37 g of BPADA, 17.0 g of HBPA, 2.15 g of THPA and 0.10 g of BTEAC in 125.2 g of PGMEA at 125 ° C for 19 hours (solid content concentration: 30.0 mass%). The obtained polyester had Mn of 1,440 and Mw of 3,080.

&Lt; Synthesis Example 4 &

A diester solution (solid concentration 30.0 mass%) was obtained by reacting 16.82 g (0.070 mol) of HBPA, 20.85 g (0.137 mol) of THPA and 0.096 g of BTEAC in 88.13 g of PGMEA at 130 캜 for 16 hours (A1).

&Lt; Synthesis Example 5 &

A diester solution (solid concentration 30.0 mass%) was obtained by reacting 8.13 g (0.070 mol) of CHDO, 20.85 g (0.137 mol) of THPA and 0.096 g of BTEAC in 67.86 g of PGMEA at 130 캜 for 16 hours (A2).

&Lt; Synthesis Example 6 &

The diester solution (solid concentration 30.0 mass%) was obtained by reacting 16.82 g (0.070 mol) of HBPA, 21.13 g (0.137 mol) of HPA and 0.096 g of BTEAC in 88.77 g of PGMEA at 130 ° C for 16 hours (A3).

&Lt; Synthesis Example 7 &

A diester solution (solid concentration 30.0 mass%) was obtained by reacting 5.50 g (0.042 mol) of CHTO, 17.08 g (0.112 mol) of THPA and 0.057 g of BTEAC in 52.83 g of PGMEA at 130 ° C for 16 hours.

&Lt; Synthesis Example 8 &

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

&Lt; Synthesis Example 9 &

A polyimide precursor solution (solid concentration: 30.0 mass%) was obtained by reacting 17.7 g of CBDA and 10.2 g of pDA in 66.4 g of NMP at 23 DEG C for 24 hours (P4). The obtained polyimide precursor had Mn of 5,800 and Mw of 12,500.

&Lt; Synthesis Example 10 &

10.9 g of MAA, 35.3 g of CHEMI, 25.5 g of HEMA and 28.3 g of MMA were used as monomer components and 5 g of AIBN was used as a radical polymerization initiator. These were polymerized in 150 g of solvent PGMEA at a temperature of 60 to 100 캜 to obtain an acrylic copolymer solution Solid concentration: 40.0% by mass) (P5). The obtained acrylic copolymer solution had Mn of 3,800 and Mw of 6,700.

&Lt; Examples 1 to 9 and Comparative Examples 1 to 3 >

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was prepared with the composition shown in Table 1, and the cured film obtained by this composition was applied to each of the compositions shown in Table 1 in the order of flatness, solvent resistance, And heat resistance (transmittance) were evaluated.

(G) 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 to P3: Polyester solution P4: Polyimide precursor solution P5: Acrylic copolymer solution

[Evaluation of planarization property]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied to a stepped substrate (glass) having a height of 1.0 mu m, a line width of 100 mu m and a laminar space of 40 mu m using a spin coater, Lt; 0 &gt; C for 120 seconds on a hot plate to form a coating film having a thickness of 2.5 mu m. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked by heating in a hot air circulating oven at 230 캜 for 30 minutes to form a cured film having a thickness of 2.0 탆.

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

Further, 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 Resistance]

Each of the compositions 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 DEG C for 120 seconds to form a layer having a thickness of 2.8 mu m To form a coating film. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was subjected to post-baking in a hot air circulating oven at 230 캜 for 30 minutes to form a cured film having a thickness of 2.5 탆.

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

[Evaluation of orientation]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was coated on an ITO substrate using a spin coater and then prebaked on a hot plate at a temperature of 100 캜 for 120 seconds to form a film having a thickness of 2.8 탆 Was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This film was subjected to post-baking in a hot-air circulating oven at 230 캜 for 30 minutes to form a cured film.

This cured film was rubbed at a rotation speed of 400 rpm, a conveying speed of 30 mm / sec, and an indentation amount of 0.4 mm. The rubbed substrate was ultrasonically cleaned with pure water for 5 minutes.

A retardation material made of a liquid crystal monomer was coated on the substrate using a spin coater and then prebaked on a hot plate at 80 DEG C for 60 seconds to form a coating film having a film thickness of 1.4 mu m. This substrate was exposed at 1,000 mJ under a nitrogen atmosphere. The prepared substrate was placed in a polarizing plate and the orientation was visually confirmed. When the substrate was tilted at 45 degrees and when it was not tilted, it was indicated that the light transmittance was remarkably changed, and when it was not changed, it was indicated by x.

[Evaluation of adhesion]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was coated on a quartz substrate using a spin coater, prebaked on a hot plate at a temperature of 100 DEG C for 120 seconds, Post baking was performed in a hot air circulating oven for 30 minutes to form a cured film.

This cured film was rubbed at a rotation speed of 400 rpm, a conveying speed of 30 mm / sec, and an indentation amount of 0.4 mm. The rubbed substrate was ultrasonically cleaned with pure water for 5 minutes.

A retardation material made of a liquid crystal monomer was coated on the substrate using a spin coater and then prebaked on a hot plate at 80 DEG C for 60 seconds to form a coating film having a thickness of 1.4 mu m. This substrate was exposed at 1,000 mJ under a nitrogen atmosphere. 25 squares of 1 mm x 1 mm were formed on the coated film, and then subjected to an adhesive tape peeling test (use tape: Cellotape (registered trademark)). Out of the 25 squares, no peeling was marked as O, and even one peeling was marked as X.

[Evaluation of transparency (transmittance)] [

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was coated on a quartz substrate using a spin coater and then prebaked on a hot plate at a temperature of 100 캜 for 120 seconds to form a film having a thickness of 2.8 탆 Was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coated film was subjected to post-baking in a hot air circulating oven at 230 캜 for 30 minutes to form a cured film.

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

[Evaluation of heat resistance (transmittance)] [

The cured film evaluated for transparency described above was further heated in a hot air circulating oven at 230 캜 for 3 hours, and then the transmittance at a wavelength of 400 nm was measured using an ultraviolet visible spectrophotometer (Shimadzu Corporation SHIMADSUUV-2550 model number).

[Results of evaluation]

The evaluation results are shown in Table 2 below.

Flattening rate (%) Solvent resistance Orientation
Adhesiveness
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 both planarization ratio, PGMEA and NMP. In addition, they all exhibited good orientation and achieved high transmittance (transparency) even after further high-temperature firing after high-temperature firing, and also had heat resistance. And all the examples had good adhesion to the retardation material.

On the other hand, in Comparative Example 1, no cured film was formed.

In Comparative Example 2, although the solvent resistance, heat resistance and orientation were good, the problem was left in the transparency, the flatness rate was very low, and the adhesiveness was deteriorated.

In Comparative Example 3, the flatness, the solvent resistance, and the transparency were good, but the orientation and adhesion were deteriorated.

As described above, in the polyester composition for forming a thermosetting film of the present invention, a glycol solvent such as propylene glycol monomethyl ether acetate can be used at the time of forming a cured film, and the obtained cured film is excellent in light transmittance, solvent resistance, Mars, adhesion and orientation All performances were good.

[Industrial Availability]

The polyester composition for forming a thermosetting film according to the present invention is extremely useful as a liquid crystal alignment layer of an optically anisotropic film or a liquid crystal display device and is also useful as a protective film for various displays such as a thin film transistor (TFT) type liquid crystal display device, , A flattening film, a material for forming a cured film such as an insulating film, particularly a material for forming 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 and the like.

Claims (18)

A polyester composition for forming a thermosetting film, which comprises a polyester as a component (A), a crosslinking agent as a component (B), and at least one diester compound represented by the following formula (1) as a component (C).

(Wherein P represents an alicyclic group, a group comprising an alicyclic group and an aliphatic group or a structure represented by the formula (2), Q represents an alicyclic group, or a group consisting of an alicyclic group and an aliphatic group. Lt; / RTI &gt;
The method according to claim 1,
Wherein the component (C) is a diester compound obtained by reacting one mole of a diol compound represented by the following formula (iii) with 1.7 to 2 moles of a dicarboxylic anhydride represented by the following formula (iv).

(Wherein P represents an alicyclic group, a group comprising an alicyclic group and an aliphatic group or a structure represented by the formula (2), Q represents an alicyclic group or a group consisting of an alicyclic group and an aliphatic group, and P and Q are each contained in each group May be substituted with an aliphatic group. In the formula (2), R represents an alkylene group.)
3. The method of claim 2,
P represents a group represented by the following formula (1P1).

(Wherein, P ¹ represents a cyclic saturated hydrocarbon group, P ¹ groups are optionally any of the hydrogen atoms are substituted with an aliphatic, each independently of the. R ¹¹ is a single bond, a carbonyl group, an ether group, a sulfonic acid group, the number of carbon atoms 1 And R ¹² and R ¹³ each independently represent a single bond or an alkylene group of 1 to 5 carbon atoms, and h represents an integer of 0 to 8, Or 1).
3. The method of claim 2,
And Q represents a group represented by the following formula (1Q1).

(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 Lt; 3 &gt;
The method according to claim 1,
And the component (C) contains at least one polyvalent ester compound represented by the following formula (1-a).

(Wherein 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 the formula (2-a), Qa represents an alicyclic group, and t represents an integer of 1 to 5. Ra in the formula (2-a) represents an alkylene group.
The method according to claim 1,
Wherein the component (A) is a polyester comprising a structural unit represented by the following formula (3).

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

(Wherein A represents a tetravalent organic group having four aliphatic groups bonded to an alicyclic group or aliphatic group and B represents a divalent organic group having two aliphatic groups bonded to an alicyclic group or aliphatic group)
The method according to claim 6,
(3), A represents at least one kind of group selected from the groups represented by the following formulas (A-1) to (A-8) and B represents at least one group selected from the following formulas (B- ). &Lt; / RTI &gt; wherein R &lt; 1 &gt; and R &lt; 2 &gt;

The method according to claim 1,
Wherein the polyester (A) has a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene.
The method according to claim 1,
The polyester composition for forming a thermosetting film further contains a phenol compound as an antioxidant as the component (D).
The method according to claim 1,
A polyester composition for forming a thermosetting film further comprising a silane coupling agent as the component (E).
The method according to claim 1,
A polyester composition for forming a thermosetting film further comprising a bismaleimide compound as the component (F).
The method according to claim 1,
3 to 50 parts by mass of the component (B) and 1 to 100 parts by mass of the component (C) based on 100 parts by mass of the component (A).
11. The method of claim 10,
(D) in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the component (A).
12. The method of claim 11,
And 0.5 to 30 parts by mass of component (E) based on 100 parts by mass of the component (A).
13. The method of claim 12,
(F) in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the component (A).
A cured film obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 16.
A liquid crystal alignment layer obtained by using the polyester composition for forming a thermosetting film according to any one of claims 1 to 16.

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