TWI488914B - Polyester composition for forming thermoset film - Google Patents

Description

Polyester composition for forming a thermosetting film

The present invention relates to a polyester composition for forming a thermosetting film and a cured film obtained therefrom. More specifically, it is a polyester composition for forming a thermosetting film having high transparency, flatness, liquid crystal alignment energy, high solvent resistance and heat resistance, a cured film thereof, and a method for applying the cured film. The polyester composition for forming a thermosetting film is suitably used as a color filter protective film which has a liquid crystal alignment function in a liquid crystal display.

In an optical device such as a liquid crystal display device, an organic EL (electroluminescent) device, or a solid-state imaging device, a protective film is provided in order to prevent exposure of the surface of the device to a solvent and heat used in manufacturing a production line. In addition to high adhesion and high solvent resistance to the substrate to be protected, the protective film is required to have properties such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state imaging device, it is generally required to have a flat color filter or a black matrix resin for planarizing the underlying substrate. , that is, the performance of the flat film. In particular, when manufacturing color display elements of the STN type and the TFT type, the color filter substrate and the counter substrate need to have a very close bonding precision, so that the cell pitch between the substrates is uniform. Further, in order to maintain the transmittance of the light transmitted through the color filter, the planarizing film like the protective film needs to have high transparency.

Further, in recent years, it has been reviewed to introduce a phase difference material into a cell of a liquid crystal display device to reduce cost and weight, and such a phase difference material which is generally used is a material which is subjected to re-photo-hardening after coating a liquid crystal cell. In order to align the phase difference material to the need thereof, the underlying film is honed to have an aligning material. Therefore, after the liquid crystal alignment layer is formed on the protective film of the color filter, a phase difference material can be formed (refer to FIG. 2(a)). The formation of a layer (see FIG. 2(b)) having the protective film of the liquid crystal alignment layer and the color filter can have advantages such as cost reduction and number of steps to be reduced, and thus such materials are strongly required.

Generally, the protective film of the color filter is made of an acrylic resin having high transparency. From the viewpoint of safety and handling properties, such acrylic resins are widely used as a glycol solvent of propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate, and an ester solvent of ethyl lactate or butyl lactate. Thermal curing and photocuring of such an acrylic resin can impart heat resistance and solvent resistance (Patent Documents 1 and 2). Although the conventional thermosetting and photocurable acrylic resin has appropriate transparency and flattening properties, sufficient aligning properties cannot be obtained by subjecting the planarizing film to honing treatment.

Further, in general, the liquid crystal alignment layer is made of a solvent-soluble polyimine and a polyamic acid. It has been reported that such materials can be subjected to post-baking to impart solvent resistance when fully imidized, and sufficient alignment can be obtained by honing treatment (Patent Document 3). However, in the case of a flattening film of a color filter, problems such as flatness and transparency are greatly reduced. Further, polyimine and polylysine are soluble in a solvent of N-methylpyrrolidone and γ-butyrolactone, but have low solubility in a glycol solvent and an ester solvent, and are difficult to be used in production. The production line of flattening film.

Based on the above, the problem to be solved by the present invention is to provide high solvent resistance, liquid orientation, heat resistance, high transparency, and high flatness after formation of a cured film, and to dissolve in a cured film. A material suitable for a glycol solvent for a production line of a flattening film of a color filter.

The inventors of the present invention have intensively studied in order to solve the above problems, and as a result, have completed the present invention.

In other words, the first aspect relates to a polyester composition for forming a thermosetting film, which is a polyester containing (A) component, a crosslinking agent of (B) component, and (C) component of the following formula (1). At least one diester compound is indicated.

(wherein P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group. In the formula (2), R is an alkylene group).

The second aspect is the polyester composition for forming a thermosetting film according to the first aspect, wherein the component (C) is a diol compound 1 mol represented by the following formula (iii), and the following formula (iv) A diester compound obtained by reacting a dicarboxylic anhydride of 1.7 to 2 moles.

(wherein P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group. Further, P and Q may each be such that any hydrogen atom contained in each group is substituted with an aliphatic group; in the formula (2), R is an alkylene group).

The third aspect is the polyester composition for forming a thermosetting film according to the second aspect, wherein P is a group represented by the following formula (1P1).

(wherein P ¹ is 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, and a carbon number of 1 to 8; a saturated hydrocarbon group or a saturated hydrocarbon group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and each of R ¹² and R ^{13 is} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and h is 0 or 1).

The fourth aspect is the polyester composition for forming a thermosetting film according to the second aspect or the third aspect, wherein Q is a group represented by the following formula (1Q1).

(wherein Q ¹ is a cycloalkyl group having 4 to 8 carbon atoms or a cycloalkenyl group, and any hydrogen atom in the Q ¹ group may be substituted by an aliphatic group or a phenyl group; X is a single bond or a carbon number 1 to 3 alkyl groups).

The fifth aspect is the polyester composition for forming a thermosetting film according to the first aspect, wherein the component (C) contains at least one polyvalent ester compound represented by the following formula (1-a).

(wherein, P _a is an alicyclic group or an aliphatic alkyl group interrupted by an oxygen atom or a nitrogen atom, or a structure represented by the formula (2-a), Q _a is an alicyclic group, and t is 1 to An integer of 5; in the formula (2-a), R _a is an alkylene group).

The polyester composition for forming a thermosetting film according to any one of the first aspect to the fifth aspect, wherein the component (A) is a polyester having a structural unit represented by the following formula (3).

(wherein, A is a tetravalent organic group in which an alicyclic group or an aliphatic group is bonded to four bonding bonds, and B is an alicyclic group or a divalent organic group in which an aliphatic group is bonded to two bonding bonds) .

The polyester composition for forming a thermosetting film according to any one of the first aspect to the sixth aspect, wherein the component (A) is a tetracarboxylic dianhydride represented by the following formula (i) (ii) a polyester obtained by reacting the represented diol compound.

(wherein, A is a tetravalent organic group in which an alicyclic group or an aliphatic group is bonded to four bonding bonds, and B is an alicyclic group or a divalent organic group in which an aliphatic group is bonded to two bonding bonds) .

The eighth aspect is the polyester composition for forming a thermosetting film according to the sixth aspect or the seventh aspect, wherein in the formula (3), A is represented by the following formula (A-1) to formula (A-8). At least one group selected from the group, and B is at least one selected from the group represented by the following formulas (B-1) to (B-5).

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

The polyester composition for forming a thermosetting film according to any one of the first aspect to the ninth aspect, further comprising a phenol compound for an antioxidant of the component (D).

The polyester composition for forming a thermosetting film according to any one of the first aspect to the tenth aspect, further comprising a decane coupling agent for the component (E).

The polyester composition for forming a thermosetting film according to any one of the first aspect to the eleventh aspect, further comprising a bismaleimide compound for the component (F).

The polyester composition for forming a thermosetting film according to any one of the first aspect to the twelfth aspect, wherein the component (B) is contained in an amount of from 3 to 50 parts by mass based on 100 parts by mass of the component (A), and C) The component is 1 to 100 parts by mass.

The polyester composition for forming a thermosetting film according to the tenth aspect, wherein the component (D) is contained in an amount of 0.01 to 5 parts by mass based on 100 parts by mass of the component (A).

The fifteenth aspect is the polyester composition for forming a thermosetting film according to the eleventh aspect, wherein the component (E) is contained in an amount of from 0.5 to 30 parts by mass based on 100 parts by mass of the component (A).

The polyester composition for forming a thermosetting film according to the twelfth aspect, wherein the (F) component contains 0.5 to 50 parts by mass based on 100 parts by mass of the component (A).

The seventeenth aspect relates to a cured film obtained by using the polyester composition for forming a thermosetting film according to any one of the first aspect to the sixteenth aspect.

The ninth aspect relates to a liquid crystal alignment layer which is obtained by using the polyester composition for forming a thermosetting film according to any one of the first aspect to the sixteenth aspect.

The polyester composition for forming a thermosetting film of the present invention can form a cured film having a liquid crystal alignment energy in addition to high flatness, high transparency, high solvent resistance, and high heat resistance, and thus is suitable as a liquid crystal alignment film and A material for forming a planarizing film. In particular, the "liquid crystal alignment layer" having the characteristics of both the previously formed liquid crystal alignment film and the protective film of the color filter can be formed at one time, so that the manufacturing process can be simplified, the number of steps can be reduced, and the cost can be reduced.

Further, since the polyester composition for forming a thermosetting film of the present invention is soluble in a glycol solvent, it is suitable for use in a production line using a planarizing film mainly using such a solvent.

(Best form of implementing the invention)

As described above, the acrylic resin and the polyimide-based cured film which have been proposed in advance cannot sufficiently satisfy all the properties such as planarization property, transparency, and alignment property required for the liquid crystal alignment film and the planarization film.

In the prior art, the alignment material of the liquid crystal display element has been proposed to use a polyester (refer to Japanese Laid-Open Patent Publication No. H5-158055, JP-A-2002-229039), but none of them have thermosetting properties and the cured film is formed. Poor solvent resistance.

The present invention is characterized in that a thermosetting polyester is used to enhance properties such as flatness, transparency, and alignment properties. That is, the present invention is a polyester composition for forming a thermosetting film comprising the polyester for (A) component, the crosslinking agent for (B) component, and the following formula (1) for (C) component. The diester compound represented.

(wherein P is an alicyclic group, a group containing an alicyclic group and a group formed by an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group The group formed by the group, and in the formula (2), R is an alkyl group).

Further, in addition to the above components (A) to (C), the polyester composition for forming a thermosetting film may further contain a phenol compound for the antioxidant of the component (D) and a decene couple for the component (E). Mixture, (F) component of the bismaleimide compound.

The components will be described in detail below.

[(A) ingredients]

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

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

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

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

The aliphatic group of the substituent at this time is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, a crosslinked cyclic hydrocarbon group such as a norenyl group or an adamantyl group or a partially or fully hydrogenated condensed polycyclic hydrocarbon group may be formed.

In the above formula, R ¹ is 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 which is substituted by a fluorine atom. Preferred are 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 which is substituted by a fluorine atom.

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

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

In the above formula (3), B is a divalent organic group in which two bonding bonds are bonded to an alicyclic group or an aliphatic group, and is preferably a group represented by the following formula (3B1) or formula (3B2).

B ¹ in the formula is 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 of the hydrogen atoms contained in the B ¹ group may be independently substituted with an aliphatic group.

The aliphatic group of the substituent at this time is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to each other to form a ring, for example, a crosslinked cyclic hydrocarbon group such as a norenyl group or an adamantyl group or a partially or fully hydrogenated condensed polycyclic hydrocarbon group can be formed.

Further B ² is a phenyl group.

In the formula, R ³ is 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 which is substituted by a fluorine atom, preferably a single bond or a carbonyl group. And 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 which is substituted by a fluorine atom.

R ⁴ and R ⁵ are each independently 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 are each independently an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 1 to 3 carbon atoms.

Also, k is 0 or 1.

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

The polyester of the component (A) preferably has a structure in which at least one selected from the group represented by the formula (3A1) to the formula (3A3) is contained in the structural unit represented by the formula (3), but It may contain a structure other than the group represented by the formula (3A1) to the formula (3A3). In the structure in which the polyester can be formed at this time, the structure thereof is not particularly limited, and at least one selected from the group consisting of the groups represented by the following formulas (3A4) to (3A5) is preferable.

In the above formula, R ⁸ , R ⁹ and R ¹⁰ are each independently 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 atomic number of 1 to 8 substituted by a fluorine atom. The hydrocarbon group 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 which is substituted by a fluorine atom.

R ^{8 is} particularly 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 by a fluorine atom, and R ^{9 is} particularly preferably 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 by a fluorine atom, and R ^{10 is} particularly preferably 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 by a fluorine atom.

Again h is 0 or 1.

Specific examples of the above formulas (3A4) to (3A5) are preferably as shown in the following formulas (a1) to (a7).

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

The polyester of the component (A) preferably has a weight average molecular weight of 1,000 to 30,000, more preferably 1,500 to 10,000. When the weight average molecular weight of the polyester of the component (A) is less than the above range, the alignment property and the solvent resistance tend to be lowered, and when it exceeds the above range, the planarization property is lowered.

<Method for producing (A) component>

The polyester of the component (A) of the present invention can be obtained, for example, by polymerizing a tetracarboxylic dianhydride and a diol compound. More preferably, a tetracarboxylic dianhydride (hereinafter also referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i) and a diol compound represented by the following formula (ii) are contained. The diol compound (hereinafter also referred to as a diol component) is obtained by reaction.

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

In the polyester of the above (A) component, the total ratio of the tetracarboxylic dianhydride (the total amount of the acid component) to the total amount of the diol compound (the total amount of the diol component), that is, the <diol compound The total number of moles>/<the total number of moles of the tetracarboxylic dianhydride compound> is preferably from 0.5 to 1.5. As with the general polycondensation reaction, the degree of polymerization of the polyester formed when the molar ratio is approximately 1 is large, and the molecular weight can be increased.

The polyester of the component (A) is preferably an acid anhydride end in order to avoid a decrease in preservation stability.

The end of the above polyester varies depending on the ratio of addition of the acid component to the glycol component. For example, when the reaction is carried out with an excess of an acid component, the terminal tends to be an acid anhydride.

Further, when polymerization is carried out with an excess of a glycol component, the terminal tends to become a hydroxyl group. At this time, the terminal hydroxyl group is reacted with a carboxylic acid anhydride, and the terminal hydroxyl group can be blocked by an acid anhydride. Such carboxylic anhydrides such as phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methyl 1,2-cyclohexanedicarboxylic anhydride, 4-phenyl-1,2-cyclohexanedicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, tetrahydrophthalic anhydride Methyltetrahydrophthalic anhydride, bicyclo[2.2.2]octene-2,3-dicarboxylic anhydride, and the like.

When the polyester of the above (A) component is produced, 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 from 100 ° C to 140 ° C, and the reaction time is from 2 to 48 hours to obtain a polyester.

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

The reaction of the above acid component with the glycol component is generally carried out in a solvent. The solvent to be used at this time may be one which does not contain a hydroxyl group and an amine group and a functional group capable of reacting with an acid anhydride, and is not particularly limited. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylammonium , tetramethyl urea, dimethyl hydrazine, hexamethylarylene, m-cresol, γ-butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2 -heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate Ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, and the like.

These solvents may be used singly or in combination, but propylene glycol monomethyl ether acetate is more preferable in terms of safety and pipeline suitability for a protective film of a color filter.

Further, in the range in which the polyester produced by the polymerization reaction is not precipitated, the solvent may be used in combination with a solvent which does not dissolve the polyester.

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

Specific examples of the catalyst used in polymerizing the polyester are, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzylidene. a quaternary ammonium salt such as tripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride or tetrapropylammonium bromide, Tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide, etc. Grade IV strontium salt.

The solution of the polyester containing the component (A) thus obtained can be used as it is for preparing a polyester composition for forming a thermosetting film. Further, the obtained polyester can be precipitated in a weak solvent such as water, methanol, ethanol, diethyl ether or hexane, and recycled.

<(B) ingredients>

The component (B) of the present invention is a crosslinking agent. The crosslinking agent is a compound such as an epoxy compound or a methylol compound, but is preferably an epoxy compound having two or more epoxy groups.

The compound is, for example, tris(2,3-epoxypropyl)trimeric isocyanate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(oxiranyl)cyclohexane , glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy Phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methyl bis(N,N-diglycidyl aniline), 3,4-epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol A-diglycidyl ether, and pentaerythritol-based polyglycidyl ether.

Further, commercially available compounds can be used from the viewpoint of availability. The following is a specific example (trade name), but it is not limited thereto. YH-434, YH434L (Dongdu Chemical Co., Ltd.) and other amine-based epoxy resins; Yepperit GT-401, GT-403, GT-301, GT-302, Shi Luoji 2021, Shi Luoji 3000, epoxy resin with cyclohexene oxide structure such as Michelin P-2021 (manufactured by Tay's Chemical Industry Co., Ltd.); Yippitol 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (above is bisphenol A type epoxy resin such as oleified shell epoxy (stock) (now manufactured by Japan Epoxy Resin Co., Ltd.); yippic 807 (oiled shell epoxy (share)) Bisphenol F type epoxy resin such as Japan Epoxy Resin Co., Ltd.; Jupiter 152, 154 (above: oleified shell epoxy (stock) (now Japanese epoxy resin) ), EPPN 201, 202 (above is Nippon Chemical Co., Ltd.) and other phenol novolac type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 ( The above is a cresol novolak type epoxy resin such as Nippon Chemical Co., Ltd., and Jupiter 180S75 (oily shell epoxy (stock) (now Japanese epoxy resin)); EX-252 (Kaihe (share) system), CY 175, CY 177, CY 179, Aier CY-182, CY-192, CY-184 (above CIBA-GEIGY, AG), Yepikulong 200, 400 (above is DIC (share) system), Yepitol 871, 872 (oiled shell epoxy (share) (now Japanese epoxy resin) ))), ED-5661, ED-5662 (above), alicyclic epoxy resin; Danakol EX-611, EX-612, EX-614, EX-622, EX - aliphatic polyglycidyl ether such as -411, EX-512, EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Kaiser).

Further, a polymer having an epoxy group of a compound having at least two epoxy groups can be used. The polymer may be any one having an epoxy group and is not particularly limited.

The above epoxy group-containing polymer can be produced, for example, by a polyaddition reaction using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl acrylate, copolymer of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and copolymer of styrene and 2-hydroxyethyl methacrylate Polyaddition polymers such as polyaddition polymers, and epoxy novolacs.

Further, the epoxy group-containing polymer may be obtained by reacting a polymer compound having a hydroxyl group with a compound having an epoxy group such as epichlorohydrin or glycidyl p-toluenesulfonate.

The weight average molecular weight of such polymers is, for example, from 300 to 200,000.

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

In the polyester composition for forming a thermosetting film of the present invention, the content of the crosslinking agent of the component (B) is preferably from 3 to 50 parts by mass, more preferably from 5 to 50 parts by mass per 100 parts by mass of the polyester of the component (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 lowered, and when it is too large, solvent resistance and storage stability are lowered.

<(C) ingredients>

The component (C) is a diester compound represented by the following formula (1). In the present invention, the diester compound of the component (C) may be used alone or in a plurality of compounds represented by the formula (1).

In the formula, P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group. The groups, P and Q may each be a group in which any hydrogen atom is replaced by an aliphatic group.

Further, in the formula (2), R is an alkylene group, R is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, particularly preferably 1 to 5 carbon atoms. 3 alkylene.

In the above formula, a preferred structure of P is represented by the above formula (2) or the following formula (1P1).

In the formula, P ¹ is 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 of the hydrogen atoms in the group P ¹ may be independently substituted with an aliphatic group.

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

In the above formula, R ¹¹ is 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 by 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 which is substituted by a fluorine atom.

R ¹² and R ¹³ are each independently 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.

Again h is 0 or 1.

Specific examples of P of the above formula (1) are preferably represented by the following formulas (P-1) to (P-5).

In the above formula (2), Q is a group formed of an alicyclic group or an alicyclic group and an aliphatic group, and is preferably a group represented by the following formula (1Q1).

In the formula, Q ¹ is a cycloalkyl group or a cycloalkenyl group having 4 to 8 carbon atoms, preferably a cycloalkyl group or a cycloalkenyl group having 4 to 6 carbon atoms. Any hydrogen atom in the group Q ¹ may be substituted with an aliphatic group.

The substituent is an aliphatic group, preferably an aliphatic group having 1 to 6 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms.

Further, X is a single bond or an alkylene group having 1 to 3 carbon atoms.

Specific examples of Q are preferably, for example, cyclobutane, methylcyclobutane, dimethylcyclobutane, cyclopentyl, cyclohexyl, methylcyclohexyl, tetrahydroindenyl or methyl. Tetrahydroindenyl and the like.

The diester compound of the component (C) of the present invention may be 1.7 to 2 moles, preferably 1.8 to 2, based on the diol 1 mole represented by the following formula (iii) and the dicarboxylic anhydride represented by the formula (iv). 2 Moore reaction derived.

In the above formula (iii) and formula (iv), P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic ring. a group formed by a formula and an aliphatic group, and in the formula (2), R is an alkylene group. Further, P, Q and R are the same as defined in the above formulas (1) and (2), and preferred embodiments are also the same as described above.

The diol compound represented by the above formula (iii) and the dicarboxylic acid anhydride represented by the formula (iv) of the present invention may be used singly or in combination of plural kinds.

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

The component (C) may be a polyvalent ester compound represented by the following formula (1-a). In the present invention, the polyvalent ester compound may be used alone or in combination of a plurality of compounds represented by the formula (1-a).

Wherein P _a is an alicyclic group or an aliphatic hydrocarbon group interrupted by an oxygen atom or a nitrogen atom, or a structure represented by the formula (2-a), Q _a is an alicyclic group, and t is 1 to 5 The integers, P _a and Q _{a ,} may each be such that any hydrogen atom in the group is replaced by an aliphatic group. Further, in the formula (2-a), R _a is an alkylene group, and R _{a is} preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, particularly preferably carbon. An alkyl group having an atomic number of 1 to 3.

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 above formula (iii-a) and formula (iv-a), P _a is an alicyclic group or an aliphatic alkyl group interrupted by an oxygen atom or a nitrogen atom, or a structure represented by the formula (2-a). t is an integer from 1 to 5, Q _a is an alicyclic group, and in the formula (2-a), R _a is an alkylene group. Further, P _a , Q _a and R _{a are the} same as defined in the above formula (1-a) and formula (2-a), and preferred embodiments are also the same as described above.

In the present invention, the polyvalent alcohol compound represented by the above formula (iii-a) and the dicarboxylic acid anhydride represented by the formula (iv-a) may be used singly or in combination of plural kinds.

The polyvalent alcohol compound represented by the above formula (iii-a) is a compound such as 1,3,5-cyclohexanetriol or pentaerythritol.

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

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

When the diester compound (or polyvalent ester compound) of the above (C) component is produced, the reaction temperature of the diol compound (or polyvalent alcohol compound) with the dicarboxylic anhydride may be from 50 to 200 ° C, preferably from 80 to 170 ° C. Choose any temperature. For example, the reaction temperature is from 100 ° C to 140 ° C, and the reaction time is from 2 to 48 hours to obtain a diester compound (or a polyvalent ester compound).

The reaction of the above diol compound (or polyvalent alcohol compound) with a dicarboxylic acid anhydride is generally carried out in a solvent. The solvent to be used at this time is not particularly limited as long as it does not contain a functional group capable of reacting with an acid anhydride such as a hydroxyl group or an amine group. For example, N,N-dimethylformamide, N,N. Dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl hydrazine, tetramethyl urea, dimethyl hydrazine, hexamethylarylene, M-cresol, γ-butyrolactone, cyclohexanone, cycloheptanone, 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, 3-ethoxypropane Ethyl acetate, ethyl 2-ethoxypropionate, and the like.

These solvents may be used singly or in combination, but propylene glycol monomethyl ether acetate is more preferable in terms of safety and pipeline suitability for a protective film of a color filter.

Further, in the range in which the diester compound produced by the polymerization reaction is not precipitated, a solvent in which the diester compound is not dissolved may be used in combination with the above solvent.

Further, a catalyst may be used in the reaction of the above diol compound (formula (iii)) (or polyvalent alcohol compound (iii-a)) with a dicarboxylic anhydride (formula (iv) or formula (iv-a)).

Specific examples of the catalyst used at this time include, for example, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, and benzyltri a quaternary ammonium salt such as propyl ammonium chloride, benzyl tripropyl ammonium bromide, tetramethyl ammonium chloride, tetraethyl ammonium bromide, tetrapropyl ammonium chloride, tetrapropyl ammonium bromide, tetraphenyl Four grades such as chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide鏻 salt.

In the polyester composition for forming a thermosetting film of the present invention, the content of the component (C) is preferably from 1 to 100 parts by mass, more preferably from 5 to 60 parts by mass, per 100 parts by mass of the polyester of the component (A). When the ratio is too small, the alignment property and flatness of the cured film obtained from the polyester composition for forming a thermosetting film are lowered, and when it is too large, the light transmittance is lowered.

<(D) ingredient>

The present invention may contain an antioxidant of the component (D). The component (D) can effectively prevent the film from discoloring due to the set high-temperature baking in the process after forming the thermosetting film.

The antioxidant of the component (D) is particularly preferably a phenol compound, which is specifically, for example, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-phenol, 2,4, 6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl) , pentaerythritol tetrakis[3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate], acetone bis(3,5-di-t-butyl-4-hydroxybenzene Thiol, 4,4'-extended methylbis(2,6-di-t-butylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)propane Methyl ester, 4,4'-thiobis(2,6-di-t-butylphenol), tris(3,5-di-t-butyl-4-hydroxybenzyl)trimeric isocyanic acid, Bis(3,5-di-t-butyl-4-hydroxybenzyl) sulfide or the like.

The phenol compound of such an antioxidant is not particularly limited to the above. Further, these may be used alone or in combination of two or more.

Among these antioxidants, 2,6-di-t-butyl-4-methylphenol, 2,4,6-tris(3',5'-di-t-butyl-4'-hydroxybenzyl group ) 4,4'-extended methyl bis(2,6-di-t-butylphenol) or the like is not preferable because it does not lower the alignment property and has high heat resistance.

The use ratio of the phenolic compound of the antioxidant of the component (D) in the present invention is preferably from 0.01 to 5 parts by mass, more preferably from 0.1 to 3 parts by mass, per 100 parts by mass of the polyester of the component (A). When the ratio is too small, sufficient effect of the antioxidant is not obtained, and when it is too large, the alignment property is lowered and the coating film is rough.

<(E) ingredient>

The present invention may contain a decane coupling agent for the component (E).

The decane coupling agent of the component (E) can effectively improve the adhesion to the phase difference material formed of the polymerizable liquid crystal.

Specific examples of such decane coupling agents include chlorodecanes such as trimethylchlorodecane, dimethylvinylchlorodecane, methyldiphenylchlorodecane, and chloromethyldimethyldecane; trimethylmethoxydecane Alkoxydecanes such as dimethyldiethoxydecane, methyltrimethoxydecane, dimethylvinylethoxysilane, diphenyldimethoxydecane, and phenyltriethoxydecane; a decyl alkane such as hexamethyldiazepine, N,N'-bis(trimethyldecyl)urea, dimethyltrimethyldecylalkylamine or trimethyldecyl imidazole; vinyl trichlorodecane , γ-aminopropyltriethoxydecane, γ-methylpropoxypropyltrimethoxydecane, γ-methylpropoxypropyltriethoxydecane, γ-glycidoxypropane a decane such as triethoxy decane or γ-(N-piperidinyl)propyl triethoxy decane; benzotriazole, benzimidazole, oxazole, imidazole, 2-mercaptobenzimidazole, 2- Heterocyclic compounds such as mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercapto imidazole, mercaptopyrimidine, and 1,1-dimethylurea, 1,3-dimethylurea, etc. Urea or urea Was such silane-coupling agents may be used alone or in combination of two.

Among these decane coupling agents, the adhesion to the phase difference material and the storage stability are particularly preferably γ-methacryloxypropyltriethoxydecane.

As the above-mentioned decane coupling agent, commercially available compounds such as Shin-Etsu Chemical Co., Ltd., MOMENTIVE, and Toray (share) can be used, and such commercial products are easily available.

The amount of the decane coupling agent to be added is usually 0.5 to 30 parts by mass, preferably 0.8 to 20 parts by mass, per 100 parts by mass of the component (A). When the amount is 20 parts by mass or more, the solvent resistance of the coating film is lowered, and when it is less than 0.5 part by mass, a sufficient decane coupling agent effect cannot be obtained.

<(F) ingredient>

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

In the above formula, 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 an organic group formed by combining a plurality of selected organic groups selected from the group. Further, Y may contain a bond such as an ester bond, an ether bond, a guanamine bond or a urethane bond.

The maleic imine compound represented by the above formula (4) is, for example, N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl- 5,5-Dimethyl)-4,4-diphenyl-methane bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, 3,3-di Phenylhydrazine, bismaleimide, 4,4-diphenylfluorene, maleimide, N,N'-p-benzophenone, bismaleimide, N,N'-diphenyl Ethyl bismaleimide, N,N'-diphenyl ether bismaleimide, N,N'-(methyl-di-ditetrahydrophenyl) bismaleimide, N , N'-(3-ethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dimethyl)-4,4-diphenylmethane double Maleic imine, N,N'-(3,3-diethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dichloro)- 4,4-diphenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N'-triazine bismaleimide, N,N'- Diphenylpropane bismaleimide, N,N'-naphthalene bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-5-methoxy Benzyl-1,3-phenylene bismaleimide, 2,2-bis(4-(4-maleimide) Phenyl)propane, 2,2-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-) Maleimide phenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-dual ( 3-propyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimide phenoxy) Phenyl)propane, 2,2-bis(3-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-() 4-maleimide phenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3- Methyl-4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl) Ethane, 1,1-bis(3-bromo-4-(4-maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimide) Oxy)phenyl)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 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' - Ethyl dimaleimide, N, N'-hexamethyl-maleimide, N, N'-twelve methyl bismaleimide, N, N'-m- Xylene bismaleimide, N,N'-p-xylene maleimide, N,N'-1,3-dual methylcyclohexane bismaleimide, N,N '-2,4-Extended benzyl bismaleimide, N,N'-2,6-benzylidene bismaleimide, etc., but is not particularly limited to the above. These may be used alone or in combination of two or more.

Preferred among these bismaleimides are 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, N,N'-4,4-diphenylmethane. Aromatic double horses such as bismaleimide, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismaleimide Come to imine.

Further, among these aromatic bismaleimine, a polymer having a molecular weight of 1,000 or less is preferable in order to obtain higher flatness.

In the present invention, the use ratio of the (B) component of the bismaleimide compound to 100 parts by mass of the polyester of the component (A) is preferably from 0.5 to 50 parts by mass, more preferably from 1 to 30 parts by mass, particularly preferably It is 2 to 20 parts by mass. When the ratio is too small, it is difficult to obtain an effect of flattening the cured film obtained by the polyester composition for forming a thermosetting film. When the ratio is too large, the light transmittance of the cured film is lowered and the coating film is roughened.

<solvent>

Most of the polyester composition for forming a thermosetting film of the present invention is dissolved in a solvent and used in a solution state. The solvent to be used at this time is a substance which dissolves (A) component to (C) component, if necessary, component (D) to component (F) and/or other additives described later, and may have such a solubility energy. The solvent, the kind and structure thereof are not particularly limited.

Such a solvent is, for example, a solvent for polymerizing (A) component and the following solvent. 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 may be used alone or in combination of two or more.

<Other additives>

Further, if the effect of the present invention is not impaired, the polyester composition for forming a thermosetting film of the present invention may contain a secondary agent such as a surfactant or a liquid flow regulator, a pigment, a dye, a preservation stabilizer, an antifoaming agent, and the like. A dissolution promoter such as a phenol or a polycarboxylic acid.

<Polyester composition for forming a thermosetting film>

The polyester composition for forming a thermosetting film of the present invention is a polyester containing the component (A), a crosslinking agent of the component (B), a diester (or a polyvalent ester of the component (C), and a desired one. (D) an antioxidant (phenol compound) of the component, a decane coupling agent of the component (E), a bismaleimide compound of the component (F), or a composition of one or more other additives. Most of the solution is dissolved in a solvent and used as a solution.

The polyester composition for forming a thermosetting film of the present invention is preferably as follows.

[1]: A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 1 to 100 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).

[2]: A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 1 to 100 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).

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

[4]: 3 parts by mass to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), 0.01 to 5 parts by mass of the component (D), and 0.5 to 5 parts by weight of the component (E) 30 parts by mass, (F) component: 0.5 to 50 parts by mass, and a polyester composition for forming a thermosetting film of a solvent.

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

The ratio of the solid content in the polyester composition for forming a thermosetting film of the present invention is not particularly limited, and the component can be uniformly dissolved in a solvent, and may be 1 to 80% by mass, preferably 5 to 60% by mass, more preferably Preferably, it is 10 to 50% by mass. The solid content at this time means a substance obtained by removing all the 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, after the component (A) is dissolved in a solvent, the solution, the component (B), and the component (C) are mixed at a constant ratio. And (D) component, (E) component, (F) component to obtain a homogeneous solution, or in a suitable stage of the preparation method, a method of mixing other additives as necessary.

When the polyester composition for forming a thermosetting film of the present invention is prepared, a polyester solution obtained by polymerization in a solvent can be used as it is. In this case, the component (B), the component (C), the component (D), the component (E), and the component (F) may be added to the solution of the component (A) to form a homogeneous solution, and then the concentration may be further adjusted. Put in the solvent. The solvent used in the process for producing the polyester at this time may be the same as or different from the solvent for adjusting the concentration when the polyester composition for forming a thermosetting film is prepared.

Further, it is preferably used after a solution of a polyester composition for forming a thermosetting film obtained by filtration using a filter having a pore size of 0.2 μm or the like.

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

The polyester composition for forming a thermosetting film of the present invention is subjected to spin coating, flow coating, roll coating, slit coating, slit coating, inkjet coating, and printing to be equal to a substrate (for example, ruthenium/dioxide). a substrate, a tantalum nitride substrate, a coated metal such as a substrate such as aluminum, molybdenum or chromium, a glass substrate, a quartz substrate or an ITO substrate, or a film (for example, a triacetyl cellulose film, a polyester film, an acrylic film, etc.) After the resin film or the like is applied above, it is prepared by drying (pre-baking) using a hot plate or an oven to form a coating film. Thereafter, the coating film is heat-treated to form a coating film.

The conditions of the heat treatment may be, for example, a temperature of from 70 ° C to 160 ° C, and a suitable heating temperature and heating time in the range of from 0.3 to 60 minutes. The heating temperature and heating time are preferably from 0.5 to 10 minutes at 80 ° C to 140 ° C.

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

Post-baking is generally carried out by using a heating temperature in the range of 140 ° C to 250 ° C for 5 to 30 minutes on a hot plate or 30 to 90 minutes in an oven.

When the polyester composition for forming a thermosetting film of the present invention is cured under the above conditions, the substrate step can be sufficiently flattened to form a cured film having high transparency.

The honing treatment of the cured film formed as described above can impart a function to a liquid crystal alignment layer even if a layer having a liquid crystal compound is aligned.

The conditions of the honing treatment are generally those using a rotation speed of 300 to 1000 rpm, a conveying speed of 3 to 200 mm/sec, and a pushing amount of 0.1 to 1 mm.

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

After the phase difference material is applied to the liquid crystal alignment layer formed as described above, the phase difference material is photocured into a liquid crystal state, and a layer having optical anisotropy can be formed.

The phase difference material used is, for example, a liquid crystal monomer having a polymerizable group, a composition containing the same, and the like.

Further, after the two substrates having the liquid crystal alignment layer formed as described above are bonded to the liquid crystal alignment layer in a face-to-face manner, the liquid crystal is injected between the substrates to obtain a liquid crystal display element in which the liquid crystal is aligned.

Further, the substrate on which the liquid crystal alignment layer is formed is in the form of a film, and can be used as a material for an optically anisotropic film.

As described above, the polyester composition for forming a thermosetting film of the present invention is suitable for use in various optically anisotropic films and liquid crystal display elements.

Moreover, since the polyester composition for forming a thermosetting film of the present invention has at least a required level of flatness, it is preferably used as a protective film or a flattening film for forming various types of displays such as a thin film transistor (TFT) type liquid crystal display element and an organic EL. The material of the cured film such as an insulating film is preferably a material suitable for a protective film of a color filter, an interlayer insulating film of a TFT liquid crystal element, or an insulating film of an organic EL element.

Example

The invention will be described in more detail below by way of examples, but the invention is not limited thereto.

[Code used in the embodiment]

The following is the meaning of the code used in the examples.

<Polyester and diester compound raw materials>

HBPDA: 3,3'-4,4'-dicyclohexyltetracarboxylic 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 Diester Compounds Polymerization Catalyst>

BTEAC: benzyl triethyl ammonium chloride

<Polyimide precursor materials>

CBDA: cyclohexane tetracarboxylic dianhydride

pDA: p-phenylenediamine

<Acrylic based copolymer raw material>

MAA: Methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<epoxy compound>

CEL: Michelin P-2021 (product name) manufactured by Taychel Chemical Industry Co., Ltd. (Compound name: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexenecarboxylate Acid ester)

<antioxidant>

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

MBP: 4,4'-extended methyl bis(2,6-di-t-butylphenol)

<decane coupling agent>

MPS: γ-methacryloxypropyltrimethoxydecane

<Bismaleimide compound>

BMI1: 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, the polyimide precursor, and the acrylic copolymer obtained in the following synthesis examples were measured by a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L) manufactured by JASCO Corporation. The dissolution solvent tetrahydrofuran was flowed in a column at a flow rate of 1 ml/min (column temperature 40 ° C) to determine the conditions for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1>

HBPS 18.0 g, BPDA 4.54 g, HBPA 15.9 g, THPA 2.01 g, and BTEAC 0.19 were reacted in PGMEA 95.1 g at 125 ° C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P1). The obtained polyester had an Mn of 1,310 and a Mw of 3,270.

<Synthesis Example 2>

12.0 g of HBPDA, 10.2 g of HBPA, 0.95 g of THPA, and 0.22 g of BTEAC were reacted at 54.58 g of PGMEA at 125 ° C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P2). The obtained polyester had an Mn of 1,980 and a Mw of 3,500.

<Synthesis Example 3>

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 were reacted at 104.2 g of PGMEA at 125 ° C for 19 hours to obtain a polyester solution (solid content concentration: 30.0% by mass) (P3). The obtained polyester had an Mn of 1,440 and a Mw of 3,080.

<Synthesis Example 4>

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

<Synthesis Example 5>

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

<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 in 88.77 g of PGMEA were reacted at 130 ° C for 16 hours to obtain a diester solution (solid content concentration: 30.0% by mass) (A3).

<Synthesis Example 7>

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

<Synthesis Example 8>

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

<Synthesis Example 9>

CBDA 17.7 g and pDA 10.2 g were reacted in NMP 66.4 g at 23 ° C for 24 hours to obtain a polyimine precursor solution (solid content concentration: 30.0% by mass) (P4). The obtained polyimide precursor had an Mn of 5,800 and a Mw of 12,500.

<Synthesis Example 10>

The monomer components used were MAA 10.9g, CHMI 35.3g, HEMA 25.5g, MMA 28.3g, and the radical polymerization initiator used was AIBN 5g, which was polymerized in a solvent PGMEA 150g at a temperature of 60 ° C to 100 ° C. The reaction was carried out to obtain an acrylic-based copolymer solution (solid content concentration: 40.0% by mass) (P5). The solution of the obtained acrylic-based copolymer was Mn of 3,800 and Mw of 6,700.

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

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was prepared according to the composition shown in Table 1, and the flatness, solvent resistance, alignment, and density of the cured film obtained from the composition were evaluated. Synergy, transparency and heat resistance (light transmittance).

[Evaluation of flatness]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied onto a stepped substrate (made of glass) having a height of 1.0 μm, a line width of 100 μm, and a space between the lines of 40 μm using a spin coater. It was pre-baked on a hot plate at 100 ° C for 120 seconds to form a coating film having a film thickness of 2.5 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was heated in a hot air circulating oven at a temperature of 230 ° C for 30 minutes for post-baking to form a cured film having a film thickness of 2.0 μm.

The film thickness difference between the coating film on the step substrate line and the coating film on the space is measured (refer to FIG. 1), and the flattening ratio (DOP)=100×[1-{film thickness difference (μm)/step difference substrate of the coating film is used. The height (1.0 μm)}] is used to obtain the flattening rate.

The condition for confirming the planarization film was at least 60% or more of the flattening ratio.

[Evaluation of Solvent Resistance]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied onto a ruthenium circuit board using a spin coater, and placed on a hot plate at 100 ° C for 120 seconds to pre-bake to form a film thickness. Coating film of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. The coating film was post-baked in a hot air circulating oven at a temperature of 230 ° C for 30 minutes to form a cured film having a film thickness of 2.5 μm.

The cured film was immersed in PGMEA or NMP for 60 seconds, and then dried at a temperature of 100 ° C for 60 seconds, and the film thickness was measured. A substance having no change in film thickness after being immersed in PGMEA or NMP was regarded as ○, and a substance having a reduced film thickness after immersion was regarded as ×.

[Assessing the alignment]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied onto an ITO substrate by a spin coater, and then placed on a hot plate at 100 ° C for 120 seconds to form a film thickness of 2.8. Μm coating film. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked for 30 minutes in a hot air circulating oven at a temperature of 230 ° C to form a cured film.

The cured film was subjected to honing treatment at a rotation speed of 400 rpm, a conveyance speed of 30 mm/sec, and a pushing amount of 0.4 mm. The substrate after the honing treatment was washed with pure water ultrasonic for 5 minutes.

A phase difference material formed of a liquid crystal monomer was applied onto the substrate by a spin coater, and then pre-baked on a hot plate at 80 ° C for 60 seconds to form a coating film having a film thickness of 1.4 μm. The substrate was exposed at 1,000 mJ under nitrogen. The obtained substrate was held by a deflecting plate, and the alignment was visually confirmed. When the substrate is inclined at 45 degrees and when there is no inclination, the light transmittance is significantly changed as ○, and the unchanged is regarded as ×.

[Evaluation of adhesion]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied onto a quartz substrate using a spin coater, and placed on a hot plate at 100 ° C for 120 seconds for prebaking, followed by temperature. After 30 seconds of post-baking in a hot air circulating oven at 230 ° C, a cured film was formed.

The cured film was subjected to honing treatment at a rotation speed of 400 rpm, a conveyance speed of 30 mm/sec, and a pushing amount of 0.4 mm. The substrate after the honing treatment was washed with pure water ultrasonic for 5 minutes.

A phase difference material formed of a liquid crystal monomer was applied onto the substrate by a spin coater, and then pre-baked on a hot plate at 80 ° C for 60 seconds to form a coating film having a film thickness of 1.4 μm. The substrate was exposed at 1,000 mJ under nitrogen. An adhesive tape peeling test (using a tape: Cello-tap (registered trademark)) was carried out by cutting 25 1 mm × 1 mm grids on the obtained coating film. The 25 uncut objects that were cut out completely were regarded as ○, and one peeled object was regarded as ×.

[Evaluation of transparency (light transmittance)]

Each of the compositions of Examples 1 to 9 and Comparative Examples 1 to 3 was applied onto a quartz substrate by a spin coater, and placed on a hot plate at 100 ° C for 120 seconds to form a film thickness of 2.8. Μm coating film. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked for 30 minutes in a hot air circulating oven at a temperature of 230 ° C to form a cured film.

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

[Evaluation of heat resistance (light transmittance)]

The cured film was evaluated by heating in a hot air circulating oven at a temperature of 230 ° C for 3 hours. The ultraviolet light visible spectrophotometer (SHIMADSU UV-2550 model manufactured by Shimadzu Corporation) was used to measure the light transmittance at a wavelength of 400 nm. rate.

[evaluation result]

The above evaluation results are shown in Table 2 below.

Each of Examples 1 to 9 has a high flattening rate and is resistant to both PGMEA and NMP. They all have good alignment properties, and after high-temperature calcination and after high-temperature calcination, high light transmittance (transparency) can be achieved, and heat resistance is provided. Further, any of the examples has good adhesion to the phase difference material 圴.

However, Comparative Example 1 did not form a cured film.

Further, in Comparative Example 2, although it had good solvent resistance, heat resistance, and alignment, it still had a problem of transparency, and the flatness was extremely low and the adhesion was poor.

In Comparative Example 3, although it had a good flatness, solvent resistance, and transparency, the alignment property and the adhesion were inferior.

As described above, the polyester composition for forming a thermosetting film of the present invention can use a glycol solvent such as propylene glycol monomethyl ether acetate when the cured film is formed, and the obtained cured film has excellent light transmittance. Any property of solvent resistance, heat resistance, flatness, adhesion and alignment.

[Industry use possibility]

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

[Previous Technical Literature] [Patent Literature]

Patent Document 1: JP-A-2000-103937

Patent Document 2: JP-A-2000-119472

Patent Document 3: JP-A-2005-037930

Fig. 1 is a schematic view showing a cured film formed when a thermosetting polyester composition is applied to a step substrate.

Fig. 2 is a schematic view showing a comparison between a liquid crystal cell (a) for forming a liquid crystal alignment film by the prior art and a liquid crystal cell (b) for forming a planarization film using the polyester composition for forming a thermosetting film of the present invention.

Claims (16)

A polyester composition for forming a thermosetting film, which comprises a component (A): a polyester having a structural unit represented by the following formula (3) and having a weight average molecular weight of 1,000 to 30,000, and (B) a component: The crosslinking agent and the component (C) are at least one diester compound represented by the following formula (1), and contain 3 to 50 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and (C) component 1 to 100 parts by mass, (wherein P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group. a base; in the formula (2), R is an alkyl group), (wherein, A is a tetravalent organic group in which an alicyclic group or an aliphatic group is bonded to four bonding bonds, and B is an alicyclic group or a divalent organic group in which an aliphatic group is bonded to two bonding bonds) . The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (C) is a diol compound represented by the following formula (iii) and is represented by the following formula (iv) a diester compound obtained by reacting a dicarboxylic anhydride of 1.7 to 2 moles, (wherein P is a group formed by an alicyclic group, an alicyclic group or an aliphatic group or a structure represented by the formula (2), and Q is an alicyclic group or an alicyclic group and an aliphatic group. Further, P and Q may each be such that any hydrogen atom contained in each group is substituted with an aliphatic group; in the formula (2), R is an alkyl group). The polyester composition for forming a thermosetting film according to the second aspect of the invention, wherein P is a group represented by the following formula (1P1), (wherein P ¹ is a cyclic saturated hydrocarbon group, and any hydrogen atom in the P ¹ group may be independently substituted by an aliphatic group; and R ¹¹ is a single bond, a carbonyl group, an ether group, a sulfonic acid group, or a carbon number of 1 to a saturated hydrocarbon group of 8 or a saturated hydrocarbon group having 1 to 8 carbon atoms which is substituted by a fluorine atom, and each of R ¹² and R ^{13 is} independently a single bond or an alkylene group having 1 to 5 carbon atoms, and h is 0 or 1). A polyester composition for forming a thermosetting film according to item 2 of the patent application, wherein Q is a group represented by the following formula (1Q1), [Chemical 4]-Q ¹ -x- (1Q1) (wherein Q ¹ is a cycloalkyl group having 4 to 8 carbon atoms or a cycloalkenyl group, and any hydrogen atom in the Q ¹ group may be substituted by an aliphatic group; X is a single bond or an alkylene group having 1 to 3 carbon atoms base). The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (C) contains at least one polyvalent ester compound represented by the following formula (1-a), (wherein, P _a is 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), Q _a is an alicyclic group, and t is 1 to An integer of 5; in the formula (2-a), R _a is an alkylene group). The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (A) is a tetracarboxylic dianhydride represented by the following formula (i) and a diol represented by the formula (ii) a polyester obtained by reacting a compound, (wherein, A is a tetravalent organic group in which an alicyclic group or an aliphatic group is bonded to four bonding bonds, and B is an alicyclic group or a divalent organic group in which an aliphatic group is bonded to two bonding bonds) . The polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein in the formula (3), A is selected from the group represented by the following formula (A-1) to formula (A-8). At least one group, B is at least one selected from the group represented by the following formulas (B-1) to (B-5), A polyester composition for forming a thermosetting film according to the first aspect of the invention, which further comprises a phenol compound for an antioxidant of the component (D). A polyester composition for forming a thermosetting film according to the first aspect of the invention, which further comprises a decane coupling agent for the component (E). The polyester composition for forming a thermosetting film according to the first aspect of the invention, which further comprises a bismaleimide compound for the component (F). For example, the polyester group for forming a thermosetting film according to item 8 of the patent application scope The product contains 0.01 to 5 parts by mass of the component (D) with respect to 100 parts by mass of the component (A). The polyester composition for forming a thermosetting film according to claim 9, wherein the component (E) is contained in an amount of from 0.5 to 30 parts by mass based on 100 parts by mass of the component (A). The polyester composition for forming a thermosetting film according to claim 10, wherein the component (F) is contained in an amount of from 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 13. A liquid crystal alignment layer obtained by using a polyester composition for forming a thermosetting film according to any one of claims 1 to 13. A liquid crystal alignment layer characterized by using a cured film as in claim 14 of the patent application.