TWI462946B - Thermoset coating forming polyester composition - 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 thereafter. More specifically, it relates to a polyester composition for forming a thermosetting film having high transparency and flatness, and having liquid crystal alignment energy and high solvent resistance, and a cured film thereof, and a cured film. The polyester composition for forming a thermosetting film is particularly suitable for a color filter protective film which has a liquid crystal alignment function in a liquid crystal display.

In general, in an optical device such as a liquid crystal display element, an organic EL (electroluminescent) element, or a solid-state imaging element, a protective film is provided in order to prevent the surface of the element from being exposed to a solvent or heat in a manufacturing step. This protective film is not only highly adhesive to the substrate to be protected, but also has high solvent resistance, and is required to have properties such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter to be used in a color liquid crystal display device or a solid-state imaging device, it is generally required to have a color filter or a black matrix resin having a base substrate flat thereon. The performance means that it has the property as a planarizing film. In particular, when a color liquid crystal display device of the STN method or the TFT method is manufactured, the bonding precision between the color filter substrate and the opposite substrate must be very strictly performed, and the gap between the substrates must be uniform. Further, in order to maintain the transmittance of light transmitted through the color filter, it is necessary to have high transparency in the planarization of the protective film.

In addition, in recent years, in the chamber of a liquid crystal display, in addition to reviewing the introduction of a phase difference material to reduce cost and weight, such a phase difference material is generally used for coating a liquid crystal cell and aligning it to light. Hardened material. In order to align the phase difference material, it is necessary to have an alignment material after the underlayer film is polished. Therefore, after the liquid crystal alignment film is formed on the protective film of the color filter, the phase difference material is formed (refer to FIG. 2(a)). If the film having the protective film of the liquid crystal alignment film and the color filter can be formed (refer to FIG. 2(b)), since the cost can be reduced and the number of process steps can be reduced, the material is quite satisfactory. look forward to.

Generally, in the protective film of the color filter, an acrylic resin having high transparency can be used. Among these acrylic resins, a glycol-based solvent such as propylene glycol monomethyl ether or propylene glycol monomethyl ether acetate or ethyl lactate or butyl lactate is used from the viewpoint of safety and workability. Ester solvents are more widely used. Such an acrylic resin can be thermally cured or photocured to impart heat resistance or solvent resistance (Patent Documents 1 and 2). However, in the past, the thermosetting or photocurable acrylic resin exhibits appropriate transparency or flattenability, and even if such a flattened film is polished, it does not exhibit sufficient alignment.

Further, a material composed of a solvent-soluble polyimine or poly-proline is usually used in the liquid crystal alignment film. In the case of such materials, it has been reported that the solvent resistance is imparted by the imidization of the ruthenium during the post-baking, and sufficient alignment property is exhibited by the polishing treatment (Patent Document 3). However, when the color filter is a flattened film, there is a problem that flatness and transparency are greatly lowered. Further, although polyacrylamide or polyaminic acid is soluble in a solvent such as N-methylpyrrolidone or γ-butyrolactone, it has low solubility in a solvent of a glycol solvent or an ester system, and is difficult to apply. In the flat film production line.

[Patent Document 1] JP-A-2000-103937

[Patent Document 2] JP-A-2000-119472

[Patent Document 3] JP-A-2005-037920

The present invention is based on the above-mentioned circumstances, and the problem to be solved is to provide a high solvent resistance, liquid crystal alignment property, heat resistance, high transparency, and high planarization property after formation of a cured film, and hardening. When the film is formed, it may be a material which can be dissolved in a glycol solvent or a lactic acid ester solvent in a production line for a flattening film of a color filter.

The inventors of the present invention have achieved the present invention by focusing on the results of the research aimed at solving the above problems.

In other words, the first aspect relates to a polyester composition for forming a thermosetting film containing the following components (A) and (B).

(A) component: a polyester containing a structural unit represented by the following formula (1),

Component (B): an epoxide having two or more epoxy groups.

[Chemical 1]

(In the formula, A is at least one selected from the group consisting of the groups represented by the following formulas (A-1) to (A-15), and B is represented by the following formula (B-1) to formula (B). -5) At least one selected from the group shown.)

[Chemical 2]

[Chemical 3]

[Chemical 4]

The polyester composition for forming a thermosetting film according to the first aspect, wherein, in the formula (1), A is a group represented by the formula (A-1) to the formula (A-8). At least one of the selected groups.

The polyester composition for forming a thermosetting film according to the first aspect or the second aspect, wherein the component (A) contains a tetracarboxylic dianhydride represented by the following formula (i) A polyester obtained by reacting a tetracarboxylic acid component with a diol compound represented by the following formula (ii).

[Chemical 5]

(wherein A and B are the same as defined in the above formula (1).)

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

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

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

The polyester composition for forming a thermosetting film according to the fifth aspect or the sixth aspect, wherein the polyester composition is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the component (A). ingredient.

The eighth aspect is a cured film obtained by using the polyester composition for forming a thermosetting film according to any one of the first aspect to the seventh aspect.

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

The polyester composition for forming a thermosetting film of the present invention can be formed into a liquid crystal alignment film by forming a cured film having a liquid crystal alignment energy in addition to high planarization property, high transparency, high solvent resistance, and high heat resistance. Or planarizing the film forming material. In particular, it is possible to form a "flattening film" having both characteristics of the liquid crystal alignment film and the color filter protective film layer which are formed independently in the prior art, thereby simplifying the manufacturing steps and reducing the number of process steps. Cost reduction, etc.

Further, the polyester composition for forming a thermosetting film of the present invention is applicable to a production line of a planarizing film mainly using such a solvent because it is soluble in a glycol solvent and a lactic acid ester solvent.

[Best Mode for Carrying Out the Invention]

As described above, in the cured film of the acrylic resin type and the polyimide film of the prior art, the flatness, transparency, and alignment which are required for the liquid crystal alignment film or the planarizing film are not sufficiently satisfied. Wait for all the performance.

In addition, in the case of the use of the polyester, there is a proposal for the use of the polyester (see Japanese Patent Laid-Open No. Hei 5-158055, No. 2002-229039), but not all of them have thermosetting properties. The formed film has poor solvent resistance.

The present invention is characterized in that it is intended to enhance the aforementioned properties by using a thermosetting polyester, that is, the present invention contains the polyester of the component (A) and the component (B) having two or more rings. A polyester composition for forming a thermosetting film of an epoxide of an oxy group. Further, in addition to the components (A) and (B), a polyester composition for forming a thermosetting film which can contain a bismaleimine compound as the component (C) is further included.

Each component will be described in detail below.

<(A) component>

The component (A) contains a polyester having a structural unit represented by the following formula (1).

[Chemical 6]

In the above formula, A is at least one selected from the group consisting of the groups represented by the following formulas (A-1) to (A-15), and B is represented by the following formula (B-1) to formula (B). -5) At least one selected from the group shown.

[Chemistry 7]

[化8]

[Chemistry 9]

Among the groups represented by the above formulas (A-1) to (A-15), it is preferred that the groups represented by the formulae (A-1) to (A-8) are also improved from the viewpoint of improving heat resistance. It is preferable to use the base selected by the formulas (A-1) and (A-2).

Further, among the groups represented by the above formulae (B-1) to (B-5), those selected by (B-1) to (B-4) are particularly preferable.

The polyester of the component (A) is preferably a polyester formed by the unit structure represented by the formula (1). In this case, the A and B systems are each independently one or more.

At this time, in addition to many other properties, in an attempt to improve heat resistance, at least 60 mol% of A of the formula (1) is a base represented by the above formula (A-1) to formula (A-8). It is better.

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

<Method for Producing (A) Component>

In the present invention, the polyester of the component (A) is reacted with a tetracarboxylic dianhydride (acid component) represented by the following formula (i) and a diol compound (diol component) represented by the following formula (ii). And got it.

[化10]

In the above formula, A and B are the same as defined in the above formula (1).

In the present invention, the acid component and the diol component may each independently be a compound of one kind or a plurality of compounds.

Further, in the present invention, by using a polyester obtained from an aliphatic tetracarboxylic dianhydride, in addition to other properties, an improvement in heat resistance can be achieved. Therefore, the polyester of the component (A) of the present invention is preferably an aliphatic tetracarboxylic dianhydride of at least 60 mol% of the acid component used, specifically, in the formula (i), A is preferably a tetracarboxylic dianhydride represented by the above formula (A-1) to formula (A-8).

In the polyester of the component (A), the blending ratio of the total amount of the tetracarboxylic dianhydride (the total amount of the acid components) and the total amount of the diol compound (the total amount of the diol components) means that the diol is The total number of moles of the compound>/<the total number of moles of the tetracarboxylic dianhydride compound> is from 0.5 to 1.5. Similarly to the general polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the resulting polyester and the higher the molecular weight.

In order to avoid a decrease in preservation stability, the end of the polyester of the component (A) is preferably protected with a dicarboxylic anhydride or an alcohol. From the point of view of the orientation, it is better to protect with an acid anhydride.

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

Further, when the diol component is excessively polymerized, the terminal tends to become a hydroxyl group. At this time, the terminal hydroxyl group is allowed to react with the carboxylic acid anhydride, and the terminal hydroxyl group can be blocked by the acid anhydride. Examples of such a carboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, anhydrous maleic acid, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-norbornene- 2,3-dicarboxylic anhydride, anhydrous itaconic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, bicyclo[2.2.2)octene-2,3-dicarboxylic anhydride, and the like.

In the production of the polyester of the component (A), the reaction temperature of the acid component and the diol component may be 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 is carried out for 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 any temperature of 50 to 200 ° C, preferably 80 to 170 ° C.

The reaction of the above acid component with the diol component is usually carried out in a solvent. The solvent which can be used at present is not particularly limited as long as it is a functional group which does not contain a hydroxyl group or an amine group and which reacts with an acid anhydride. For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl Azulene, tetramethyl urea, dimethyl hydrazine, hexamethyl hydrazine, 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, 3-methoxy Ethyl propionate, 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 preferred from the viewpoint of safety and suitability for a production line of a protective film for a color filter.

Further, even a solvent which does not dissolve the polyester may be used in the above solvent in the range in which the polyester formed by the polymerization reaction is not precipitated.

Further, when the acid component (formula (i)) and the diol component (formula (ii)) are reacted, a catalyst may be used.

Specific examples of the catalyst used in the polymerization of the polyester include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, and benzyltriethylamine. Base ammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide Quaternary ammonium salt, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium a quaternary phosphonium salt such as chloride or ethyltriphenylphosphonium bromide.

The solution containing the polyester of the component (A) obtained in this manner can be directly used for the preparation of the polyester composition for thermosetting film formation. Further, the polyester may be precipitated and isolated in a poor solvent such as water, methanol, ethanol, diethyl ether or hexane to be recovered and used.

<(B) component>

The epoxide having two or more epoxy groups in the component (B) of the present invention may, for example, be bis(2,3-epoxypropyl)isocyanate or 1,4-butanediol diglycidyl ether or 1, 2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1, 1,3-parade [p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylene double (N, N-diglycidylaniline, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether and bisphenol-A-di Glycidyl ether, pentaerythritol polyglycidyl ether, and the like.

Further, in view of the ease of obtaining, a compound of a commercially available product can also be used. The specific examples (trade names) are listed below, and are not limited to these: amine-based epoxy resins such as YH-434 and YH434L (made by Toho Chemical Co., Ltd.); EPOLEADGT-401, EPOLEADGT-403, Epoxy resin having a cyclohexene oxide structure such as EPOLEADGT-301, EPOLEADGT-302, CELLOXIDE 2021, CELLOXIDE 3000 (manufactured by DAICEL Chemical Industry Co., Ltd.); EPIKOTE1001, EPIKOTE1002, EPIKOTE1003, EPIKOTE1004, EPIKOTE1007, EPIKOTE1009, EPIKOTE1010, EPIKOTE828 (above, oiled SHELL epoxy (shares) (now Japan Epoxy resin)) bisphenol A type epoxy resin; EPIKOTE807 (oiled SHELL epoxy (stock) (now Japanese epoxy resin) (Fly))) bisphenol F type epoxy resin; EPIKOTE 152, EPIKOTE 154 (above, oiled SHELL epoxy (stock) (now Japanese epoxy resin)), EPPN201, EPPN202 (above, Japan) Phenolic novolac type epoxy resin such as chemical (stock) system; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.) ), EPIKOTE 180S75 (oiled SHELL epoxy (stock) (now Japan Epoxy resin)) cresol novolak type ring Oxygen resin; DENACOLEX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, manufactured by CIBA-GEIGY AG), EPICLON 200, EPICLON 400 (above) , Dainippon Ink Chemical Industry Co., Ltd., EPIKOTE871, EPIKOTE872 (above, oiled SHELL epoxy (shares) (now Japanese epoxy resin)), ED-5661, ED-5662 (above, CELANESE) Epoxy epoxy resin such as COATING (density); DENACOL EX-611, DENACOLE EX-612, DENACOLE EX-614, DENACOLE EX-622, DENACOLE EX-411, DENACOLE EX-512, DENACOLE EX-522, An aliphatic polyglycidyl ether such as DENACOLE EX-421, DENACOLE EX-313, DENACOLE EX-314, DENACOLE EX-321 (manufactured by Nagase ChemteX Co., Ltd.).

Further, as the compound having at least two epoxy groups, a polymer having an epoxy group can be used. In the case of such a polymer, those having an epoxy group can be used without particular limitation.

The above-mentioned epoxy group-containing polymer can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl polyacrylate, a copolymer of glycidyl methacrylate and methyl ethyl acrylate, a glycidyl methacrylate and a copolymer of styrene and 2-hydroxymethyl ethyl acrylate, etc. A polycondensation polymer such as an addition polymerization polymer or an epoxy novolac.

Alternatively, the above epoxy group-containing polymer can be produced by reacting a polymer compound having a hydroxyl group with an epoxy group-containing compound such as epichlorohydrin or glycidyl tosylate. .

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

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

The epoxide having two or more epoxy groups of the component (B) in the polyester composition for forming a thermosetting film of the present invention, and the content thereof is based on 100 parts by mass of the polyester of the component (A). It is preferably 3 to 50 parts by mass, more preferably 5 to 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. On the other hand, when the ratio is too large, the solvent resistance is lowered and the storage stability is lowered.

<(C) component>

In the present invention, the component (C) may contain a bismaleimine compound represented by the following formula (2).

The bismaleimide compound of the component (C) can improve the planarization property.

[11]

In the formula, R ₁ 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 selected from a plurality of organic groups selected from the group. Next, R ₁ may also contain a bond such as an ester bond, an ether bond, a guanamine bond, or a urethane bond.

In the case of such a bismaleimide compound, for example, N,N'-3,3-biphenylmethane bismaleimide, N,N'-(3,3-diethyl- 5,5-Dimethyl)-4,4-biphenyl-methane bismaleimide, N,N'-4,4-biphenylmethane bismaleimide, 3,3-linkage Phenylhydrazine, bismaleimide, 4,4-biphenylindole, bismaleimide, N,N'-p-benzophenone, bismaleimide, N,N'-biphenyl Ethyl bismaleimide, N,N'-biphenyl ether bismaleimide, N,N'-(methyldi-ditetrahydrophenyl) bismaleimide, N, N'-(3-ethyl)-4,4-biphenylmethane bismaleimide, N,N'-(3,3-dimethyl)-4,4-biphenylmethane醯imine, N,N'-(3,3-diethyl)-4,4-biphenylmethane bismaleimide, N,N'-(3,3-dichloro)-4 , 4-biphenylmethane bismaleimide, N, N'-isophorone bismaleimide, N, N'-tolidine bismaleimide, N, N'- Biphenylpropane bismaleimide, N,N'-naphthalene bismaleimide, N,N'-m-phenyl bismaleimide, N,N'-5-methoxy -1,3-phenylene bismaleimide, 2,2-bis(4-(4-maleimide) Phenoxy)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 - bis(3-propyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimide) Oxy)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-double (3-methyl-4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimide phenoxy) Phenyl)ethane, 1,1-bis(3-bromo-4-(4-maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-malay) Iminophenoxy)phenyl)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-maleimidophenoxy)phenyl) Propane, 1,1,1,3,3,,-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'-hexamethylene bismaleimide, N, N'-dodecyl bismaleimide, N, N'- M-xylene bismaleimide, N,N'-p-xylene bismaleimide, N,N'-1,3-dimethylcyclohexane bismaleimide, N , N'-2,4-toluene bismaleimide, N,N'-2,6-toluene bismaleimide, and the like. Such bismaleimide compounds are not particularly limited to those mentioned above. These may be used alone or in combination of two or more.

Among these bismaleimides, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, N,N'-4,4-biphenyl Aroma of methane bismaleimide, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-biphenyl-methane bismaleimide It is better to have a family of bimaleimide.

Further, among these aromatic bismaleimides, in order to obtain higher flatness, a molecular weight of 1,000 or less is preferred.

In the present invention, the proportion of the bismaleimide compound of the component (C) is preferably 0.5 to 50 parts by mass, more preferably 1 to 30, based on 100 parts by mass of the polyester of the component (A). The mass fraction is particularly preferably 2 to 20 parts by mass. When the ratio is too small, the flattening property of the cured film obtained from the polyester composition for forming a thermosetting film is lowered. When the ratio is too large, the transmittance of the cured film is lowered and the coating film is rough.

<solvent>

The polyester composition for forming a thermosetting film of the present invention is often used in the form of a solution dissolved in a solvent. The solvent to be used in the present invention dissolves the component (A) and the component (B), and if necessary, the component (C) is dissolved, and/or the other additives described later are dissolved, and the type and structure are not particularly limited as long as they have such a dissolving ability. .

Examples of such a solvent include a solvent used for the polymerization of the component (A) or a solvent described below. For example, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol butyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether, ethyl lactate, lactic acid Butyl ester, cyclohexanol, ethyl acetate, butyl acetate, and the like.

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

<Other additives>

Further, the polyester composition for forming a thermosetting film of the present invention is limited to the effect of the present invention, and it is considered that it is necessary to contain a surfactant, a rheology modifier, a decane coupling agent, and the like. , dyes, storage stabilizers, antifoaming agents, dissolution promoters such as polyvalent phenols or polyvalent carboxylic acids, antioxidants, and the like.

In terms of antioxidants, phenols are particularly preferred, and specific examples thereof include 2,6-di-t-butyl-4-methylphenol and 2,6-di-t-butyl-phenol. 4,6-parade (3',5'-di-t-butyl-4'-hydroxybenzyl) mesitylene, pentaerythritol 肆[3-(3',5'-di-t-butyl-4 '-Hydroxyphenyl)propionate], acetone bis(3,5-di-t-butyl-4-hydroxyphenyl)thiol, 4,4'-methylene bis (2,6-di- T-butylphenol), methyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,4'-thiobis(2,6-di-t- Butylphenol), ginseng (3,5-di-t-butyl-4-hydroxybenzyl)isocyanuric acid, bis(3,5-di-t-butyl-4-hydroxybenzyl) sulfide, etc. .

<Polyester composition for forming a thermosetting film>

The polyester composition for forming a thermosetting film of the present invention contains the polyester of the component (A) and the epoxide having two or more epoxy groups of the component (B), and may contain (C) as desired. The bimaleimide compound of the component may further contain one or more of other additives. Moreover, these solutions dissolved in a solvent are usually used in many cases.

Among them, a more preferable example of the polyester composition for forming a thermosetting film of the present invention is as follows.

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

[3]: A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 0.5 to 50 parts by mass of the component (C) based on 100 parts by mass of the component (A).

[4] A polyester composition for forming a thermosetting film containing 3 to 50 parts by mass of the component (B) and 0.5 to 50 parts by mass of the component (C) and a solvent, based on 100 parts by mass of the component (A).

The polyester composition for forming a thermosetting film of the present invention is used as a solution blending ratio, a preparation method, and the like, and is 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 as long as the respective components are uniformly dissolved in the solvent, but it is 1 to 80% by mass, preferably 5 to 60% by mass. %, more preferably 10 to 50% by mass. Here, the solid content is determined 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. However, in the preparation method, for example, the component (A) is dissolved in a solvent, and the solution is mixed in a certain ratio ( B) A component or even a mixture of (C) components, a method of forming a homogeneous solution, or a method of mixing other additives as needed in an appropriate stage of the preparation method.

In the preparation of the polyester composition for forming a thermosetting film of the present invention, a polyester solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, in the solution of the component (A), the component (B), the component (C), and the like may be placed in the same manner as described above, and the solvent may be added for the purpose of concentration adjustment. In this case, the solvent used in the formation of the polyester and the solvent used for the concentration adjustment in the preparation of the polyester composition for forming a thermosetting film may be the same or different.

Further, it is preferred that the solution of the polyester composition for forming a thermosetting film to be prepared is filtered by a filter having a pore diameter of about 0.2 μm or the like.

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

The polyester composition for forming a thermosetting film of the present invention is applied to a substrate (for example, a tantalum/yttria-coated substrate, a tantalum nitride substrate, a metal, a coated substrate such as aluminum, molybdenum or chromium, a glass substrate, or a quartz substrate) , ITO substrate, etc.) or a film (for example, a resin film such as a cellulose triacetate film, a polyester film, or an acrylic film) or the like by spin coating, cast coating, roll coating, or slit coating. The coating is continued by spin coating, inkjet coating, printing or the like of the slit, and then, by preliminary drying (prebaking) by a hot plate or an oven, a coating film can be formed. Thereafter, the coating film is heat-treated to form a film.

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

In addition, 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 step difference of the substrate to be used or the optical and electrical properties.

In terms of post-baking, in general, it can be selected from the heating temperature selected in the range of 140 ° C to 250 ° C, 5 to 30 minutes on the hot plate, and 30 to 90 minutes in the oven. The method.

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

The cured film formed in this manner can be subjected to a polishing treatment to form a liquid crystal material alignment film, and it is intended to have an alignment layer function even if a liquid crystal compound is aligned.

In terms of the conditions of the polishing treatment, generally, a rotation speed of 300 to 1000 rpm, a traveling speed of 3 to 20 mm/sec, and a pushing amount of 0.1 to 1 mm are used.

Thereafter, the generated residue is removed by washing and polishing with ultrasonic waves such as pure water.

After the phase difference material is applied to the formed liquid crystal alignment film, the phase difference material is made into a liquid crystal state to be photohardened, and a layer having optical anisotropy can be formed.

As the phase difference material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same can be used.

Further, in the case where the substrate on which the liquid crystal alignment film is formed is a film, it can be used as an optically anisotropic film.

Further, the two substrates having the liquid crystal alignment film formed as described above are passed through a spacer so that the liquid crystal alignment film is opposed to each other, and then liquid crystal is injected between the substrates to form a liquid crystal alignment liquid crystal. Display component.

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

In addition, the polyester composition for forming a thermosetting film of the present invention can be used in various displays such as a thin film transistor (TFT) liquid crystal display device or an organic EL device because it has at least a required level of planarization. The material of the cured film such as a protective film, a flattening film, or an insulating film is particularly suitable as a material for a protective film material of a color filter, an interlayer insulating film of a TFT-type liquid crystal element, or an insulating film of an organic EL element.

[Examples]

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

[Simplified mark used in the embodiment]

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

<Polyester raw materials>

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

HPMDA: 1,2,4,5-cyclohexyltetracarboxylic dianhydride

BPDA: biphenyltetracarboxylic dianhydride

TDA: 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydro-ca- 1,2-dicarboxylic anhydride [4-(2,5-dioxotetrahydrofuran-3- Yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride]

6FDA: 4,4'-(hexafluoroisopropyl)phthalic dianhydride

PMDA: pyromellitic dianhydride

ODPA: bis(3,4-dicarboxyphenyl)ether dianhydride

<acid dianhydride>

HBPA: hydrogenated bisphenol A

CHDO: 1,4-cyclohexanediol

pXG: p-xylene glycol

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

<catalyst>

BTEAC: benzyl triethyl ammonium chloride

<Polyimide precursor material>

CBDA: cyclohexane tetracarboxylic dianhydride

pDA: p-phenylenediamine

<acrylic acid copolymer raw material>

MAA: Methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxymethyl ethyl acrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<epoxy compound>

CEL: CELLOXIDE P-2021 (product name) manufactured by DAICEL Chemical Co., Ltd. (Compound name: 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate)

<Bismaleimide compound>

BMI1: N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-biphenyl-methane bismaleimide

<solvent>

PGMEA: propylene glycol monomethyl ether acetate

NMP: N-methylpyrrolidone

According to 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, a GPC apparatus (Shodex (registered trademark) column KF803L and KF804L manufactured by JASCO Corporation was used. The dissolution solvent tetrahydrofuran was measured by flowing at a flow rate of 1 ml/min in a column (column temperature of 40 ° C) to dissolve it. In addition, the following 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>

By reacting 12.0 g of HBPDA, 10.2 g of HBPA, 0.95 g of THPA, and 0.22 g of BTEAC as a catalyst, the reaction was carried out at 120 ° C for 19 hours in PGMEA 54.48 g to obtain a polyester solution (solid content concentration: 30.0% by mass) (P1) ). The obtained polyester had an Mn of 2,280 and a Mw of 4,200.

<Synthesis Example 2>

A polyester solution (solid content concentration: 30.0% by mass) was obtained by reacting HBPDA 18.0 g, BPDA 4.54 g, HBPA 15.9 g, THPA 2.01 g, and BTEAC 0.19 g as a catalyst in PGMEA 95.1 g at 120 ° C for 19 hours. ) (P2). The obtained polyester had an Mn of 1,510 and a Mw of 3,570.

<Synthesis Example 3>

A polyester solution (solid content concentration: 30.0% by mass) was obtained by reacting HPMDA 14.0 g, BPDA 4.60 g, HBPA 16.9 g, THPA 2.14 g, and BTEAC 0.09 g as a catalyst in PGMEA 88.6 g at 120 ° C for 19 hours. ) (P3). The obtained polyester had Mn of 1,643 and Mw of 2,380.

<Synthesis Example 4>

After reacting BPDA 40.0 g, HBPA 35.3 g, and BTEAC 0.77 g in PGMEA 175.7 g at 120 ° C for 1 hour, THPA 3.31 g was added and reacted for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0 mass). %) (P4). The obtained polyester polymer had an Mn of 1,100 and a Mw of 2,580.

<Synthesis Example 5>

By reacting TDA 15.0 g, pXG7.25 g, and BTEAC 0.28 g in PGMEA 51.9 g at 120 ° C for 1 hour, THPA 0.76 g was added and reacted for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0 mass). %) (P5). The obtained polyester polymer had an Mn of 1,200 and a Mw of 2,800.

<Synthesis Example 6>

By reacting 6FDA 40.0 g, CHDO 11.3 g, and BTEAC 0.51 g in PGMEA 119.7 g at 120 ° C for 1 hour, THPA 2.19 g was added and reacted for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0 mass). %) (P6). The obtained polyester polymer had an Mn of 2,100 and a Mw of 3,800.

<Synthesis Example 7>

After reacting PMDA 40.0 g, HBPA 47.6 g, and BTEAC 1.04 g in PGMEA 204.4 g at 120 ° C for 1 hour, 4.76 g of THPA was added and reacted for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0 mass). %) (P7). The obtained polyester polymer had an Mn of 1,100 and a Mw of 2,850.

<Synthesis Example 8>

By reacting ODPA 20.0 g, CHDO 8.10 g, and BTEAC 0.37 g in PGMEA 65.5 g at 120 ° C for 1 hour, 1.57 g of THPA was added and reacted for 19 hours to obtain a polyester polymer solution (solid content concentration: 30.0 mass). %) (P8). The obtained polyester polymer had an Mn of 1,400 and a Mw of 2,730.

<Synthesis Example 9>

By reacting CBDA 17.7 g and pDA 10.2 g in NMP 66.4 g at 23 ° C for 24 hours, a polyimine precursor solution (solid content concentration: 30.0% by mass) (P9) was obtained. The obtained polyimide intermediate precursor had an Mn of 5,800 and a Mw of 12,500.

<Synthesis Example 10>

MAA 10.9g, CHMI 35.3g, HEMA 25.5g, MMA 28.3g were used as the monomer components, and AIBN 5g was used as the radical polymerization initiator, which was equal to 150 g of the solvent PGMEA by the temperature of 60 ° C to 100 ° C. The polymerization reaction was carried out to obtain an acrylic copolymer solution (solid content concentration: 40.0% by mass) (P10). The solution of the obtained acrylic copolymer had an Mn of 3,800 and a Mw of 6,700.

<Examples 1 to 10 and Comparative Examples 1 to 3>

Each of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was prepared in the composition shown in Table 2, and the flatness, solvent resistance, transmittance, and alignment were evaluated.

[Evaluation of flatness]

Each of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was coated on a stepped substrate (made of glass) having a height of 0.5 μm, a line width of 10 μm, and a line spacing of 50 μm using a spin coater. After the cloth, prebaking was performed on a hot plate at a temperature of 100 ° C for 120 seconds to form a coating film having a film thickness of 2.8 μm. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked by heating at a temperature of 230 ° C for 30 minutes to form a cured film having a film thickness of 2.5 μm.

The film thickness difference between the coating film on the step substrate line and the coating film on the interval was measured (refer to FIG. 1), and the flatness ratio (DOP)=100×[1-{film thickness difference (μm)/step difference substrate of the coating film was used. The height (0.5 μm)}] is used to determine the flattening rate.

[Evaluation of Solvent Tolerance]

Each of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was coated on a tantalum wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. And a coating film having a film thickness of 2.8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked by heating 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. The film thickness after immersion of PGMEA or NMP was ○, and the film thickness after immersion was found to be ×.

[Evaluation of light transmittance (transparency)]

Each of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was applied onto a quartz substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 2.8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked by heating at a temperature of 230 ° C for 30 minutes to form a cured film.

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

[Evaluation of alignment]

Each of the compositions of Examples 1 to 10 and Comparative Examples 1 to 3 was applied onto an ITO substrate by a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C for 120 seconds. On the other hand, a coating film having a film thickness of 2.8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. The film was post-baked by heating at 230 ° C for 30 minutes to form a cured film.

This cured film was subjected to a polishing treatment at a rotation speed of 700 rpm, a traveling speed of 10 mm/sec, and a pushing amount of 0.45 mm. The ground substrate was washed with pure water for 5 minutes. The phase difference material made of the liquid crystal monomer was coated on the substrate by a spin coater, and then prebaked on a hot plate at 100 ° C for 40 seconds and 55 ° C for 30 seconds to form a film having a film thickness of 1.1 μm. membrane. The substrate was exposed to 2,000 mJ under a nitrogen atmosphere. The prepared substrate was placed in a deflecting plate to visually confirm the alignment property. The light transmittance when the substrate was tilted at 45 degrees and the light transmittance when not tilted was ○, and the change without change was ×.

[Evaluation of heat resistance]

Each of the compositions of Examples 1 to 4 and Comparative Examples 1 to 3 was applied onto a quartz substrate by a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C for 120 seconds. The temperature was 30 minutes on a hot plate at 230 ° C, post-baking to form a cured film, and the film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the cured film was placed on a hot plate at a temperature of 230 ° C for 60 minutes, and the film thickness was measured again to calculate the film thickness change rate after post-baking. Further, it is considered that the cured film having heat resistance is desirably having a performance at least a film thickness change rate of less than ±5%.

[Results of evaluation]

The results of the above evaluations are shown in Table 3 below.

Each of Examples 1 to 10 has a flattening ratio and is resistant to any of PGMEA and NMP. Both of them showed good alignment, and after high-temperature firing, high transmittance (transparency) was also achieved. In particular, in Examples 1 to 4, a cured film having a film thickness change rate of less than ±5% was obtained, and it was confirmed that it had heat resistance.

Further, in Comparative Example 1, a cured film could not be formed.

Further, as a result of Comparative Example 2, although the solvent resistance, heat resistance and alignment property were good, the flattening ratio was extremely low.

Then, as a result of Comparative Example 3, although the planarization ratio, heat resistance, solvent resistance, and transmittance were good, the alignment property was poor.

As described above, in the polyester composition for forming a thermosetting film of the present invention, a diol-based solvent such as propylene glycol monomethyl ether acetate can be used in the formation of the cured film, and the obtained cured film is excellent. The results of any of light transmittance, solvent resistance, heat resistance, planarization, and alignment are good.

[Industrial availability]

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

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

[Fig. 2] shows a comparison between a liquid crystal chamber (a) which forms a liquid crystal alignment film by the prior art and a liquid crystal chamber (b) which forms a liquid crystal alignment film using the polyester composition for forming a thermosetting film of the present invention. Pattern diagram.

Claims (7)

A liquid crystal alignment film obtained by using a polyester composition for forming a thermosetting film, comprising the following components (A) and (B), and component (A) comprising a structural unit represented by the following formula (1) Polyester, (B) component: an epoxide having two or more epoxy groups; (In the formula, A is at least one selected from the group consisting of the groups represented by the following formulas (A-1) to (A-15), and the B system is represented by the following formula (B-1) to (B). -5) at least one selected from the group shown by the base) The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein in the above formula (1), the A system is represented by the formula (A-1) to the formula (A-8). At least one selected from the group represented by the base. The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (A) is a tetracarboxylic acid containing a tetracarboxylic dianhydride represented by the following formula (i). a polyester obtained by reacting an acid component with a diol compound represented by the following formula (ii), (wherein A and B are the same as defined in the above formula (1)). The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the weight average molecular weight of the polyester of the component (A) is 1,000 to 30,000 in terms of polystyrene. The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the first aspect of the invention, further comprising a bismaleimide compound as the component (C). The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the first aspect of the invention, wherein the component (B) is contained in an amount of 3 to 50 parts by mass based on 100 parts by mass of the component (A). The liquid crystal alignment film obtained by using the polyester composition for forming a thermosetting film according to the fifth or sixth aspect of the invention, wherein the component (C) is contained in an amount of 0.5 to 50 parts by mass based on 100 parts by mass of the component (A). .