WO2010119868A1

WO2010119868A1 - Photosensitive polyester composition for use in forming thermally cured film

Info

Publication number: WO2010119868A1
Application number: PCT/JP2010/056601
Authority: WO
Inventors: 真畑中; 勲安達
Original assignee: 日産化学工業株式会社
Priority date: 2009-04-14
Filing date: 2010-04-13
Publication date: 2010-10-21
Also published as: KR20120013941A; TWI500657B; KR101660827B1; CN102395614A; JPWO2010119868A1; CN102395614B; TW201107367A; JP5626536B2

Abstract

Disclosed is a material which enables pattern formation in an alkaline developer, and shows high solvent resistance, liquid crystal orientation, heat resistance, high transparency, and high planarity after being formed into a cured film, and can be dissolved in a glycol solvent which can be applied to the production line of a planarized film of a color filter while being formed into a cured film. Specifically disclosed is a photosensitive polyester composition for use in forming thermally cured film, containing component (A), component (B), component (C), and component (D): component (A): a modified polyester obtained by reacting a compound having a functional group selected from a glycidyl group and an isocyanate group with a polyester containing a structural unit represented by formula (1); component (B): an epoxy compound having two or more epoxy groups; component (C): an amino group-containing carboxylic acid compound obtained by reacting a diamine compound with dicarboxylic acid dianhydride; and component (D): 1,2-quinone diazide compound. In formula (1), A and B each independently represent an organic group containing a cyclic structure.

Description

Photosensitive polyester composition for thermosetting film formation

The present invention relates to a photosensitive polyester composition for forming a thermosetting film and a cured film formed from the composition. In more detail, the photosensitive polyester composition for thermosetting film formation which can form the cured film which has high transparency and planarization property, liquid crystal orientation ability, and high solvent tolerance, its cured film, and this hardening It relates to the application of membranes. This photosensitive polyester composition for forming a thermosetting film is particularly suitable for a color filter overcoat agent having a liquid crystal alignment function in a liquid crystal display.

Generally, in an optical device such as a liquid crystal display element, an organic EL (Electro Luminescent) element, and a solid-state imaging element, a protective film is provided to prevent the element surface from being exposed to a solvent or heat during the manufacturing process. This protective film requires not only high adhesion to the substrate to be protected and high solvent resistance, but also performance such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state imaging device, generally the performance of flattening the color filter or black matrix resin of the underlying substrate, that is, flattening It is required to have performance as a film. In particular, when manufacturing a color liquid crystal display element of STN method or TFT method, it is necessary to perform the bonding accuracy between the color filter substrate and the counter substrate very strictly, and it is necessary to make the cell gap between the substrates uniform. It is essential. In addition, in order to maintain the transmittance of light passing through the color filter, the planarizing film as the protective film needs to have high transparency.

On the other hand, in recent years, cost reduction and weight reduction have been studied by introducing a phase difference material into a cell of a liquid crystal display. A liquid crystal monomer is applied to such a phase difference material and oriented, followed by photocuring. Materials are generally used. In order to orient this retardation material, the lower layer film needs to be a material having orientation after the rubbing treatment. Therefore, after forming a liquid crystal alignment layer on the overcoat of the color filter, a retardation material is formed (see FIG. 2A). If a film that doubles as a liquid crystal alignment layer and a color filter overcoat (see FIG. 2B) can be formed, it is possible to obtain significant advantages such as cost reduction and a reduction in the number of processes. ing.

Generally, highly transparent acrylic resin is used for the overcoat of this color filter. For these acrylic resins, glycol solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate and ester solvents such as ethyl lactate and butyl lactate are safe, easy to handle, and prevent elution of pigment components from color filters. Widely used. Such an acrylic resin is given heat resistance and solvent resistance by thermosetting or photocuring (Patent Documents 1 and 2). However, although conventional thermosetting and photo-curing acrylic resins show appropriate transparency and flatness, even if such a flattened film is rubbed, sufficient orientation cannot be shown. .

On the other hand, a material made of solvent-soluble polyimide or polyamic acid is usually used for the liquid crystal alignment layer. It has been reported that these materials can impart solvent resistance by being completely imidized at the time of post-baking, and show sufficient orientation by rubbing treatment (Patent Document 3). However, when these materials are used as a flattening film of a color filter, there is a problem that flatness and transparency are greatly deteriorated.

In addition, polyester-polyamic acid and polyester-polyimide copolymers have been reported to improve flatness (Patent Document 4). However, these polyester-polyamide acids and polyester-polyimide copolymers are soluble in solvents such as N-methylpyrrolidone and γ-butyrolactone, like polyimides and polyamic acids, but glycol-based solvents and ester-based solvents. Therefore, it was difficult to apply to a flattened film production line due to the elution of pigment components and liquid crystal contamination components from the color filter during polyimide film production.

In addition, in order to improve the adhesion strength with the sealing material used when the substrate is bonded to the TFT array side, it is desired that the film at the adhesion portion can be removed using a photolithography process.
Further, no planarization film having photosensitivity and orientation has been reported so far.

JP 2000-103937 A JP 2000-119472 A JP 2005-037920 A JP 2008-033244 A

The present invention has been made on the basis of the above circumstances, and the problem to be solved is that pattern formation is possible with an alkali developer, and high solvent resistance, liquid crystal orientation, and high transparency after formation of a cured film. It is to provide a material that can be dissolved in a glycol-based solvent and a lactic acid ester-based solvent that can be applied in a production line for a color filter flattening film when forming a cured film. .

As a result of intensive studies to solve the above problems, the present inventors have found the present invention.
That is, as a first viewpoint,
Photosensitive polyester composition for thermosetting film formation containing (A) component, (B) component, (C) component, and (D) component.
Component (A): Modified polyester (B) component obtained by reacting a polyester containing a structural unit represented by the following formula (1) with a compound having a functional group selected from a glycidyl group and an isocyanate group: Epoxy compound (C) component having two or more epoxy groups: Amino group-containing carboxylic acid compound (D) component obtained by reacting a diamine compound and dicarboxylic dianhydride: 1,2-quinonediazide compound

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

As a second aspect, the polyester containing the structural unit represented by the formula (1) comprises a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (i) and the following formula (ii): The photosensitive polyester composition for thermosetting film formation as described in the 1st viewpoint which is polyester obtained by making the diol component containing the diol compound represented by these react.

{In Formulas (i) and (ii), A and B have the same definitions as in Formula (1). }

As a third aspect, in the formula (1), A represents at least one group selected from the groups represented by the following formulas (A-1) to (A-8), and B represents the following formula (B- 1) The photosensitive polyester composition for forming a thermosetting film according to the first aspect or the second aspect, which represents at least one group selected from the groups represented by formula (B-5).

As a fourth aspect, the modified polyester of the component (A) has a weight average molecular weight of 1,000 to 3,000 in terms of polystyrene, and is described in any one of the first to third aspects. Photosensitive polyester composition for thermosetting film formation.
As a fifth aspect, the component (C) is an amino group-containing carboxylic acid compound obtained by reacting 1 mol of a diamine compound with 1.7 to 2 mol of a dicarboxylic dianhydride. The photosensitive polyester composition for thermosetting film formation as described in any one of 4 viewpoints.
As a sixth aspect, based on 100 parts by mass of the component (A), 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), 5 to 80 parts by mass of the ( D) The photosensitive polyester composition for thermosetting film formation as described in any one of 1st viewpoint thru | or 5th viewpoint each containing a component.
As a seventh aspect, the photosensitive polyester composition for thermosetting film formation according to any one of the first aspect to the fifth aspect, further comprising a bismaleimide compound as the component (E).
As an eighth aspect, for thermosetting film formation according to the sixth aspect, containing 0.5 to 50 parts by mass of the (E) component according to the seventh aspect based on 100 parts by mass of the component (A). Photosensitive polyester composition.
As 9th viewpoint, the cured film formed from the photosensitive polyester composition for thermosetting film formation as described in any one of 1st viewpoint thru | or 8th viewpoint.
As a tenth aspect, a liquid crystal alignment layer obtained using the photosensitive polyester composition for thermosetting film formation according to any one of the first aspect to the eighth aspect.

The photosensitive polyester composition for thermosetting film formation of the present invention has photosensitivity, and forms a cured film having liquid crystal alignment ability in addition to high flatness, high transparency, high solvent resistance, and high heat resistance. Therefore, it can be used as a material for forming a liquid crystal alignment film or a planarization film. In particular, it is possible to form the liquid crystal alignment film and the overcoat layer of the color filter, which have been conventionally formed independently, as a “liquid crystal alignment layer” having both characteristics at the same time, simplifying the manufacturing process and the number of processes. Cost reduction by reduction can be realized.
Furthermore, since the photosensitive polyester composition for forming a thermosetting film of the present invention is soluble in a glycol solvent and a lactic acid ester solvent, it can be suitably used in a production line for a planarized film mainly using these solvents.

FIG. 1 is a model diagram showing a cured film formed when a thermosetting polyester composition is applied to a stepped substrate. It is a model figure which contrasts the liquid crystal aligning layer (a) by a prior art, and the liquid crystal aligning layer (b) using the photosensitive polyester composition for thermosetting film formation of this invention.

As described above, the conventionally proposed acrylic resin-based and polyimide resin-based cured films have sufficient performance such as flatness, transparency, and orientation required for liquid crystal alignment films and flattening films. There was nothing satisfactory.
In addition, there have been proposals for the use of polyester as an alignment material for liquid crystal display elements (see Japanese Patent Application Laid-Open Nos. H5-158055 and 2002-229039). It was not curable and the solvent resistance of the formed film was poor.

Therefore, the present invention is characterized in that the above-described performance improvement is achieved using a thermosetting polyester. That is, the present invention includes (A) component polyester, (B) component epoxy compound having two or more epoxy groups, (C) amino group-containing carboxylic acid compound, (D) component 1, It is a photosensitive polyester composition for thermosetting film formation containing a 2-quinonediazide compound. Furthermore, the present invention relates to a photosensitive polyester for thermosetting film which can contain a bismaleimide compound as the component (E) in addition to the components (A), (B), (C) and (D). It is a composition.
Hereinafter, details of each component will be described.

<(A) component>
The polyester of component (A) is obtained by reacting a polyester having a structural unit represented by the following formula (1) (hereinafter also referred to as a specific polymer) with a compound having a functional group selected from a glycidyl group and an isocyanate group. It is a modified polyester obtained in this way. Preferably, it is a modified polyester obtained by reacting a polyester having a structural unit represented by the following formula (1) with a compound having a functional group selected from a glycidyl group and an isocyanate group.

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

{In the formulas (1Al), (1A2), and (1A3), A ¹ represents a cyclic saturated hydrocarbon group, R ¹ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, or a group having 1 to 8 carbon atoms. It represents a saturated hydrocarbon group or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom. R ² represents a saturated hydrocarbon group having 1 to 8 carbon atoms. }

In the above formula, A ¹ preferably represents a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. In addition, any hydrogen atom contained in the A ¹ group may be independently substituted with an aliphatic group, and two of them may be bonded to each other to form a 4- to 6-membered ring. Also good.
Here, the aliphatic group as the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, it becomes a bridged cyclic hydrocarbon group such as a norbornene group or an adamantane group, or a condensed polycyclic hydrocarbon group in which part or all of them are hydrogenated.
R ¹ is preferably a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom. To express.
R ² preferably represents a saturated hydrocarbon group having 1 to 5 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

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

In the above formula (1), B represents a divalent organic group in which two bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, preferably a group represented by the following formula (1B1) or formula (1B2) It is.

{In the formulas (1B1) and (1B2), B ¹ represents a cyclic saturated hydrocarbon group, and B ² represents a phenylene group. R ³ represents a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or a saturated hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom, R ⁴ and R ⁵ each independently represents a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁶ and R ⁷ each independently represents an alkylene group having 1 to 5 carbon atoms. Furthermore, k represents 0 or 1. }

In the above formula, B ¹ preferably represents a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. In addition, any hydrogen atom contained in the B ¹ group may be independently substituted with an aliphatic group.
Here, the aliphatic group as the substituent is preferably an aliphatic group having 1 to 5 carbon atoms, more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents are bonded to form a ring, for example, it becomes a bridged cyclic hydrocarbon group such as a norbornene group or an adamantane group, or a condensed polycyclic hydrocarbon group in which part or all of them are hydrogenated.
R ³ preferably represents a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom. .
R ⁴ and R ⁵ are preferably a single bond or an alkylene group having 1 to 3 carbon atoms.
Further, R ⁶ and R ⁷ preferably represent an alkylene group having 1 to 3 carbon atoms.

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

The specific polymer preferably includes at least one structure selected from the group consisting of groups represented by the above formulas (1Al) to (1A3) in the structural unit represented by the above formula (1). May contain structures other than the groups represented by the above formulas (1Al) to (1A3). In that case, as long as the structure of polyester is formed, the structure is not particularly limited, but is preferably at least one structure selected from the groups represented by the following formulas (1A4) and (1A5).

{In Formula (1A4) and Formula (1A5), R ⁸ , R ⁹ and R ¹⁰ are each independently a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 8 carbon atoms, or A saturated hydrocarbon group having 1 to 8 carbon atoms substituted with a fluorine atom is represented. H represents 0 or 1. }

In the above formula, R ⁸ , R ⁹ and R ¹⁰ are preferably a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms or a carbon atom substituted with a fluorine atom. To 5 saturated hydrocarbon groups.
In particular, R ⁸ is a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom. Is preferred.
R ⁹ is preferably an ether bond, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom.
R ¹⁰ is preferably an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group having 1 to 5 carbon atoms, or a saturated hydrocarbon group having 1 to 5 carbon atoms substituted with a fluorine atom.

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

In the specific polymer, at least 60 mol% of at least one structural unit selected from the group consisting of groups in which A of the structural unit represented by the above formula (1) is represented by the above formula (1Al) to (1A3) It is preferable to include the above.
The modified polyester as the component (A) can be obtained by reacting a specific polymer with a compound having a functional group selected from a glycidyl group and an isocyanate group, as described later.

The weight average molecular weight of the modified polyester of component (A) is preferably 1,000 to 30,000, more preferably 1,500 to 10,000 in terms of polystyrene. When the weight average molecular weight of this polyester is smaller than the above range, the orientation and solvent resistance of the cured film formed from the photosensitive polyester composition for thermosetting film formation of the present invention tend to be reduced. The flatness may be reduced.

<Method for producing specific polymer>
In the present invention, the specific polymer is represented by a tetracarboxylic dianhydride component (hereinafter, also referred to as an acid component) containing a tetracarboxylic dianhydride represented by the following formula (i), and the following formula (ii). It is obtained by reacting with a diol compound (hereinafter also referred to as a diol component).

{In Formula (i) and (ii), A and B are synonymous with the definition in said Formula (1). }

Moreover, about said A and B, a preferable form is the same as what was mentioned above.
In the present invention, the tetracarboxylic dianhydride represented by the formula (i) and the diol compound represented by the formula (ii) may be used independently or in combination of two or more. it can.

In the production of the specific polymer, not only the tetracarboxylic dianhydride represented by the formula (i) as an acid component but also other tetracarboxylic dianhydrides (hereinafter also referred to as other acid dianhydrides). ) Can be used in combination. At that time, other acid dianhydrides are not particularly limited as long as the effects of the present invention are not impaired. A tetracarboxylic dianhydride represented by the following formula (i2) is preferable.

{In Formula (i2), W represents at least one structure selected from the groups represented by Formula (1A4) and Formula (1A5) defined in Formula (1), and R ⁸ , R ⁹ , R ¹⁰ and h are as defined above. }

In addition, preferred specific examples of the formula (1A4) and the formula (1A5) are also represented by the formula (al) to the formula (a7).
In the present invention, the tetracarboxylic dianhydride represented by the above formula (i) preferably contains at least 60 mol% or more of the acid component.

In the specific polymer, the mixing ratio of the total amount of tetracarboxylic dianhydride (total amount of acid component) and the total amount of diol compound (total amount of diol component), that is, <total number of moles of diol compound> / < The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.95 to 1.5. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1, the higher the degree of polymerization of the specific polymer produced, and the higher the molecular weight.

The terminal of the specific polymer varies depending on the compounding ratio of the acid component and the diol component. For example, when the acid component is reacted excessively, the terminal tends to be an acid anhydride.
Moreover, when it superposes | polymerizes using a diol component excessively, the terminal tends to become a hydroxyl group. In this case, the terminal hydroxyl group can be reacted with a carboxylic acid anhydride, and the terminal hydroxyl group can be sealed with an acid anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid An acid anhydride, itaconic anhydride, tetrahydrophthalic anhydride, etc. can be mentioned.
When reacting with a compound having a glycidyl group in the subsequent addition reaction, the generated hydroxyl group and acid anhydride react to cause gelation. Therefore, the end of the specific polymer is changed to a hydroxyl group or the terminal hydroxyl group is sealed with an acid anhydride. It is necessary to stop.

In the production of the specific polymer, the reaction temperature between the acid component and the diol component can be selected from 50 to 200 ° C., preferably 80 to 170 ° C. For example, the reaction temperature is 100 to 140 ° C., and the specific polymer can be obtained in a reaction time of 2 to 48 hours.
The reaction temperature for protecting the terminal hydroxyl group with an acid anhydride can be selected from 50 to 200 ° C., preferably 80 to 170 ° C.

The reaction between the acid component and the diol component is usually performed in a solvent (hereinafter, the solvent used for polymerizing the specific polymer is referred to as “polymerization solvent”). The solvent that can be used in this case is not particularly limited as long as it does not contain a functional group that reacts with an acid anhydride, such as a hydroxyl group or an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ -Butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, 2-methoxypropion Acid methyl, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate 2-ethyl ethoxypropionate, and the like.
These solvents may be used alone or as a mixture, but propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and applicability to a color filter overcoat agent line.
Furthermore, even if it is a solvent which does not melt | dissolve a specific polymer, you may mix and use it for the said solvent in the range in which the specific polymer produced | generated by the polymerization reaction does not precipitate.

A catalyst can also be used in the reaction of the acid component (formula (i) and formula (i2)) with the diol component (formula (ii)).
Specific examples of the catalyst used in the polymerization of the specific polymer include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethylammonium chloride. Quaternary ammonium salts such as tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyl Trifeni Quaternary phosphonium salts such as bromide and the like.

<Manufacture of (A) component>
The polyester of component (A) can be obtained by adding 10 to 90 mol% of a compound having a functional group selected from a glycidyl group and an isocyanate group and reacting with the carboxyl group of the specific polymer. In that case, it is possible to use the polymerization solution of a specific polymer as it is.
Further, it is preferable to coexist with an alcohol solvent since gelation during the reaction can be suppressed. Specific examples of such alcohol solvents (hereinafter also referred to as reaction solvents) are given. Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, methyl cellosolve, butyl cellosolve, ethyl lactate, butyl lactate, methanol, Examples include ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, cyclohexanol and the like. These solvents can be used alone or in combination of two or more.

Specific examples of the compound having a glycidyl group to be added to the carboxyl group of the specific polymer include glycidyl methacrylate, glycidyl acrylate, methyl glycidyl ether, ethyl glycidyl ether, allyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, glycidyl phenyl ether. Glycidyl-2-methylphenyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidyl butyl ether, glycidyl-tert-butyl ether, 2-biphenyl glycidyl ether, glycidyl-4-methoxyphenyl ether, and the like.

Specific examples of the compound having an isocyanate group to be added to the carboxyl group of the specific polymer include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, tert-butyl. Isocyanate, phenyl isocyanate, 2-toluyl isocyanate, 3-toluyl isocyanate, 4-toluyl isocyanate, 1-naphthyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, 2-isocyanate ethyl methacrylate, 2-methoxyphenyl Examples include isocyanate, 3-methoxyphenyl isocyanate, 4-methoxyphenyl isocyanate, pentyl isocyanate, hexyl isocyanate, and the like. .

The reaction temperature between the carboxyl group of the specific polymer and the compound having a functional group selected from a glycidyl group and an isocyanate group to be reacted with the carboxyl group may be selected from 50 to 160 ° C., preferably 80 to 140 ° C. it can. For example, the component (A) polyester used in the present invention can be obtained at a reaction temperature of 100 to 130 ° C. and a reaction time of 2 to 48 hours.

The solution containing the polyester of component (A) thus obtained can be used as it is for the preparation of the photosensitive polyester composition for thermosetting film formation of the present invention. Further, the polyester can be precipitated and isolated in a poor solvent such as water, methanol, ethanol, diethyl ether, hexane, etc. and recovered for use.

<(B) component>
Examples of the epoxy compound having two or more epoxy groups as the component (B) of the present invention include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, and 1,2-epoxy. -4- (epoxyethyl) 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′-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl D And ether, bisphenol A diglycidyl ether, and pentaerythritol polyglycidyl ether.
A commercially available compound may be used because it is easily available. Specific examples (trade names) are listed below, but are not limited to these: epoxy resins having amino groups such as YH-434, YH434L (manufactured by Tohto Kasei Co., Ltd.); Epolide GT-401, Epoxy resin having a cyclohexene oxide structure such as GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Epicoat 1001, 1002, 1003, 1004, Bisphenol A type epoxy resins such as 1007, 1009, 1010, 828 (Oilized Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)); Epicoat 807 (Oilized Shell Epoxy Co., Ltd. (current) Bisphenol F type epoxy resin such as manufactured by Japan Epoxy Resin Co., Ltd .; Epi Phenol novolac type epoxy resins such as EP 152, 154 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)), EPPN 201, 202 (manufactured by Nippon Kayaku Co., Ltd.); EOCN-102 , EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Okasei Shell Epoxy Co., Ltd. (current Japan Epoxy Resin Co., Ltd.)) ) Cresol novolac type epoxy resin; Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (CIBA-GEIGY A.G ), Epicron 200, 400 (Dai Nippon Ink Chemical Co., Ltd. ( )), Epicoat 871, 872 (Oka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5661 (Celanese Coating Co., Ltd.), etc. Epoxy resin: Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX -314, EX-321 (manufactured by Nagase ChemteX Corp.) and the like.

A polymer having an epoxy group can be used as the compound having at least two epoxy groups. As such a polymer, any polymer having an epoxy group can be used without particular limitation.
The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Examples include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and condensation polymerization polymers such as epoxy novolac. .
Alternatively, the polymer having an epoxy group may be produced by a reaction between a polymer compound having a hydroxyl group and a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate. The weight average molecular weight of such a polymer is polystyrene. In terms of conversion, for example, 300 to 200,000.

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

The content of the component (B) in the photosensitive polyester composition for thermosetting film formation of the present invention is preferably 3 to 50 parts by mass, more preferably 5 based on 100 parts by mass of the polyester of the component (A). Thru | or 40 mass parts, Most preferably, it is 10 thru | or 30 mass parts. If this ratio is too small, the solvent resistance and heat resistance of the cured film formed from the photosensitive polyester composition for thermosetting film formation will decrease, whereas if it is excessive, the solvent resistance will decrease. Storage stability may be reduced.

<(C) component>
The component (C) is an amino group-containing carboxylic acid compound obtained by reacting a diamine compound with dicarboxylic dianhydride. Specifically, 1 mol of a diamine compound represented by the following formula (iii) is reacted with 1.7 to 2 mol, preferably 1.8 to 2 mol of a dicarboxylic dianhydride represented by the following formula (iv). It is an amino group containing carboxylic acid compound obtained by making it.

{In Formula (iii) and Formula (iv), P and Q each independently represent a divalent organic group. }

Therefore, the compound represented by the following formula (2) is obtained by reacting the diamine compound represented by the formula (iii) with the dicarboxylic acid represented by the formula (iv).

{In the formula, P and Q have the same definitions as in the formulas (iii) and (iv). }

In the present invention, each of the diamine compound and the dicarboxylic dianhydride may be used alone or in combination. Therefore, as the amino group-containing carboxylic acid compound of the component (C) of the present invention, not only one type of compound represented by the formula (2) but also a plurality of types can be used.
P and Q are preferably divalent organic groups each independently having a ring structure. Here, examples of the ring structure include a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon.

In the formula (iii), the ring structure of P is preferably a benzene ring, an alicyclic group having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms.
Accordingly, specific examples of the diamine compound having such a ring structure include the following: p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6 -Diaminotoluene, 2,4-dimethyl-1,3-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene, 2,3,5,6-tetramethyl-1,4-diaminobenzene, 2, 4-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, N, N-diallyl-2,4-diaminoaniline, N, N-diallyl-2,5-diaminoaniline, 4-aminobenzylamine, 3-aminobenzylamine, 2- (4-aminophenyl) ethyl Amine, 2- (3-aminophenyl) ethylamine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4′-diaminobiphenyl, 3,4′-diaminobiphenyl, 3,3′-diaminobiphenyl, 2,2′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′- Dihydroxy-4,4′-diaminobiphenyl, 3,3′-dicarboxy-4,4′-diaminobiphenyl, 3,3′-difluoro-4,4′-diaminobiphenyl, 2,2′-trifluoromethyl- 4,4'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenyl 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl Sulfone, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diamino) Diphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzanilide 1,2-bis (4-aminophenyl) ethane, 1,2-bis (3-a Nophenyl) ethane, 4,4′-diaminotolane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane 2,2-bis (3-aminophenyl) propane, 2,2-bis (3-amino-4-methylphenyl) propane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2- Bis (3-aminophenyl) hexafluoropropane, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4 -Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-a Nophenoxy) heptane, 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, 1,11-bis ( 4-aminophenoxy) undecane, 1,12-bis (4-aminophenoxy) dodecane, bis (4-aminophenyl) propanedioate, bis (4-aminophenyl) butanedioate, bis (4-aminophenyl) pentane Geoate, bis (4-aminophenyl) hexane geoate, bis (4-aminophenyl) heptane geoate, bis (4-aminophenyl) octane geoate, bis (4-aminophenyl) nonanedioate, bis (4 -Aminophenyl) decanedioate, 1,4-bis (4-aminophenyl) benzene, 1 , 3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminobenzyl) benzene 1,3-bis (4-aminobenzyl) benzene, bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone], 1,3-phenylenebis [(4-aminophenyl) methanone], 1, 3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoer) ), 1,4-phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), N, N ′-( 1,4-phenylene) bis (4-aminobenzamide), N, N ′-(1,3-phenylene) bis (4-aminobenzamide), N, N ′-(1,4-phenylene) bis (3- Aminobenzamide), N, N ′-(1,3-phenylene) bis (3-aminobenzamide), bis (4-aminophenyl) terephthalamide, bis (3-aminophenyl) terephthalamide, bis (4-aminophenyl) ) Isophthalamide, bis (3-aminophenyl) isophthalamide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4 Aminophenoxy) phenyl] hexafluoropropane, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5- Triazine, 2,6-diaminodibenzofuran, 2,7-diaminodibenzofuran, 3,6-diaminodibenzofuran, 2,6-diaminocarbazole, 2,7-diaminocarbazole, 3,6-diaminocarbazole, 2,4-diamino- 6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, bis ( 4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) me Emissions, and the like.

In the formula (iv), the ring structure of Q is preferably a benzene ring, an alicyclic group having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms. More preferable Q is a benzene ring, an alicyclic group having 4 to 8 carbon atoms, or a condensed polycyclic hydrocarbon having 7 to 16 carbon atoms.
Specific examples of the dicarboxylic dianhydride having such a ring structure include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene -2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like.

In the production of the component (C) compound, the reaction temperature between the diamine compound and dicarboxylic dianhydride can be selected from 5 to 80 ° C., preferably 10 to 50 ° C.

The reaction is usually performed in a solvent. The solvent that can be used in this case is not particularly limited as long as it does not contain a functional group that reacts with an acid anhydride, such as a hydroxyl group or an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylimidazole, dimethylsulfoxide, tetramethylurea, dimethylsulfone, hexamethylsulfoxide , M-cresol, γ-butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate Ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate , Methyl cellosolve acetate, ethyl cellosolve acetate, methyl cellosolve, ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, propylene glycol propyl ether, cyclohexanol, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, etc. Can do.
These solvents may be used alone or in combination, but from the viewpoint of solubility, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylimidazole Is preferred.
Further, even a solvent that does not dissolve the amino group-containing carboxylic acid compound may be used by mixing with the solvent as long as the compound produced by the polymerization reaction does not precipitate.

The content of the component (C) in the polyester composition for forming a thermosetting film of the present invention is preferably 3 to 50 parts by weight, more preferably 5 to 40 based on 100 parts by weight of the polyester of the component (A). Part by mass. When this ratio is too small, the orientation of the cured film formed from the polyester composition for thermosetting film formation of the present invention is lowered. On the other hand, when it is too large, the transmittance is lowered or flattened. May decrease.

<(D) component>
The 1,2-quinonediazide compound as component (D) is a compound having either a hydroxyl group or an amino group, both a hydroxyl group and an amino group, and these hydroxyl groups or amino groups (of hydroxyl groups and amino groups). In the case where both are included, a compound in which 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total amount) is esterified or amidated with 1,2-quinonediazidesulfonic acid is used. be able to.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris (4-hydroxyphenyl). ) Butane, 4,4-isopropylidenediphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenylsulfone, 4,4 -Hexafluoroisopropylidenediphenol, 4,4 ', 4' '-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4- Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphe 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,3,4,4′-tetrahydroxybenzophenone, 2,2 Phenol compounds such as', 3,4,4'-pentahydroxybenzophenone, 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, Examples thereof include aliphatic alcohols such as propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p- Examples thereof include anilines such as phenylenediamine, 4,4′-diaminophenylmethane, and 4,4′-diaminodiphenyl ether, and aminocyclohexane.

Further, examples of the compound containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. 4,4′-diamino-4 ″ -hydroxytriphenylmethane, 4-amino-4 ′, 4 ″ -dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, Bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3- Aminophenols such as carboxy-5-hydroxyphenyl) hexafluoropropane, 2-amino Ethanol, 3-aminopropanol, mention may be made of alkanolamines, such as 4-amino-cyclohexanol.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

The content of the component (D) in the photosensitive polyester composition for thermosetting film formation of the present invention is preferably 5 to 80 parts by mass, more preferably 8 to 60 parts by mass with respect to 100 parts by mass of the component (A). Part, particularly preferably 10 to 50 parts by weight. When this ratio is too small, the difference in the dissolution rate in the developer becomes small, and patterning by development may be difficult. If the amount exceeds 100 parts by mass, the 1,2-quinonediazide compound will not be sufficiently decomposed by exposure in a short time and the sensitivity will decrease, or the component (D) will absorb light and the transparency of the cured film. May be reduced.

<(E) component>
In the present invention, a bismaleimide compound represented by the following formula (3) may be contained as the component (E).
The bismaleimide compound as component (E) can improve planarization.

(Wherein M ₁ represents an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or an organic group consisting of a combination of a plurality of organic groups selected from these groups) M ₁ may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.)

Examples of such bismaleimide compounds include 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-diphenylsulfone bismaleimide, 4,4-diphenylsulfone bismaleimide, N, N′-p-benzophenone bismaleimide, N, N′— Diphenylethane bismaleimide, N, N′-diphenyl ether bismaleimide, N, N ′-(methylenedi-ditetrahydrophenyl) bismaleimide, N, N ′-(3-ethyl) -4,4-diphenylmethane bismaleimide, N, N ′-(3,3-dimethyl) -4,4-diphenylmethane bismaleimide, N, N ′-(3,3-die Til) -4,4-diphenylmethane bismaleimide, N, N ′-(3,3-dichloro) -4,4-diphenylmethane bismaleimide, N, N′-isophorone bismaleimide, N, N′-tolidine bismaleimide, N, N′-diphenylpropane bismaleimide, N, N′-naphthalene bismaleimide, N, N′-m-phenylene bismaleimide, N, N′-5-methoxy-1,3-phenylene bismaleimide, 2,2 -Bis (4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-chloro-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-bromo-4- ( 4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-ethyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2- Bis (3-propyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-isopropyl-4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-butyl- 4- (4-maleimidophenoxy) phenyl) propane, 2,2-bis (3-methoxy-4- (4-maleimidophenoxy) 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-maleimidophenoxy) phenyl) pen 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'-ethylenedimaleimide, N, N'-hexamethylene bismaleimide, N, N'-dodecamethylene bismaleimide, N, N'-m-xylene Bismaleimide, N, N′-p-xylene bismaleimide, N, N′-1,3-bismethylenecyclohexane bismaleimide, N, N′-2,4-tolylene bismaleimide, N, N′-2, 6-Trilembi And maleimide. These bismaleimide compounds are not particularly limited to those described above.
These can be used alone or in combination of two or more components.

Among these bismaleimides, 2,2-bis (4- (4-maleimidophenoxy) phenyl) propane, N, N′-4,4-diphenylmethane bismaleimide, N, N ′-(3,3-diethyl- Aromatic bismaleimides such as 5,5-dimethyl) -4,4-diphenyl-methane bismaleimide are preferred.

Also, among these aromatic bismaleimides, those having a molecular weight of 1,000 or less are preferable in order to obtain higher flatness.

In the photosensitive polyester composition for forming a thermosetting film of the present invention, the content of the component (E) is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the polyester of the component (A). Preferably it is 1 thru | or 30 mass parts, Most preferably, it is 2 thru | or 20 mass parts. When this ratio is too small, the flatness of the cured film formed from the photosensitive polyester composition for thermosetting film formation of the present invention is lowered, and when it is too large, the transmittance of the cured film is lowered. Or the paint film may become rough.

<Solvent>
The photosensitive polyester composition for forming a thermosetting film of the present invention is often used in a solution state dissolved in a solvent. The solvent used in that case is a component that dissolves the components (A) to (D), and if necessary, the component (E) and / or other additives described later, and has such solubility. If it is a solvent, the kind and structure thereof are not particularly limited.

Examples of such a solvent include the solvent (polymerization solvent) used for the polymerization of the specific polymer and the reaction solvent described above, and in addition, ethyl acetate, butyl acetate and the like. These solvents can be used alone or in combination of two or more.

<Other additives>
Furthermore, the photosensitive polyester composition for forming a thermosetting film of the present invention, as long as the effects of the present invention are not impaired, an adhesion aid such as a surfactant, a rheology modifier, a silane coupling agent, Pigments, dyes, storage stabilizers, antifoaming agents, dissolution accelerators such as polyhydric phenols and polycarboxylic acids can be contained.

<Photosensitive polyester composition for thermosetting film formation>
The photosensitive polyester composition for forming a thermosetting film of the present invention comprises (A) component polyester, (B) component epoxy compound having two or more epoxy groups, (C) amino group-containing carboxylic acid compound, ( The composition contains a 1,2-quinonediazide compound as component D) and can optionally contain one or more of the bismaleimide compound as component (E) and other additives. Usually, they are often used as a solution in which they are dissolved in a solvent.

Especially, the preferable example of the photosensitive polyester composition for thermosetting film formation of this invention is as follows.
[1]: Based on 100 parts by mass of component (A), 3 to 50 parts by mass of component (B), 3 to 50 parts by mass of component (C), and 5 to 80 parts by mass of component (D). Photosensitive polyester composition for thermosetting film formation.
[2]: Based on 100 parts by mass of component (A), 3 to 50 parts by mass of component (B), 3 to 50 parts by mass of component (C), 5 to 80 parts by mass of component (D), and solvent. A photosensitive polyester composition for forming a thermosetting film.
[3]: Based on 100 parts by mass of component (A), 3 to 50 parts by mass of component (B), 3 to 50 parts by mass of component (C), 5 to 80 parts by mass of component (D), A photosensitive polyester composition for forming a thermosetting film containing 5 to 50 parts by mass of the component (E).
[4]: Based on 100 parts by mass of component (A), 3 to 50 parts by mass of component (B), 3 to 50 parts by mass of component (C), 5 to 80 parts by mass of component (D), The photosensitive polyester composition for thermosetting film formation containing 5 thru | or 50 mass parts (E) component and a solvent.

The blending ratio, preparation method, and the like when the photosensitive polyester composition for forming a thermosetting film of the present invention is used as a solution will be described in detail below.
The ratio of the solid content in the photosensitive polyester composition for thermosetting film formation of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is 1 to 80% by mass, The amount is preferably 5 to 60% by mass, more preferably 10 to 50% by mass. Here, solid content means what remove | excluded the solvent from all the components of the photosensitive polyester composition for thermosetting film formation.

Although the preparation method of the photosensitive polyester composition for thermosetting film formation of this invention is not specifically limited, As the preparation method, (A) component is melt | dissolved in a solvent, for example, (B) component, ( C) component, (D) component, and further (E) component are mixed at a predetermined ratio to make a uniform solution, or other additives may be added as necessary at an appropriate stage of this preparation method. The method of adding and mixing is mentioned.

In preparing the photosensitive 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, when the (B) component, the (C) component, the (D) component, the (E) component, etc. are added to the solution of the (A) component in the same manner as described above, the purpose is to adjust the concentration. Further, an additional solvent may be added. At this time, the solvent used in the production process of the polyester and the solvent used for adjusting the concentration when preparing the photosensitive polyester composition for thermosetting film formation may be the same or different.

Thus, the prepared solution of the photosensitive polyester composition for forming a thermosetting film is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film, cured film and liquid crystal alignment layer>
The photosensitive polyester composition for forming a thermosetting film of the present invention is coated with a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a substrate coated with a metal such as aluminum, molybdenum, chromium, etc., a glass substrate, quartz Substrate, ITO substrate, etc.) and film (for example, resin film such as triacetyl cellulose film, polyester film, acrylic film), etc., spin coating, flow coating, roll coating, slit coating, spin coating following slit, A coating film can be formed by coating by inkjet coating, printing, etc., and then pre-drying (pre-baking) with a hot plate or oven. Then, a coating film is formed by heat-processing this coating film.

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

Moreover, the film thickness of the film formed from the photosensitive polyester composition for thermosetting film formation is, for example, 0.1 to 30 μm, and is appropriately selected in consideration of the level difference of the substrate to be used and optical and electrical properties. Can do.

In general, post-baking is performed at a heating temperature selected from the range of 140 to 250 ° C. for 5 to 30 minutes when using a hot plate and 30 to 90 minutes when using an oven. The method is taken.

By curing the photosensitive polyester composition for thermosetting film formation of the present invention under the above conditions, the step of the substrate can be sufficiently flattened and a cured film having high transparency can be formed. Can do.

The cured film thus formed can be made to function as a liquid crystal material alignment layer, that is, a layer for aligning a compound having liquid crystallinity, by performing a rubbing treatment.
As conditions for the rubbing treatment, generally, conditions of a rotational speed of 300 to 1000 rpm, a feed speed of 3 to 200 mm / second, and an indentation amount of 0.1 to 1 mm are used.
Thereafter, the residue generated by rubbing is removed by ultrasonic cleaning using pure water or the like.

After coating the retardation material on the liquid crystal alignment layer thus formed, the retardation material can be photocured in a liquid crystal state to form a layer having optical anisotropy.
As the retardation material, for example, a liquid crystal monomer having a polymerizable group or a composition containing the same is used.

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

Further, after bonding the two substrates having the liquid crystal alignment layer formed as described above so that the liquid crystal alignment layer faces each other through a spacer, liquid crystal is injected between the substrates, and the liquid crystal The liquid crystal display element can be oriented.

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

In addition, since the photosensitive polyester composition for forming a thermosetting film of the present invention has at least a necessary level of flatness, protective films and flattening in various displays such as thin film transistor (TFT) type liquid crystal display elements and organic EL elements. It is also useful as a material for forming a cured film such as a film or an insulating film, and is particularly suitable as a material for forming an overcoat material for a color filter, an interlayer insulating film for a TFT liquid crystal element, an insulating film for an organic EL element, or the like. It is.

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

[Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
<Polyester raw material>
BPDA: biphenyltetracarboxylic dianhydride HBPDA: 3,3′-4,4′-bicyclohexyltetracarboxylic dianhydride HBPA: hydrogenated bisphenol A
THPA: 1,2,5,6-tetrahydrophthalic anhydride BTEAC: benzyltriethylammonium chloride TPPB: tetraphenylphosphonium bromide GMA: glycidyl methacrylate GME: glycidyl methyl ether DTBC: di-tert-butylcresol <polyimide precursor and amino Group-containing carboxylic acid compound raw material>
CBDA: cyclohexanetetracarboxylic dianhydride DA-4P: 1,3-bis (4-aminophenyl) benzene DA-1M: 4,4′-bis (4-aminophenoxy) diphenyl sulfone TA: trimellitic anhydride DDS: 4,4′-diaminodiphenyl sulfone pDA: p-phenylenediamine <Acrylic copolymer raw material>
MAA: methacrylic acid MMA: methyl methacrylate HEMA: 2-hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: azobisisobutyronitrile <epoxy compound>
CEL: Daicel Chemical Industries, Ltd. Celoxide P-2021 (product name) (compound name: 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexene carboxylate)
<Bismaleimide compound>
BMI1: N, N ′-(3,3-diethyl-5,5-dimethyl) -4,4-diphenyl-methane bismaleimide <1,2-quinonediazide compound>
QD1: a compound synthesized by a condensation reaction of 1 mol of 1,3,3-tris (4-hydroxyphenyl) butane and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.
QD2: synthesized by a condensation reaction of 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride Compound.
<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether DMAc: N, N-dimethylacetamide NMP: N-methyl-2-pyrrolidone

The number average molecular weight and weight average molecular weight of the polyester, polyimide precursor, and acrylic copolymer obtained according to the following synthesis examples are eluted using a GPC apparatus (Shodex (registered trademark) columns KF803L and KF804L) manufactured by JASCO Corporation. The measurement was performed under the condition that the solvent tetrahydrofuran was allowed to flow through the column at a flow rate of 1 ml / min (column temperature 40 ° C.) for elution. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) were expressed in terms of polystyrene.

<Synthesis Example 1>
By reacting 40.0 g of HBPDA, 8.23 g of BPDA, 49.3 g of HBPA, 5.96 g of THPA, 0.18 g of BTEAC and 0.33 g of TPPB in PGMEA 241.96 g at 120 ° C. for 17 hours, a specific polymer (Solid content concentration: 30.0 mass%) was obtained (P1). The obtained specific polymer had Mn of 1,500 and Mw of 3,430.

<Synthesis Example 2>
A solution (P1) of the specific polymer obtained in Synthesis Example 1 was added 18.42 g of GMA, 0.057 g of DTBC and 42.99 g of PGME to 252.00 g and reacted at 110 ° C. for 9 hours to obtain a polyester solution (solid content (Concentration: 30.0% by mass) was obtained (P2). Mn of the obtained polyester was 1,260 and Mw was 6,880.

<Synthesis Example 3>
A polyester solution (solid content concentration: 30.0) was prepared by adding 11.16 g of GME and 26.05 g of PGME to 252.00 g of the specific polymer solution (P1) obtained in Synthesis Example 1 and reacting at 110 ° C. for 9 hours. % By mass) was obtained (P3). Mn of the obtained polyester was 1,450 and Mw was 5,340.

<Synthesis Example 4>
DA-1M 15.14 g and THPA 10.64 g were reacted in PGME 60.15 g at 23 ° C. for 24 hours to obtain an amino group-containing carboxylic acid compound solution (solid content concentration 30.0 mass%) ( A1). The obtained amino group-containing carboxylic acid compound was confirmed to be free of THPA using high performance liquid chromatography.

<Synthesis Example 5>
By reacting 10.43 g of DA-4P and 10.64 g of THPA in 48.71 g of PGME at 23 ° C. for 24 hours, an amino group-containing carboxylic acid compound solution (solid content concentration: 30.0% by mass) was obtained ( A2). The obtained amino group-containing carboxylic acid compound was confirmed to be free of THPA using high performance liquid chromatography.

<Synthesis Example 6>
By reacting 40.0 g of BPDA, 35.3 g of HBPA, 3.31 g of THPA, 0.77 g of BTEAC in PGMEA 175.7 g at 120 ° C. for 19 hours, a solution of a specific polymer (solid content concentration: 30.0) Mass%). The obtained specific polymer had Mn of 1,100 and Mw of 2,580. By adding 18.42 g of GMA, 0.057 g of DTBC and 42.99 g of PGME to 252.00 g of this specific polymer solution and reacting at 110 ° C. for 9 hours, a polyester solution (solid content concentration: 30.0 mass%) was obtained. Obtained (P4). Mn of the obtained polyester was 1,580 and Mw was 7,540.

<Synthesis Example 7>
By reacting 17.7 g of CBDA and 10.2 g of pDA in 66.4 g of NMP at 23 ° C. for 24 hours, a polyimide precursor solution (solid content concentration: 30.0 mass%) was obtained (P5). Mn of the obtained polyimide precursor was 5,800 and Mw was 12,500.

<Synthesis Example 8>
As monomer components, MAA 10.9 g, CHMI 35.3 g, HEMA 25.5 g, MMA 28.3 g are used, and AIBN 5 g is used as a radical polymerization initiator, and these are used in a solvent PGMEA 150 g at a temperature of 60 ° C. to 100 ° C. An acrylic copolymer solution (solid content concentration: 40.0% by mass) was obtained by performing a polymerization reaction at ° C (P6). Mn of the obtained acrylic copolymer solution was 3,800, and Mw was 6,700.

<Examples 1 to 5 and Comparative Examples 1 to 5>
Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was prepared with the composition shown in Table 1, and the cured film obtained from the composition was flattened, solvent resistant, oriented, heat resistant, and patterned. Formability and transmittance were evaluated.

[Evaluation of flatness]
Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied on a stepped substrate (made of glass) having a height of 0.5 μm, a line width of 10 μm, and a space between lines of 50 μm using a spin coater. Thereafter, pre-baking was performed on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film having a 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 thickness of 2.5 μm.
The film thickness difference between the coating film on the stepped substrate line and the coating film on the space is measured (see FIG. 1), and the flattening ratio (DOP) = 100 × [1− {film thickness difference (μm) / step difference The flattening rate was obtained using the formula of height of substrate (0.5 μm)}].

[Evaluation of pattern formability]
Each composition of Example 1 to Example 5 and Comparative Example 1 to Comparative Example 5 was applied on a glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to obtain a film thickness of 2 A film having a thickness of 8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was irradiated with 100 mJ / cm ² of ultraviolet light having a light intensity of 5.5 mW / cm ² at 365 nm through an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. through a mask having a 10 μm line & space pattern. Thereafter, development was performed by immersing in a 0.2 mass% aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, followed by washing with running ultrapure water for 20 seconds. The obtained line & space pattern was observed with an optical microscope. The pattern obtained according to the mask design was indicated as ◯, and the pattern not resolved or dissolved during development was indicated as x.

[Evaluation of solvent resistance]
After each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a silicon wafer using a spin coater, it was pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2. An 8 μm coating film was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This coating film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film having a thickness of 2.5 μm.
This 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 case where there was no change in the film thickness after immersion in PGMEA or NMP was marked with ○, and the case where the film thickness decreased after immersion was marked with x.

[Evaluation of light transmittance (transparency)]
Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied on a quartz substrate using a spin coater, and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A film having a thickness of 8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. Development was performed by immersing this coating film in a 0.2% by weight TMAH aqueous solution for 60 seconds, and then washing with running ultrapure water for 20 seconds. Thereafter, ultraviolet light having a light intensity at 365 nm of 5.5 mW / cm ² was irradiated with 500 mJ / cm ² by an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc. This coating film was post-baked on a hot plate 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 using an ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number, manufactured by Shimadzu Corporation).

[Evaluation of orientation]
Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied on an ITO substrate using a spin coater and then pre-baked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2 A film having a thickness of 8 μm was formed. The film thickness was measured using F20 manufactured by FILMETRICS. This film was post-baked on a hot plate at a temperature of 230 ° C. for 30 minutes to form a cured film.
The cured film was rubbed at a rotational speed of 300 rpm, a feed speed of 10 mm / second, and an indentation amount of 0.45 mm. The rubbed substrate was ultrasonically cleaned with pure water for 5 minutes. A retardation material composed of a liquid crystal monomer was applied onto the substrate using a spin coater, and then prebaked on a hot plate at 100 ° C. for 40 seconds and at 55 ° C. for 30 seconds to form a coating film having a thickness of 1.1 μm. . This substrate was exposed at 2,000 mJ in a nitrogen atmosphere. The produced substrate was sandwiched between deflection plates, and the orientation was confirmed visually. The case where the light transmittance changed significantly when the substrate was tilted at 45 degrees and the case where the substrate was not tilted was evaluated as ◯, and the case where the substrate did not change as x.

[Evaluation of heat resistance]
After applying each composition of Examples 1 to 5 and Comparative Examples 1 to 5 on a quartz substrate using a spin coater, prebaking on a hot plate at a temperature of 100 ° C. for 120 seconds, Post-baking was performed on a hot plate at 230 ° C. for 30 minutes to form a cured film, and the film thickness was measured using F20 manufactured by FILMETRICS. Thereafter, the cured film was further baked on a hot plate at a temperature of 230 ° C. for 60 minutes, the film thickness was measured again, and the rate of change in film thickness after post-baking was calculated. In order to be recognized as a heat-resistant cured film, it is desirable that the film has a performance of at least a film thickness change rate of less than ± 5%.

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

In Examples 1 to 5, pattern formation was possible, the flattening rate and heat resistance were high, and resistance to both PGMEA and NMP was observed. Moreover, all showed favorable orientation and achieved high transmittance (transparency) even after high-temperature firing.

In Comparative Example 1, the unexposed part was also dissolved in the developer and the pattern could not be formed.
In Comparative Example 2, the exposed portion was not dissolved in the developer and the pattern could not be formed.
In Comparative Example 3, the heat resistance was low and the pattern could not be formed.
In Comparative Example 4, the flattening rate was low and pattern formation could not be performed.
On the other hand, in Comparative Example 5, pattern formation was possible, and a result that the flattening rate, heat resistance, solvent resistance, and transmittance were good was obtained, but the orientation was poor.

As described above, the photosensitive polyester composition for forming a thermosetting film of the present invention can use a glycol-based solvent such as propylene glycol monomethyl ether acetate when forming the cured film. Moreover, it is possible to form a pattern with an alkali developer, and the obtained cured film gives excellent results in all of the properties of excellent light transmittance, solvent resistance, heat resistance, flatness and orientation. It was.

The photosensitive polyester composition for forming a thermosetting film according to the present invention is very useful as a liquid crystal alignment layer of an optically anisotropic film or a liquid crystal display element, and further, a thin film transistor (TFT) type liquid crystal display element, an organic EL element, etc. Materials for forming cured films such as protective films, flattening films, insulating films, etc. in various displays, especially materials for forming interlayer insulating films for TFT liquid crystal elements, protective films for color filters, insulating films for organic EL elements, etc. It is also suitable.

Claims

Photosensitive polyester composition for thermosetting film formation containing (A) component, (B) component, (C) component, and (D) component.
Component (A): Modified polyester (B) component obtained by reacting a polyester containing a structural unit represented by the following formula (1) with a compound having a functional group selected from a glycidyl group and an isocyanate group: Epoxy compound (C) component having two or more epoxy groups: amino group-containing carboxylic acid compound (D) component obtained by reacting a diamine compound and dicarboxylic dianhydride: 1,2-quinonediazide compound

(In the formula, A represents a tetravalent organic group in which four bonds are bonded to an alicyclic skeleton or an aliphatic skeleton, and B is a divalent group in which two bonds are bonded to an alicyclic skeleton or an aliphatic skeleton. Represents an organic group of
The polyester containing the structural unit represented by the formula (1) is represented by a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the following formula (i) and the following formula (ii): The photosensitive polyester composition for thermosetting film formation of Claim 1 which is polyester obtained by making the diol component containing a diol compound react.

{In Formula (i) and (ii), A and B are synonymous with the definition in said Formula (1). }
In the formula (1), A represents at least one group selected from the groups represented by the following formulas (A-1) to (A-8), and B represents the following formulas (B-1) to ( The photosensitive polyester composition for forming a thermosetting film according to claim 1 or 2, which represents at least one group selected from the group represented by B-5).
4. The thermosetting film forming device according to claim 1, wherein the polyester modified with the component (A) has a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene. 5. Photosensitive polyester composition.
Any one of Claim 1 thru | or 4 whose said (C) component is an amino-group containing carboxylic acid compound obtained by making 1 mol of diamine compounds and 1.7-2 mol of dicarboxylic acid dianhydrides react. The photosensitive polyester composition for thermosetting film formation as described in any one.
Based on 100 parts by mass of the component (A), 3 to 50 parts by mass of the component (B), 3 to 50 parts by mass of the component (C), and 5 to 80 parts by mass of the component (D). The photosensitive polyester composition for thermosetting film formation as described in any one of Claims 1 thru | or 5 containing.
Furthermore, the photosensitive polyester composition for thermosetting film formation as described in any one of Claims 1 thru | or 5 which contains a bismaleimide compound as (E) component.
The photosensitive polyester composition for thermosetting film formation according to claim 6, comprising 0.5 to 50 parts by mass of the component (E) according to claim 7 based on 100 parts by mass of the component (A). .
A cured film formed from the photosensitive polyester composition for thermosetting film formation according to any one of claims 1 to 8.
A liquid crystal alignment layer obtained using the photosensitive polyester composition for thermosetting film formation according to any one of claims 1 to 8.