KR20120013941A - Photosensitive polyester composition for thermosetting film formation - Google Patents

Abstract

It is possible to form patterns with alkaline developer, and after the cured film is formed, it shows high solvent resistance, liquid crystal alignment, heat resistance, high transparency, and high flattening property, and when forming the cured film, glycol type applicable to the production line of flattening film of color filter Provide a material that is soluble in a solvent.
The photosensitive polyester composition for thermosetting film formation containing (A) component, (B) component, (C) component, and (D) component. (A) component: The modified polyester obtained by making the polyester containing the structural unit represented by following formula (1) react with the compound which has a functional group selected from glycidyl group and an isocyanate group, (B) component: Two epoxy groups Epoxy compound which has the above, (C) component: The amino-group containing carboxylic acid compound obtained by making a diamine compound and dicarboxylic dianhydride react, (D) component: 1,2-quinonediazide compound (1) (In formula, A, B represents an organic group containing a ring structure.)

Description

Photosensitive polyester composition for thermosetting film formation {PHOTOSENSITIVE POLYESTER COMPOSITION FOR USE IN FORMING THERMALLY CURED FILM}

This invention relates to the photosensitive polyester composition for thermosetting film formation, and the cured film formed from this composition. More specifically, it relates to the photosensitive polyester composition for thermosetting film formation, the cured film, and application of this cured film which can form the cured film which has high transparency, planarization property, and has the liquid crystal orientation ability and high solvent tolerance. This photosensitive polyester composition for thermosetting film formation is especially suitable for the color filter overcoat agent which has a liquid crystal aligning function in a liquid crystal display.

Generally, in optical devices such as liquid crystal display devices, organic electroluminescent (EL) devices, and solid-state imaging devices, a protective film is provided to prevent the surface of the device from being exposed to solvents or heat during the manufacturing process. This protective film has high adhesion to the substrate to be protected, high solvent resistance, and also requires performance such as transparency and heat resistance.

When such a protective film is used as a protective film for a color filter used in a color liquid crystal display device or a solid-state image sensor, it is generally expected to have the performance of flattening the color filter or the black matrix resin of the base substrate, that is, the performance of the flattening film. Required. In particular, when manufacturing a color liquid crystal display device of the STN method or TFT method, the bonding accuracy between the color filter substrate and the counter substrate must be very precise and the cell gap between the substrates must be uniform. In addition, in order to maintain the transmittance of light passing through the color filter, these planarization films, which are their protective films, require high transparency.

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

Generally, high transparency acrylic resin is used for the overcoat of this color filter. In such 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 used for safety, handling, and prevention of dissolution of pigment components from color filters. It is widely used in view of. Such acrylic resins have given heat resistance and solvent resistance by thermosetting or photocuring (Patent Documents 1 and 2). However, in conventional thermosetting or photocurable acrylic resins, proper transparency and flatness are exhibited, but rubbing treatment of such a planarization film does not show sufficient orientation.

On the other hand, the material which consists of solvent-soluble polyimide and a polyamic acid is used normally for a liquid crystal aligning layer. It is reported that these materials can provide solvent resistance by fully imidating at the time of post-baking, and show sufficient orientation by a rubbing process (patent document 3). However, when these materials were regarded as the flattening film of the color filter, there were problems such as a great decrease in the flatness and transparency.

Moreover, in order to improve flatness, the polyester polyamic acid and the polyester polyimide copolymer are reported (patent document 4). However, these polyester-polyamic acids and polyester-polyimide copolymers are also dissolved in solvents such as N-methylpyrrolidone and γ-butyrolactone, like polyimide and polyamic acid, but are glycol-based solvents and esters. The solubility in the solvent of the system was low and the pigment component and the liquid crystal contamination component were eluted in the color filter during the production of the polyimide film, and thus it was difficult to apply to the planarization film production line.

Moreover, in order to improve the adhesive strength with the sheet | seat material used when bonding with the board | substrate of the TFT array side, it is calculated | required that the film | membrane of an adhesion part can be removed using a photolithography process.

In addition, there have been no reports on flattening films having photosensitivity and exhibiting orientation.

Japanese Patent Application Laid-Open No. 2000-103937 Japanese Patent Application Laid-Open No. 2000-119472 Japanese Patent Laid-Open No. 2005-037920 Japanese Patent Laid-Open No. 2008-033244

The present invention has been made on the basis of the above circumstances, and the problem to be solved is that the pattern can be formed with an alkaline developer, and after the formation of the cured film, it shows high solvent resistance, liquid crystal alignment, high transparency and high flattening property, and furthermore, a cured film At the time of formation, it is providing a material which is melt | dissolved in the glycol solvent and lactic-ester solvent applicable in the manufacturing line of the flattening film of a color filter.

MEANS TO SOLVE THE PROBLEM This inventor discovered this invention as a result of earnestly researching in order to solve the said subject.

In other words, to the first point of view

The photosensitive polyester composition for thermosetting film formation containing (A) component, (B) component, (C) component, and (D) component:

(A) component: The modified polyester obtained by making the polyester containing the structural unit represented by following formula (1) react with the compound which has a functional group selected from glycidyl group and an isocyanate group.

(B) component: The epoxy compound which has two or more epoxy groups

(C) component: The amino-group containing carboxylic acid compound obtained by making a diamine compound and dicarboxylic dianhydride react

(D) component: 1,2-quinonediazide compound.

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

The diol compound represented by the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by following formula (i) by the polyester containing the structural unit represented by said Formula (1) by a 2nd viewpoint is represented by 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 react.

{In formula (i) and (ii), A and B are the same as the definition in said formula (1).}

As a 3rd viewpoint, A shows at least 1 sort (s) of group chosen from group represented by following formula (A-1)-formula (A-8) in said formula (1), B is following formula (B-1)- The photosensitive polyester composition for thermosetting film formation as described in the 1st viewpoint or 2nd viewpoint which shows at least 1 sort (s) of group chosen from group represented by Formula (B-5).

The modified polyester which is the said (A) component by the 4th viewpoint is the photosensitive polyester composition for thermosetting film formation in any one of the 1st viewpoint thru | or 3rd viewpoint which has a weight average molecular weight of 1,000-3,000 in polystyrene conversion.

Thermosetting according to any one of the first to fourth aspects, wherein the component (C) is an amino group-containing carboxylic acid compound obtained by reacting 1 mole of a diamine compound with 1.7 to 2 moles of dicarboxylic dianhydride from a fifth viewpoint. Photosensitive polyester composition for film formation.

From the 6th viewpoint, based on 100 mass parts of said (A) components, 3-50 mass parts of said (B) components, 3-50 mass parts of said (C) component, and 5-80 mass parts of said (D) component, respectively The photosensitive polyester composition for thermosetting film formation in any one of 1st viewpoint thru | or 5th viewpoint containing.

The photosensitive polyester composition for thermosetting film formation as described in any one of a 1st viewpoint thru | or a 5th viewpoint which further contains a bismaleimide compound as (E) component as a 7th viewpoint.

The photosensitive polyester composition for thermosetting film formation as described in a 6th viewpoint containing (E) component of 0.5-50 mass parts of 7th viewpoint based on 100 mass parts of said (A) component as an 8th viewpoint.

The cured film formed from the photosensitive polyester composition for thermosetting film formation in any one of a 1st viewpoint thru | or an 8th viewpoint as a 9th viewpoint.

The liquid crystal aligning layer obtained using the photosensitive polyester composition for thermosetting film formation as described in any one of a 1st viewpoint thru | or an 8th viewpoint as a 10th viewpoint.

The photosensitive polyester composition for forming a thermosetting film of the present invention has a photosensitivity and can form a cured film having a liquid crystal alignment ability in addition to high flatness, high transparency, high solvent resistance, and high heat resistance, thereby forming a liquid crystal alignment film or a flattening film. Can be used as a material. In particular, it is possible to form the liquid crystal alignment layer and the overcoat layer of the color filter, which have been independently formed in the past, at one time with a "liquid crystal alignment layer" having both characteristics, thereby simplifying the manufacturing process and reducing the cost by reducing the number of processes. It can be realized.

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

1 is a model diagram illustrating a cured film formed when a thermosetting polyester composition is applied to a stepped substrate.
FIG. 2 is a model diagram in which the liquid crystal alignment layer (a) according to the prior art and the liquid crystal alignment layer (b) using the photosensitive polyester composition for forming a thermosetting film of the present invention are compared.

As mentioned above, in the cured film of the acrylic resin system and polyimide resin system conventionally proposed, it was not able to fully satisfy all the performances, such as planarity, transparency, and orientation required for a liquid crystal aligning film and a planarizing film.

In addition, there have been some proposals for the use of polyester as an alignment material for liquid crystal display devices (see Japanese Patent Application Laid-Open Nos. 5-158055 and 2002-229039). However, all of them do not have thermosetting properties and have solvent resistance of the formed film. Was deteriorated.

Therefore, this invention has the characteristics in the point which aimed at the above-mentioned performance improvement using the thermosetting polyester. That is, this invention is the epoxy compound which has two or more epoxy groups which are polyester (A) component and (B) component, the amino-group containing carboxylic acid compound which is (C) component, and 1,2-quinone diazide which is (D) component. It is a photosensitive polyester composition for thermosetting film formation containing a compound. Moreover, this invention is the photosensitive polyester composition for thermosetting film formation which can also contain a bismaleimide compound as (E) component in addition to (A) component, (B) component, (C) component, and (D) component. .

Hereinafter, each component is explained in full detail.

<(A) component>

The polyester as the component (A) is a modified formula obtained by reacting a polyester containing 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 glycidyl and isocyanate groups Polyester. Preferably it is modified polyester obtained by making the polyester which consists of a structural unit represented by following formula (1) react with the compound which has a functional group selected from glycidyl group and an isocyanate group.

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

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

In Formulas (1Al), (1A2) and (1A3), A ¹ represents a cyclic saturated hydrocarbon group, R ¹ represents a single bond, an ether bond, a carbonyl group, a sulfonic acid group, a saturated hydrocarbon group of 1 to 8, or a fluorine atom. Saturated hydrocarbon groups having 1 to 8 carbon atoms are shown. In addition, R ² represents a saturated hydrocarbon group having 1 to 8 carbon atoms. }

In the formula, A ¹ preferably represents a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, and more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. In addition, arbitrary hydrogen atoms contained in the A ¹ group may be each independently substituted with an aliphatic group, and two of these substituents may be bonded to each other to form a 4 to 6 membered ring.

The aliphatic group which is this substituent here is preferably an aliphatic group having 1 to 5 carbon atoms, and more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents combine and form a ring, it becomes a condensed polycyclic hydrocarbon group in which some or all hydrogenated is bridge | crosslinked cyclic hydrocarbon groups, such as a norbornene group and an adamantane group, for example.

R ¹ 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.

In addition, R ² preferably represents a saturated hydrocarbon group having 1 to 5 carbon atoms, and more preferably a saturated hydrocarbon group having 1 to 3 carbon atoms.

Preferable specific examples of A which is a tetravalent organic group in said Formula (1) are shown to following formula (A-1)-formula (A-8). Among 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 said Formula (1), B represents the bivalent organic group which two bond water couple | bonded with an alicyclic skeleton or an aliphatic skeleton, Preferably it is group represented by following formula (1Bl) or formula (1B2).

In 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, and R ⁴ and R ⁵ are each Independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and R ⁶ and R ⁷ each independently represent an alkylene group having 1 to 5 carbon atoms. K represents 0 or 1.}

In the above formula, B ¹ preferably represents a cyclic saturated hydrocarbon group having 4 to 8 carbon atoms, and more preferably a cyclic saturated hydrocarbon group having 4 to 6 carbon atoms. In addition, arbitrary hydrogen atoms contained in the B ¹ group may be each independently substituted with an aliphatic group.

The aliphatic group which is this substituent here is preferably an aliphatic group having 1 to 5 carbon atoms, and more preferably an aliphatic group having 1 to 3 carbon atoms. When these substituents combine and form a ring, it becomes a condensed polycyclic hydrocarbon group in which some or all hydrogenated is bridge | crosslinked cyclic hydrocarbon groups, such as a norbornene group and an adamantane group, for example.

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.

In addition, R ⁴ and R ⁵ preferably represent a single bond and an alkylene group having 1 to 3 carbon atoms.

R ⁶ and R ⁷ preferably represent an alkylene group having 1 to 3 carbon atoms.

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

It is preferable that a specific polymer contains at least 1 sort (s) of structure chosen from the group which A has from group represented by said Formula (1Al)-Formula (1A3) among the structural units represented by said Formula (1), However, said Formula (1Al) ) To structures other than the group represented by Formula (1A3). At this time, if the structure of polyester is formed, the structure is not specifically limited, It is preferable that it is at least 1 sort (s) of structure chosen from group represented by following formula (1A4) and formula (1A5).

{In formula (1A4) and (1A5), R <^8> , R <^9> , R <^10> is respectively independently substituted by a single bond, an ether bond, a carbonyl group, a sulfonic acid group, the saturated hydrocarbon group of 1-8 carbon atoms, or a fluorine atom. A saturated hydrocarbon group having 1 to 8 carbon atoms is shown. And h represents 0 or 1.}

In the above formula, R ⁸ , R ⁹ , 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 saturated carbon atom having 1 to 5 carbon atoms substituted with a fluorine atom Hydrocarbon group is represented.

In particular, R ⁸ 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.

Moreover, it is preferable that R <^9> is a C1-C5 saturated hydrocarbon group substituted by the ether bond, C1-C5 saturated hydrocarbon group, or a fluorine atom.

And 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.

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

It is preferable that A of the structural unit represented by said Formula (1) in a specific polymer contains at least 60 mol% or more of at least 1 sort (s) of structural unit chosen from the group which consists of group represented by said Formula (1Al)-Formula (1A3). Do.

Modified polyester which is (A) component can be obtained by making the specific polymer react with the compound which has a functional group chosen from glycidyl group and an isocyanate group, as mentioned later.

The weight average molecular weight of the modified polyester (A) component is preferably 1,000 to 30,000 and more preferably 1,500 to 10,000 in terms of polystyrene. When the weight average molecular weight of this polyester is smaller than the said range, the orientation and solvent resistance of the cured film formed from the photosensitive polyester composition for thermosetting film formation of this invention tend to fall, and when exceeding the said range, flattening property will fall. There is a case.

<Method for Producing Specific Polymer>

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

{A and B in the formulas (i) and (ii) have the same definitions as in formula (1) above.}

In addition, the preferable form with respect to said A and B is as having mentioned above.

In this invention, the tetracarboxylic dianhydride represented by the said Formula (i) and the diol compound represented by the said Formula (ii) may respectively be used independently, or 2 or more types may be used.

In manufacture of the said specific polymer, not only tetracarboxylic dianhydride represented by said formula (i) as an acid component but other tetracarboxylic dianhydride (henceforth another acid dianhydride) can also be used together. At this time, the other acid dianhydride is not particularly limited as long as the effect of the present invention is not impaired. Preferably, it is tetracarboxylic dianhydride represented by following formula (i2).

{W in formula (i2) represents at least one structure selected from the group represented by said formula (1A4) and formula (1A5) defined by said formula (1), and R <^8> , R <^9> , R <^10> and h are Same as above definition.}

Preferable specific examples of the formulas (1A4) and (1A5) are also represented by the formulas (al) to (a7).

In this invention, it is preferable that the tetracarboxylic dianhydride represented by said Formula (i) contains at least 60 mol% or more in an acid component.

The compounding ratio of the total amount (the total amount of the acid component) and the total amount (the total amount of the diol component) of the dicarboxylic acid compound, i.e., the total number of moles of the diol compound> / <the total number of tetracarboxylic dianhydride compounds> in the specific polymer Is preferably from 0.95 to 1.5. As with conventional polycondensation reactions, the closer this molar ratio is to 1, the greater the degree of polymerization and the higher molecular weight of the particular polymer produced.

The terminal of the specific polymer changes depending on the blending ratio of the acid component and the diol component. For example, when an acid component is made to overreact, the terminal becomes an acid anhydride easily.

Moreover, when superposing | polymerizing using an diol component excessively, a terminal becomes a hydroxyl group easily. In this case, carboxylic anhydride can be made to react with this terminal hydroxyl group, and a terminal hydroxyl group can be sealed by acid anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, tetrahydrophthalic acid Anhydrides etc. are mentioned.

In the subsequent addition reaction, when reacting with a compound having a glycidyl group, the resulting hydroxyl group and acid anhydride react with each other to cause gelation. Therefore, it is necessary to seal the terminal of the specific polymer with a hydroxyl group or an end hydroxyl group with an acid anhydride.

In the preparation of certain polymers, the reaction temperature of the acid component and the diol component may be selected at any temperature of 50 to 200 ° C, preferably 80 to 170 ° C. For example, reaction temperature is 100-140 degreeC, and a specific polymer can be obtained by reaction time 2 to 48 hours.

In addition, the reaction temperature in the case of protecting a terminal hydroxyl group with an acid anhydride can select arbitrary temperature of 50-200 degreeC, Preferably it is 80-170 degreeC.

Reaction of the said acid component and the said diol component is normally performed in a solvent (Hereinafter, the solvent used when superposing | polymerizing a specific polymer is called "polymerization solvent."). The solvent which can be used at this time is not specifically limited if it does not contain the functional group reacting with an acid anhydride, such as a hydroxyl group and an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, dimethyl sulfone, 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, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2-E Ethyl oxypropionate, and the like.

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

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

In addition, a catalyst can also be used at the time of reaction of the said acid component (formula (i) and formula (i2)) with the said diol component (formula (ii)).

Specific examples of the catalyst used in the polymerization of a specific polymer include benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltripropylammonium chloride, benzyltripropylammonium bromide, tetramethyl Quaternary ammonium salts such as ammonium chloride, tetraethylammonium bromide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, benzyltriphenylphosphonium chloride, benzyltriphenylphosphonium bromide, ethyl And quaternary phosphonium salts such as triphenylphosphonium chloride and ethyltriphenylphosphonium bromide.

<Production of (A) Component>

The polyester of component (A) can be obtained by adding 10-90 mol% of compounds which have a functional group chosen from glycidyl group and an isocyanate group with respect to the carboxyl group of a specific polymer, and making it react. At this time, the polymerization solution of a specific polymer can be used as it is.

Moreover, coexistence of the alcohol solvent is preferable because the gelation during the reaction can be suppressed. Specific examples of such alcohol solvents (hereinafter also referred to as reaction solvents) include 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 Cellulsolve, Butyl Cellulsolve, Ethyl Lactic Acid, Butyl Lactate, Methanol, Ethanol, 1-Propanol, 2-Propanol, 1-Butanol, 2-Butanol, tert-Butanol, Cyclo Hexanol and the like. These solvents can be used individually or in combination of 2 or more types.

Specific examples of the compound having a glycidyl group added to the carboxyl group of the specific polymer include glycidyl methacrylate, glycidyl acrylate, methylglycidyl ether, ethylglycidyl ether, allylglycidyl ether, 4 tert-butylphenylglycidyl ether, glycidyl phenyl ether, glycidyl-2-methylphenyl ether, glycidyl propyl ether, glycidyl isopropyl ether, glycidylbutyl ether, glycidyl-tert- Butyl ether, 2-biphenylglycidyl ether, glycidyl-4-methoxyphenyl ether and the like.

In addition, specific examples of the compound having an isocyanate group added to the carboxyl group of a specific polymer include methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropyl isocyanate, butyl isocyanate, isobutyl isocyanate, tert-butyl isocyanate, phenyl isocyanate and 2-toluyl Isocyanate, 3-toluyl isocyanate, 4-toluyl isocyanate, 1-naphthyl isocyanate, cyclohexyl isocyanate, benzyl isocyanate, 2-isocyanate ethyl methacrylate, 2-methoxyphenyl isocyanate, 3-methoxyphenyl isocyanate, 4 -Methoxyphenyl isocyanate, pentyl isocyanate, hexyl isocyanate, etc. are mentioned.

The reaction temperature of the compound having a carboxyl group and a compound having a functional group selected from a glycidyl group and an isocyanate group reacted thereto may be selected from any temperature of 50 to 160 ° C, preferably 80 to 140 ° C. For example, polyester of the component (A) used for this invention can be obtained by reaction temperature 100-130 degreeC and reaction time 2 to 48 hours.

The solution containing the polyester which is thus obtained (A) component can be used as it is for preparation of the photosensitive polyester composition for thermosetting film formation of this invention. The polyester may also be recovered by being precipitated and isolated in an empty solvent such as water, methanol, ethanol, diethyl ether or hexane.

<(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-diglycidylphenylglycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N- diglycidylaniline), 3,4- Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethanetriglycidyl ether, bisphenol A diglycidyl ether, pentaerythritol polyglycidyl ether, and the like.

Moreover, you may use a commercially available compound from the point which is easy to acquire. Although the specific example (brand name) is given to the following, it is not limited to this: Epoxy resin which has amino groups, such as YH-434 and YH434L (made by Tohto Kasei Co., Ltd.); Epoxy resins having a cyclohexene oxide structure such as EPOLEAD GT-401, GT-403, GT-301, GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (manufactured by Daicel Chemical Industries Limited); Bisphenol A epoxy resins such as Epikote 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010 and copper 828 (manufactured by YUKA SHELL EPOXY KK (currently Japan Epoxy Resins Co., Ltd.)); Bisphenol F type epoxy resins such as Epikote 807 (manufactured by YUKA SHELL EPOXY KK (currently Japan Epoxy Resins Co., Ltd.)); Phenol novolak-type epoxy resins, such as Epikote 152, copper 154 (made by YUKA SHELL EPOXY KK (now Japan Epoxy Resins Co., Ltd.), EPPN201, copper 202 (made by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (YUKA SHELL EPOXY KK (now Japan Epoxy Resins Co., Ltd) Cresol novolak type epoxy resins such as. Denacol EX-252 (manufactured by Negase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, copper CY-192, copper CY-184 (manufactured by CIBA-GEIGYA.G), Epiclon 200, copper 400 (Dainippon Ink & Chemical Inc.), Epikote 871, copper 872 (YUKA SHELL EPOXY KK (now manufactured by Japan Epoxy Resins Co., Ltd.)), alicyclic epoxy resins such as ED-5661 and ED-5662 (manufactured by Celanese Coating Company); Denacol EX-611, Copper EX-612, Copper EX-614, Copper EX-622, Copper EX-411, Copper EX-512, Copper EX-522, Copper EX-421, Copper EX-313, Copper EX-314, Aliphatic polyglycidyl ethers such as EX-321 (manufactured by Negase ChemteX Corporation).

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

The polymer which has the said epoxy group can be manufactured by addition polymerization using the addition polymerizable monomer which has an epoxy group, for example. Examples include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxy ethyl methacrylate, Polycondensation polymers, such as an epoxy novolak, are mentioned.

Or the polymer which has the said epoxy group can also be manufactured by reaction with the high molecular compound which has a hydroxyl group, and the compound which has epoxy groups, such as epichlorohydrin and glycidyl tosylate.

As a weight average molecular weight of such a polymer, it is 300-200,000 in polystyrene conversion, for example.

The epoxy compound which has two or more of these epoxy groups can be used individually or in combination of 2 or more types.

It is preferable that content of (B) component in the photosensitive polyester composition for thermosetting film formation of this invention is 3-50 mass parts based on 100 mass parts of polyester which is (A) component, More preferably, it is 5-5 It is 40 mass parts, Especially preferably, it is 10-30 mass parts. When this ratio is too small, the solvent tolerance and heat resistance of the cured film formed from the photosensitive polyester composition for thermosetting film formation fall, and when too large, solvent resistance may fall or storage stability may fall.

&Lt; Component (C) >

(C) component is an amino-group containing carboxylic acid compound obtained by making a diamine compound and dicarboxylic dianhydride react. Specifically, it is an amino-group containing carboxylic compound obtained by making 1 mol of diamine compounds represented by following formula (iii), and 1.7-2 mol, preferably 1.8-2 mol of dicarboxylic dianhydrides represented by following formula (iv).

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

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

{In formula, P and Q are the same as the definition in said Formula (iii) and Formula (iv).}

In the present invention, each of the diamine compound and the dicarboxylic dianhydride may be used in one kind or two or more kinds. Therefore, as an amino group containing carboxylic acid compound which is (C) component of this invention, not only one type but multiple types of compounds represented by said Formula (2) can be used.

It is preferable that said P and Q are bivalent organic groups which have ring structure each independently, respectively. Examples of the ring structure include a benzene ring, an alicyclic ring, and a condensed polycyclic hydrocarbon.

In said formula (iii), as a ring structure which P has, a benzene ring, a C4-C8 alicyclic ring, and a C7-C16 condensed polycyclic hydrocarbon are preferable.

Thus, 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) ethylamine, 2 -(3-aminophenyl) ethylamine, 1,5-naphthalenediamine, 2,7-naphthalenediamine, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-dia Minobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 ' -Diaminobiphenyl, 3,3'-dihydroxyl -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'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 3,4'-diamino Diphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3, 4'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3,3'-diaminodiphenyl) 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-aminophenyl) ethane, 4,4'-diaminotolan, 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 C) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) 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) propane diacid, bis (4-aminophenyl) butane diacid, bis (4-aminophenyl) pentane diacid, bis (4-aminophenyl) hexane diacid, bis (4-aminophenyl Heptane diacid, bis (4- Minophenyl) octanoic acid, bis (4-aminophenyl) nonanoic acid, bis (4-aminophenyl) decanoic acid, 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-aminobenzoate), 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-phenyl ) Bis (4-aminobenzamide), N, N '-(1,4-phenylene) bis (3-aminobenzamide), N, N'-(1,3-phenylene) bis (3-amino Benzamide), 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-dia Minocyclohexane, bis (4-aminocyclohexyl) me There may be mentioned bis (4-amino-3-methylcyclohexyl) methane.

Moreover, in said formula (iv), as a ring structure which Q has, a benzene ring, the alicyclic ring of 4-8 carbon atoms, and the condensed polycyclic hydrocarbon of 7-16 carbon atoms are preferable. More preferred Q is a benzene ring, an alicyclic ring having 4 to 8 carbon atoms, and 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 preparation of the compound of component (C), the reaction temperature of the diamine compound and the dicarboxylic dianhydride can be selected from any temperature of 5 to 80 ° C, preferably 10 to 50 ° C.

The reaction is usually carried out in a solvent. The solvent which can be used at this time is not specifically limited if it does not contain the functional group which reacts with acid anhydrides, such as a hydroxyl group and an amino group. For example, N, N-dimethylformamide, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylimidazole, dimethyl sulfoxide , Tetramethyl urea, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, cyclohexanone, cyclopentanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, propylene glycol monomethyl ether Acetate, propylene glycol propyl ether acetate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, 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, lactic acid And the like.

These solvents may be used alone or may be used after mixing, but in view of solubility, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N, N-dimethylacetoamide, N-methyl-2-pyrrolidone, Dimethylimidazole is preferred.

Moreover, even if the solvent which does not melt | dissolve an amino-group containing carboxylic acid compound, you may mix and use it with the said solvent in the range which does not precipitate this compound produced | generated by the polymerization reaction.

It is preferable that content of (C) component in the polyester composition for thermosetting film formation of this invention is 3-50 mass parts based on 100 mass parts of polyester of (A) component, More preferably, it is 5-40 It is a mass part. When this ratio is too small, the orientation of the cured film formed from the polyester composition for thermosetting film formation of this invention falls, and when too large, the transmittance | permeability may fall or planarization property may fall.

<(D) component>

As the (D) component 1,2-quinone diazide compound, it is a compound which has either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, among these hydroxyl groups or an amino group (when it has both a hydroxyl group and an amino group, these are total amounts) Preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% can be used compounds esterified or amidated with 1,2-quinonediazidesulfonic acid.

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-hydride). Hydroxyphenyl) butane, 4,4-isopropylidenediphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-di Hydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4 ', 4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone , 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, Phenolic compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethyl And aliphatic alcohols such as ethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

In addition, examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, and m-phenylene. Aniline, such as diamine, p-phenylenediamine, 4,4'- diaminophenylmethane, and 4,4'- diamino diphenyl ether, and aminocyclohexane are mentioned.

Moreover, as a compound containing both the said hydroxyl group and an amino group, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3- diaminophenol, 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, Aminophenols, such as 2-bis (4-amino-3- carboxy-5-hydroxyphenyl) hexafluoro propane, Alkanolamines, such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol, are mentioned. Can be.

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

Content of (D) component in the photosensitive polyester composition for thermosetting film formation of this invention becomes like this. Preferably it is 5-80 mass parts, More preferably, 8-60 mass parts, with respect to 100 mass parts of (A) component, Especially preferably, it is 10-50 mass parts. When this ratio is too small, the difference in the dissolution rate in a developing solution may become small, and patterning by image development may be difficult. Moreover, when it exceeds 100 mass parts, since a 1, 2- quinonediazide compound will not fully decompose | disassemble by short time exposure, a case where a sensitivity may fall or (D) component may absorb light and may reduce transparency of a cured film.

<(E) component>

In this invention, you may contain the bismaleimide compound represented by following formula (3) as (E) component.

The bismaleimide compound which is (E) component can improve planarization property.

(In the formula, M ₁ is an aliphatic group, an aliphatic group and the organic group is selected from the aromatic group the group consisting of containing a cyclic structure, or represents an organic group which is a combination of a plurality of organic groups selected from these groups, and, M ₁ is It may also contain bonds such as ester bonds, ether bonds, amide bonds, and urethane bonds.)

Such bismaleimide compounds include, for example, N, N'-3,3-diphenylmethanebismaleimide, N, N '-(3,3-diethyl-5,5-dimethyl) -4,4 -Diphenyl-methanebismaleimide, N, N'-4,4-diphenylmethanebismaleimide, 3,3-diphenylsulfonbismaleimide, 4,4-diphenylsulfonbismaleimide, N, N '-p-benzophenonebismaleimide, N, N'-diphenylethanebismaleimide, N, N'-diphenyletherbismaleimide, N, N'-(methylene-ditetrahydrophenyl) bismaleimide , N, N '-(3-ethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3,3-dimethyl) -4,4-diphenylmethanebismaleimide, N, N '-(3,3-diethyl) -4,4-diphenylmethanebismaleimide, N, N'-(3,3-dichloro) -4,4-diphenylmethanebismaleimide, N, N ' Isophorone bismaleimide, N, N'-tolidine bismaleimide, N, N'-diphenylpropanebismaleimide, N, N'-naphthalene bismaleimide, N, N'-m-phenylene bis Maleimide, N, N'-5-methoxy-1,3-phenyl Bismaleimide, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-chloro-4- (4-maleimidephenoxy) phenyl) propane, 2, 2-bis (3-bromo-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-ethyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2 -Bis (3-propyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-isopropyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2- Bis (3-butyl-4- (4-maleimidephenoxy) phenyl) propane, 2,2-bis (3-methoxy-4- (4-maleimidephenoxy) phenyl) propane, 1,1-bis (4- (4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3-methyl-4- (4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3-chloro-4 -(4-maleimidephenoxy) phenyl) ethane, 1,1-bis (3-bromo-4- (4-maleimidephenoxy) phenyl) ethane, 3,3-bis (4- (4-maleic Midphenoxy) phenyl) pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, 1,1,1, 3,3,3-hex Fluoro-2,2-bis (3,5-dimethyl-4- (4-maleimidephenoxy) phenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,5-dibromo-4- (4-maleimidephenoxy) phenyl) propane, N, N'-ethylenedimaleimide, N, N'-hexamethylenebismaleimide, N, N'-dode Cmethylenebismaleimide, N, N'-m-xylenebismaleimide, N, N'-p-xylenebismaleimide, N, N'-1,3-bismethylenecyclohexanebismaleimide, N, N '-2,4-tolylene bismaleimide, N, N'-2,6-tolylene bismaleimide, and the like. These bismaleimide compounds are not specifically limited to what was mentioned above.

These can use together single or 2 types or more of components.

Of these bismaleimides, 2,2-bis (4- (4-maleimidephenoxy) phenyl) propane, N, N'-4,4-diphenylmethanebismaleimide, N, N '-(3,3 Aromatic bismaleimides such as -diethyl-5,5-dimethyl) -4,4-diphenyl-methanebismaleimide are preferred.

Moreover, in order to acquire higher planarity among these aromatic bismaleimide, the thing of molecular weight 1,000 or less is preferable.

It is preferable that content of (E) component in the photosensitive polyester composition for thermosetting film formation of this invention is 0.5-50 mass parts with respect to 100 mass parts of polyester which is (A) component, More preferably, it is 1-30 It is a mass part, Especially preferably, it is 2-20 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 this invention falls, and when too large, the transmittance | permeability of a cured film may fall or a coating film may become rough.

<Solvent>

The photosensitive polyester composition for thermosetting film formation of this invention is used in the solution state melt | dissolved in the solvent in many cases. The solvent used at this time dissolves (A) component-(D) component, (E) component and / or the other additives mentioned later as needed, and if the solvent which has such a dissolving ability, the kind, structure, etc. are especially It is not limited.

As such a functional solvent, the solvent (polymerization solvent) used for superposition | polymerization of a specific polymer, the reaction solvent mentioned above, ethyl acetate, butyl acetate, etc. are mentioned. These solvents can be used individually or in combination of 2 or more types.

<Other additives>

Further, the photosensitive polyester composition for forming a thermosetting film of the present invention, if necessary, as long as the effects of the present invention are not impaired, adhesion aids such as surfactants, rheology regulators, silane coupling agents, pigments, dyes, storage stabilizers, A defoaming agent, dissolution accelerators, such as a polyhydric phenol and a polycarboxylic acid, etc. can be contained.

<Photosensitive polyester composition for thermosetting film formation>

The photosensitive polyester composition for thermosetting film formation of this invention is an epoxy compound which has two or more epoxy groups which are polyester which is (A) component, and (B) component, the amino-group containing carboxylic acid compound which is (C) component, and (D) component It is a composition which contains a phosphorus 1,2-quinonediazide compound and can contain 1 or more types of bismaleimide compounds which are (E) component as needed, and other additives as needed. And usually, they are often used as a solution dissolved in a solvent.

Especially, the preferable example of the photosensitive polyester composition for thermosetting film formation of this invention is as follows.

[1]: thermosetting film formation containing 3 to 50 parts by mass (B) component, 3 to 50 parts by mass (C) component and 5 to 80 parts by mass (D) component based on 100 parts by mass of (A) component Photosensitive polyester composition for.

[2]: thermosetting containing 3 to 50 parts by mass (B) component, 3 to 50 parts by mass (C) component, 5 to 80 parts by mass (D) component and solvent based on 100 parts by mass of (A) component Photosensitive polyester composition for film formation.

[3]: 3 to 50 parts by mass of (B) component, 3 to 50 parts by mass of (C) component, 5 to 80 parts by mass of (D) component, 0.5 to 50 parts by mass based on 100 parts by mass of (A) component ( E) Photosensitive polyester composition for thermosetting film formation containing a component.

[4]: 3 to 50 parts by mass of (B) component, 3 to 50 parts by mass of (C) component, 5 to 80 parts by mass of (D) component, 0.5 to 50 parts by mass based on 100 parts by mass of (A) component ( E) Component and the photosensitive polyester composition for thermosetting film formation containing a solvent.

The compounding ratio, preparation method, etc. at the time of using the photosensitive polyester composition for thermosetting film formation of this invention as a solution are explained in full detail below.

Although the ratio of solid content in the photosensitive polyester composition for thermosetting film formation of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, it is 1-80 mass%, Preferably it is 5-60 mass%. More preferably, it is 10-50 mass%. Solid content means here the thing remove | excluding 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 and (C) component in this solution. And (D) component, and (E) component may be mixed in a predetermined ratio to make a uniform solution, or other additives may be added and mixed as necessary in a suitable step of this preparation method. have.

In preparation of the photosensitive polyester composition for thermosetting film formation of this invention, the solution of the polyester obtained by the polymerization reaction in a solvent can be used as it is. In this case, when (B) component, (C) component, (D) component, (E) component, etc. are put into the solution of this (A) component, and it makes a uniform solution, a solvent for the purpose of concentration adjustment You may add additional. At this time, the solvent used in the production process of polyester and the solvent used for concentration adjustment at the time of preparation of the photosensitive polyester composition for thermosetting film formation may be same or different.

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

<Film, Cured Film, and Liquid Crystal Alignment Layer>

The photosensitive polyester composition for forming a thermosetting film of the present invention may be a substrate (for example, a silicon / silicon dioxide coated substrate, a silicon nitride substrate, a metal, for example, a substrate coated with aluminum, molybdenum, chromium, glass substrate, quartz, etc.). Spin coating, flow coating, roll coating, slit coating, slit followed by spin coating, inkjet onto a substrate, an ITO substrate, etc.) or a film (for example, a resin film such as a triacetyl cellulose film, a polyester film, an acrylic film), or the like. After apply | coating by application | coating, printing, etc., a coating film can be formed by predrying (prebaking) with a hotplate or oven. Then, a film is formed by heat-processing this coating film.

As conditions of this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70-160 degreeC and time 0.3-60 minutes are employ | adopted, for example. The heating temperature and the heating time are preferably 80 to 140 ° C. and 0.5 to 10 minutes.

In addition, the film thickness of the film formed from the photosensitive polyester composition for thermosetting film formation is 0.1-30 micrometers, for example, and can select suitably in consideration of the level | step difference of the board | substrate to be used, and the optical and electrical property.

Post-baking is generally employed a method of treatment for 5 to 30 minutes when using a hot plate at a heating temperature selected in the range of 140 to 250 ℃, 30 to 90 minutes when using an oven.

By hardening the photosensitive polyester composition for thermosetting film formation of this invention on condition mentioned above, the level | step difference of a board | substrate can fully be planarized and the cured film which has high transparency can be formed.

The cured film thus formed can be subjected to a rubbing treatment to function as a liquid crystal material alignment layer, that is, a layer in which a compound having liquid crystallinity is oriented.

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

Thereafter, residues generated by rubbing by ultrasonic cleaning using pure water or the like are removed.

After retardation material is apply | coated on the liquid crystal aligning layer formed in this way, a layer which has optical anisotropy can be formed by photocuring a retardation material to a liquid crystal state.

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

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

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

For this purpose, the photosensitive polyester composition for thermosetting film formation of this invention can be used suitably for various optically 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 the required level of flatness, a protective film, a flattening film, an insulating film, etc. in various displays such as a thin film transistor (TFT) type liquid crystal display device, an organic EL device, etc. It is also useful as a material for forming a cured film of a film, and is particularly suitable as a material for forming an overcoat material of a color filter, an interlayer insulating film of a TFT type liquid crystal device, an insulating film of an organic EL device, and the like.

Example

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples.

[Weak symbol used in the Example]

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

<Polyester 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: glycidylmethyl ether

DTBC: Di-tert-Butyl Cresol

<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) diphenylsulfone

TA: trimellitic anhydride

DDS: 4,4'-diaminodiphenylsulfone

pDA: p-phenylenediamine

<Acrylic copolymer raw material>

MAA: Methacrylic acid

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

CHMI: N-cyclohexylmaleimide

AIBN: azobisisobutyronitrile

<Epoxy compound>

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

<Bismaleimide compound>

BMI1: N, N '-(3,3-diethyl-5,5-dimethyl) -4,4-diphenyl-methanebismaleimide

<1,2-quinonediazide compound>

QD1: A compound synthesized by the condensation reaction of 1 mol of 1,3,3-tris (4-hydroxyphenyl) butane with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride.

QD2: 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride Compound synthesized by condensation reaction.

<Solvent>

PGMEA: Propylene glycol monomethyl ether acetate

PGME: Propylene Glycol Monomethyl Ether

DMAc: N, N-dimethylacetoamide

NMP: N-methyl-2-pyrrolidone

The number average molecular weight and the weight average molecular weight of the polyester, polyimide precursor, and acrylic copolymer obtained according to the following synthesis examples were obtained by using the GPC apparatus (Shodex® columns KF803L and KF804L) manufactured by Nippon Spectroscopy Co., Ltd. Tetrahydrofuran was measured under the conditions of eluting | pouring in a column (column temperature 40 degreeC) at a flow volume of 1 ml / min. In addition, the following number average molecular weight (henceforth Mn.) And weight average molecular weight (henceforth Mw.) Were shown by polystyrene conversion value.

Synthesis Example 1

HBPDA 40.0 g, BPDA 8.23 g, HBPA 49.3 g, THPA 5.96 g, BTEAC 0.18 g, and TPPB 0.33 g were reacted for 17 hours at 120 ° C. in 241.96 g of PGMEA to obtain a solution of a specific polymer (solid content concentration: 30.0 mass%) ( P1). Mn of the obtained specific polymer was 1,500 and Mw was 3,430.

&Lt; Synthesis Example 2 &

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

&Lt; Synthesis Example 3 &

11.16 g of GME and 26.05 g of PGME were added to 252.00 g of the solution (P1) of the specific polymer obtained in Synthesis Example 1 and reacted at 110 ° C for 9 hours to obtain a polyester solution (solid content concentration: 30.0 mass%) (P3). Mn of obtained polyester was 1,450 and Mw was 5,340.

&Lt; Synthesis Example 4 &

The amino group containing carboxylic acid compound solution (solid content concentration 30.0 mass%) was obtained by making DA-1M 15.14g and THPA 10.64g react at 23 degreeC in PGME 60.15g for 24 hours (A1). The obtained amino group containing carboxylic acid compound confirmed that THPA does not remain using high performance liquid chromatography.

&Lt; Synthesis Example 5 &

An amino group containing carboxylic acid compound solution (solid content concentration of 30.0 mass%) was obtained by making DA-4P 10.23g and THPA 10.64g react in 24.71g of PGME at 23 degreeC for 24 hours (A2). The obtained amino group containing carboxylic acid compound confirmed that THPA does not remain using high performance liquid chromatography.

&Lt; Synthesis Example 6 &

40.0 g of BPDA, 35.3 g of HBPA, 3.31 g of THPA, and 0.77 g of BTEAC were reacted for 19 hours at 120 ° C. in 175.7 g of PGMEA to obtain a solution of a specific polymer (solid content concentration: 30.0% by mass). Mn of the obtained specific polymer was 1,100 and Mw was 2,580. 18.42g of GMA, 0.057g of DTBC, and 42.99g of PGME were added to 252.00g of this specific polymer, and it was made to react at 110 degreeC for 9 hours, and the polyester solution (solid content concentration: 30.0 mass%) was obtained (P4). Mn of obtained polyester was 1,580 and Mw was 7,540.

&Lt; Synthesis Example 7 &

The polyimide precursor solution (solid content concentration: 30.0 mass%) was obtained by making CBDA17.7g and pDA10.2g react in NMP66.4g for 24 hours at 23 degreeC (P5). Mn of the obtained polyimide precursor was 5,800 and Mw was 12,500.

&Lt; Synthesis Example 8 &

As the monomer component, 10.9 g of MAA, 35.3 g of CHMI, 25.5 g of HEMA, and 28.3 g of MMA were used and 5 g of AIBN as a radical polymerization initiator, and they were polymerized at 150 g of solvent PGMEA at a temperature of 60 ° C. to 100 ° C. to obtain an acrylic copolymer solution. (Solid content concentration: 40.0 mass%) was obtained (P6). Mn of the obtained acrylic copolymer solution was 3,800 and Mw was 6,700.

<Examples 1-5 and Comparative Examples 1-5>

Each composition of Examples 1-5 and Comparative Examples 1-5 was prepared with the composition shown in Table 1, and the flattening property, solvent tolerance, orientation property, heat resistance, pattern formation property, and the transmittance | permeability were evaluated about the cured film obtained by this composition. did.

Solution (g) of (A) component (B) Component (g) (C) component (g) (D) component (g) (E) component (g) Solvent (g) Example 1 P2
20 CEL
1.2 A1
3.0 QD 1
2.1 PGME
14.5 Example 2 P2
20 CEL
1.2 A1
3.0 QD 1
2.1 BMI1
0.3 PGME
15.4 Example 3 P2
20 CEL
1.2 A1
3.0 QD 1
2.1 BMI1
0.3 PGME
15.4 Example 4 P3
20 CEL
1.2 A1
3.0 QD 1
2.1 BMI1
0.3 PGME
15.4 Example 5 P2
20 CEL
1.2 A1
3.0 QD 1
2.1 BMI1
0.3 PGME
15.4 Comparative Example 1 P1
20 CEL
1.2 A1
3.0 QD 1
2.1 - PGME
14.5 Comparative Example 2 P2
20 CEL
1.2 A1
3.0 - PGME
8.2 Comparative Example 3 P4
20 CEL
1.2 A1
3.0 QD 1
2.1 PGME
14.5 Comparative Example 4 P5
20 CEL
1.2 QD 1
2.1 - NMP
13.9 Comparative Example 5 P6
20 CEL
1.6 QD 1
2.4 - PGMEA
24.0

* P1: Specific polymer solution P2-P4: Polyester solution P5: Polyimide precursor solution P6: Acrylic copolymer solution

[Evaluation of Flatness]

Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was coated on a stepped substrate (made of glass) with a height of 0.5 μm, a line width of 10 μm, and an interline space of 50 μm using a spin coater, followed by temperature 110 Prebaking was performed on the hotplate at 120 degreeC for 120 second, and the coating film of 2.8 micrometers in thickness was formed. The film thickness was measured using F20 by FILMETRICS. Post-baking was performed by heating this coating film at the temperature of 230 degreeC for 30 minutes, and the cured film with a film thickness of 2.5 micrometers was formed.

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 x [1- {film thickness difference (μm) of the film / step height (0.5μm) )}] Was used to determine the planarization rate.

[Evaluation of Pattern Formability]

Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was coated 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 2.8 μm. Formed a coating film. The film thickness was measured using F20 by FILMETRICS. This coating film was irradiated with 100 mJ / cm ² of ultraviolet rays having a light intensity of 5.5 mW / cm ² at 365 nm with a Canon Inc. ultraviolet irradiation device PLA-600FA through a mask having a 10 μm line and space pattern. Thereafter, the solution was developed by immersing in a 0.2% by mass aqueous tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution for 60 seconds, and then washed with ultrapure water for 20 seconds. The obtained line & space pattern was observed with an optical microscope to indicate that a pattern according to the mask design was obtained, and that the pattern was not resolved or dissolved at the time of development was indicated by x.

[Evaluation of Solvent Tolerance]

Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied to a silicon wafer using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to achieve a film thickness of 2.8 μm. A coating film was formed. The film thickness was measured using F20 by FILMETRICS. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film with a film thickness of 2.5 micrometers was formed.

The cured film was immersed in PGMEA or NMP for 60 seconds, and then dried at a temperature of 100 ° C. for 60 seconds to measure the film thickness. (Circle) that there was no change in film thickness after PGMEA or NMP immersion, and (x) that no decrease in film thickness was found after immersion.

[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 prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. Formed a coating film. The film thickness was measured using F20 by FILMETRICS. After developing by coating this coating film in 0.2 mass% of TMAH aqueous solution for 60 second, it flowed in ultrapure water for 20 second. Then, 500 mJ / cm <^2> of ultraviolet-rays whose light intensity in 5.5 nm was 5.5 mW / cm < ² > were irradiated with Canon Inc. ultraviolet irradiation device PLA-600FA. This coating film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

The transmittance | permeability at the wavelength of 400 nm was measured for this cured film using the ultraviolet-visible spectrophotometer (SHIMADSU UV-2550 model number 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 prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds to obtain a film thickness of 2.8 μm. Formed a coating film. The film thickness was measured using F20 by FILMETRICS. This film was post-baked on the hotplate for 30 minutes at the temperature of 230 degreeC, and the cured film was formed.

This cured film was rubbed at a rotational speed of 300 rpm, a feed rate of 10 mm / sec, and an indentation amount of 0.45 mm. The rubbed substrate was ultrasonically cleaned for 5 minutes with pure water. After apply | coating the phase difference material which consists of liquid crystal monomers on this board | substrate using a spin coater, it prebaked on the hotplate for 40 second at 100 degreeC, and 30 second at 55 degreeC, and formed the coating film of 1.1 micrometer in thickness. This substrate was exposed to 2,000 mJ under a nitrogen atmosphere. The orientation was visually confirmed through the produced substrate through the polarizing plate. (Circle) and the thing which does not change markedly change the light transmittance when the board | substrate was inclined 45 degree | times and not.

[Evaluation of Heat Resistance]

Each composition of Examples 1 to 5 and Comparative Examples 1 to 5 was applied onto a quartz substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds, followed by a temperature of 230 ° C. Post-baking was performed on the hotplate for 30 minutes at and the cured film was formed, and the film thickness was measured using F20 by FILMETRICS. Thereafter, the cured film was further baked at a temperature of 230 ° C. for 60 minutes on a hot plate, and the film thickness was measured again to calculate the rate of change of the film thickness after postbaking. In addition, in order to be recognized as a cured film having heat resistance, it is required to have a performance of at least a film thickness change rate of less than ± 5%.

[Evaluation results]

The above evaluation is performed and the results are shown in Table 2.

Planarization rate (%) Solvent resistance Orientation
Heat resistance
Pattern formation
Transmittance
PGMEA NMP Example 1 81 ○ ○ ○ -2% ○ 91% Example 2 83 ○ ○ ○ -2% ○ 91% Example 3 83 ○ ○ ○ -3% ○ 90% Example 4 83 ○ ○ ○ -2% ○ 91% Example 5 80 ○ ○ ○ -One% ○ 88% Comparative Example 1 80 ○ ○ ○ -2% × 90% Comparative Example 2 85 ○ ○ ○ -2% × 95% Comparative Example 3 80 ○ ○ ○ -18% × 88% Comparative Example 4 40 ○ ○ ○ -One% × 65% Comparative Example 5 88 ○ ○ -0.5% ○ 93%

Examples 1 to 5 can form a pattern, have a high planarization rate, high heat resistance, and exhibit resistance to both PGMEA and NMP. Moreover, all showed favorable orientation and achieved high transmittance (transparency) after high temperature baking.

In Comparative Example 1, the unexposed portion could not be dissolved in the developer to form pattern formation.

In Comparative Example 2, the exposed portion was not dissolved in the developing solution, and thus pattern formation was not possible.

Comparative Example 3 was low in heat resistance and could not be patterned.

In Comparative Example 4, the planarization rate was low and pattern formation was not possible.

On the other hand, in Comparative Example 5, pattern formation was possible and the flattening rate, heat resistance, solvent resistance and transmittance were good, but the orientation was deteriorated.

As mentioned above, the photosensitive polyester composition for thermosetting film formation of this invention can use glycol solvents, such as propylene glycol monomethyl ether acetate, at the time of cured film formation. In addition, pattern formation was possible with the alkaline developer, and the obtained cured film had excellent performance in all of excellent light transmittance, solvent resistance, heat resistance, planarization, and orientation.

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 device, and can be used in various displays such as thin film transistor (TFT) type liquid crystal display devices and organic EL devices. It is also suitable as a material for forming a cured film such as a protective film, a planarization film, or an insulating film, in particular, a material for forming an interlayer insulating film of a TFT type liquid crystal element, a protective film of a color filter, an insulating film of an organic EL element, or the like.

Claims (10)

(A) component: The modified polyester obtained by making the polyester containing the structural unit represented by following formula (1) react with the compound which has a functional group chosen from a glycidyl group and an isocyanate group,
(B) component: The epoxy compound which has two or more epoxy groups,
(C) component: The amino-group containing carboxylic acid compound obtained by making a diamine compound and dicarboxylic dianhydride react, and
(D) component: 1,2-quinonediazide compound
The photosensitive polyester composition for thermosetting film formation containing.
[Formula 1]

(In formula, A represents the tetravalent organic group which four bond number couple | bonded with an alicyclic skeleton or an aliphatic skeleton, B shows the bivalent organic group which two bond number couple | bonded with an alicyclic skeleton or an aliphatic skeleton.)
The method of claim 1,
Diol containing the tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by following formula (i), and the polyester containing the structural unit represented by said Formula (1) represented by following formula (ii) The photosensitive polyester composition for thermosetting film formation which is polyester obtained by making a component react.
(2)

{In formula (i) and (ii), A and B are the same as the definition in said formula (1).}
3. The method according to claim 1 or 2,
In said Formula (1), A represents at least 1 sort (s) of group chosen from group represented by following formula (A-1)-formula (A-8), B is following formula (B-1)-formula (B- The photosensitive polyester composition for thermosetting film formation which shows at least 1 sort (s) of group chosen from group represented by 5).
(3)

[Chemical Formula 4]

4. The method according to any one of claims 1 to 3,
The modified polyester as the component (A) is a photosensitive polyester composition for forming a thermosetting film having a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene.
The method according to any one of claims 1 to 4,
The photosensitive polyester composition for thermosetting film formation 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 dianhydrides react.
The method according to any one of claims 1 to 5,
Thermosetting containing 3-50 mass parts of said (B) component, 3-50 mass parts of said (C) component, and 5-80 mass parts of said (D) component based on 100 mass parts of said (A) component, respectively. Photosensitive polyester composition for film formation.
The method according to any one of claims 1 to 5,
Furthermore, the photosensitive polyester composition for thermosetting film formation containing a bismaleimide compound as (E) component.
The method of claim 6,
The photosensitive polyester composition for thermosetting film formation containing 0.5-50 mass parts of (E) component based on 100 mass parts of said (A) component.
The cured film formed from the photosensitive polyester composition for thermosetting film formation in any one of Claims 1-8.
The liquid crystal aligning layer obtained using the photosensitive polyester composition for thermosetting film formation in any one of Claims 1-8.

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