KR20180007299A - Photosensitive compositions - Google Patents

Abstract

The present invention relates to a protective film photosensitive composition which not only has good heat resistance, but also has good line pattern shape linearity during short time development. The photosensitive composition of the present invention comprises a polyester amide acid (A), an epoxy group-containing copolymer (B) and a 1,2-quinonediazid compound (C), wherein the polyester amide acid (A) includes a constituent unit represented by chemical formula (1) and a constituent unit represented by chemical formula (2), the epoxy group-containing copolymer (B) is a copolymer of an epoxy group-containing polymerizable compound (b1) and a polymerizable compound (b2) except for the epoxy group-containing polymerizable compound (b1), and the polymerizable compound (b2) includes a phenolic hydroxyl group-containing polymerizable compound.

Description

[0001] PHOTOSENSITIVE COMPOSITIONS [0002]

INDUSTRIAL APPLICABILITY The present invention can be used for forming an insulating material in an electronic part, a passivation film in a semiconductor device, a buffer coat film, an interlayer insulating film, a planarizing film, or an interlayer insulating film or a protective film for a color filter in a display element Sensitive composition, a cured film thereof, and an electronic component having the cured film.

In the case where a protective film is formed only in a necessary portion, or when a hole pattern is formed in an insulating film, a photosensitive composition is used. As an example of the photosensitive composition, there can be mentioned an acrylic positive photosensitive composition (Patent Document 1). With the improvement of the reliability required characteristics for display, the heat resistance required for the display member is improved, and the material described in Patent Document 1 is a further high heat resistance problem. In order to solve the problem, a positive photosensitive composition of polyester amide acid type having good heat resistance has been proposed (Patent Document 2). In order to cope with the recent low cost of display, time is shortened for each step in order to increase the number of manufacturing per unit time. Among them, in the positive photosensitive composition described in Patent Document 2, when the developing time is short, the line pattern shape does not become a straight line, and a problem is caused that it becomes a wavy pattern. If the line pattern shape is wavy, the panel display quality is degraded.

Japanese Unexamined Patent Publication No. 5-165214 Japanese Patent Application Laid-Open No. 2008-102351

Disclosure of the Invention The object of the present invention is to provide a photosensitive composition for a protective film or an insulating film which has good heat resistance and is excellent in line pattern shape linearity at the time of short-time development.

Means for Solving the Problems As a result of intensive investigations to solve the above problems, the present inventors have found that a composition comprising a polyester amide acid, an epoxy group-containing copolymer and a 1,2-quinonediazide compound, and a cured film obtained by curing the composition And the present invention has been accomplished on the basis of these findings.

The present invention includes the following configuration.

[1] A photosensitive composition comprising a polyester amide acid (A), an epoxy group-containing copolymer (B) and a 1,2-quinonediazide compound (C);

The polyester amide acid (A) comprises a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (2);

The epoxy group-containing copolymer (B) is a copolymer of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) other than (b1);

Wherein the polymerizable compound (b2) comprises a polymerizable compound having a phenolic hydroxyl group.

In the formula (1), R ¹ is an organic group having 2 to 1000 carbon atoms and R ² is an organic group having 2 to 1000 carbon atoms;

In the formula (2), R ³ is an organic group having 2 to 1000 carbon atoms and R ⁴ is an organic group having 2 to 100 carbon atoms.

[2] The structural unit represented by the above-mentioned formula (1) is a structural unit comprising a compound (a1) having two or more acid anhydride groups and a diamine (a2) as raw materials;

The photosensitive composition according to item [1], wherein the constituent unit represented by the formula (2) is a constituent unit derived from a compound (a1) having two or more acid anhydride groups and a polyhydric hydroxy compound (a3) as raw materials.

[3] the compound (a1) having at least two acid anhydride groups is at least one compound selected from tetracarboxylic acid dianhydride and styrene-maleic anhydride copolymer;

Wherein the polyester amide acid (A) is at least one compound selected from the group consisting of X mol of tetracarboxylic acid dianhydride, Y mol of diamine, and Z mol of polyhydric hydroxy compound of the following formula (3) By weight based on the total weight of the photosensitive composition.

0.2? Z / Y? 8.0 (3)

0.2? (Y + Z) / X? 5.0 (4)

[4] the polymerizable compound (b1) having an epoxy group is at least one selected from (meth) acrylates having an epoxy group;

The photosensitive composition according to item (1), wherein the polymerizable compound having a phenolic hydroxyl group is at least one selected from a compound represented by the following formula (5) and a compound represented by the following formula (6).

In the formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbon atoms, R ⁶ is a single bond or -C (= O) -, R ⁷ to R ¹¹ each independently represent a hydroxyl group, 7. Provided that at least one of R ⁷ to R ¹¹ is a hydroxyl group;

In formula (6), R ¹² is hydrogen or an organic group having 1 to 7 carbon atoms, R ¹³ is -O- or -NH-, R ¹⁴ is a single bond or a divalent organic group having 1 to 40 carbon atoms, R ¹⁵ to R ¹⁹ each independently represent a hydroxyl group or an organic group having 1 to 7 carbon atoms. Provided that at least one of R ¹⁵ to R ¹⁹ is a hydroxyl group.

[5] the (meth) acrylate having an epoxy group is glycidyl (meth) acrylate;

Wherein the compound represented by the formula (5) is at least one selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenylvinylketone;

Wherein the compound represented by the formula (6) is at least one compound selected from 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide and 4-hydroxyphenyloxyethyl , And the photosensitive composition described in item [4].

[6] The epoxy resin composition according to any one of [1] to [5], wherein the content of the epoxy group-containing copolymer (B) in the total amount of the polyester amide acid (A) and the epoxy group- The photosensitive composition according to item (1), wherein the amount of the 1,2-quinonediazide compound (C) is 5 to 40 parts by weight based on 100 parts by weight of the total amount of the epoxy group-containing copolymer (B).

[7] A cured film obtained from the photosensitive composition according to any one of [1] to [6].

The photosensitive composition according to the preferred embodiment of the present invention is a material having good heat resistance and good line pattern shape linearity at the time of short-time development. When used as a color filter protective film of a color display element, the photosensitive composition can improve reliability and display quality And the productivity in manufacturing the color filter protective film can be improved. It can also be used as a protective film and an insulating film for various optical materials.

1 is an optical microscope photograph of a state in which no line is present in a line pattern shape.
Fig. 2 is an optical microscope photograph of a state in which a line pattern shape is wavy.

In the present specification, in order to express one or both of "acrylic acid" and "methacrylic acid", the term "(meth) acrylic acid" may be used. (Meth) acrylate " to denote one or both of " acrylate " and " methacrylate ", and one or both of " acrylamide & (Meth) acrylamide " to denote one or both of " acryloxy " and " methacryloxy " have.

<1. Photosensitive composition>

The photosensitive composition according to the present invention is a composition comprising a polyester amide acid (A), an epoxy group-containing copolymer (B) and a 1,2-quinonediazide compound (C).

A preferable composition ratio of the polyester amide acid (A), the epoxy group-containing copolymer (B) and the 1,2-quinonediazide compound (C) is preferably such that the total amount of the polyester amide acid (A) and the epoxy group- Wherein the content of the epoxy group-containing copolymer (B) is 20 to 90% by weight and the content of the polyester amide acid (A) and the epoxy group-containing copolymer (B) And the zide compound (C) is 5 to 40 parts by weight.

Further, the photosensitive composition according to the present invention may further contain other components in addition to the above-mentioned components in the range in which the effect of the present invention can be obtained.

<1-1. The polyester amide acid (A)

The polyester amide acid (A) has a structural unit represented by the formula (1) and a structural unit represented by the formula (2).

The polyester amide acid (A) can be obtained by reacting a compound (a1) having two or more acid anhydride groups, a diamine (a2), and a polyhydric hydroxy compound (a3) as essential components. In that case, the formula (1) and (2) the method, R ¹ and R ³ is a residue obtained by removing the two -CO-O-CO- from the compound (a1) having an acid anhydride group two or more, R ² is Is a residue obtained by removing two -NH ₂ from the diamine (a2), and R ⁴ is a residue obtained by removing two -OH from the polyhydric hydroxy compound (a3).

At least a solvent is required for the synthesis of the polyester amide acid (A). The photosensitive composition may be prepared by using a liquid or gel-like polyester amide acid solution in which the solvent is left as it is, taking into consideration the handling property, etc., and the solvent is removed to obtain a photosensitive polyester amide acid A composition may also be prepared.

In addition, the synthesis of the polyester amide acid (A) may contain other compounds than the above insofar as the object of the present invention is not impaired. Examples of other raw materials include a monoamine having a monohydroxy compound and an alkoxysilyl group.

<1-1-1. Compound (a1) having two or more acid anhydride groups>

In the present invention, a compound (a1) having two or more acid anhydride groups is used as a raw material for obtaining the polyester amide acid (A).

Examples of preferable compounds of the compound (a1) having two or more acid anhydride groups include aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride, and maleic anhydride and other compounds . &Lt; / RTI &gt;

As specific examples of the compound (a1) having two or more acid anhydride groups, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid, which is a compound used in the examples and is an aromatic tetracarboxylic acid dianhydride 1,2,3,4-butanetetracarboxylic acid dianhydride (hereinafter abbreviated as &quot; BT-100 &quot;) which is an aliphatic tetracarboxylic acid dianhydride, and Styrene-maleic anhydride copolymer, which is a copolymer of maleic anhydride and another compound.

Specific examples of the compound (a1) having two or more acid anhydride groups include aromatic tetracarboxylic acid dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic acid dianhydride, 2 , 2 ', 3,3'-benzophenonetetracarboxylic acid dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-diphenylsulfone Tetracarboxylic acid dianhydride, 2,2 ', 3,3'-diphenylsulfone tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenylsulfone tetracarboxylic acid dianhydride, 2,2 ' ', 3,3'-diphenyl ether tetracarboxylic acid dianhydride, 2,3,3', 4'-diphenyl ether tetracarboxylic acid dianhydride, 2,2- [bis (3,4- Phenyl)] hexafluoropropane dianhydride, and ethylene glycol bis (anhydrotrimellitate); Cyclobutanetetracarboxylic acid dianhydride, cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic dianhydride, which are alicyclic tetracarboxylic acid dianhydrides, cyclobutanetetracarboxylic acid dianhydride, methylcyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, and cyclohexanetetracarboxylic dianhydride; And ethane tetracarboxylic acid dianhydride, which is an aliphatic tetracarboxylic acid dianhydride, and at least one of the specific examples of the compound (a1) having two or more of the above-mentioned acid anhydride groups can be used.

Among the specific examples of the compound (a1) having two or more of these acid anhydride groups, the compound giving a polyester amide acid (A) which is easily available and has good compatibility with the epoxy group-containing copolymer (B) (3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, ODPA, 2,2- [bis (3,4-dicarboxyphenyl)] hexafluoropropane dianhydride, BT- More preferred are glycols (anhydrotrimellitate) and styrene-maleic anhydride copolymers, and 3,3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, ODPA, BT-100 and Styrene-maleic anhydride copolymers are particularly preferred.

As a specific example of commercially available styrene / maleic anhydride copolymer, SMA3000P (molar ratio of styrene / maleic anhydride: 3, weight average molecular weight: 9,500, number average molecular weight: 3,800), SMA2000P (molar ratio of styrene / maleic anhydride: , A weight average molecular weight of 7,500 and a number average molecular weight of 3,000) and SMA1000P (molar ratio of styrene / maleic anhydride: 1, weight average molecular weight: 5,500, number average molecular weight: 2,000) (all trade names; Kawahara Yuka Co., . The average number of carbon atoms per molecule of SMA3000P is 330, the average number of carbon atoms per molecule of SMA2000P is 240, and the average number of carbon atoms per molecule of SMA1000P is 120, calculated from the molar ratio of styrene / maleic anhydride in the catalog and the number average molecular weight.

<1-1-2. Diamine (a2) &gt;

In the present invention, a diamine (a2) is used as a raw material for obtaining the polyester amide acid (A).

Examples of preferred compounds of the diamine (a2) include diamines having two benzene rings and diamines having four benzene rings.

Specific examples of the diamine (a2) include 3,3'-diaminodiphenylsulfone (hereinafter abbreviated as "DDS"), which is a compound used in the examples and is a diamine having two benzene rings .

Specific examples of the diamine (a2) include, in addition to the above-mentioned compounds, 4,4'-diaminodiphenylsulfone and 3,4'-diaminodiphenylsulfone, which are diamines having two benzene rings; Bis [4- (4-aminophenoxy) phenyl] sulfone, bis [3- (4-aminophenoxy) phenyl] sulfone, diamine having four benzene rings, Phenyl] sulfone, [4- (3-aminophenoxy) phenyl] [3- (4-aminophenoxy) phenyl] Phenyl] sulfone, and 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane. Of the specific examples of the diamine (a2) .

Among the specific examples of these diamines (a2), DDS and bis [4- ((meth) acryloyloxyethyl) amide compounds which give a polyester amide acid (A) which is easily available and has good compatibility with the epoxy group- 3-aminophenoxy) phenyl] sulfone is more preferable, and DDS is particularly preferable.

<1-1-3. The polyhydric hydroxy compound (a3) &gt;

In the present invention, a polyhydric hydroxy compound (a3) is used as a raw material for obtaining the polyester amide acid (A).

Examples of preferred compounds of the polyhydric hydroxy compound (a3) include aliphatic diols, compounds represented by the following formula (H-1), compounds represented by the following formula (H-2), and polyhydric alcohols having an isocyanuric ring .

In formula (H-1), R ¹⁰¹ is a single bond or an organic group having 1 to 10 carbon atoms;

In the formula (H-2), R ¹⁰² is an organic group having 1 to 10 carbon atoms.

Specific examples of the polyhydroxy compound (a3) include 1,4-butanediol, which is a compound used in the examples and is an aliphatic diol.

As specific examples of the polyhydric hydroxy compound (a3), in addition to the above-mentioned compounds, aliphatic diols such as ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, And 1,8-octanediol; 2,2-bis (4-hydroxycyclohexyl) propane, which is a compound represented by the formula (H-1), and 4,4'-dihydroxydicyclohexyl; 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol and 2- (4-hydroxyphenyl) ethanol; compounds represented by formula (H-2); And isocyanurate tris (2-hydroxyethyl) as a polyhydric alcohol having an isocyanurate ring, and at least one of the specific examples of the polyhydric hydroxy compound (a3) may be used.

Among these specific examples of the polyhydric hydroxy compound (a3), the compound giving a polyester amide acid (A) which is easily available and has a good compatibility with the epoxy group-containing copolymer (B) Butanediol and 1,6-hexanediol are more preferable, and 1,4-butanediol is particularly preferable.

<1-1-4. Monohydroxy compound>

The raw material for the polyester amide acid (A) may contain other raw materials as needed insofar as the object of the present invention is not impaired, and examples of other raw materials include monohydroxy compounds.

Examples of preferable compounds of the monohydroxy compound include aliphatic monohydric alcohols, compounds represented by the following formula (H-3), alicyclic monohydric alcohols, and aromatic monohydric alcohols.

In the formula (H-3), R ¹⁰³ to R ¹⁰⁶ are each independently hydrogen or a methyl group, R ¹⁰⁷ is an organic group having 1 to 10 carbon atoms, and m is an integer of 1 to 10.

Specific examples of the monohydroxy compound include benzyl alcohol, which is a compound used in the examples and is an aromatic monoalcohol.

Specific examples of the monohydroxy compound include isopropyl alcohol, which is an aliphatic monoalcohol in addition to the above-mentioned compounds; Examples of the compound represented by the formula (H-3) include benzyl alcohol, propylene glycol monoethyl ether, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, terpineol, and 3-ethyl-3-hydroxymethyloxetane; And dimethylbenzylcarbinol, which is an aromatic monoalcohol.

Among the specific examples of these monohydroxy compounds, compounds which can be obtained easily and which give a polyester amide acid (A) having good compatibility with the epoxy group-containing copolymer (B) include benzyl alcohol, propylene glycol monoethyl Ethers and 3-ethyl-3-hydroxymethyloxetane are more preferable, and benzyl alcohol is particularly preferable.

When a monohydroxy compound is used as the raw material of the polyester amide acid (A), the amount of the monohydroxy compound to be used is not particularly limited so far as the amount of the compound (a1), diamine (a2), and polyhydric hydroxy compound is preferably 100 parts by weight or less, more preferably 50 parts by weight or less, based on 100 parts by weight of the total amount of (a3).

<1-1-5. Monoamine having an alkoxysilyl group &gt;

The synthesis of the polyester amide acid (A) may include, if necessary, other raw materials other than the above, within the range not impairing the object of the present invention. Examples of other raw materials include monoamines having an alkoxysilyl group have.

Specific examples of the alkoxysilyl group-containing monoamine used in the present invention include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxy Silane, 4-aminobutyltrimethoxysilane, 4-aminobutyltriethoxysilane, 4-aminobutylmethyldiethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, p-amino Phenylmethyldimethoxysilane, p-aminophenylmethyldiethoxysilane, m-aminophenyltrimethoxysilane, and m-aminophenylmethyldiethoxysilane. At least one of them may be used.

Among the specific examples of the monoamines having alkoxysilyl groups, compounds which are easily available and which give a polyester amide acid (A) having good compatibility with the epoxy group-containing copolymer (B) include 3-aminopropyltri Ethoxysilane and p-aminophenyltrimethoxysilane are more preferable, and 3-aminopropyltriethoxysilane is particularly preferable.

When a monoamine having an alkoxysilyl group is used as the raw material of the polyester amide acid (A), the amount of the monoamine having an alkoxysilyl group to be used is such that the amount of the compound (a1) having two or more acid anhydride groups, the diamine (a2) Is preferably 50 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the total amount of the hydroxy compound (a3).

<1-1-6. Solvent used for synthesis reaction of polyester amide acid (A)

Specific examples of the solvent used in the synthesis reaction for obtaining the polyester amide acid (A) include methyl 3-methoxypropionate (hereinafter abbreviated as "MMP"), ethyl 3-ethoxypropionate, ethyl lactate, diethylene glycol dimethyl Diethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter abbreviated as &quot; PGMEA &quot;), and cyclohexanone . Of these, MMP, diethylene glycol methyl ethyl ether, and PGMEA are preferable.

<1-1-7. Synthesis method of polyester amide acid (A)

The synthesis method of the polyester amide acid (A) used in the present invention is a method of synthesizing the polyester amide acid (A) by using the compound (a1) having two or more acid anhydride groups, the diamine (a2), and the polyhydric hydroxy compound (a3) The reaction is carried out in a solvent used for the reaction.

The preferable ratio of the raw materials of the polyester amide acid (A) is such that the relationship of the formula (3) and the formula (4) is satisfied when X mol of tetracarboxylic acid dianhydride, Y mol of diamine and Z mol of polyhydric hydroxy compound . Within this range, the solubility of the polyester amide acid (A) in a solvent is high, and the applicability of the photosensitive composition to a substrate is good.

In the formula (3), preferably 0.7? Z / Y? 7.0, and more preferably 1.0? Z / Y? 5.0. In the formula (4), 0.5? (Y + Z) / X? 4.0, and more preferably 0.6? Y + Z / X? 2.0.

In the synthesis of the polyester amide acid (A), an acid anhydride group (-CO-O-CO-) at the terminal is obtained under the condition that X is excessively used for Y + Z within the range of the formula (4) It is considered that the molecule is excessively generated at a terminal end than a molecule having an amino group or hydroxyl group. On the other hand, when a monoamine having a monohydroxy compound and an alkoxysilyl group is added in the case of reacting with such a monomer composition, the terminal can be esterified and amidated by reacting with an acid anhydride group at the terminal of the molecule. The polyester amide acid (A) obtained by reacting the mono hydroxy compound with the addition of the monohydroxy compound can further improve the coatability of the photosensitive composition, and the polyester amide acid (A) obtained by reacting the monoamine having an alkoxysilyl group added thereto, The adhesion of the cured film and the substrate can be improved.

When the solvent used in the synthesis reaction is used in an amount of 100 parts by weight or more per 100 parts by weight of the total amount of the compound (a1), diamine (a2) and polyhydric hydroxy compound (a3) having two or more acid anhydride groups, So that it is preferable. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

The order of addition of the raw materials to the reaction system is not particularly limited. Namely, a method of simultaneously adding a compound (a1), an amine (a2) and a polyhydric hydroxy compound (a3) having two or more acid anhydride groups to a reaction solvent, a method of reacting a diamine (a2) and a polyhydric hydroxy compound (a3) (A1) having two or more acid anhydride groups, a compound (a1) having two or more acid anhydride groups and a polyhydric hydroxy compound (a3) are reacted in advance, and then the reaction product (A1) having two or more acid anhydride groups and a diamine (a2) are preliminarily reacted with a solution containing a diamine (a2) in a solution containing a hydroxyl group ) May be added, or any other method may be used.

When the monohydroxy compound is reacted, it may be added at any point in the reaction.

(A1), diamine (a2), and polyhydric hydroxy compound (a3) having two or more acid anhydride groups, a solution containing the reaction product is added to the solution of 40 Deg.] C or less, adding a monoamine having an alkoxysilyl group, and reacting at 10 to 40 DEG C for 0.1 to 6 hours.

The polyester amide acid (A) thus synthesized contains the structural unit represented by the formula (1) and the structural unit represented by the formula (2), and the terminal thereof is a compound having two or more acid anhydride groups an amino group, a hydroxyl group, and an alkoxysilyl group derived from any of a monoamine having a hydroxyl group (a1), a diamine (a2), a polyhydric hydroxy compound (a3), a monohydroxy compound, and an alkoxysilyl group, It is composed of additives other than compounds.

The weight average molecular weight of the resulting polyester amide acid (A) is preferably 1,000 to 200,000, more preferably 3,000 to 50,000. Within these ranges, the applicability of the photosensitive composition to the substrate is favorable.

The weight average molecular weight in the present specification is a value calculated by polystyrene conversion determined by GPC method (column temperature: 35 캜, flow rate: 1 ml / min). As the standard polystyrene, polystyrene having a molecular weight of 645 to 132,900 (for example, polystyrene calibration kit PL2010-0102 manufactured by Agilent Technologies Co., Ltd.), PLgel MIXED-D (Agilent Technologies Co., Ltd.) used as a column, THF Can be measured. The weight average molecular weights of commercially available products in this specification are the catalog values.

<1-2. Epoxy group-containing copolymer (B)

The epoxy group-containing copolymer (B) is a copolymer of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) other than (b1).

At least a solvent is required for the synthesis of the epoxy group-containing polymer (B). The photosensitive composition may be prepared by using a liquid or gel epoxy group-containing polymer solution which is left in the solvent as it is, taking into account the handling property, etc., and the solvent may be removed to remove the photosensitive composition by using a solid epoxy- .

<1-2-1. Polymerizable compound (b1) having an epoxy group>

In the present invention, a polymerizable compound (b1) having an epoxy group is used as a raw material for obtaining the epoxy group-containing copolymer (B).

The polymerizable compound (b1) having an epoxy group used in the present invention is a compound having at least one epoxy group in one molecule and at least one polymerizable group.

The polymerizable group contained in the polymerizable compound (b1) having an epoxy group used in the present invention is preferably a radically polymerizable group.

As specific examples of the polymerizable compound (b1) having an epoxy group, glycidyl methacrylate used in the examples may be preferably used.

As specific examples of the polymerizable compound (b1) having an epoxy group, glycidyl acrylate, methyl glycidyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) And at least one of the specific examples of the above-mentioned polymerizable compound (b1) having an epoxy group can be used.

Among the specific examples of the polymerizable compound (b1) having such an epoxy group, as the compound giving an epoxy group-containing copolymer (B) which is easily available and has good compatibility with the polyester amide acid (A) Dly (meth) acrylate is more preferable, and glycidyl methacrylate is particularly preferable.

<1-2-2. Polymerizable compound (b2)>

In the present invention, a polymerizable compound (b2) other than (b1) is used as a raw material for obtaining the epoxy group-containing copolymer (B).

The polymerizable compound (b2) used in the present invention is a compound excluding the polymerizable compound (b1) having the above epoxy group among the compounds having at least one polymerizable group in one molecule.

The polymerizable group contained in the polymerizable compound (b2) used in the present invention is preferably a radically polymerizable group.

The raw material of the epoxy group-containing copolymer (B) of the present invention essentially contains a polymerizable compound having a phenolic hydroxyl group as the polymerizable compound (b2).

<1-2-2-1. Polymerizable compound having a phenolic hydroxyl group>

The polymerizable compound having a phenolic hydroxyl group used in the present invention is a compound having at least one phenolic hydroxyl group in one molecule and at least one polymerizable group.

Examples of preferable compounds of the polymerizable compound having a phenolic hydroxyl group include a compound represented by the formula (5) and a compound represented by the formula (6).

As specific examples of the polymerizable compound having a phenolic hydroxyl group, 4-hydroxystyrene and 4-hydroxyphenylvinyl ketone, which are compounds used in Examples and which are represented by the formula (5), are preferably used. And 4-hydroxyphenyl methacrylate, which is a compound represented by the formula (6).

Specific examples of the polymerizable compound having a phenolic hydroxyl group include compounds other than the above-described compounds represented by the formula (5) such as 2-hydroxystyrene, 3-hydroxystyrene, 2-hydroxymethylstyrene, 3- Hydroxymethylstyrene, 4-hydroxymethylstyrene, 2-hydroxyphenylvinylketone, and 3-hydroxyphenylvinylketone; (Meth) acrylate, 3-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl acrylate, 2-hydroxyphenyl (meth) acrylamide and the like represented by the formula (Meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide, 4-hydroxybenzyl (Meth) acrylate, and at least one of the above specific examples of the polymerizable compound having a phenolic hydroxyl group may be used.

Among these specific examples of the polymerizable compound having a phenolic hydroxyl group, compounds which give an epoxy group-containing copolymer (B) which is easily available and has a good compatibility with the polyester amide acid (A) (Meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl Acrylate is more preferable, and 4-hydroxystyrene, 4-hydroxyphenyl vinyl ketone, and 4-hydroxyphenyl (meth) acrylate are particularly preferable.

<1-2-2-2. Of the polymerizable compound (b2), the polymerizable compound having no phenolic hydroxyl group>

As specific examples of the compound having no phenolic hydroxyl group in the polymerizable compound (b2), methacrylic acid, benzyl methacrylate and N-cyclohexylmaleimide used in the examples are preferably used.

Specific examples of the polymerizable compound having no phenolic hydroxyl group in the polymerizable compound (b2) include acrylic acid, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) (Meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i- (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl acrylate, 2-methoxyethyl (meth) acrylate, 2- Propoxy) ethyl (meth) acrylate, 2- (n-butoxy) ethyl (meth) acrylate, 2- (Meth) acrylate, 2- (sec-butoxy) ethyl (meth) acrylate, 2- (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-methoxypropyl (meth) (Trimethylsilyloxy) silyl] propyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, mono (meth) acryloxypropyl modified polydimethylsiloxane, 3- [ (Meth) acrylate, 3-trimethoxysilylpropyl (meth) acrylate, 3-trimethoxysilylpropyl (meth) acrylate, styrene, methylstyrene , And N-phenylmaleimide. Of the polymerizable compounds (b2), at least one of the specific examples of the compounds not represented by any of the formulas (5) and (6) can be used.

Of these polymerizable compounds (b2), among the specific examples of the polymerizable compound having no phenolic hydroxyl group, an epoxy group-containing copolymer (B) which is easily available and has good compatibility with the polyester amide acid (A) Examples of the compound to be imparted include n-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) Propyl (meth) acrylate, styrene, N-cyclohexylmaleimide, and N-phenylmaleimide are more preferable, and n-butyl (meth) (Meth) acrylate, benzyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, N-cyclohexylmaleimide, Hi is preferred.

Of these polymerizable compounds (b2), specific examples of the polymerizable compound having no phenolic hydroxyl group are those which are easily available and which impart good solubility to the developer when the epoxy group-containing copolymer (B) is produced The compound is more preferably (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate or 3-trimethoxysilylpropyl Methacrylic acid, 2-hydroxyethyl (meth) acrylate are particularly preferable.

<1-2-3. Solvent used in the polymerization reaction of the epoxy group-containing copolymer (B)

Specific examples of the solvent used in the polymerization reaction for obtaining the epoxy group-containing copolymer (B) include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, methoxyacetate, , Methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxybutyl acetate, methyl 3-oxypropionate, ethyl 3-hydroxypropionate, MMP, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethoxypropionate, methyl 2-hydroxypropionate, methyl 2-hydroxypropionate, methyl 2-hydroxypropionate, propyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Ethyl propionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2- methylpropionate, Ethyl, ethyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy- -Butanediol, propylene glycol monomethyl ether, PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and di Ethylene glycol methyl ethyl ether is preferred.

<1-2-4. Method of Polymerization of Epoxy Group-Containing Copolymer (B)

The polymerization method of the epoxy group-containing copolymer (B) used in the present invention is a polymerization method in which a polymerizable compound (b1) having an epoxy group and a polymerizable compound having a phenolic hydroxyl group are used as essential raw materials, Respectively.

The preferable proportion of the raw material of the epoxy group-containing copolymer (B) is 20 to 90% by weight of the polymerizable compound having an epoxy group in 100% by weight of the total amount of the polymerizable compound (b1) having an epoxy group and the polymerizable compound (b2) And 1 to 40% by weight of a polymerizable compound having a phenolic hydroxyl group. Within this range, the line pattern shape linearity at the time of short-time development of the photosensitive composition is particularly good.

The solvent used in the polymerization reaction is preferably 100 parts by weight or more based on 100 parts by weight of the total amount of the polymerizable compound (b1) having an epoxy group and the polymerizable compound (b2) because the reaction proceeds smoothly. The reaction is preferably carried out at 40 ° C to 200 ° C for 0.2 to 20 hours.

The polymerization method of the epoxy group-containing polymer (B) is not particularly limited, but radical polymerization in a solution using a solvent is preferable. The polymerization temperature is not particularly limited as long as radicals are sufficiently generated from the polymerization initiator to be used, but is usually in the range of 50 to 150 占 폚. The polymerization time is not particularly limited, but is usually in the range of 1 to 24 hours. The polymerization can be carried out under any pressure, such as a pressure, a reduced pressure or an atmospheric pressure.

<1-3. 1,2-quinone diazide compound (C)

The 1,2-quinonediazide compound (C) used in the present invention is a compound having at least one 1,2-quinonediazide group in one molecule.

As the 1,2-quinonediazide compound (C), a condensate of a compound having a phenolic hydroxyl group and a sulfonic acid chloride having a 1,2-quinonediazide group is readily available, and therefore, it is suitable for use.

Specific examples of the compound having a phenolic hydroxyl group include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone , 2,3,3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis (2,4-dihydroxyphenyl) methane, bis Tri (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl-4-hydroxyphenyl) - [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5- 3 ', 3'-tetramethyl-1,1'-spirobindene-5,6,7,5', 6 ', 7'-hexanol, 2,2,4-trimethyl- &Apos; -trihydroxyflavone. &Lt; / RTI &gt;

Specific examples of the sulfonic acid chloride having a 1,2-quinonediazide group include 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 1,2-naphthoquinonediazide-5-sulfonic acid chloride .

As concrete examples of the 1,2-quinonediazide compound (C) using the specific examples of the compound having a phenolic hydroxyl group and the specific example of the sulfonic acid chloride having a 1,2-quinonediazide group, Condensation of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic chloride Water can be heard.

As the 1,2-quinonediazide compound (C) using specific examples of the compound having a phenolic hydroxyl group and a specific example of a sulfonic acid chloride having a 1,2-quinonediazide group, it is easy to obtain and a polyester amide acid Examples of the compound having good compatibility with A) include 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1- methylethyl] phenyl] ethylidene] bisphenol and 1,2- Sulfonic acid chloride and a condensate of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1 , And condensates of 2-naphthoquinonediazide-5-sulfonic acid chloride are more preferable, and 4,4 '- [1- [4- [1- [4- hydroxyphenyl] Ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic chloride are particularly preferable.

<1-4. Additives>

Various additives may be added to the photosensitive composition of the present invention in order to improve coating uniformity, adhesion, heat resistance, curability, and ultraviolet light deterioration resistance. Examples of additives include antioxidants such as anionic, cationic, nonionic, fluorine or silicone leveling agents and surfactants, coupling agents such as silane coupling agents, hindered phenol-based, hindered amine-based, phosphorus- An epoxy curing agent, an ultraviolet absorber, an anti-aggregation agent, a thermal crosslinking agent, and an epoxy compound other than the epoxy group-containing copolymer (B).

<1-4-1. Surfactants>

To the photosensitive composition of the present invention, a surfactant may be added to improve coating uniformity. Specific examples of the surfactant include Polyflow No.45, Polyflow KL-245, Polyflow No. 75, Polyflow No. 90, Polyflow No. 95 (all trade names, manufactured by Kyowa Chemical Co., Ltd.) Disperbyk 161, Disper Bake 162, Disper Bake 163, Disper Bake 164, Disper Bake 166, Disper Bake 170, Disper Bake 180, Disper Bake 181, Disper Bake 182, BYK-300, BYK-306, BYK-310, BYK-320, BYK-330, BYK-342, BYK-346, BYK-361N, BYK- Surflon-SC-101, Surplon-KH-40, Surplon-S611 (all trade names, manufactured by Shin-Etsu Chemical Industry Co., Ltd.), KF- Fotogen, FTX-218 and FTX-218, all of which are commercially available under the trade name of AGC SEIMI CHEMICAL Co., Ltd.), Fotentel 222F, Fotogent 208G, Fotogent 251, Fotogent 710FL, Fotogent 710FM, Fotogent 710FS, Fotogent 601AD, Fotogent 602A, (all EFTOP EF-351, EFTOP EF-601, EFTOP EF-801, EFTOP EF-802 (both trade names; manufactured by Mitsubishi Materials Corporation), Megafac F- 474, Megapack F-477, Megapack F-552, Megapack F-553, Megafac F-477, Megafac F-477, Megafac F- MEGA PARK F-554, MEGA PARK F-555, MEGA PARK F-556, MEGA PARK F-558, MEGA PARK F-559, MEGA PARK R-30, MEGA PARK R- TEGO Twin 4100, TEGO Flow 370, TEGO Glide 420, TEGO Glide 440, TEGO Glide 450 (all trade names, manufactured by DIC Corporation), RS-72-K, Megafac RS- , TEGO Rad 2200N, TEGO Rad 2250N (all trade names; Fluoroalkylbenzenesulfonic acid salts, fluoroalkylcarboxylic acid salts, fluoroalkyl polyoxyethylene ethers, fluoroalkylammonium iodides, fluoroalkyl betaines, fluoroalkyl sulfonic acid salts, (Fluoroalkylpolyoxyethylene ether), fluoroalkyltrimethylammonium salt, fluoroalkylaminosulfonic acid salt, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene Polyoxyethylene stearyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene laurate, polyoxyethylene oleate, polyoxyethylene stearate, poly Oxyethylene laurylamine, sorbitan laurate, sorbitan palmitate, sorbitol Sorbitan fatty acid esters, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate, polyoxyethylene naphthyl alcohol, polyoxyethylene sorbitan fatty acid esters, Ether, alkylbenzenesulfonic acid salts, and alkyl diphenyl ether disulfonic acid salts. It is preferable to use at least one selected from these.

Specific examples of these surfactants include BYK-306, BYK-342, BYK-346, KP-341, KP-358, KP-368, Surplon-S611, MEGA PARK F-559, MEGA PARK RS-72-k, Megapark DS-21, TEGO Twin 4000, fluoroalkylbenzenesulfonic acid salts, The coating uniformity of the photosensitive composition is high when at least one selected from a fluoroalkyl carboxylate, a fluoroalkyl polyoxyethylene ether, a fluoroalkylsulfonate, a fluoroalkyltrimethylammonium salt, and a fluoroalkylaminosulfonate is used .

The content of the surfactant in the photosensitive composition of the present invention is preferably 0.01 to 10% by weight based on the total amount of the photosensitive composition.

<1-4-2. Coupling agent>

The photosensitive composition of the present invention may further contain a coupling agent from the viewpoint of further improving the adhesion between the cured film to be formed and the substrate.

As such a coupling agent, for example, a silane-based, aluminum-based or titanate-based coupling agent can be used. Specific examples thereof include 3-glycidyloxypropyldimethylethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane (for example, trade name: Sylla Aces S510 , JNC Co., Ltd.), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (for example, trade name: Silica Ace S530, JNC Co., Ltd.), 3-mercaptopropyltrimethoxysilane Silane-based coupling agents such as copolymers of 3-glycidyloxypropyltrimethoxysilane (for example, trade name: CoatOSil MP200, Momentive Performance Materials Co., Ltd.), trade name: Silica Ace S810, An aluminum-based coupling agent such as acetoalkoxy aluminum diisopropylate, and a titanate-based coupling agent such as tetraisopropyl bis (dioctylphosphite) titanate.

Among them, 3-glycidyloxypropyltrimethoxysilane is preferable because it has a large effect of improving adhesion.

The content of the coupling agent is preferably 0.01% by weight or more and 10% by weight or less based on the total amount of the photosensitive composition, because adhesion between the formed cured film and the substrate is improved.

<1-4-3. Antioxidants>

The photosensitive composition of the present invention may further contain an antioxidant from the viewpoint of improving the heat resistance.

To the photosensitive composition of the present invention, an antioxidant such as a hindered phenol-based, hindered amine-based, phosphorus-based, or sulfur-based compound may be added. Among them, the hindered phenol system is preferable from the viewpoint of weather resistance. Concrete examples are, Irganox1010, Irganox1010FF, Irganox1035, Irganox1035FF, Irganox1076, Irganox1076FD, Irganox1076DWJ, Irganox1098, Irganox1135, Irganox1330, Irganox1726, Irganox1425 WL, Irganox1520L, Irganox245, Irganox245FF, Irganox245DWJ, Irganox259, Irganox3114, Irganox565, Irganox565DD, Irganox295 (all trade names ; ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70 and ADK STAB AO-80 . Of these, Irganox 1010 and ADK STAB AO-60 are more preferable.

The antioxidant is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

<1-4-4. Epoxy curing agent>

The photosensitive composition of the present invention may further contain an epoxy curing agent to improve curability. Examples of the epoxy curing agent include acid anhydride curing agents, amine curing agents, phenol curing agents, imidazole curing agents, catalyst type curing agents, and thermosensitive acid generators such as sulfonium salts, benzothiazonium salts, ammonium salts, and phosphonium salts However, from the viewpoint of compatibility with the polyester amide acid (A), an acid anhydride type curing agent or an imidazole type curing agent is preferable.

Specific examples of the acid anhydride-based curing agent include aliphatic dicarboxylic acid anhydrides such as maleic anhydride, anhydrous tetrahydrophthalic acid, anhydrous hexahydrophthalic acid, methylhexahydrophthalic anhydride, and hexahydrotrimellitic anhydride; Carboxylic acid anhydrides such as phthalic anhydride and trimellitic anhydride. Among them, trimellitic acid anhydride and hexahydrotrimellitic acid anhydride which can improve the curability without inhibiting the solubility of the photosensitive composition in a solvent are particularly preferable.

Specific examples of the imidazole-based curing agent include 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, -1H-pyrrolo [1,2-a] benzimidazole, and 1-cyanoethyl-2-undecylimidazolium trimellitate. Among them, 2-undecylimidazole which can improve the curability without inhibiting the solubility of the photosensitive composition in a solvent is particularly preferable.

The ratio of the epoxy curing agent to the epoxy group-containing copolymer (B) is 0.1 to 60 parts by weight of the epoxy curing agent relative to 100 parts by weight of the epoxy group-containing copolymer (B).

<1-4-5. UV absorbers>

The photosensitive composition of the present invention may contain an ultraviolet absorber from the viewpoint of further improving the ultraviolet deterioration resistance of the formed cured film.

Specific examples of the ultraviolet absorber include TINUVIN P, TINUVIN 120, TINUVIN 144, TINUVIN 213, TINUVIN 234, TINUVIN 326, TINUVIN 571, and TINUVIN 765 (all trade names, BASF Japan KK).

The ultraviolet absorber is used in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

<1-4-6. Anti-aggregation agent>

The photosensitive composition of the present invention may contain an anti-aggregation agent in order to harmonize the solid content with a solvent and prevent agglomeration.

Specific examples of the coagulation inhibitor include Disperbyk-145, Disperfect-161, Disperfect-162, Disperfect-163, Disperfect-164, Disperfect-182, DISK Bake-2163, DISK Bake-2164, DISK Bake-2164, DISK Bake-181, Disperse Bake-2163, ), FTX-218, Ftergent 710FM, and Ftergent 710FS (both trade names: Neos), Flowren G-600 and Flowren G-700 (all trade names, manufactured by Kyowa Chemical Industry Co., Ltd.).

The antiflocculating agent is used in an amount of 0.01 to 10 parts by weight based on the total amount of the photosensitive composition.

<1-4-7. Thermal crosslinking agents>

The photosensitive composition of the present invention may contain a heat crosslinking agent from the viewpoint of further improving the curability and heat resistance.

Specific examples of thermal crosslinking agents include NIKARAK MW-30HM, NIKARAK MW-100LM, NIKARAK MW-270, NIKARAK MW-280, NIKARAK MW-290, NIKARAK MW-390, All manufactured by SANWA CHEMICAL CO., LTD.).

The heat crosslinking agent is used in an amount of 0.1 to 10 parts by weight based on the total amount of the photosensitive composition.

<1-4-8. Epoxy compounds other than the epoxy group-containing copolymer (B)>

The photosensitive composition of the present invention may further contain an epoxy compound other than the epoxy group-containing copolymer (B) in order to improve the curability.

The epoxy compound other than the epoxy group-containing copolymer (B) is added in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the total amount of the polyester amide acid (A) and the epoxy group-containing copolymer (B).

Examples of the epoxy compound other than the epoxy group-containing copolymer (B) include epoxy compounds such as bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, glycidyl ether type epoxy compounds, biphenyl type epoxy compounds, phenol novolak type epoxy compounds, A phenol-type epoxy compound, a phenol-type epoxy compound, a phenol-type epoxy compound,

Specific examples of commercially available bisphenol A type epoxy compounds include jER 828, 1004 and 1009 (both trade names; manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available bisphenol F type epoxy compounds include jER 806 and 4005P (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of the commercially available glycidyl ether type epoxy compound include TECHMORE VG3101L (trade name: PRINTEC), EPPN-501H, 502H (all trade names, manufactured by Nippon Kayaku Co., Ltd.), jER 1032H60 (trade name, manufactured by Mitsubishi Chemical Corporation) Can be heard; Specific examples of commercially available biphenyl type epoxy compounds include jER YX4000, YX4000H, and YL6121H (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available phenol novolac epoxy compounds include EPPN-201 (trade name, manufactured by Nippon Kayaku Co., Ltd.), jER 152 and 154 (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available cresol novolak epoxy compounds include EOCN-102S, 103S, 104S, and 1020 (all trade names, manufactured by Nippon Kayaku Co., Ltd.); Specific examples of commercially available bisphenol A novolac epoxy compounds include jER 157S65 and 157S70 (all trade names, manufactured by Mitsubishi Chemical Corporation); Specific examples of commercially available alicyclic epoxy compounds include Celloxide 2021P and EHPE-3150 (all trade names, Daicel Co., Ltd.). Further, TECHMORE VG3101L, a glycidyl ether type epoxy compound, can be obtained by reacting 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- Ethyl] phenyl] propane and 1,3-bis [4- [1- [4- (2,3-epoxypropoxy) phenyl] -1- [4- [1- [ 4- (2,3-epoxypropoxy) phenyl] -1-methylethyl] phenyl] ethyl] phenoxy] -2-propanol.

<1-5. Solvent optionally added to the photosensitive composition>

A solvent may be added to the photosensitive composition of the present invention in addition to the solvent used for the polymerization reaction of the polyester amide acid (A) and the solvent used for the polymerization reaction of the epoxy group-containing copolymer (B). (A), an epoxy group-containing copolymer (B), and a 1,2-quinonediazide compound (C), which are optionally added to the photosensitive composition of the present invention And the like are preferable. Specific examples of the diluting solvent include ethyl acetate, butyl acetate, propyl acetate, butyl propionate, ethyl lactate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, Methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-hydroxypropionate, methyl 2- hydroxypropionate, methyl 2- Propyl methoxypropionate, propyl 2-methoxypropionate, ethyl 2-ethoxypropionate, methyl 2-hydroxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, , Ethyl 2-hydroxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, , Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 4-hydroxy-4-methyl-2-pentanone, 1,4-butanediol, propylene glycol monomethyl ether, PGMEA , Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, cyclohexanone, cyclopentanone, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol methyl ethyl ether. At least one of the specific examples of the diluting solvent may be used.

<1-6. Preservation of photosensitive composition &gt;

When the photosensitive composition of the present invention is stored in the range of -30 占 폚 to 25 占 폚, the stability of the composition over time tends to be favorable. When the storage temperature is -20 占 폚 to 10 占 폚, precipitates are not present, which is more preferable.

<2. Cured film of photosensitive composition>

The photosensitive composition of the present invention can be obtained by mixing a polyester amide acid (A), an epoxy group-containing copolymer (B), a 1,2-quinonediazide compound (C), and an additive, And uniformly mixing and dissolving them. As the additive, a coupling agent, a surfactant, and other additives may be selected and used depending on the intended characteristics, if necessary.

A coating film can be formed by applying the photosensitive composition prepared as described above (after dissolving in a solvent in a solid state without solvent) to the surface of the substrate and removing the solvent, for example, by heating. The application of the photosensitive composition to the surface of the substrate can be carried out by a conventionally known method such as a spin coating method, a roll coating method, a dipping method, a flexo printing method, a spraying method, and a slit coating method. Subsequently, this coating film is heated (prebaked) by a hot plate, an oven or the like. The heating conditions vary depending on the kind of each component and the blending ratio, but it is usually 70 to 150 ° C, for an oven for 5 to 15 minutes, and for a hot plate, for 1 to 5 minutes.

Then, the coating film is irradiated with ultraviolet rays through a mask having a desired pattern shape. The amount of ultraviolet radiation is suitably 5 to 1,000 mJ / cm 2 by i-line. The photosensitive composition in the portion irradiated with ultraviolet rays is solubilized in an alkaline developer by improving the alkali solubility of the 1,2-quinonediazide compound.

Subsequently, the coating film is immersed in an alkaline developing solution by a shower phenomenon, a spray phenomenon, a puddle phenomenon, a dip phenomenon or the like, and unnecessary portions are dissolved and removed. Specific examples of the alkali developing solution include aqueous solutions of inorganic alkalis such as sodium carbonate, sodium hydroxide, and potassium hydroxide, and aqueous solutions of organic alkalis such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. In addition, an appropriate amount of methanol, ethanol, and a surfactant may be added to the alkali developing solution.

Finally, in order to completely cure the coating film, the cured film can be obtained by heating at 180 to 250 ° C, preferably 200 to 250 ° C for 30 to 90 minutes in an oven and 5 to 30 minutes in a hot plate.

The cured film obtained in this manner has the following properties: 1) the polyamic acid portion of the polyester amide acid (A) is dehydrated and cyclized to form an imide bond; and 2) the carboxyl group of the polyester amide acid (A) Is very strong and has excellent heat resistance because it is reacted with the epoxy group-containing copolymer (B) to have a high molecular weight. Therefore, the cured film of the present invention is effective when used as a protective film for a color filter, and a liquid crystal display element or a solid-state imaging element can be manufactured using a color filter. The cured film of the present invention is effective when used as a transparent insulating film formed between a TFT and a transparent electrode or an insulating film formed between a transparent electrode and an oriented film, in addition to a protective film for a color filter. Further, the cured film of the present invention is also effective as a protective film for an LED light-emitting body.

Example

Next, the present invention will be described concretely with Synthesis Examples, Comparative Synthesis Examples, Examples, and Comparative Examples, but the present invention is not limited at all by these Examples.

The compounds used in Reference Synthesis Examples, Synthesis Examples, Comparative Synthesis Examples, Reference Examples, Examples, and Comparative Examples are listed for each component.

Among the compounds (a1) having two or more acid anhydride groups, tetracarboxylic acid dianhydride:

a1-1: ODPA: 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride

a1-2: BT-100: 1,2,3,4-butanetetracarboxylic acid dianhydride

Among the compounds (a1) having two or more acid anhydride groups, styrene-maleic anhydride copolymer:

a1-3: trade name SMA-1000P, Satoromer Co., Ltd., hereinafter abbreviated as "SMA-1000P"

Diamine (a2):

a2-1: DDS: 3,3'-diaminodiphenyl sulfone

Polyhydric hydroxy compound (a3):

a3-1: 1,4-butanediol

Monohydroxy compound:

a4-1: Benzyl alcohol

Solvent used for synthesis reaction of polyester amide acid (A)

MMP: methyl 3-methoxypropionate

PGMEA: Propylene glycol monomethyl ether acetate

Polymerizable compound (b1) having an epoxy group:

b1-1: glycidyl methacrylate

Among the other polymerizable compounds (b2), the polymerizable compound having a phenolic hydroxyl group:

b2-1: 4-hydroxystyrene

b2-2: 4-hydroxyvinyl ketone

b2-3: 4-Hydroxyphenyl methacrylate

Among the other polymerizable compounds (b2), a polymerizable compound having no phenolic hydroxyl group:

b2-4: methacrylic acid

b2-5: benzyl methacrylate

b2-6: N-Cyclohexylmaleimide

Polymerization initiator used in the polymerization reaction of the epoxy group-containing copolymer (B):

Dimethyl 2,2'-azobis (2-methylpropionic acid) (V-601, Wako Pure Chemical Industries, hereinafter abbreviated as "V-601"

Solvent used in the polymerization reaction of the epoxy group-containing copolymer (B)

PGMEA: Propylene glycol monomethyl ether acetate

1,2-quinonediazide compound (C):

Condensation of 4,4 '- [1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic chloride Water (average esterification rate: 58%, abbreviated as &quot; PAD &quot; hereinafter)

Dilution solvent:

PGMEA: Propylene glycol monomethyl ether acetate

Additive-1: 3-glycidyloxypropyltrimethoxysilane (trade name: SILA ACE S510, JNC Corporation, hereinafter abbreviated as "S510") which is a silane coupling agent,

Additive-2: Megafac F-556 (trade name, abbreviated as "F-556" by DIC Co., Ltd.), which is a fluorine surfactant,

A polyester amide acid solution containing reaction products of tetracarboxylic acid dianhydride, diamine, polyhydric hydroxy compound and the like was synthesized as shown below (Synthesis Examples 1 and 2).

[Synthesis Example 1] Synthesis of polyester amide acid solution (A1)

In a 1,000 ml four-necked flask equipped with a thermometer, a stirrer, a feedstock inlet, and a nitrogen gas inlet, 446.96 g of MMP as a solvent for use in the synthesis reaction, 31.93 g of 1,4-butanediol as a polyhydroxy compound, 25.54 g of benzyl alcohol as a hydroxy compound and 183.20 g of ODPA as a tetracarboxylic acid dianhydride were charged and stirred at 130 DEG C for 3 hours in a dry nitrogen stream. Thereafter, the solution after the reaction was cooled to 25 占 폚, 29.33 g of DDS as a diamine and 183.04 g of MMP were added and stirred at 20 to 30 占 폚 for 2 hours and then stirred at 115 占 폚 for 1 hour and cooled To obtain a 30 wt% solution (A1) of light yellow transparent polyester amide acid. The weight average molecular weight measured by GPC was 4,200.

[Z / Y = 3, (Y + Z) / X = 0.8]

The term "30 wt% solution (A1) of polyester amide acid" herein means that the concentration of the solids is 30% by weight, calculated from the weight of the solids and the weight of the solvent, . The following synthesis examples and comparative synthesis examples are also the same.

[Synthesis Example 2] Synthesis of polyester amide acid solution (A2)

604.80 g of PGMEA as a solvent for use in the synthesis reaction, 34.47 g of BT-100 as a tetracarboxylic acid dianhydride, 15 g of styrene - 164.11 g of SMA-1000P as a maleic anhydride copolymer, 50.17 g of benzyl alcohol as a monohydroxy compound and 10.45 g of 1,4-butanediol as a polyvalent carboxyl compound were charged and heated at 130 DEG C for 3 hours Lt; / RTI &gt; Thereafter, the solution after the reaction was cooled to 25 DEG C, 10.80 g of DDS as diamine and 25.20 g of PGMEA were added and stirred at 20 to 30 DEG C for 2 hours and then stirred at 115 DEG C for 1 hour and cooled to 30 DEG C or less To obtain a 30 wt% solution (A2) of light yellow transparent polyester amide acid. The weight average molecular weight measured by GPC was 10,000.

[Z / Y = 2.7, (Y + Z) / X = 0.9]

An epoxy group-containing copolymer solution containing a reaction product of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) was synthesized as shown below (Synthesis Examples 3 to 12 and Comparative Synthesis Examples 1 to 2) .

[Synthesis Example 3] Synthesis of epoxy group-containing copolymer solution (B1)

In a four-necked flask equipped with a stirrer, PGMEA as a solvent used in the polymerization reaction, glycidyl methacrylate as an epoxy group-containing polymerizable compound (b1), and polymerization with a phenolic hydroxyl group in another polymerizable compound (b2) Methacrylic acid and benzyl methacrylate as a polymerizable compound having no phenolic hydroxyl group and V-601 as a polymerization initiator in the other polymerizable compound (b2) were injected in the following composition , Heated at 80 ° C for 3 hours, and then heated at 90 ° C for 1 hour.

70.80 g of glycidyl methacrylate

4.80 g of 4-hydroxystyrene

Methacrylic acid 8.40 g

Benzyl methacrylate 36.00 g

V-601 18.00 g

PGMEA 280.00 g

The solution after completion of the polymerization reaction was cooled to room temperature to obtain a 30 wt% solution (B1) of an epoxy group-containing copolymer. The weight average molecular weight determined by GPC analysis was 17,000.

[Synthesis Examples 4 to 10, Reference Synthesis Examples 1 to 3, and Comparative Synthesis Examples 1 and 2]

According to the method of Synthesis Example 3, polymerization reaction was carried out using each component as a raw material in the ratio (unit: g) described in Table 1 to obtain an epoxy group-containing copolymer solution. The weight-average molecular weight of the obtained epoxy group-containing copolymer is also shown in Table 1.

[Referential Example 1]

(B'1) as the epoxy amide acid solution (A1) as the polyester amide acid (A), the epoxy group containing copolymer solution (B'1) as the epoxy group containing copolymer (B), PAD as the 1,2-quinonediazide compound S510 and F-556 as additives, and PGMEA as a diluting solvent were mixed and dissolved in the following composition to obtain a photosensitive composition.

Polyester amide acid solution (A1) 20.00 g

30.00 g of an epoxy group-containing copolymer solution (B'1)

PAD 2.40 g

S510 0.30 g

F-556 0.03 g

PGMEA 10.51 g

The total amount of the solvent contained in the composition is the total amount of the MMP contained in the polyester amide acid solution (A1), the PGMEA contained in the epoxy group-containing copolymer solution (B'1), and the diluting solvent PGMEA, Was adjusted so that the solid concentration in the process was approximately 28% by weight. REFERENCE EXAMPLE 2 The same applies to the following examples and comparative examples.

The photosensitive composition was spin-coated on a glass substrate at 700 rpm for 10 seconds and pre-baked on a hot plate at 100 캜 for 2 minutes. Next, light having a wavelength of 350 nm or less was cut through a wavelength cut filter using a proximity phototray TME-150PRC (trade name: Topcon Co., Ltd.) through a mask having a line pattern with a width of 50 탆 in air to obtain g, h, i line was drawn out and exposed. The exposure amount was 200 mJ / cm 2, as measured with an integrated photometer UIT-102 (trade name, manufactured by Ushio Co., Ltd.) and a photodetector UVD-365PD (trade name; The coated film after exposure was subjected to puddle development with a 2.38 wt% tetramethylammonium hydroxide aqueous solution for 60 seconds, and then the coating film was cleaned with pure water for 20 seconds, followed by drying with a hot plate at 100 DEG C for 2 minutes. Post-baking was performed in an oven at 230 캜 for 30 minutes to obtain a glass substrate on which a cured film having a line pattern with a film thickness of 3.0 탆 and a pattern width of approximately 50 탆 was formed.

[Evaluation method of heat resistance]

The glass substrate on which the cured film having the obtained line pattern was formed was reheated at 240 DEG C for one hour. Then, the film thickness before heating and the film thickness after heating were measured, and the residual film ratio was calculated by the following calculation expression. For measuring the film thickness, a step, surface roughness, fine shape measuring device (trade name: P-16 +, KLA TENCOR Co., Ltd.) was used. A case where the residual film ratio after heating was 95% or more was evaluated as &amp; cir &amp; and a case where the residual film ratio after heating was less than 95% was evaluated as poor.

Remaining film ratio = (film thickness after heating / film thickness before heating) 占 100%

[How to confirm the presence of wave pattern of line pattern]

The pattern of the glass substrate on which the cured film having the obtained line pattern was formed was observed using an optical microscope, and the presence or absence of the wave pattern of the line pattern was confirmed. Fig. 1 shows a state in which there is no wave in the line pattern shape, and Fig. 2 shows a state in which the line pattern shape is wavy.

[Reference Examples 2 to 3]

Each component was mixed and dissolved at the ratio shown in Table 2 (unit: g) in accordance with the method of Reference Example 1 to obtain a photosensitive composition.

The evaluation results of the heat resistance using the photosensitive compositions of Reference Examples 2 to 3 and the results of confirming the presence or absence of the wave pattern shape are shown in Table 2.

[Examples 1 to 8 and Comparative Examples 1 to 2]

Each component was mixed and dissolved at the ratio shown in Table 2 (unit: g) in accordance with the method of Reference Example 1 to obtain a photosensitive composition.

Using these photosensitive compositions thus obtained, a glass substrate on which a cured film having a line pattern with a pattern width of approximately 50 占 퐉 was formed in accordance with the method of Reference Example 1 was obtained. However, in the method of Reference Example 1, the time of the development process in which puddle development was performed for 60 seconds with a 2.38 wt% tetramethylammonium hydroxide aqueous solution was changed from 60 seconds to 30 seconds.

Using the glass substrate on which the cured film having the obtained line pattern was formed, evaluation of heat resistance and confirmation of the presence or absence of wave in the line pattern shape were carried out in accordance with the method of Reference Example 1. [ The results are shown in Table 2.

[Evaluation method of shape pattern linearity in short-time development]

In Examples 1 to 8 and Comparative Examples 1 and 2, in which the development process time was 30 seconds, the line pattern shape linearity at the time of short-time development was O, and the wave pattern of the line pattern shape , The line pattern shape linearity at the time of short-time development was evaluated as x.

(B), which is a photosensitive composition containing no polymerizable compound having a phenolic hydroxyl group, was added to the raw material of the epoxy group-containing copolymer (B) under the condition that the development process time was 60 seconds. There was no difference between the reference materials 2 to 3 which are photosensitive compositions containing a polymerizable compound having a phenolic hydroxyl group.

Comparative Example 1, which is a photosensitive composition containing no polymerizable compound having a phenolic hydroxyl group, in the raw material of the epoxy group-containing copolymer (B) under the condition that the development time is shortened to 30 seconds, Problems were seen. However, in Examples 1 to 8, which are photosensitive compositions containing a polymerizable compound having a phenolic hydroxyl group, in the raw material of the epoxy group-containing copolymer (B), there is no problem of wave pattern generation in a line pattern shape.

In the case where the time of the developing step is 60 seconds and the time of the developing step is 30 seconds and the time of the manufacturing step is required to be shortened, The line pattern linearity at the time of development was clearly superior.

It is also understood that Comparative Example 2, which is a photosensitive composition containing no polyester amide acid (A), has poor heat resistance.

The cured film obtained from the photosensitive composition of the present invention is excellent in heat resistance and excellent in line pattern shape linearity at the time of short-time development. Therefore, it can be used as a protective film for various optical materials such as color filters, LED light- It can be used as an insulating film formed between the electrodes and between the transparent electrode and the alignment film.

Claims (7)

1. A photosensitive composition comprising a polyester amide acid (A), an epoxy group-containing copolymer (B) and a 1,2-quinonediazide compound (C);
The polyester amide acid (A) comprises a constituent unit represented by the following formula (1) and a constituent unit represented by the following formula (2);
The epoxy group-containing copolymer (B) is a copolymer of a polymerizable compound (b1) having an epoxy group and a polymerizable compound (b2) other than (b1); And,
Wherein the polymerizable compound (b2) comprises a polymerizable compound having a phenolic hydroxyl group.

In the formula (1), R ¹ is an organic group having 2 to 1000 carbon atoms and R ² is an organic group having 2 to 100 carbon atoms;

In the formula (2), R ³ is an organic group having 2 to 1000 carbon atoms and R ⁴ is an organic group having 2 to 100 carbon atoms. The method according to claim 1,
The structural unit represented by the above-mentioned formula (1) is a structural unit comprising a compound (a1) having two or more acid anhydride groups and a diamine (a2) as raw materials;
Wherein the constituent unit represented by the formula (2) is a constituent unit comprising a compound (a1) having two or more acid anhydride groups and a polyhydric hydroxy compound (a3) as raw materials. 3. The method of claim 2,
The compound (a1) having at least two acid anhydride groups is at least one compound selected from tetracarboxylic acid dianhydride and styrene-maleic anhydride copolymer;
Wherein the polyester amide acid (A) is at least one compound selected from the group consisting of X mol of tetracarboxylic acid dianhydride, Y mol of diamine, and Z mol of polyhydric hydroxy compound of the following formula (3) By weight based on the total weight of the photosensitive composition.
0.2? Z / Y? 8.0 (3)
0.2? (Y + Z) / X? 5.0 (4) The method according to claim 1,
The polymerizable compound (b1) having an epoxy group is at least one selected from (meth) acrylates having an epoxy group;
Wherein the polymerizable compound having a phenolic hydroxyl group is at least one selected from a compound represented by the following formula (5) and a compound represented by the following formula (6).

In the formula (5), R ⁵ is hydrogen or an organic group having 1 to 7 carbon atoms, R ⁶ is a single bond or -C (= O) -, R ⁷ to R ¹¹ each independently represent a hydroxyl group, 7. Provided that at least one of R ⁷ to R ¹¹ is a hydroxyl group;

In formula (6), R ¹² is hydrogen or an organic group having 1 to 7 carbon atoms, R ¹³ is -O- or -NH-, R ¹⁴ is a single bond or a divalent organic group having 1 to 40 carbon atoms, R ¹⁵ to R ¹⁹ each independently represent a hydroxyl group or an organic group having 1 to 7 carbon atoms. Provided that at least one of R ¹⁵ to R ¹⁹ is a hydroxyl group. 5. The method of claim 4,
(Meth) acrylate having an epoxy group is glycidyl (meth) acrylate;
Wherein the compound represented by the formula (5) is at least one selected from 4-hydroxystyrene, 4-hydroxymethylstyrene, and 4-hydroxyphenylvinylketone;
Wherein the compound represented by the formula (6) is at least one compound selected from 4-hydroxyphenyl (meth) acrylate, 4-hydroxyphenyl (meth) acrylamide and 4-hydroxyphenyloxyethyl , &Lt; / RTI &gt; The method according to claim 1,
Wherein the content of the epoxy group-containing copolymer (B) in the total amount of the polyester amide acid (A) and the epoxy group-containing copolymer (B) is 20 to 90% by weight and the content of the polyester amide acid (A) Wherein the 1,2-quinonediazide compound (C) is contained in an amount of 5 to 40 parts by weight based on 100 parts by weight of the total amount of the copolymer (B). A cured film obtained from the photosensitive composition according to any one of claims 1 to 6.

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