KR20160128216A - Photosensitive resin composition, method for producing cured film, cured film, liquid crystal display device, organic electroluminescence display device, and touch panel - Google Patents

Abstract

The purpose of the present invention is to provide a photosensitive resin composition having excellent heat-resistant transparency and patternability, to a method for manufacturing a cured film using the same, a cured film, a liquid crystal display device, an organic electroluminescence display device, and a touch panel. The photosensitive resin composition contains a polybenzoxazole precursor, a photoacid generator for generating an acid having pKa of 3 or smaller, a thermal base generator, and a solvent, wherein the polybenzoxazole precursor is a polybenzoxazole precursor of which at least a portion of the phenolic hydroxyl group is protected by an acid degradable group, and the thermal base generator is a compound represented by formula (X). In formula (X), m is an integer of 1-4; R^1, R^2, and R^3 are each independently an alkyl group having 1 to 5 carbon atoms; R^4 represents an m-valent organic group that may have a heteroatom. When m is 2-4, a plurality of R^1, R^2, and R^3 may be the same as or different from each other.

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, a liquid crystal display device, an organic electroluminescence display device and a touch panel, AND TOUCH PANEL}

The present invention relates to a photosensitive resin composition, a method for producing a cured film, a cured film, a liquid crystal display, an organic electroluminescence display, and a touch panel.

In an image display apparatus such as a liquid crystal display apparatus and an organic electroluminescence display apparatus, or an input apparatus such as a touch panel, a patterned interlayer insulating film is generally formed.

A photosensitive resin composition is widely used for the reason that the number of processes for obtaining a pattern shape necessary for forming the interlayer insulating film is small and sufficient flatness is obtained.

For example, Patent Document 1 describes a positive photosensitive resin composition comprising "an alkali-soluble resin (A), a photosensitizer (B) and a thermal base generator (C) Claim 1]).

Japanese Patent Application Laid-Open No. 2013-152381

In recent years, attempts have been made to perform heat treatment or film formation at a higher temperature (for example, about 300 deg. C) than conventionally in order to improve the efficiency of production and the performance of an image display device.

Therefore, the inventors of the present invention found that, as a result of film formation at a high temperature using the photosensitive resin composition described in Patent Document 1, transparency (hereinafter referred to as "heat-resistant transparency") and patterning property may be deteriorated depending on the kind of the heat- Made clear.

Therefore, it is an object of the present invention to provide a photosensitive resin composition excellent in heat-resistant transparency and patternability, a method of producing a cured film using the same, a cured film, a liquid crystal display, an organic electroluminescence display, and a touch panel.

As a result of intensive studies to achieve the above object, the present inventors have found that a photosensitive resin composition comprising a predetermined polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less and a thermal base generator having a specific structure And that when used, the heat-resistant transparency and patterning property of the resulting cured film become good, and the present invention has been accomplished.

That is, it has been found that the above object can be achieved by the following constitution.

[1] A polybenzoxazole precursor composition comprising a polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator,

Wherein the polybenzoxazole precursor is a polybenzoxazole precursor wherein at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group,

Wherein the thermal base generator is a compound represented by the following formula (X).

Herein, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having m ≪ / RTI > When m is 2 to 4, plural R ¹ , R ² and R ³ may be the same or different.

[2] The photosensitive resin composition according to [1], wherein the polybenzoxazole precursor has a repeating unit represented by the following formula (1).

(1), X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, and each R independently represents a hydrogen atom, an alkyl group, a structure represented by the following formula (2) --CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.

In the formula (2), * represents a bonding position with an oxygen atom, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, R ¹⁰¹ and R ¹⁰² are all be except when the hydrogen atoms and the R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether.

[3] The photosensitive resin composition according to [1] or [2], wherein the content of the heat nucleating agent is 0.1 to 30 parts by mass relative to 100 parts by mass of the polybenzoxazole precursor.

[4] The photosensitive resin composition according to any one of [1] to [3], wherein R ⁴ in the formula (X) includes at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkyleneoxy group and an alkoxysilyl group.

[5] The photosensitive resin composition according to any one of [1] to [4], wherein m in the formula (X) is 2 and R ⁴ in the formula (X) is a bivalent aliphatic hydrocarbon group which may have a hetero atom.

[6] The photosensitive resin composition according to [4], wherein m in the formula (X) is 1.

[7] The polybenzoxazole precursor according to any one of [1] to [4], wherein the repeating unit A represented by the formula (1) in which Y is a cyclic aliphatic group having 3 to 15 carbon atoms and Y in the formula (1) The photosensitive resin composition according to any one of [2] to [6], which contains a repeating unit B represented by an aliphatic group.

[8] The photosensitive resin composition according to any one of [2] to [6], wherein the polybenzoxazole precursor contains at least an aromatic group having 6 to 20 carbon atoms in the formula (1).

[9] The polybenzoxazole precursor according to any one of [1] to [3], wherein the polybenzoxazole precursor contains the repeating unit A and the repeating unit B in total in a proportion of 70 mol% or more of the total repeating units in the polybenzoxazole precursor, Is in a molar ratio of 9: 1 to 3: 7. The photosensitive resin composition according to < 7 >

[10] The photosensitive composition according to any one of [1] to [9], wherein the polybenzoxazole precursor is protected by an acid-decomposable group in an amount of 10 to 60% of the phenolic hydroxyl groups of all the repeating units of the polybenzoxazole precursor Resin composition.

[11] A process for producing a photosensitive resin composition, comprising the steps of applying the photosensitive resin composition described in any one of [1] to [10]

Removing the solvent from the applied photosensitive resin composition;

A step of exposing the photosensitive resin composition from which the solvent has been removed to actinic radiation;

A step of developing the exposed photosensitive resin composition with a developer,

And a step of thermally curing the developed photosensitive resin composition to obtain a cured film.

[12] The method for producing a cured film according to [11], which comprises a step of exposing the developed photosensitive resin composition after the developing step and before the heat curing step.

[13] A cured film obtained by curing the photosensitive resin composition according to any one of [1] to [10].

[14] A cured film according to [13], which is an interlayer insulating film.

[15] A liquid crystal display device having the cured film according to [13] or [14].

[16] An organic electroluminescent display device having the cured film according to [13] or [14].

[17] A touch panel having the cured film according to [13] or [14].

(Effects of the Invention)

According to the present invention, it is possible to provide a photosensitive resin composition excellent in heat-resistant transparency and patterning property, a method of producing a cured film using the same, a cured film, a liquid crystal display, an organic electroluminescence display, and a touch panel.

Hereinafter, the present invention will be described in detail.

The following description of the constituent elements described below may be made on the basis of exemplary embodiments of the present invention, but the present invention is not limited to such embodiments.

In the present specification, the numerical range indicated by using " ~ " means a range including numerical values before and after " ~ " as a lower limit value and an upper limit value.

In the notation of the group (atomic group) in the present specification, the notation in which substitution and non-substitution are not described includes those having a substituent and having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (an unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In this specification, the solid content is a solid content at 25 占 폚.

In the present specification, the weight average molecular weight and number average molecular weight of the polymer are defined as polystyrene reduced values by GPC (gel permeation chromatograph) measurement. The polymer had a weight average molecular weight and number average molecular weight of, for example, HLC-8120 (Tosoh Corporation), TSK gel Multipore HXL-M (tester, 7.8 mm ID x 30.0 cm) as a column and THF Tetrahydrofuran).

[Photosensitive resin composition]

The photosensitive resin composition of the present invention contains a polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent.

The polybenzoxazole precursor is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid decomposable group.

The thermal base generator is a compound represented by the following formula (X).

Herein, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having m ≪ / RTI > When m is 2 to 4, plural R ¹ , R ² and R ³ may be the same or different.

The photosensitive resin composition of the present invention contains the above-described polybenzoxazole precursor and the photoacid generator that generates the acid having a pKa of 3 or less and generates the acid generator represented by the above formula (X) The patterning property is improved.

Although this is not clear in detail, the present inventors have assumed the following.

First, the polybenzoxazole precursor is fired at a high temperature to be cyclized (forming a benzoxazole ring), resulting in polybenzoxazole exhibiting excellent heat resistance and insulation.

If an acid (for example, an acid generated by pyrolysis of the photoacid generator) is present in the sintering process (post-baking process), the phenolic hydroxyl group that is deprotected is oxidized, and the cyclization reaction of the benzoxazole precursor Other side reactions proceed and the transparency of the resultant cured film is lowered.

On the other hand, it is effective to add a base compound in order to suppress side reactions at the time of thermal curing by an acid, but when an unprotected base compound is added, the acid generated from the photoacid generator is neutralized and the patterning property is lowered.

In the present invention, by using the compound represented by the above formula (X) protecting the primary amine as a thermal base generator, it is possible to suppress the side reaction in the firing process without lowering the patterning property, It is considered that the transparency and the patterning property are improved.

The photosensitive resin composition of Patent Document 1 also contains a thermal base generator. However, as shown in Comparative Examples (particularly Comparative Examples 1 and 6) to be described later, a secondary amine having a heterocyclic structure containing a nitrogen atom It is considered that the side reaction in the firing process can not be suppressed because the transparency or the patterning property is lowered when used.

The photosensitive resin composition of the present invention can be preferably used as a positive photosensitive resin composition and can be preferably used as a chemically amplified positive photosensitive resin composition.

Hereinafter, the polybenzoxazole precursor, the photoacid generator, the thermal base generator and the optional additives, which generate an acid having a pKa of 3 or less, contained in the photosensitive resin composition of the present invention will be described in detail.

[Polybenzoxazole Precursor]

The polybenzoxazole precursor contained in the photosensitive resin composition of the present invention is a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid decomposable group.

Here, the " phenolic hydroxyl group " is a group formed by replacing a hydrogen atom of an aromatic ring with a hydroxyl group. The "aromatic ring" may be a monocyclic or polycyclic ring, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring.

The term "acid-decomposable group" refers to a group which is decomposed by the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, and examples thereof include an acetal group, a silyl group, a silyl ether group, Among them, an acetal group is preferable from the viewpoint of sensitivity. The acetal group means a group containing an oxygen atom bonded to R in the formula (1) to be described later.

In the present invention, it is preferable that the polybenzoxazole precursor has a repeating unit represented by the following formula (1) from the viewpoints of heat resistance, insulation, film strength and the like.

(1), X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, and each R independently represents a hydrogen atom, an alkyl group, a structure represented by the following formula (2) --CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.

In the formula (2), * represents a bonding position with an oxygen atom, R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, R ¹⁰¹ and R ¹⁰² is, except for the case of a hydrogen atom, also be a R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether.

As the tetravalent organic group containing an aromatic ring represented by X in the above formula (1), specifically, for example, the following organic groups are preferably exemplified.

In the tetravalent organic group shown below, it is preferable that one of "* 1" and "* 2" represents a connecting part with -OR in the formula (1) And -NH- in the formula (I). Likewise, "* 3" and "* 4" each represent a connecting portion with -OR in the formula (1), and the other represents a connecting portion with -NH- in the formula (1) .

Examples of the divalent organic group represented by Y in the formula (1) include divalent aliphatic hydrocarbon groups and divalent aromatic groups, and specifically, a cyclic aliphatic group having 3 to 15 carbon atoms, a cycloaliphatic group having 4 to 14 carbon atoms A linear or branched aliphatic group having 5 to 20 carbon atoms, or an aromatic group having 5 to 100 carbon atoms.

Examples of the cyclic aliphatic group having 3 to 15 carbon atoms include a cyclic alkylene group, a cyclic alkenylene group, and a cyclic alkynylene group, and a cyclic alkylene group is preferable. A cyclic alkylene group can provide a cured film excellent in light resistance and chemical resistance.

The cyclic aliphatic group has 3 to 15 carbon atoms, preferably 6 to 12 carbon atoms. When the number of carbon atoms is within the above range, a cured film excellent in light resistance and chemical resistance can be obtained. The cyclic aliphatic group is preferably a 6-membered ring. The cyclic aliphatic group having 3 to 15 carbon atoms may have a substituent or may be unsubstituted. Non-substitution is preferred.

Examples of the substituent include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogen atom.

When the cyclic aliphatic group has a substituent, the number of carbon atoms of the cyclic aliphatic group is the number excluding the carbon number of the substituent.

Specific examples of the cyclic aliphatic group having 3 to 15 carbon atoms include the residue (cyclic aliphatic group) remaining after the removal of the carboxyl group of the cyclic aliphatic dicarboxylic acid. Specifically, the following groups may be mentioned, and a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a biscyclohexylene group and an adamantylene group are preferable, and a cyclohexylene group or a biscyclohexylene The value of g is more preferable. In the following groups, * means a bonding position to a carbon atom (carbonyl carbon) constituting a carbonyl group adjacent to Y in the formula (1).

Examples of the straight chain or branched aliphatic group having 4 to 20 carbon atoms include an alkylene group, an alkenylene group, an alkynylene group and a polyoxyalkylene group, preferably an alkylene group, an alkenylene group or an alkynylene group, The value of g is more preferable.

The carbon number of the straight chain or branched aliphatic group is 4 to 20, preferably 4 to 15, and more preferably 4 to 12. When the number of carbon atoms is within the above range, solvent solubility is good.

Specific examples of the straight chain or branched aliphatic group having 4 to 20 carbon atoms include a linear aliphatic dicarboxylic acid or a residue (aliphatic group) remaining after the removal of the carboxyl group of the aliphatic dicarboxylic acid in the branch.

Examples of the straight chain aliphatic dicarboxylic acid include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane diacid, dodecane diacid, tridecanedioic acid, tetradecanedioic acid, Decanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, and docosanoic acid.

Examples of the branched aliphatic dicarboxylic acid include 3-methylglutaric acid, 3,3-dimethylglutaric acid, 2-methyladipic acid, 2-ethyladipic acid, 3-methyl adipic acid, 3-tert-butyl adipic acid, 2,3-dimethyl adipic acid, 2,4-dimethyl adipic acid, 3,3-dimethyl adipic acid, 3 , 4-dimethyladipic acid, 2,4,4-trimethyladipic acid, 2,2,5,5-tetramethyladipic acid, 2-methylpimelic acid, 3-methylpimelic acid, Acid, 2-methyl sebacic acid, and nonane-2,5-dicarboxylic acid.

The aromatic group having 5 to 100 carbon atoms is preferably an aromatic group having 6 to 20 carbon atoms, and specific examples thereof include the following groups.

In the following groups, * represents the bonding position with the carbonyl carbon in the formula (1), A represents -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO- and -C (CF ₃ ) ₂ -.

In the above formula (1), the alkyl group represented by R may be any of linear, branched and cyclic. In the case of a linear alkyl group, the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. In the case of a branched alkyl group, the number of carbon atoms is preferably from 3 to 20, more preferably from 3 to 15, and still more preferably from 3 to 10. In the case of the cyclic alkyl group, the number of carbon atoms is preferably from 3 to 15, more preferably from 5 to 15, and still more preferably from 5 to 10. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, octyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl. The alkyl group may have a substituent or may be unsubstituted.

Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a cyano group, an amide group and a sulfonylamide group.

In the formula (1), the structure represented by the formula (2) represented by R is a structure corresponding to the protective group of a phenolic hydroxyl group protected with an acid-decomposable group.

The alkyl group represented by R ¹⁰¹ , R ¹⁰² and R ¹⁰³ in the formula (2) is the same as the alkyl group described in R, and the preferable range is also the same. The alkyl group may have a substituent or may be unsubstituted. As the substituent, those described above may be mentioned.

Examples of the cyclic ether formed by linking R ¹⁰¹ or R ¹⁰² and R ¹⁰³ in the formula (2) include the following structures. In the structures shown below, * represents a bonding position with an oxygen atom. The structure shown below is also referred to as an acetal group when an oxygen atom bonded at the position * is included.

Rc represents an alkyl group or an aryl group.

The alkyl group represented by Rc is the same as the alkyl group described in R, and the preferable range is also the same. The alkyl group may have a substituent or may be unsubstituted. As the substituent, those described above may be mentioned.

The aryl group represented by Rc is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 14 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group and a naphthyl group. The aryl group may have a substituent or may be unsubstituted. As the substituent, those described above may be mentioned.

In the present invention, from the viewpoint of sensitivity, it is preferable that the polybenzoxazole precursor is such that 10 to 60% of the phenolic hydroxyl groups of the entire polybenzoxazole precursor have an acid-decomposable group (in particular, Structure], and it is more preferable that 15-50% is protected.

Here, the phenolic hydroxyl group possessed by all of the repeating units of the polybenzoxazole precursor means a phenolic hydroxyl group possessed by all the repeating units of the polybenzoxazole precursor before the protection by the acid decomposable group is carried out.

In the present invention, the polybenzoxazole precursor is preferably a repeating unit A in which Y in the formula (1) is represented by a cyclic aliphatic group having 3 to 15 carbon atoms and Y in the formula (1) And a repeating unit B represented by a straight chain or branched aliphatic group having from 2 to 20 carbon atoms.

Here, the cyclic aliphatic group having 3 to 15 carbon atoms and the straight or branched aliphatic group having 4 to 20 carbon atoms are the same as the respective aliphatic groups described for Y in the formula (1), and the preferable range is also the same.

In the present invention, from the viewpoint of light resistance, the polybenzoxazole precursor preferably contains the repeating unit A and the repeating unit B in a total amount of 70 mol% or more of the total repeating units in the polybenzoxazole precursor , More preferably in a proportion of 70 to 100 mol%, more preferably in a proportion of 80 to 100 mol%, particularly preferably substantially composed of only the repeating unit A and the repeating unit B Do. According to this embodiment, a cured film excellent in light resistance is easily obtained.

In the present invention, the term "substantially composed of only the repeating unit A and the repeating unit B" means that the content of the repeating unit other than the repeating unit A and the repeating unit B is, for example, 5 mol% or less, and 1 mol % Or less, and still more preferably no content.

In the present invention, from the viewpoint of light resistance, the polybenzoxazole precursor preferably has a molar ratio of the repeating unit A to the repeating unit B in a molar ratio of 9: 1 to 3: 7, more preferably 8.5: 1.5 to 3.5: 6.5 More preferably 8: 2 to 4: 6.

For example, when Y in the formula (1) has a repeating unit represented by a cyclohexylene group or a bis-cyclohexylene group as a repeating unit A, and Y in the formula (1) , The ratio of the content of the repeating unit A to the content of the repeating unit B in the molar ratio is preferably from 8.5: 1.5 to 4: 6, more preferably from 7.5: 2.5 to 4: 6 More preferably 7.5: 2.5 to 5.5: 4.5, still more preferably 7.5: 2.5 to 6: 4.

For example, when Y in formula (1) has a repeating unit represented by adamantylene group as repeating unit A and Y in formula (1) as repeating unit B is a straight or branched aliphatic group having 4 to 20 carbon atoms The ratio of the content of the repeating unit A to the content of the repeating unit B in the molar ratio is preferably from 6.5: 3.5 to 4: 6, more preferably from 6: 4 to 5: 5.

In the present invention, the polybenzoxazole precursor may contain a repeating unit other than the repeating unit A and the repeating unit B (hereinafter also referred to as " another repeating unit ").

Examples of other repeating units include repeating units represented by the general formula (a1), repeating units represented by the general formula (a2), and repeating units represented by the general formula (a3).

In the general formula (a1), X ¹⁰ represents a tetravalent organic group containing an aromatic ring, Y ¹⁰ represents an aromatic ring group, R ¹¹ and R ¹² each independently represent a hydrogen atom, an alkyl group, an acid- .

In the general formula (a1), X ¹⁰ is in the same range as X described in the above formula (1), and the preferable range is also the same. In the general formula (a1), R ¹¹ and R ¹² are in the same range as R described in the above formula (1), and preferable ranges are also the same.

In the general formula (a1), Y ¹⁰ represents an aromatic ring group. The aromatic ring may be monocyclic or polycyclic. The aromatic ring may be a heteroaromatic ring group containing a hetero atom. Specific examples of the aromatic ring include aromatic rings such as a benzene ring, a naphthalene ring, a pentane ring, an indene ring, an azuren ring, a heptane ring, an indene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, A thiazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indole ring ring, an indole ring ring , Benzofuran ring, benzothiophen ring, isobenzofuran ring, quinolin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring , Acridine ring, phenanthroline ring, thianthrene ring, chromane ring, xanthine ring, phenoxystine ring, phenothiazine ring, and phenanthrene ring.

In the general formula (a2), Y ¹¹ represents an aromatic ring group, a cyclic aliphatic group, a straight chain aliphatic group, a branched aliphatic group or a group represented by -CH ₂ -, -O-, -S-, -SO ₂ -, - -CO-, -NHCO-, and -C (CF ₃ ) ₂ -, X ¹¹ represents an aromatic ring group, a cyclic aliphatic group, or a group formed by combining these with -CH ₂ -, -O-, -S-, -SO ₂ -, -CO-, -NHCO-, and -C (CF ₃ ) ₂ -.

The aromatic group, the cyclic aliphatic group, the straight-chain aliphatic group and the branched aliphatic group can be mentioned above, and the preferable range is also the same.

(A3), Y ¹² represents an aromatic ring group, a cyclic aliphatic group, a straight chain aliphatic group, a branched aliphatic group, or a group represented by -CH ₂ -, -O-, -S-, -SO ₂ -, -CO -, -NHCO-, and -C (CF ₃ ) ₂ -, and X ¹² represents a group containing a silicon atom.

The aromatic group, the cyclic aliphatic group, the straight-chain aliphatic group and the branched aliphatic group can be mentioned above, and the preferable range is also the same.

The group represented by X ¹² , which contains a silicon atom, is preferably a group represented by the following formula.

R ²⁰ and R ²¹ each independently represent a divalent organic group, and R ²² and R ²³ each independently represent a monovalent organic group.

The divalent organic group represented by R ²⁰ and R ²¹ is not particularly limited, but specifically includes a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, a divalent aliphatic aliphatic group having 3 to 20 carbon atoms Or a group formed by combining these groups.

The number of carbon atoms of the straight chain or branched alkylene group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 6. Specific examples thereof include a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group and a t-butylene group.

The number of carbon atoms of the arylene group is preferably from 6 to 20, more preferably from 6 to 14, and still more preferably from 6 to 10. Specific examples of the arylene group include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a naphthylene group and an anthracenylene group.

The bivalent cyclic aliphatic group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms, and still more preferably 5 to 6 carbon atoms. Examples of the divalent cyclic aliphatic group include a 1,4-cyclohexylene group, a 1,3-cyclohexylene group and a 1,2-cyclohexylene group.

The straight chain or branched alkylene group having 1 to 20 carbon atoms, the arylene group having 6 to 20 carbon atoms, and the divalent cyclic aliphatic group having 3 to 20 carbon atoms may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

The group formed by combining a straight chain or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms is not particularly limited, but a divalent cyclic group having 3 to 20 carbon atoms And a group formed by combining aliphatic groups. Specific examples of the group formed by combining a linear or branched alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent cyclic aliphatic group having 3 to 20 carbon atoms include the following: It is not.

Examples of the monovalent organic group represented by R ²² and R ²³ include a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

The number of carbon atoms of the linear or branched alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to 6. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group.

The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 14 carbon atoms, and still more preferably 6 to 10 carbon atoms. Specific examples of the aryl group include a phenyl group, a toluyl group, a mesityl group, and a naphthyl group.

A straight chain or branched alkyl group having 1 to 20 carbon atoms or an aryl group may have a substituent. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

It is preferable that the polybenzoxazole precursor in the present invention has a structure in which the terminal is sealed with monovalent acid chloride. According to this embodiment, a cured film having a good transmittance tends to be obtained. Examples of the monovalent europium chloride include chlorides such as acetyl chloride, butyryl chloride, propionyl chloride, 2-ethylhexanoic chloride, cyclohexanecarboxylic chloride, benzoyl chloride, naphthoyl chloride, Butyryl chloride, methoxyacetyl chloride, acetoxyacetyl chloride, isobutyryl chloride, isononanoyl chloride, neodecane oil chloride, octanoyl chloride, pivaloyl chloride, valeroyl chloride, methoxyacetyl chloride, , Phenyl acetyl chloride, cinnamyl chloride, methacrylic chloride, 2-furoyl chloride, 3-chloropropionyl chloride, 4-chlorobutyryl chloride, 5-chlorobalyl chloride, Methyl chloroformate, ethyl chloroformate, propyl chloroformate, n-butyl chloroformate, sec-butyl chloroformate, pentyl chloroformate, n-hexyl chloride Ethylhexyl chloroformate, cyclohexyl chloroformate, 4-tert-butylcyclohexyl chloroformate, cetyl chloroformate, benzyl chloroformate, 2-chloroethyl Chloroformate and the like.

From the viewpoint of solvent solubility, an acid chloride of 3 or more carbon atoms is preferable. From the viewpoint of solvent resistance, acid chlorides having 12 or less carbon atoms are preferred. From the viewpoint of thermal stability, a carboxylic acid chloride is preferable.

The polybenzoxazole precursor in the present invention is preferably a group having one end or both ends represented by the general formula (b1), and more preferably both ends are groups represented by the general formula (b1).

In general formula (b1)

In the general formula (b1), Z represents a single bond, a carbon atom or a sulfur atom, R ³⁰ represents a monovalent organic group, n represents 0 or 1, a represents 0 when Z is a single bond, Z represents A is 1 when Z is a sulfur atom, 2 is a when Z is a sulfur atom, and two R ^{30 s} may be bonded to each other to form a ring when n is 0.

Z represents a single bond, a carbon atom or a sulfur atom, preferably a single bond or a carbon atom.

R ³⁰ represents a monovalent organic group. The monovalent organic group is not particularly limited, but it is exemplified that the food per molecule is 20 to 500. The atom constituting the monovalent organic group is preferably selected from a carbon atom, an oxygen atom, a nitrogen atom, a hydrogen atom and a sulfur atom, more preferably selected from a carbon atom, an oxygen atom, a nitrogen atom and a hydrogen atom.

Specific examples thereof include an alkyl group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenyl group (preferably having 2 to 10 carbon atoms, more preferably having 2 to 6 carbon atoms) (Preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), an aryl group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 10 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms, A carboxyl group, a crosslinkable group, and an oxygen atom, a carbonyl group, a sulfonyl group, an arylene group (preferably a carbon number of 6 to 20, more preferably a carbon number of 6 to 10), an alkylene group (Preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms), and an alkynylene group Preferably 2 to 6 carbon atoms), an alkenyl group, an alkynyl group, an aryl group, Beam group, a carboxyl group, more preferably an oxygen atom, an alkylene group, an alkynyl group or a group comprising a combination of an arylene group.

These groups may have a substituent, and examples of the substituent include a hydroxyl group, an alkyl group, a halogen atom, a cyano group, an amide group, and a sulfonylamide group.

Specific examples of the group represented by the general formula (b1) include, but are not limited to, the following. In the formulas, Ph represents a phenyl group, and n-Pr represents an n-propylene group.

The polybenzoxazole precursor preferably has a weight average molecular weight (Mw) of 3,000 to 200,000. The lower limit is more preferably 4,000 or more, and more preferably 5,000 or more. The upper limit is more preferably 100,000 or less, and still more preferably 50,000 or less. The number average molecular weight (Mn) is preferably 1,000 to 50,000. The lower limit is more preferably 2,000 or more, and still more preferably 3,000 or more. The upper limit is more preferably 40,000 or less, and still more preferably 30,000 or less. By setting this range, lithography performance and physical properties of the cured film can be made excellent.

In the present invention, the content of the polybenzoxazole precursor in the photosensitive resin composition is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and more preferably 40 parts by mass or more per 100 parts by mass of the total solid content of the photosensitive resin composition Is particularly preferable. The upper limit is preferably 99 parts by mass or less, more preferably 80 parts by mass or less, and particularly preferably 70 parts by mass or less. When two or more polybenzoxazole precursors are used, the total amount is preferably in the above range.

The polybenzoxazole precursor used in the present invention can be synthesized by taking the description of JP-A-2008-224970 into consideration. The end sealing by the monovalent diacid chloride can be carried out at one time by mixing the monovalent activator chloride in the polymerization reaction, for example.

[Photo acid generator]

The photoacid generator of the photosensitive resin composition of the present invention is a photoacid generator that generates an acid having a pKa of 3 or less.

Here, pKa basically indicates pKa in water at 25 占 폚. What can not be measured in water indicates that the measurement was made by changing to a solvent suitable for measurement. Specifically, the pKa described in the Chemical Manual can be referred to.

The acid having a pKa of 3 or less is preferably a sulfonic acid or a phosphonic acid, more preferably a sulfonic acid.

The photoacid generator preferably generates an acid having a pKa of 2 or less.

The photoacid generator is preferably a compound that generates an acid upon exposure to an actinic ray having a wavelength of 300 nm or more, preferably 300 to 450 nm, but is not limited to the chemical structure thereof. Further, in the case of a photoacid generator which does not directly react with an actinic ray having a wavelength of 300 nm or more, a compound capable of generating an acid in response to an actinic ray having a wavelength of 300 nm or more by being used in combination with a sensitizer can be preferably used in combination with a sensitizer.

Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazine, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imidosulfonate compounds and oxime sulfonate compounds . Of these, onium salt compounds, imidosulfonate compounds and oxime sulfonate compounds are preferable, and onium salt compounds and oxime sulfonate compounds are particularly preferable. The photoacid generators may be used alone or in combination of two or more.

Specific examples of trichloromethyl-s-triazine, diaryl iodonium salts, triarylsulfonium salts, quaternary ammonium salts, and diazomethane compounds are disclosed in Japanese Patent Laid-Open Publication No. 2011-221494 And the compounds described in paragraphs 0013 to 0049 of JP-A No. 2011-105645, the contents of which are incorporated herein by reference.

Specific examples of the imidosulfonate compounds include the compounds described in paragraphs 0065 to 0077 of WO2011 / 087011, the contents of which are incorporated herein by reference.

It is also preferable to use triarylsulfonium salts having the following structures.

As the oxime sulfonate compound, that is, the compound having an oxime sulfonate structure, a compound containing an oxime sulfonate structure represented by the following general formula (B1-1) can be preferably exemplified.

In general formula (B1-1)

In the general formula (B1-1), R ²¹ represents an alkyl group or an aryl group. The dashed line indicates the combination with other tiles.

The alkyl group in R ²¹ may be linear, branched, or cyclic. The permissible substituents are described below.

As the alkyl group for R ²¹ , a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ²¹ is preferably a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cycloalkyl group (including a bridged alicyclic group such as a 7,7-dimethyl- May be substituted with a bicycloalkyl group or the like).

As the aryl group for R ^21, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ²¹ may be substituted with a lower alkyl group, an alkoxy group or a halogen atom.

It is also preferable that the compound containing the oxime sulfonate structure represented by the general formula (B1-1) is an oxime sulfonate compound described in paragraphs 0108 to 0133 of JP-A-2014-238438.

As the imidosulfonate compound, a naphthaleneimide compound is preferable, and the description of WO 01/087011 can be taken into account, the contents of which are incorporated herein by reference.

In the present invention, the content of the photoacid generator is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total solid content of the photosensitive resin composition. The lower limit is more preferably 0.2 parts by mass or more, for example, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.

The content of the photoacid generator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.1 to 8 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.

The photoacid generator may be used alone or in combination of two or more. When two or more kinds of photoacid generators are used, the total amount is preferably in the above range.

[Heat Base Generator]

The heat base generator contained in the photosensitive resin composition of the present invention is a compound represented by the following formula (X).

Herein, in the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represents an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents an alkyl group having m ≪ / RTI > When m is 2 to 4, plural R ¹ , R ² and R ³ may be the same or different.

In the formula (X), the number of carbon atoms of the alkyl group represented by R ¹ , R ² and R ³ is 1 to 5, preferably 1 to 3, and more preferably 1 or 2. The total number of carbon atoms of the alkyl group represented by R ¹ , R ² and R ³ is preferably 3 or 4.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group.

In the present invention, for the reason that the patterning property becomes better, it is preferable that the thermal base generator is a compound wherein R ⁴ in the formula (X) contains at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkyleneoxy group and an alkoxysilyl group .

Among them, R ⁴ in the formula (X) is more preferably a compound containing a hydroxyl group and / or a carboxyl group, and more preferably a compound containing a hydroxy group.

Specific examples of the compound in which R ⁴ in the formula (X) includes a carboxyl group include compounds represented by the following formulas.

Examples of the compound in which R ⁴ in the formula (X) includes a hydroxyl group include compounds represented by the following formulas, for example.

As the compound in which R ⁴ in the formula (X) includes both a hydroxyl group and a carboxyl group, specifically, for example, a compound represented by the following formula can be given.

Specific examples of the compound in which R ⁴ in the formula (X) includes an alkoxysilyl group include compounds represented by the following formulas.

As the compound containing such a functional group, it is preferable that m in the formula (X) is 1 from the viewpoint of heat resistance transparency and patterning property.

In the present invention, from the viewpoint of heat-resistant transparency, it is preferable that the thermal base generator be a divalent aliphatic hydrocarbon group in which m in the formula (X) is 2 and R ⁴ in the formula (X) may have a hetero atom Compound.

Specific examples of such a compound include compounds represented by the following formulas.

Examples of the thermal base generator other than the compound specifically exemplified above include compounds represented by the following formulas.

In the present invention, the content of such a thermal base generator is preferably 0.1 to 10% by mass, more preferably 0.3 to 10% by mass, more preferably 0.5 to 9% by mass, based on the total solid content, Is more preferable.

The content of the thermobase generator is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, and still more preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the polybenzoxazole precursor.

〔solvent〕

The solvent contained in the photosensitive resin composition of the present invention is not particularly limited, and a known solvent can be used.

Further, it is preferable that the photosensitive resin composition of the present invention is prepared as a solution in which the above-described essential components and optional components described later are dissolved in a solvent. As the solvent, it is preferable that the essential components and optional components are dissolved and not reacted with the respective components.

Specific examples of the solvent include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ethers (For example, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether and the like), diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene Glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, lactones, and the like. Also, the solvent described in paragraphs 0174 to 0178 of Japanese Patent Application Laid-Open Publication No. 2011-221494 and the solvent described in paragraphs 0167 to 0168 of Japanese Patent Application Laid-Open Publication No. 2012-194290 can be cited. do.

In these solvents, if necessary, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, A solvent such as benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate and propylene carbonate may be further added. These solvents may be used alone or in combination of two or more.

The solvent may be used alone, or two or more solvents may be used. When two or more of them are used, for example, propylene glycol monoalkyl ether acetates and dialkyl ethers, diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates are used in combination .

The solvent is preferably a solvent having a boiling point of 130 캜 or more and less than 160 캜, a solvent having a boiling point of 160 캜 or more, or a mixture thereof.

Propylene glycol monomethyl ether acetate (boiling point: 146 占 폚), propylene glycol monoethyl ether acetate (boiling point: 158 占 폚), propylene glycol methyl n-butyl ether (boiling point: 155 占 폚), propylene glycol Methyl-n-propyl ether (boiling point 131 占 폚). As the solvent having a boiling point of 160 캜 or more, ethyl 3-ethoxypropionate (boiling point: 170 캜), diethylene glycol methyl ethyl ether (boiling point: 176 캜), propylene glycol monomethyl ether propionate (boiling point: 160 캜), dipropylene glycol methyl ether acetate (Boiling point: 213 占 폚), 3-methoxybutyl ether acetate having a boiling point of 171 占 폚, diethylene glycol diethyl ether having a boiling point of 189 占 폚, diethylene glycol dimethyl ether having a boiling point of 162 占 폚, propylene glycol diacetate having a boiling point of 190 占), Diethylene glycol monoethyl ether acetate (boiling point 220 占 폚), dipropylene glycol dimethyl ether (boiling point 175 占 폚), and 1,3-butylene glycol diacetate (boiling point 232 占 폚).

In the present invention, the content of the solvent is preferably 50 to 95 parts by mass with respect to 100 parts by mass of the total components in the photosensitive resin composition. The lower limit is more preferably 60 parts by mass or more. The upper limit is more preferably 90 parts by mass or less.

The content of the solvent is preferably 500 to 2,000 parts by mass, more preferably 700 to 1,800 parts by mass based on 100 parts by mass of the polybenzoxazole precursor.

The solvent may be used alone, or two or more solvents may be used. When two or more kinds are used, the total amount is preferably in the above range.

[Adhesion improver]

The photosensitive resin composition of the present invention may contain an adhesion improver. Examples of the adhesion improver include alkoxysilane compounds.

The alkoxysilane compound is preferably a compound which improves the adhesion of an inorganic substance to be a substrate, for example, a silicon compound such as silicon, silicon oxide, or silicon nitride, or a metal such as gold, copper, molybdenum, titanium or aluminum.

Specific examples of the adhesion improver include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane and the like methacryloxypropyltrialkoxysilane such as? -glycidoxypropyltrialkoxysilane,? -glycidoxypropyldialkoxysilane, 3-methacryloxypropylmethyldimethoxysilane,? -methacryloxypropyltrialkoxysilane,? -methacryloxypropyldialkoxyl Silane,? -Chloropropyltrialkoxysilane,? -Mercaptopropyltrialkoxysilane,? - (3,4-epoxycyclohexyl) ethyltrialkoxysilane, and vinyltrialkoxysilane. Among these,? -Glycidoxypropyltrialkoxysilane and? -Methacryloxypropyltrialkoxysilane are preferable,? -Glycidoxypropyltrialkoxysilane is more preferable, and 3-methacryloxypropylmethyldimethoxysilane , And 3-glycidoxypropyltrimethoxysilane are more preferable. These may be used singly or in combination of two or more.

The content of the adhesion improver is preferably 0.001 to 15 parts by mass, more preferably 0.005 to 10 parts by mass based on 100 parts by mass of the total solid component of the photosensitive resin composition. Only one type of adhesion improver may be used, or two or more types may be used. When two or more kinds are used, the total amount is preferably in the above range.

[Sensitizer]

The photosensitive resin composition of the present invention may contain a sensitizer. The sensitizer absorbs the actinic ray to become an electron-excited state. The sensitizer in the electron excited state comes into contact with the photoacid generator to generate electron transfer, energy transfer, heat generation, and the like. Accordingly, the photoacid generator decomposes by chemical change to generate an acid. Therefore, decomposition of the photoacid generator can be promoted by containing a sensitizer. Examples of the preferable sensitizer include compounds having an absorption wavelength in a wavelength range of 350 to 450 nm belonging to the following compounds.

Polynuclear aromatic compounds such as pyrene, perylene, triphenylene, anthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene, 3,7-dimethoxyanthracene, 9,10- Anthracene), xanthines (for example, fluorescein, eosin, erythrosine, rhodamine B, and rose bengal), xanthones (for example, xanthone, thioxanthone, dimethylthioxanthone, Thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbons, thiocarbocyanines, oxacarbocyanines, (Such as acridine orange, chloroflavin, acriflavine), acridones (such as acridone, acridine, acridine), acridine (for example, thionine, methylene blue, toluidine blue) 2-chloroacridone), anthraquinones (for example, anthraquinone), squaryliums (for example, squalium), styryls, bases (For example, 2- [2- [4- (dimethylamino) phenyl] ethenyl] benzoxazole), coumarins Methylcoumarin, 2,3,6,7-tetrahydro-9-methyl-1H, 5H, 11H [1] benzopyrano [6,7,8-ij] quinolizine-11-pne).

Of these sensitizers, polynuclear aromatic compounds, acridones, styryls, base styryls and coumarins are preferable, and polynuclear aromatic compounds are more preferable. Of the polynuclear aromatics, anthracene derivatives are most preferred.

When the photosensitive resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.001 to 100 parts by mass based on 100 parts by mass of the total solid content in the photosensitive resin composition. The lower limit is more preferably 0.1 part by mass or more, for example, and still more preferably 0.5 parts by mass or more. The lower limit is more preferably 50 parts by mass or less, and still more preferably 20 parts by mass or less. Two or more sensitizers may be used in combination. When two or more kinds of sensitizers are used in combination, the total amount is preferably in the above range.

[Crosslinking agent]

The photosensitive resin composition of the present invention may contain a crosslinking agent. By containing a cross-linking agent, a harder cured film can be obtained.

The crosslinking agent is not limited as long as it is crosslinked by heat. For example, a compound having two or more epoxy groups or oxetanyl groups in a molecule, a block isocyanate compound, a crosslinking agent containing an alkoxymethyl group, and a compound having an ethylenically unsaturated double bond. Specifically, it is preferable to use the compounds described in paragraphs 0153 to 0163 of International Publication No. 2014/050730.

≪ Other cross-linking agent &

As the other crosslinking agent, an alkoxymethyl group-containing crosslinking agent, a compound having an ethylenically unsaturated double bond, and the like described in paragraphs 0107 to 0108 of Japanese Patent Application Laid-Open Publication No. 2012-8223 can be preferably used. As the alkoxymethyl group-containing crosslinking agent, alkoxymethylated glycoluril is preferable.

When the photosensitive resin composition of the present invention has a crosslinking agent, the content of the crosslinking agent is preferably 0.01 to 50 parts by mass based on 100 parts by mass of the polybenzoxazole precursor. The lower limit is more preferably 0.1 part by mass or more, for example, and still more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less. Within this range, a cured film excellent in mechanical strength and solvent resistance can be obtained. The crosslinking agent may be used alone or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

[Basic compound]

The photosensitive resin composition of the present invention may contain a basic compound. As the basic compound, any of those used as a chemically amplified positive resist can be used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, quaternary ammonium salts of carboxylic acids, and the like. Specific examples thereof include compounds described in paragraphs 0204 to 0207 of Japanese Patent Laid-Open Publication No. 2011-221494, the contents of which are incorporated herein by reference.

Specific examples of the aliphatic amine include aliphatic amines such as trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di- Ethanolamine, triethanolamine, dicyclohexylamine, dicyclohexylmethylamine, and the like.

Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.

Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl- Benzimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinic acid amide, quinoline, 8-oxy N-cyclohexyl-N '- [2- (4-morpholinyl) pyrimidine, Ethyl] thiourea, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-undecene.

The quaternary ammonium hydroxide includes, for example, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, benzyltrimethylammonium hydroxide, tetra-n-butylammonium hydroxide, Tetra-n-hexylammonium hydroxide, and the like.

Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate and tetra-n-butylammonium benzoate.

When the photosensitive resin composition of the present invention contains a basic compound, the content of the basic compound is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 1 part by mass based on 100 parts by mass of the total solid components in the photosensitive resin composition. The basic compounds may be used singly or in combination of two or more. When two or more kinds are used, the total amount is preferably in the above range.

〔Surfactants〕

The photosensitive resin composition of the present invention may contain a surfactant. As the surfactant, any of anionic, cationic, nonionic or amphoteric surfactants can be used, but preferred surfactants are nonionic surfactants. As the surfactant, for example, those described in paragraphs [0201] to [0205] of Japanese Patent Application Laid-Open Publication No. 2012-88459, and those described in paragraphs 0185 to 0188 of Japanese Patent Laid-Open Publication No. 2011-215580 may be used. Which is incorporated herein by reference.

Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicones, and fluorine surfactants. (Trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 99C (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Mitsubishi Materials Fair), Megapack (Made by OMNOVA), SH-8400 (manufactured by Toray Industries, Inc.), F-554 (made by DIC), Fluoradov Nove FC-4430 (made by Sumitomo 3M), Surflon S- Dow Corning Silicone) and POTGENT FTX-218G (manufactured by Neos Co., Ltd.).

Also, as the surfactant, the compounds described in paragraphs 0151 to 0155 of JP-A-2014-238438 are preferably used.

The surfactants may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention has a surfactant, the content of the surfactant is preferably 10 parts by mass or less, more preferably 0.001 to 10 parts by mass, and most preferably 0.01 to 3 parts by mass, per 100 parts by mass of the total solid component of the photosensitive resin composition. The mass part is more preferable.

[Antioxidant]

The photosensitive resin composition of the present invention may contain an antioxidant. As the antioxidant, a known antioxidant may be contained. By adding an antioxidant, coloring of the cured film can be prevented. In addition, there is an advantage in that reduction in film thickness due to decomposition can be reduced and excellent heat-resistant transparency can be obtained.

Examples of the antioxidant include phosphorus antioxidants, amides, hydrazides, hindered amine antioxidants, sulfur antioxidants, phenol antioxidants, ascorbic acid, zinc sulfate, sugars, nitrite, sulfite, thiosulfate, And a hydroxylamine derivative. Among them, a phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, an amide-based antioxidant, a hydrazide-based antioxidant and a sulfur-based antioxidant are preferable from the viewpoint of coloring of a cured film and reduction in film thickness, Antioxidants are most preferred. These may be used singly or in combination of two or more kinds.

Specific examples thereof include compounds described in paragraphs Nos. 0026 to 0031 of Japanese Patent Application Laid-Open No. 2005-29515 and compounds described in paragraphs 0106 to 0116 of Japanese Patent Application Laid-Open No. 227106, do.

Preferred commercial products are adecastab AO-20, adecastab AO-60, adecastab AO-80, adecastab LA-52, adecastab LA-81, adecastab AO-412S, adecastab PEP- 36, Ilganox 1035, Ilganox 1098, and Tinuvin 144.

When the photosensitive resin composition of the present invention has an antioxidant, the content of the antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, and most preferably 0.5 to 5 parts by mass based on 100 parts by mass of the total solid component of the photosensitive resin composition. To 4 parts by mass is particularly preferable. When the content is in this range, sufficient transparency of the formed film can be obtained and sensitivity at the time of pattern formation can be improved.

[Acid growth agent]

For the purpose of improving the sensitivity, the photosensitive resin composition of the present invention can use an acid growth agent.

The acid-proliferating agent is a compound capable of increasing the acid concentration in the reaction system by further generating an acid by an acid catalyzed reaction, and is a compound stably present in the absence of acid.

Specific examples of acid proliferators include the acid proliferators described in paragraphs 0226 to 0228 of JP-A-2011-221494, the contents of which are incorporated herein by reference.

When the photosensitive resin composition of the present invention contains an acid-proliferating agent, the content of the acid-proliferating agent is preferably 10 to 1000 parts by mass based on 100 parts by mass of the photoacid generator from the viewpoint of dissolution contrast between the exposed portion and the unexposed portion, More preferably 20 to 500 parts by mass. The acid proliferating agent may be used singly or in combination of two or more species. When two or more kinds of acid-proliferating agents are used, the total amount is preferably in the above range.

[Development promoter]

The photosensitive resin composition of the present invention may contain a development accelerator.

As the development promoter, those described in paragraphs 0171 to 0172 of Japanese Patent Application Laid-Open Publication No. 2012-042837 can be taken into consideration, the contents of which are incorporated herein by reference.

The development accelerator may be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention has a development accelerator, the addition amount of the development accelerator is preferably 0 to 30 parts by mass, more preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the total solid content of the photosensitive resin composition from the viewpoints of sensitivity and residual film ratio And most preferably 0.5 to 10 parts by mass.

[Other components]

In the photosensitive resin composition of the present invention, one or more known additives such as a heat radical generator, a thermal acid generator, an ultraviolet absorber, a thickener, and an organic or inorganic precipitation inhibitor may be independently added.

As these compounds, for example, compounds described in paragraphs 0201 to 0224 of Japanese Patent Application Laid-Open No. 88459/1987 can be used, and the content of these compounds is disclosed in the present specification.

The heat radical generator described in paragraphs 0120 to 0121 of Japanese Patent Application Publication No. 2012-8223, the nitrogen containing compound described in WO2011 / 136074A1, and a thermal acid generation system can be used, and the contents thereof are incorporated herein.

<Impurities>

Since the photosensitive resin composition of the present invention may lead to deterioration of storage stability of the composition or contamination of the apparatus, it is preferable that the content of the impurities is small.

Specific examples of the impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin or their ions, free halogen or halide ions.

The content of these impurities is preferably 1000 ppb or less, more preferably 500 ppb or less, and further preferably 100 ppb or less in the photosensitive resin composition of the present invention. Particularly, a metal impurity content of 20 ppb or less is particularly preferable. The lower limit is not particularly specified, but it may be 10 ppt or more or 100 ppt or more from the viewpoint of realistic reduction and measurement limit.

As the method for reducing the impurities in this manner, it is preferable to use a material which does not contain these impurities in the raw material of the resin or the additive, to prevent these impurities from being mixed at the time of combining the compositions, The amount of water can be kept within the above range. These impurities can be quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and the like.

In addition, the photosensitive resin composition of the present invention includes compounds such as benzene, formaldehyde, trichlorethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, .

The content of these compounds in the photosensitive resin composition of the present invention is preferably 500 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. Although the lower limit is not specially defined, it can be 0.1 ppb or more or 1 ppb or more from the viewpoint of practical limitations and measurement limit.

These impurities can be suppressed in the same manner as the impurities of the metal and can be quantified by a known measuring method.

[Method for preparing photosensitive resin composition]

The photosensitive resin composition of the present invention can be prepared by mixing the respective components at a predetermined ratio, by any method, and by stirring and dissolving. For example, the photosensitive resin composition of the present invention may be prepared by preparing a solution in which each component is dissolved in a solvent in advance, and then mixing them in a predetermined ratio. The composition solution thus prepared may be used after being filtered using, for example, a filter having a pore size of 0.2 mu m.

Here, the bore diameter of the filter can be appropriately adjusted according to the intended purity, etc., and in addition to 0.2 탆, 0.05 탆, 0.1 탆, 0.3 탆, 0.5 탆 and the like can be exemplified. The material of the filter can be appropriately selected in accordance with the solvent used in the composition and the like. Examples thereof include polypropylene, polyethylene, polyester, nylon, polytetrafluoroethylene, metal, activated carbon, cellulose and the like. The filtration may be repeated. For example, it may be filtrated twice, filtered five times, or filtered several times by circulation filtration.

The photosensitive resin composition of the present invention can adjust the solid content concentration, viscosity, and surface tension according to the purpose.

In the case of slit coating, the solid content concentration of the photosensitive resin composition is preferably from 2 to 40 mass%, more preferably from 3 to 30 mass%, and even more preferably from 4 to 20 mass%.

The viscosity when slit-coated is preferably 1 to 40 mPa · s, more preferably 2 to 25 mPa · s, and even more preferably 3 to 20 mPa · s. In the present invention, the viscosity is a value at 25 占 폚.

In the case of spin-coating, the solid content concentration of the composition is preferably 5 to 60 mass%, more preferably 7 to 50 mass%, and even more preferably 10 to 40 mass%.

On the other hand, the viscosity when spin-coating is preferably 5 to 100 mPa · s, more preferably 8 to 70 mPa · s, and even more preferably 10 to 50 mPa · s.

The surface tension is preferably 10 to 100 mN / m, more preferably 15 to 80 mN / m, and still more preferably 20 to 50 mN / m from the viewpoint of coating ability.

As a preferable specific example, a composition for a slit coat having a solid content concentration of 15 mass%, a viscosity of 5 mPa s, and a surface tension of 27 mN / m can be mentioned.

[Storage Method of Photosensitive Resin Composition]

The photosensitive resin composition of the present invention can be stored by a known method, for example, in a sealed container made of glass or metal.

At this time, it is also possible to use the atmosphere as the atmosphere or nitrogen. From the viewpoint of preventing unexpected oxidation of the photosensitive resin composition, it is preferable to use a nitrogen atmosphere.

The storage temperature may be a known temperature, for example, room temperature (20 to 25 ° C), refrigeration (0 to 5 ° C), and freezing (-50 ° C to -10 ° C). From the standpoint of preventing unexpected deterioration of the photosensitive resin composition, it is preferable to freeze or refrigerate, and freezing is more preferable. Concretely, 5 占 폚, -10 占 폚, -20 占 폚, -30 占 폚 can be mentioned, and -20 占 폚 is preferable.

In addition, the composition is not particularly limited in the storage period. For example, the composition may be used after being prepared at -10 ° C for 3 days, at 20 ° C for 20 days, at -30 ° C for 150 days And a form to be used later.

[Process for producing a cured film]

The method for producing the cured film of the present invention preferably includes the following steps (1) to (5).

(1) Step of applying the photosensitive resin composition of the present invention onto a substrate (coating step)

(2) a step of removing the solvent from the applied photosensitive resin composition (solvent removing step)

(3) a step of exposing the photosensitive resin composition from which the solvent has been removed by an actinic ray (exposure step)

(4) a step of developing the exposed photosensitive resin composition with a developing solution (developing step)

(5) a step of thermally curing the developed photosensitive resin composition to obtain a cured film (post baking step)

Each step will be described below in order.

In the step (1), it is preferable that the photosensitive resin composition of the present invention is applied onto a substrate to form a wet film containing a solvent.

The substrate may be subjected to cleaning such as alkaline cleaning or plasma cleaning before the step (1) is performed. In addition, the surface of the substrate after cleaning may be treated with hexamethyldisilazane or the like. The method of treating the surface of the substrate with hexamethyldisilazane is not particularly limited, and for example, a method of exposing the substrate to hexamethyldisilazane vapor may be mentioned.

Examples of the substrate include an inorganic substrate, a resin, and a resin composite material.

Examples of the inorganic substrate include glass, quartz, silicon, silicon nitride, and composite substrates obtained by depositing molybdenum, titanium, aluminum, copper, or the like on a substrate such as glass, quartz, silicon or silicon nitride.

Examples of the resin include polybutylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyarylate, allyldiglycol carbonate, polyamide, polyimide, polyamide Acrylic resin, epoxy resin, silicone resin, ionomer resin, polyimide resin, polyimide resin, polyimide resin, polyimide resin, And a synthetic resin such as a cyanate resin, a crosslinked fumaric acid diester, a cyclic polyolefin, an aromatic ether, a maleimide olefin, a cellulose, or an episulfide compound.

These substrates may have a multi-layered laminate structure such as a thin film transistor (TFT) device, depending on the shape of the final product.

The method of applying the photosensitive resin composition to the substrate is not particularly limited, and for example, slit coat method, spray method, roll coating method, spin coating method, spin coating method, slit-and-spin method and the like can be used.

In the case of the slit coat method, the relative moving speed of the substrate and the slit die is preferably 50 to 120 mm / sec.

The wet film thickness upon application of the photosensitive resin composition is not particularly limited, and can be applied with a film thickness according to the application. For example, it is preferably 0.5 to 10 mu m.

Before applying the photosensitive resin composition of the present invention to a substrate, it is also possible to apply the so-called pre-wet method as described in JP-A-2009-145395.

In the step (2), the solvent is removed from the wet film formed by applying the photosensitive resin composition by vacuum (vacuum pressure) and / or heating to form a dried film on the substrate. The heating condition of the solvent removing step is preferably about 70 to 130 占 폚 for 30 to 300 seconds. When the temperature and the time are within the above range, the adhesion of the pattern is better when the step (4) described below is performed, and the residue tends to be further reduced.

(3), the substrate on which the dry film is formed is irradiated with an actinic ray of a predetermined pattern. In this step, a phenolic hydroxyl group is generated in the exposed portion, and the solubility in the developing solution in the exposed portion is improved. That is, in the form including the polybenzoxazole precursor having a group in which a phenolic hydroxyl group is protected with an acid-decomposable group and a photoacid generator, the photoacid generator is decomposed by irradiation of an actinic ray to generate an acid. Then, the catalytic action of the generated acid hydrolyzes the acid-decomposable group to generate a phenolic hydroxyl group.

Examples of the light source of the active light beam include a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a chemical lamp, a light emitting diode (LED) (436 nm), and the like can be preferably used. If necessary, the irradiation light may be adjusted by passing through a spectral filter such as a long wavelength cut filter, a short wavelength cut filter, or a band pass filter. The exposure dose is preferably 1 to 500 mJ / cm 2.

As the exposure apparatus, various types of exposure apparatus such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a micro lens array, a lens scanner, and a laser exposure can be used. It is also possible to perform exposure using so-called super resolution technology. Examples of the super resolution technique include multiple exposures for exposing a plurality of times, a method using a phase shift mask, and an annular band illumination method. By using these super-resolution techniques, more precise pattern formation becomes possible, which is preferable.

In the step (4), the polybenzoxazole precursor is developed using a developer. A positive image is formed by removing the exposed region having a carboxyl group and / or a phenolic hydroxyl group which is easily dissolved in the developing solution.

The developing solution used in the developing step preferably contains an aqueous solution of a basic compound. Examples of the basic compound include alkali metal hydroxide such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Alkali metal carbonates such as sodium carbonate, potassium carbonate and cesium carbonate; Alkali metal bicarbonates such as sodium bicarbonate and potassium bicarbonate; Tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and diethyldimethylammonium hydroxide; cholines such as choline (such as hydroxy Alkyl) trialkylammonium hydroxides; Silicates such as sodium silicate and sodium metasilicate; Alkylamines such as ethylamine, propylamine, diethylamine and triethylamine; Alcohol amines such as dimethylethanolamine and triethanolamine; Alicyclic amines such as 1,8-diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used.

Of these, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, choline (2-hydroxyethyltrimethylammonium hydroxide) .

An aqueous solution in which an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant is added to the aqueous alkaline solution may be used as a developer.

The pH of the developing solution is preferably 10.0 to 14.0.

The developing time is preferably 30 to 500 seconds, and the developing method may be any of a liquid filling method (paddle method), a shower method, and a dipping method.

After the development, a rinsing process may be performed. In the rinsing step, the developed substrate is cleaned with pure water or the like to remove the attached developing solution and remove the developing residue. As the rinsing method, known methods can be used. Examples thereof include shower rinses and deep rinses.

(5), a cured film can be formed by heating the obtained positive image to thermally decompose the acid-decomposable group to generate a phenolic hydroxyl group and to carry out cyclization (forming a benzoxazole ring). The cured film may also be formed by crosslinking a phenolic hydroxyl group with a cross-linking agent or the like. Further, in the present invention, the polybenzoxazole precursor can be ring-closed (cured) by heating to form a cured film even in a form that does not contain a crosslinkable group or a crosslinking agent.

This heating is preferably performed using a heating apparatus such as a hot plate or an oven. The heating temperature is preferably 200 ° C to 350 ° C, more preferably 250 ° C to 350 ° C. The heating time is preferably 5 to 90 minutes for a hot plate and 30 to 120 minutes for an oven. By conducting a cyclization reaction or a crosslinking reaction by heating, a cured film excellent in heat resistance, hardness and the like can be formed. Further, when the heat treatment is performed, the transparency can be further improved by performing the heat treatment in a nitrogen atmosphere.

The lower the oxygen concentration in the heating atmosphere, the better. In the case of heating in a nitrogen substitution atmosphere, the oxygen concentration (in terms of mol) in the heating atmosphere is preferably 1.0 ppt to 10%, more preferably 1.0 ppb to 5%, and 1.0 ppm to 3% desirable.

Examples of the post-baking step include heating in an oven at 100 ° C of oxygen partial pressure by nitrogen substitution at 90 ° C for 30 minutes, at 120 ° C for 30 minutes, at 180 ° C for 40 minutes, and at 320 ° C for 60 minutes .

Further, in the present invention, middle baking performed at a relatively low temperature can be added before post-baking. In the case of performing the middle baking, post-baking is preferably performed at a high temperature of 200 ° C or higher after heating at 90 to 150 ° C for 1 to 60 minutes. In addition, middle baking and post baking may be divided into three or more stages and heated. By such a study of middle baking and post baking, the taper angle of the pattern can be adjusted. The heating of these can be performed by a known heating method such as a hot plate, an oven, or an infrared heater.

In addition, prior to the post-baking, the substrate having the pattern formed thereon is subjected to front exposure (post exposure) with an actinic ray and then post baked to generate an acid from the photoacid generator present in the unexposed portion to accelerate the cross- And the curing reaction of the film can be promoted. When the post exposure step is included, the preferable exposure amount is preferably 100 to 3,000 mJ / cm2, and particularly preferably 100 to 500 mJ / cm2.

When the post exposure process is performed, the taper angle of the pattern when the pattern is formed can be increased. On the other hand, when the post-exposure step is not performed, the taper angle of the pattern can be reduced. The presence or absence of the post exposure step and the exposure amount at the time of performing the post exposure can be appropriately adjusted by the taper angle of the target pattern. The taper angle of the pattern is, for example, 15 deg., 30 deg., 45 deg., 60 deg., 75 deg., And 90 deg. Among them, when a cured film is used as an insulating film, taper angles of 30 °, 45 °, 60 °, and 75 ° are preferable.

The cured film obtained from the photosensitive resin composition of the present invention may be used as a dry etching resist. When the cured film obtained by thermal curing by the post-baking step is used as a dry etching resist, dry etching such as ashing, plasma etching, and ozone etching can be performed as the etching processing.

[Coating film]

The cured film of the present invention is a cured film obtained by curing the above-mentioned photosensitive resin composition of the present invention. It is preferable that the cured film of the present invention is a cured film obtained by the above-described method of forming a cured film of the present invention.

The cured film of the present invention can be preferably used as an interlayer insulating film and a protective film.

The photosensitive resin composition of the present invention can obtain an interlayer insulating film having high transparency even when baked at a high temperature. The interlayer insulating film formed using the photosensitive resin composition of the present invention has high transparency and is useful for applications such as a liquid crystal display device, an organic electroluminescence display device, and a touch panel.

The cured film of the present invention may have various physical properties depending on the application.

When used in an interlayer insulating film such as a semiconductor device, it is preferable that the dielectric constant is low from the viewpoint of reducing the parasitic capacitance generated in the device. In this case, the relative dielectric constant is preferably 1.5 to 4.0, more preferably 2.2 to 3.2.

When the cured film of the present invention is used for an insulating film, it is preferable that the volume resistance is high from the viewpoint of improving the insulating property. The volume resistivity is preferably 1.0 × 10 ^{10 to} 1.0 × 10 ²⁰ Ω · cm, more preferably 1.0 × 10 ^{13 to} 1.0 × 10 ¹⁸ Ω · cm.

When the cured film of the present invention is used for applications requiring antistatic performance, the volume resistance is preferably 1.0 x 10 ^{4 to} 1.0 x 10 ¹³ Ω · cm, more preferably 1.0 × 10 ^{6 to} 1.0 × 10 ¹¹ Ω · cm Is more preferable.

From the viewpoint of improving the pulling property of the electronic device when the electronic device is formed using the cured film, the Young's modulus of the cured film is preferably high. The Young's modulus may be 0.5 to 8.0 kPa or 1.0 to 4.0 kPa as a preferred example.

From the viewpoint of improving the pullability of the electronic device when the electronic device is formed using the cured film, it is preferable that the cured film has a high elongation at break. The breaking elongation may be 20 to 200% or 50 to 150% as a preferable example.

The glass transition temperature (Tg) of the cured film is preferably 100 to 500 占 폚, more preferably 150 to 400 占 폚, from the viewpoint of improving the pullability of the electronic device when the electronic device is formed using the cured film, And most preferably from 200 to 300 캜.

From the viewpoint of preventing warping of the substrate on which the cured film is formed, it is preferable that the coefficient of linear expansion of the cured film is close to the coefficient of linear expansion of the substrate. For example, in the case of using a metal substrate, a glass substrate, and a silicon substrate having a coefficient of linear expansion in the range of 2 to 20 ppm / ° C, the coefficient of linear expansion of the cured film is preferably 10 to 100 ppm / desirable. Specific examples of the coefficient of linear expansion of the cured film in this case include 15 ppm / ° C and 25 ppm / ° C. When a resin substrate having a coefficient of linear expansion in the range of 20 to 120 ppm / 占 폚 is used, the coefficient of linear expansion of the cured film is preferably 20 to 120 ppm / 占 폚, and more preferably 40 to 80 ppm / 占 폚. Specific examples of the coefficient of linear expansion of the cured film in this case are 48 ppm / ° C, 59 ppm / ° C, and 69 ppm / ° C. Further, the coefficient of linear expansion means the coefficient of linear expansion at or below the temperature of Tg when the cured film has Tg.

When the cured film of the present invention is used for a lens material, it is preferable that the refractive index is high. In this case, for example, the refractive index at 400 nm is preferably 1.5 to 2.0, more preferably 1.6 to 1.8.

When the cured film of the present invention is used in an antireflection film, the refractive index is preferably low. In this case, for example, the refractive index at 400 nm is preferably 1.0 to 1.6, more preferably 1.2 to 1.4.

When the cured film of the present invention is used for display purposes, the minimum visible light transmittance of 400 nm to 700 nm per 1.0 μm of film thickness is preferably 80% or more, and more preferably 90% or more. The haze is preferably 3.0 or less, more preferably 1.0 or less. When the chromaticity is represented by the L * a * b * colorimetric system, the a * value is preferably -3.0 to 3.0, and the b * value is preferably -3.0 to 3.0. A particularly preferable specific example is a cured film having an a * value of 0.0 and a b * value of 0.0.

When the cured film of the present invention is used for display purposes, the in-plane retardation of the cured film is preferably 10 nm or less, more preferably 5 nm or less, further preferably 3 nm or less.

The in-plane retardation is a value measured by a photoelastic constant measuring apparatus at 25 DEG C and a wavelength of 550 nm. More specifically, the refractive index of the cured film is measured by a photoelastic constant measuring apparatus, and the direction in which the refractive index becomes maximum is referred to as the X axis, and the direction perpendicular to the X axis is referred to as the Y axis. When the refractive index in the X-axis direction is nx, the refractive index in the Y-axis direction is ny, and the thickness of the cured film is d, a value represented by (nx-ny) xd is referred to as in-plane retardation. As a preferable specific example, a cured film having a film thickness of 20 mu m and an in-plane retardation of 0.5 nm can be mentioned.

[Liquid crystal display device]

The liquid crystal display device of the present invention has the cured film of the present invention.

The liquid crystal display of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and may be a known liquid crystal display device employing various structures.

For example, specific examples of TFTs included in the liquid crystal display device of the present invention include amorphous silicon-TFT, low temperature polysilicon-TFT, and oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

As a liquid crystal driving method that can be employed in the liquid crystal display of the present invention, a twisted nematic (TN) method, a VA (virtual alignment) method, an in-place switching (IPS) method, a FFS (Optical Compensated Bend) method.

In the panel structure, the cured film of the present invention can also be used in a COA (Color Filter on All) type liquid crystal display device. For example, the organic insulating film 115 of Japanese Patent Application Laid-Open No. 2005-284291, And can be used as the organic insulating film 212 of JP-A-346054. Specific examples of the alignment method of the liquid crystal alignment film that can be employed in the liquid crystal display of the present invention include a rubbing alignment method and a photo alignment method. It may also be polymer-oriented supported by the PSA (Polymer Sustained Alignment) technique described in Japanese Patent Application Laid-Open Nos. 2003-149647 and 2011-257734.

Further, the photosensitive resin composition of the present invention and the cured film of the present invention are not limited to the above-mentioned use, and can be used for various purposes. For example, in addition to a planarizing film and an interlayer insulating film, a protective film for a color filter, a spacer for keeping the thickness of the liquid crystal layer in the liquid crystal display device constant, and a microlens provided on the color filter in the solid- Can be used.

For details of the liquid crystal display device, reference can be made to the description of Japanese Patent Application Laid-Open Nos. 2007-328210 and 2014-238438, the contents of which are incorporated herein by reference.

[Organic electroluminescence display device]

The organic electroluminescence (organic EL) display device of the present invention has the cured film of the present invention.

The organic EL display device of the present invention is not particularly limited, except that it has a planarizing film or an interlayer insulating film formed by using the photosensitive resin composition of the present invention, and various known organic EL display devices employing various structures, liquid crystal display Devices.

For example, specific examples of the TFTs included in the organic EL display device of the present invention include an amorphous silicon TFT, a low temperature polysilicon TFT, and an oxide semiconductor TFT. Since the cured film of the present invention is excellent in electric characteristics, it can be preferably used in combination with these TFTs.

For details of the liquid crystal display device, reference may be made to the disclosure of Japanese Patent Application Laid-Open No. 2014-238438, the contents of which are incorporated herein.

As another mode of the organic EL display device, the pixel defining film 19 and the planarization film 17 described in Fig. 1 of Japanese Patent Application Laid-Open No. 20-20121 can be formed using the photosensitive resin composition of the present invention. The high resistance layer 18, the inter-pixel insulating film 16, the interlayer insulating film 14, and the interlayer insulating film 12c shown in FIG. 1 of Japanese Patent Laid-Open Publication No. 2013-196919 can be formed by using the photosensitive resin composition of the present invention .

[Touch panel and touch panel display device]

The touch panel of the present invention is a touch panel in which all or a part of the insulating layer and / or the protective layer is made of a cured product of the photosensitive composition of the present invention. Further, the touch panel of the present invention preferably has at least a transparent substrate, an electrode, and an insulating layer and / or a protective layer.

The touch panel display device of the present invention is preferably a touch panel display device having the touch panel of the present invention. As the touch panel of the present invention, any of known methods such as a resistance film type, a capacitance type, an ultrasonic type, and an electromagnetic induction type may be used. Among them, a capacitance type is preferable.

Examples of capacitive touch panels include those disclosed in Japanese Patent Application Laid-Open No. 2010-28115, and those disclosed in International Publication No. 2012/057165.

Examples of the touch panel display device include a so-called in-cell type (for example, Japanese Laid-Open Patent Publication No. 2012-517051, FIGS. 5, 6, 7 and 8) (Fig. 14 of the publication, Fig. 2 (b) of International Publication No. 2012/141148), OGS type, TOL type, and other configurations (for example, Fig. 6 of JP-A-2013-164871).

(1) to (5) on the noncontact side of the front plate, and the insulating layer of (4) is a cured film using the photosensitive resin composition of the present invention desirable.

(1) frame layer

(2) a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction through connection portions

(3) a plurality of second transparent electrode patterns, which are electrically insulated from the first transparent electrode pattern and which are formed of a plurality of pad portions extending in a direction crossing the first direction,

(4) An insulating layer for electrically insulating the first transparent electrode pattern and the second transparent electrode pattern

(5) The display device according to any one of (1) to (4), wherein the first transparent electrode pattern and the second transparent electrode pattern are electrically connected to at least one of the first transparent electrode pattern and the second transparent electrode pattern,

The capacitive input device of the present invention is also preferably provided with a transparent protective layer so as to cover all or a part of the elements (1) to (5), more preferably the transparent protective layer is the cured film of the present invention Do.

Example

Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the contents of processing, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following embodiments. Unless specifically stated, &quot; part &quot; and &quot;% &quot; are based on mass.

[Synthesis of polybenzoxazole precursor A-1]

To a three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube was added 73.25 g (0.200 mol) of hexafluoro-2,2-bis (3-amino-4-hydroxyphenyl) propane (Bis- 30.20 g (0.382 mol) of pyridine and 330 g of N-methylpyrrolidone (NMP) were added. This was stirred at room temperature and then cooled to -15 DEG C in a dry ice / methanol bath. To this solution, 27.51 g (0.132 mol) of 1,4-cyclohexyldicarbonyl chloride (trade name: 14-CHDC, manufactured by Nippon Kayaku Chemical Co., Ltd.) and 13.49 and a mixed solution of 0.45 g (0.006 mol) of acetyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 260.5 g of NMP were added dropwise over 2 hours. After completion of the dropwise addition, the obtained mixture was stirred at room temperature for 1 hour.

Subsequently, this reaction solution was cooled to -5 deg. C or lower in an ice / methanol bath, and 1.80 g (0.023 mol) of acetyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise while maintaining the reaction temperature at -0 deg. After completion of the dropwise addition, stirring was continued for 1 hour.

This reaction solution was diluted with 550 g of NMP and charged into a vigorously stirred 4 L deionized / methanol (80/20 volume ratio) mixture. The precipitated white powder was recovered by filtration and washed with deionized water. The polymer was dried at 50 캜 under vacuum for 2 days to obtain Resin A-1a.

25.00 g of resin A-1a, 125 g of NMP, 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Kasei Kogyo KK) and 5.12 g (0.065 mol) of 2,3-dihydrofuran Manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 1.5 hours. To the obtained solution, 0.37 g of triethylamine and 150 g of NMP were added and diluted.

The obtained solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, and the precipitated white powder was recovered by filtration and washed with deionized water. The polymer was dried at 50 DEG C under vacuum for 2 days to obtain polybenzoxazole (PBO) precursor A-1. The weight average molecular weight of the obtained PBO precursor A-1 was 2.9 million (polystyrene reduced value in gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-1 was 30% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-1a ( ¹ H-NMR). The structure of the PBO precursor A-1 is shown below.

<PBO precursor A-1>

[Synthesis of polybenzoxazole precursor A-2]

The resin A-1a prepared in the synthesis of the PBO precursor A-1 was used as the PBO precursor A-2.

The weight average molecular weight of the PBO precursor A-2 used was 2.8 million (polystyrene reduced value in gel permeation chromatography). The PBO precursor A-2 used did not protect the phenolic hydroxyl group, so the protection rate is 0%. The structure of the PBO precursor A-2 is shown below.

<PBO precursor A-2>

[Synthesis of polybenzoxazole precursor A-3]

In the same manner as Resin A-1a except that 5-norbornene-2,3-dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of acetyl chloride in the synthesis of Resin A-1a, A-3a was synthesized.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-3a was used instead of the resin A-1a, to obtain the PBO precursor A-3.

The weight average molecular weight of the obtained PBO precursor A-3 was 2.8 million (polystyrene reduced value in gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-3 was 30% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-3a ( ¹ H-NMR). The structure of the PBO precursor A-3 is shown below.

<PBO precursor A-3>

[Synthesis of polybenzoxazole precursor A-4]

In the synthesis of the resin A-1a, the same method as that of the resin A-1a except that 1,4-cyclohexyldicarbonyl chloride was not used and 0.188 mol of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) To synthesize Resin A-4a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-4a was used instead of the resin A-1a, to obtain the PBO precursor A-4.

The obtained PBO precursor A-4 had a weight average molecular weight of 2.8 million (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-4 was 30% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-4a ( ¹ H-NMR). The structure of the PBO precursor A-4 is shown below.

<PBO precursor A-4>

[Synthesis of polybenzoxazole precursor A-5]

(3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Kagaku Kogyo Co., Ltd.) instead of 1,4-cyclohexyldicarbonyl chloride (trade name: Resin A-5a was synthesized in the same manner as Resin A-1a, except that 0.132 mmols of methyl ethyl ketone (manufactured by Seiko Instruments Inc.) was used.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-5a was used instead of the resin A-1a, to obtain the PBO precursor A-5.

The weight average molecular weight of the obtained PBO precursor A-5 was 2.5 thousands (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-5 was 28% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-5a. The structure of the PBO precursor A-5 is shown below.

<PBO precursor A-5>

[Synthesis of polybenzoxazole precursor A-6]

(3-amino-4-hydroxyphenyl) propane was used in place of 1,4-cyclohexyldicarbonyl chloride (trade name: 14-CHDC, manufactured by Nippon Kayaku Chemical Co., Resin A-6a was synthesized in the same manner as Resin A-1a except that 0.132 mmol of fluorene (produced by Tokyo Chemical Industry Co., Ltd.) was used.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-6a was used instead of the resin A-1a, to obtain the PBO precursor A-6.

The weight average molecular weight of the obtained PBO precursor A-6 was 2.4 thousand (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-6 was 26% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-6a. The structure of the PBO precursor A-6 is shown below.

<PBO precursor A-6>

[Synthesis of polybenzoxazole precursor A-7]

In the synthesis of Resin A-1a, 3,3'-dihydroxybenzidine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used in place of 1,4-cyclohexyldicarbonyl chloride (trade name: 14-CHDC, Resin A-7a was synthesized in the same manner as Resin A-1a except that 0.132 mol of Compound A-1a was used.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-7a was used instead of the resin A-1a, to obtain the PBO precursor A-7.

The weight average molecular weight of the obtained PBO precursor A-7 was 23,000 (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-7 was 27% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-7a ( ¹ H-NMR). The structure of the PBO precursor A-7 is shown below.

<PBO precursor A-7>

[Synthesis of polybenzoxazole precursor A-8]

In Synthesis of Resin A-1a, 0.094 mol of 1,4-cyclohexyldicarbonyl chloride (trade name: 14-CHDC, manufactured by Nippon Kayaku Co.) was used, and sebacoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Resin A-8a was synthesized in the same manner as Resin A-1a except that 0.094 mol was used.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-8a was used instead of the resin A-1a, to obtain the PBO precursor A-8.

The weight average molecular weight of the obtained PBO precursor A-8 was 2.8 million (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-8 was 25% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-8a. The structure of the PBO precursor A-8 is shown below.

<PBO precursor A-8>

[Synthesis of polybenzoxazole precursor A-9]

A resin A-8a was synthesized in the same manner as in Resin A-8a except that 0.094 mol of soroyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of sebacoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) Resin A-9a was synthesized.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-9a was used instead of the resin A-1a, to obtain the PBO precursor A-9.

The weight average molecular weight of the obtained PBO precursor A-9 was 2.8 million (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-9 was 31% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-9a ( ¹ H-NMR). The structure of the PBO precursor A-9 is shown below.

<PBO precursor A-9>

[Synthesis of polybenzoxazole precursor A-10]

The procedure of resin A-1a was repeated except that 0.056 mol of soroyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used in place of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) Resin A-10a was synthesized.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-10a was used instead of the resin A-1a, to obtain the PBO precursor A-10.

The weight average molecular weight of the obtained PBO precursor A-10 was 2.8 million (polystyrene reduced value by gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-10 was 29% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-10a ( ¹ H-NMR). The structure of the PBO precursor A-10 is shown below.

<PBO precursor A-10>

[Synthesis of polybenzoxazole precursor A-11]

In the same manner as Resin A-1a, except that 0.0560 mol of adipoyl chloride (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of sebacoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) A-11a was synthesized.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-11a was used instead of the resin A-1a, to obtain the PBO precursor A-11.

The obtained PBO precursor A-11 had a weight average molecular weight of 2.8 million (polystyrene reduced value by gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-11 was 30% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-11a ( ¹ H-NMR). The structure of the PBO precursor A-11 is shown below.

<PBO precursor A-11>

[Synthesis of polybenzoxazole precursor A-12]

In the synthesis of Resin A-1a, except that 0.178 mol of 1,4-cyclohexyldicarbonyl chloride (trade name: 14-CHDC, manufactured by Nippon Kayaku Chemical Co., Ltd.) was used instead of sebacoyl chloride, Resin A-12a was synthesized by the same method as in 1a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-12a was used instead of the resin A-1a, to obtain the PBO precursor A-12.

The weight average molecular weight of the obtained PBO precursor A-12 was 2.8 million (polystyrene reduced value by gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-12 was 27% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-12a ( ¹ H-NMR). The structure of the PBO precursor A-12 is shown below.

<PBO precursor A-12>

[Synthesis of polybenzoxazole precursor A-13]

124 g of the resin A-9a obtained in the synthesis of the PBO precursor A-9, 125 g of NMP, 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Kasei Kogyo KK) and 5.47 g -Dihydro-2H-pyran (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 1.5 hours. To the obtained solution, 0.37 g of triethylamine and 150 g of NMP were added and diluted.

The obtained solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, and the precipitated white powder was recovered by filtration and washed with deionized water. The polymer was dried at 50 DEG C under vacuum for 2 days to obtain PBO precursor A-13.

The PBO precursor A-13 thus obtained had a weight average molecular weight of 2.8 million (polystyrene reduced value by gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-13 was 27% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-9a ( ¹ H-NMR). The structure of the PBO precursor A-13 is shown below.

<PBO precursor A-13>

[Synthesis of polybenzoxazole precursor A-14]

In the synthesis of Resin A-1a, 4,4'-oxybis (benzoyl chloride) (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of sebacoyl chloride and 1,4-cyclohexyldicarbonyl chloride Resin A-14a was synthesized in the same manner as Resin A-1a except that 0.188 mol was used.

Next, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-14a was used instead of the resin A-1a, to obtain the PBO precursor A-14.

The obtained PBO precursor A-14 had a weight average molecular weight of 2.8 million (polystyrene reduced value by gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.2.

The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-14 was 26% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-14a. The structure of the PBO precursor A-14 is shown below.

<PBO precursor A-14>

[Synthesis of polybenzoxazole precursor A-15]

In the synthesis of the resin A-1a, except that sebacoolyl chloride and 1,4-cyclohexyldicarbonyl chloride were not used and 0.188 mol of isophthaloyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used, the resin A Resin A-15a was synthesized by the same method as that of -1a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-15a was used in place of the resin A-1a to obtain the PBO precursor A-15.

The PBO precursor A-15 thus obtained had a weight average molecular weight of 2.7 million (polystyrene reduced value by gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0.

The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-15 was 25% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-15a. The structure of the PBO precursor A-15 is shown below.

<PBO precursor A-15>

[Synthesis of polybenzoxazole precursor A-16]

In the synthesis of Resin A-1a, 0.094 mmol of 4,4'-oxybis (benzoyl chloride) was used without using sebacoyl chloride and 1,4-cyclohexyldicarbonyl chloride, Resin A-16a was synthesized in the same manner as Resin A-1a except that 0.094 mmol of talloyl chloride was used.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-16a was used instead of the resin A-1a, to obtain the PBO precursor A-16.

The PBO precursor A-16 thus obtained had a weight average molecular weight of 2.5 million (polystyrene reduced value in gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0.

The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-16 was 25% ( ¹ H-NMR) relative to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-16a. The structure of the PBO precursor A-16 is shown below.

&Lt; PBO precursor A-16 >

[Synthesis of polybenzoxazole precursor A-17]

124 g of the resin A-16a obtained in the synthesis of the PBO precursor A-16, 125 g of NMP, 0.43 g (1.85 mmol) of camphorsulfonic acid (manufactured by Tokyo Kasei Kogyo KK) and 4.69 g (0.065 mol) of ethyl vinyl ether (Manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 1.5 hours. To the obtained solution, 0.37 g of triethylamine and 150 g of NMP were added and diluted.

The obtained solution was poured into a vigorously stirred 2 L deionized water / methanol (80/20 volume ratio) mixture, and the precipitated white powder was recovered by filtration and washed with deionized water. The polymer was dried at 50 DEG C under vacuum for 2 days to obtain PBO precursor A-17.

The obtained PBO precursor A-17 had a weight average molecular weight of 2.5 thousands (polystyrene reduced value in gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0. The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-17 was 28% ( ¹ H-NMR) relative to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-16a. The structure of the PBO precursor A-17 is shown below.

<PBO precursor A-17>

[Synthesis of polybenzoxazole precursor A-18]

Resin A-18a was synthesized in the same manner as Resin A-16a, except that 5-norbornene-2,3-dicarboxylic acid anhydride was used in place of acetyl chloride in Synthesis of Resin A-16a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-17 except that the resin A-18a was used in place of the resin A-16a to obtain the PBO precursor A-18.

The obtained PBO precursor A-18 had a weight average molecular weight of 2.6 million (polystyrene reduced value in gel permeation chromatography) and a weight average molecular weight / number average molecular weight of 2.0.

The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-18 was 27% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-18a ( ¹ H-NMR). The structure of the PBO precursor A-18 is shown below.

<PBO precursor A-18>

[Synthesis of polybenzoxazole precursor A-19]

A PBO precursor A-19 was synthesized in the same manner as the PBO precursor A-17 except that the resin A-1a was used in place of the resin A-16a in the synthesis of the PBO precursor A-17.

The weight average molecular weight of the obtained PBO precursor A-19 was 2.5 thousands (polystyrene reduced value in gel permeation chromatography). The weight average molecular weight / number average molecular weight was 2.0.

The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-19 was 26% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-1a ( ¹ H-NMR). The structure of the PBO precursor A-19 is shown below.

<PBO precursor A-19>

[Synthesis of polybenzoxazole precursor A-20]

Resin A-20a was synthesized in the same manner as Resin A-1a, except that propionyl chloride (Daicel) was used instead of acetyl chloride in the synthesis of Resin A-1a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-20a was used instead of the resin A-1a, to obtain the PBO precursor A-20.

The weight average molecular weight of the obtained PBO precursor A-20 was 2.7 thousand (polystyrene reduced value in gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-20 was 29% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-20a ( ¹ H-NMR). The structure of the PBO precursor A-20 is shown below.

<PBO precursor A-20>

[Synthesis of polybenzoxazole precursor A-21]

A PBO precursor A-21 was synthesized in the same manner as the PBO precursor A-17, except that the resin A-20a was used instead of the resin A-16a in the synthesis of the PBO precursor A-17.

The weight average molecular weight of the obtained PBO precursor A-21 was 2.9 million (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-21 was 28% ( ¹ H-NMR) with respect to the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-20a. The structure of the PBO precursor A-21 is shown below.

<PBO precursor A-21>

[Synthesis of polybenzoxazole precursor A-22]

Resin A-22a was synthesized in the same manner as Resin A-16a except that propionyl chloride (Daicel) was used instead of acetyl chloride in the synthesis of Resin A-16a.

Subsequently, the phenolic hydroxyl group was protected in the same manner as in the case of the PBO precursor A-1 except that the resin A-22a was used in place of the resin A-16a to obtain the PBO precursor A-22.

The weight average molecular weight of the obtained PBO precursor A-22 was 2.7 million (polystyrene reduced value in gel permeation chromatography). The protective rate of the phenolic hydroxyl group of the obtained PBO precursor A-22 was 29% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-22a ( ¹ H-NMR). The structure of the PBO precursor A-22 is shown below.

<PBO precursor A-22>

[Synthesis of polybenzoxazole precursor A-23]

A PBO precursor A-23 was synthesized in the same manner as the PBO precursor A-17 except that the resin A-22a was used instead of the resin A-16a in the synthesis of the PBO precursor A-17.

The weight average molecular weight of the obtained PBO precursor A-23 was 2.7 thousand (polystyrene reduced value in gel permeation chromatography). The protection rate of the phenolic hydroxyl group of the obtained PBO precursor A-23 was 30% based on the amount (molar amount) of the total phenolic hydroxyl groups of the resin A-22a ( ¹ H-NMR). The structure of the PBO precursor A-23 is shown below.

<PBO precursor A-23>

[Photo acid generator]

As the photoacid generator, the following compounds were used.

<B-1>

(PAG-103, a photo acid generator that generates an acid having a pKa of 3 or less, which is a product of BASF)

<B-2>

(PAI-101 manufactured by Midori Kagaku Co., Ltd., a photo-acid generator that generates an acid having a pKa of 3 or less), and Me represents a methyl group.

<B-3>

(The photoacid generator which generates an acid having a pKa of 3 or less, the synthesis example will be described later).

<B-4>

A structure shown below (a photo acid generator that generates an acid having a pKa of 3 or less, a synthesis example will be described later), and Ts represents a tosyl group.

<B-5>

(A photo acid generator that generates an acid having a pKa of 3 or less, a synthesis example will be described later)

<B-6>

A structure shown below (GSID-26-1, a triarylsulfonium salt (made by BASF), a photoacid generator that generates an acid having a pKa of 3 or less]

<B-7>

TAS-200 (naphthoquinone diazide, manufactured by Toyoka Seiko)

〔solvent〕

As the solvent, the following solvents were used.

C-1: High-Solv EDM (manufactured by Tohoku Kagaku)

C-2: Propylene glycol monomethyl ether acetate (PGMEA, die cell)

C-3:? -Butyrolactone

[Heat Base Generator]

As the photoacid generator, the following compounds were used.

<S-1>

The structure shown below

(Synthesis of S-1)

200 g (1.74 mol) of trans-4-aminocyclohexanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) and 810 g of methanol were added to a three-necked flask equipped with a thermometer, a stirrer and a nitrogen inlet tube. Lt; / RTI &gt; While this solution was stirred, 379.0 g (1.74 mol) of di-tert-butyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was added dropwise. After completion of the dropwise addition, the resulting mixture was stirred at 40 ° C for 1 hour, and then concentrated under reduced pressure at 50 ° C for 1 hour to obtain 360g of objective S-1.

<S-2>

The structure shown below

(Synthesis of S-2)

S-1 was prepared in the same manner as S-1 except that 1.74 mols of 3-aminopropyltriethoxysilane (manufactured by Tokyo Kasei Kogyo K.K.) was used in place of trans-4-aminocyclohexanol in the synthesis of S- 2 was synthesized.

<S-3>

The following structure [1- (tert-butoxycarbonyl) -4-hydroxypiperidine, Tokyo Kasei Kogyo Co., Ltd.]

<S-4>

The structure shown below (trans-4-aminocyclohexanol, manufactured by Tokyo Chemical Industry Co., Ltd.)

<S-5>

(3-amino-1- (tert-butoxycarbonyl) pyrrolidine, Tokyo Kasei Kogyo Co., Ltd.)

<S-6>

The structure shown below

(Synthesis of S-6)

Except that 1.74 mol of 1,4-butanediol bis (3-aminopropyl) ether (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used in place of trans-4-aminocyclohexanol in the synthesis of S-1 S-6 was synthesized by the method described above.

<S-7>

The structure shown below

(Synthesis of S-7)

S-1 was obtained in the synthesis of S-1 except that 1.74 mols of 4-hydroxy-D - (-) - 2-phenylglycine (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of trans- S-7 was synthesized by the same method.

<S-8>

The structure shown below [N- (tert-butoxycarbonyl) glycine, Tokyo Kasei Kogyo Co., Ltd.]

<S-9>

The structure shown below

(Synthesis of S-9)

S-9 was synthesized by the same method as in S-1 except that 1.74 mol of di-tert-amyl dicarbonate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of di-tert- Synthesized.

<S-10>

The structure shown below

(Synthesis of S-10)

Except that 1.74 mol of 2- (2-aminoethoxy) ethanol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used instead of trans-4-aminocyclohexanol in the synthesis of S-1 S-10 was synthesized.

<S-11>

The following structure [4- (tert-amyloxycarbonylamino) cyclohexanecarboxylic acid, Tokyo Kasei Kogyo Co., Ltd.]

[Other components]

<Alkoxysilane compound>

J-1: 3-glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical Co., Ltd.)

J-2: 1,2-bis (triethoxysilyl) ethane (KBE-3026, Shin-Etsu Chemical)

<Increase / decrease>

J-3: 9,10-dibutoxyanthracene (Anthracure UVS-1331, manufactured by Kawasaki Chemical Industry Co., Ltd.)

<Surfactant>

W-1: Fluorine-based surfactant (FTX-218, made by Neos)

W-2: Perfluoroalkyl group-containing nonionic surfactant (F-554, manufactured by DIC) represented by the following structural formula:

&Lt; Synthesis method of B-3 >

Aluminum chloride (10.6 g) and 2-chloropropionyl chloride (10.1 g) were added to a stirring solution of 2-naphthol (10 g) and chlorobenzene (30 ml), and the mixture was heated to 40 ° C and reacted for 2 hours. Under ice cooling, 4N HCl aqueous solution (60 mL) was added dropwise to the reaction solution, and ethyl acetate (50 mL) was added to separate the layers. Potassium carbonate (19.2 g) was added to the organic layer, and the mixture was reacted at 40 占 폚 for 1 hour. 2N HCl aqueous solution (60 mL) was added to separate the layers. The organic layer was concentrated, and the crystals were reslurried with diisopropyl ether Filtered and dried to obtain a ketone compound (6.5 g).

Acetic acid (7.3 g) and a 50 mass% hydroxylamine aqueous solution (8.0 g) were added to the resulting solution of the ketone compound (3.0 g) and methanol (30 ml), and the mixture was heated to reflux. After allowing to stand still, water (50 mL) was added to the precipitated crystals, and the precipitated crystals were filtered, washed with cold methanol, and dried to obtain an oxime compound (2.4 g).

The resulting oxime compound (1.8 g) was dissolved in acetone (20 mL), triethylamine (1.5 g) and p-toluenesulfonyl chloride (2.4 g) were added under ice-cooling, and the mixture was allowed to react at room temperature for 1 hour. Water (50 mL) was added to the reaction solution, and the precipitated crystals were filtered out and then slurry was made into a slurry with methanol (20 mL), followed by filtration and drying to obtain a compound (the above-described structure) (2.3 g) of B-3.

In addition, ¹ H-NMR spectrum of _{B-3 (300㎒, CDCl 3} ) is δ = 8.3 (d, 1H) , 8.0 (d, 2H), 7.9 (d, 1H), 7.8 (d, 1H), 7.6 (d, 1H), 7.4 (dd, 1H), 7.3 (d, 2H), 7.1 (d, 1H), 5.6 (q,

<Synthesis method of B-4>

4.0 g of 1-amino-2-naphthol hydrochloride (manufactured by Tokyo Kasei Kogyo KK) was suspended in 16 g of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.), 3.4 g of sodium hydrogencarbonate (Wako Pure Chemical Industries) 4.9 g of methyl 4,4-dimethyl-3-oxovalerate (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the mixture was heated at 120 캜 for 2 hours in a nitrogen atmosphere. After the mixture was allowed to cool, the reaction mixture was partitioned between water and ethyl acetate, and the organic phase was dried over magnesium sulfate, filtered, and concentrated to give crude B-1-2A. The crude B-1-2A was purified by silica gel column chromatography to obtain 1.7 g of intermediate C-1-2A.

C-1-2A (1.7 g) and p-xylene (6 mL) were mixed, and 0.23 g of p-toluenesulfonic acid monohydrate (Wako Pure Chemical Industries, Ltd.) was added and heated at 140 占 폚 for 2 hours. After the mixture was allowed to cool, the reaction mixture was partitioned by adding water and ethyl acetate, and the organic phase was dried over magnesium sulfate, followed by filtration and concentration to obtain crude C-1-2B.

(THF) (2 mL) and the crude C-1-2B were mixed, 6.0 mL of a 2M hydrochloric acid / THF solution was added dropwise under ice-cooling, and then isopentyl nitrite (Wako Pure Chemical Industries, Ltd.) (0.84 g) And stirred for 2 hours. Water and ethyl acetate were added to the reaction mixture to separate the layers. The organic layer was washed with water, dried over magnesium sulfate, filtered, and concentrated to obtain Intermediate C-1-2c.

The whole amount of intermediate C-1-2C was mixed with acetone (10 mL), and then 1.2 g of triethylamine (Wako Pure Chemical Industries, Ltd.) and 1.4 g of p-toluenesulfonyl chloride (manufactured by Tokyo Kasei) After the addition, the mixture was heated to room temperature and stirred for 1 hour. Water and ethyl acetate were added to the resulting reaction mixture to separate the layers. The organic layer was dried over magnesium sulfate, filtered, and concentrated to give crude C-4. The crude C-4 was reslurried in cold methanol, filtered and dried to obtain B-4 (1.2 g).

¹ H-NMR spectrum (300 MHz, CDCl ₃ ) of B-4 was 隆 = 8.5-8.4 (m, 1H), 8.0-7.9 (m, 4H), 7.7-7.6 (m, 2H), 7.6-7.5 m, 1H), 7.4 (d, 2H), 2.4 (s, 3H), 1.4 (s, 9H).

<Synthesis method of B-5>

Into a separable flask equipped with a stirrer and a thermometer, 33.6 g of N-hydroxynaphthalimide sodium salt, 0.72 g of 4-dimethylaminopyridine and 300 ml of tetrahydrofuran were added, and the mixture was stirred and dissolved at a room temperature of 25 ° C. Subsequently, 42 g of (+) 10-camphorsulfonyl chloride was added and stirred for 3 hours. Then, 15 g of triethylamine was added, and the mixture was stirred at room temperature for 10 hours. Subsequently, the reaction solution was put into 300 milliliters of distilled water, and the precipitated precipitate was filtered. This precipitation was repeated several times using acetone and hexane to obtain 12 g of N-camphorsulfonyloxy-1,8-naphthalimide.

[Examples 1 to 48 and Comparative Examples 1 to 6]

Each of the above-mentioned components was mixed in the kind and amount added as shown in the following table and filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 탆 to obtain respective photosensitive resin compositions.

For Example 44, evaluation was carried out in the same manner as in the other Examples except that each photosensitive resin composition was slit-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)) with a slit nozzle coater of Toray Engineering Co. I did.

〔evaluation〕

Each of the prepared photosensitive resin compositions was evaluated for heat resistance transparency, patterning properties and pattern shapes according to the following methods and standards. The results are shown in the following table.

<Heat resistance transparency>

Each of the photosensitive resin compositions was spin-coated on a glass substrate (Corning 1737, 0.7 mm thick (Corning)), and then prebaked on a hot plate at 90 deg. C / 120 seconds to volatilize the solvent to obtain a photosensitive resin composition Layer.

Thereafter, this substrate was heated in an oven at 300 DEG C / 60 minutes under nitrogen to obtain a cured film.

The cured film was further heated in an oven under nitrogen at 300 ° C / 60 minutes, and then measured for transmittance at a wavelength of 400 nm using a transmittance meter (MCPD-3000, manufactured by Otsuka Denshi) and evaluated according to the following criteria. The higher the transmittance, the higher the heat resistance and transparency, and the evaluation 1 and 2 are in the practical range.

1: 95% or more

2: 93% or more

3: 90% or more

4: 85% or more

<Patterning property>

Each of the photosensitive resin compositions was spin-coated on a glass substrate (EAGLE XG, 0.7 mm thick (Corning)) exposed for 30 seconds under a steam of hexamethyldisilazane (HMDS) Baked and the solvent was volatilized to form a film of a photosensitive resin composition layer having a film thickness of 4.0 m.

Subsequently, the formed film was exposed through a mask having a hole pattern of 10 mu m formed using MPA 5500CF (high-pressure mercury lamp) manufactured by Canon. Then, the exposed film was developed with an alkali developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) at 23 DEG C for 60 seconds, and rinsed with ultrapure water for 20 seconds. The exposure amount when the hole diameter equivalent to the mask is resolved by these operations is referred to as an optimal i-line exposure amount Eopt.

Further, the film thus formed was exposed at the optimum i-line exposure through a mask having a pattern of holes having a diameter of 4, 6, and 8 탆. Then, the exposed film was developed with an alkali developing solution (2.38% aqueous solution of tetramethylammonium hydroxide) at 23 DEG C for 60 seconds, and rinsed with ultrapure water for 20 seconds.

The formed pattern was observed with a scanning electron microscope and the actual hole diameter was measured. The actual hole diameter is defined by the size of the bottom (bottom) of the film.

Then, the ratio of the size difference between the hole diameter of 4 mu m and the actual hole pattern diameter corresponding thereto was calculated.

Similarly, the ratio of the size difference between the hole diameter of 6 mu m and the actual hole pattern diameter corresponding thereto was calculated.

Similarly, the ratio of the size difference between the hole diameter of 8 mu m and the actual hole pattern diameter corresponding thereto was calculated.

The calculated ratios were evaluated based on the following criteria. The smaller the difference between the actual hole diameter and the mask diameter is, the better the patterning property is, and the panel design becomes easier. Evaluation 1, 2 and 3 are practical ranges.

1: The average of the ratio of size difference of each diameter of 4, 6, 8 μm is within 10%

2: The average of the ratio of the sizes of the diameters of 4, 6 and 8 μm is more than 10% and not more than 20%

3: The average of the ratio of the sizes of the diameters of 4, 6 and 8 μm is more than 20% and not more than 30%

4: The average of the ratio of the sizes of the diameters of 4, 4, 6 and 8 μm is more than 30% and not more than 40%

5: The average of the ratio of the size difference of each diameter of 4, 6, and 8 ㎛ exceeds 40%

<Pattern shape>

In the above patterning evaluation, the substrate having the hole pattern formed on the film was heated in an oven under nitrogen at 300 DEG C for 60 minutes by using a mask having a hole diameter of 6 mu m.

The substrate after heating was cut and the cross-sectional shape of the hole pattern was observed from the horizontal direction with a scanning electron microscope. The angle (taper angle) between the bottom (bottom) and top (top) of the hole pattern was measured.

The measured angles were evaluated based on the following criteria. The higher the taper angle, the easier the design of the finer panel, and the evaluation 1 and 2 are in the practical range.

1: 70-80

2: 60-70 °

3: 50-60

4: 50 ° or less

As is evident from the results shown in the above table, when a thermal base generating agent not corresponding to the compound represented by the formula (X) was used, it was found that either the heat-resistant transparency or the patterning property of the obtained cured film was lowered (Comparative Examples 1, 3 and 6). In addition, Comparative Examples 1 and 3 are examples using the heat nucleating agent exemplified in Patent Document 1 (Japanese Patent Laid-Open Publication No. 2013-152381).

In addition, when the polybenzoxazole precursor A-2 which does not protect the phenolic hydroxyl group was used, it was found that either the heat-resistant transparency or the patterning property of the obtained cured film was lowered (Comparative Examples 2 and 4). It was also found that the pattern shapes of Comparative Examples 2 and 4 were all lowered.

Further, when a photoacid generator that does not generate an acid having a pKa of 3 or less was used, the heat-resistant transparency was inferior and the pattern shape was also found to be poor (Comparative Example 5).

On the other hand, a polybenzoxazole precursor in which at least a part of the phenolic hydroxyl group is protected with an acid-decomposable group, a photoacid generator that generates an acid with a pKa of 3 or less, a thermal base generator represented by the formula (X) It was found that both the heat-resistant transparency and the patterning property of the obtained cured film were good and the formed pattern was good (Examples 1 to 48).

Further, from the comparison of Examples 1 to 8, it was found that the heat-resistant base resin tends to have better heat-resistant transparency and patternability if R ⁴ in the formula (X) contains a hydroxyl group.

From the comparison of Examples 1, 13 and 21, it is also confirmed that the polybenzoxazole precursor is a mixture of the repeating unit A in which Y in the formula (1) is a cyclic aliphatic group having 3 to 15 carbon atoms and the repeating unit A in the formula (1) It has been found that when Y has a repeating unit B represented by a linear or branched aliphatic group having 4 to 20 carbon atoms, heat resistance transparency, patterning property and pattern shape tend to be better.

[Example 101]

In the liquid crystal display device shown in Fig. 1 of Japanese Patent Laid-Open No. 2007-328210, the organic insulating film PAS was formed by the following method to obtain a liquid crystal display device.

First, according to Japanese Patent Laid-Open No. 2007-328210, an array substrate formed up to just before the organic insulating film PAS of the liquid crystal display device shown in Fig. 1 of Japanese Patent Application Laid-Open No. 2007-328210 was produced.

Subsequently, the substrate was exposed for 30 seconds under HMDS vapor, and then the photosensitive resin composition of Example 1 was coated with a slit, followed by prebaking on a hot plate at 90 DEG C for 2 minutes to volatilize the solvent to obtain a photosensitive resin To form a composition layer.

Subsequently, the resulting photosensitive resin composition layer was exposed to an optimum exposure amount through a mask having a hole pattern of 6 mu m phi, using MPA 7800CF manufactured by Canon Inc., and heated on a hot plate at 70 DEG C / 90 seconds.

Then, the exposed resin composition layer was developed with an alkaline developer (0.6% tetramethylammonium hydroxide aqueous solution) and rinsed with ultrapure water. Subsequently, the entire surface of the substrate was exposed using an ultra-high pressure mercury lamp so that the accumulated irradiation dose was 320 mJ / cm 2 (energy intensity: 20 mW / cm 2, measured by i-line), and then the substrate was heated in an oven at 320 ° C. for 60 minutes An organic insulating film PAS was obtained.

Thereafter, a liquid crystal display device was obtained according to Japanese Patent Application Laid-Open No. 2007-328210. Further, in this embodiment, since a material having high heat resistance is used for the PAS, the interlayer insulating film IN3 is formed at a temperature equal to that of the interlayer insulating film IN2. As a result, IN3 could be made into a dense film.

As a result of applying a driving voltage to the obtained liquid crystal display device, it was found that the liquid crystal display device exhibited very good display characteristics and was highly reliable.

[Examples 102 to 150]

A liquid crystal display device was prepared in the same manner as in Example 101 except that the compositions of Example 1 were replaced with the compositions of Examples 2 to 50, respectively. It is a liquid crystal display device having good display characteristics and high reliability.

Claims (22)

A polybenzoxazole precursor, a photoacid generator that generates an acid having a pKa of 3 or less, a thermal base generator, and a solvent,
Wherein the polybenzoxazole precursor is a polybenzoxazole precursor wherein at least a part of the phenolic hydroxyl group is protected with an acid decomposable group,
Wherein the thermobilizer is a compound represented by the following formula (X).

In the formula (X), m represents an integer of 1 to 4, R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 5 carbon atoms, and R ⁴ may have a hetero atom m represents an organic group. When m is 2 to 4, plural R ¹ , R ² and R ³ may be the same or different. The method according to claim 1,
Wherein the polybenzoxazole precursor has a repeating unit represented by the following formula (1).

Wherein X represents a tetravalent organic group containing an aromatic ring, Y represents a divalent organic group, and each R independently represents a hydrogen atom, an alkyl group, a structure represented by the following formula (2) Or -CORc, and at least one R represents a structure represented by the following formula (2). Rc represents an alkyl group or an aryl group.

Wherein R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group, and R ¹⁰³ represents an alkyl group. However, R ¹⁰¹ and R ¹⁰² are all be except when the hydrogen atoms and the R ¹⁰¹ or R ¹⁰² and R ¹⁰³ may be connected to form a cyclic ether. 3. The method according to claim 1 or 2,
Wherein the content of the thermobilizer is 0.1 to 30 parts by mass relative to 100 parts by mass of the polybenzoxazole precursor. 3. The method according to claim 1 or 2,
R ⁴ in the formula (X) includes at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkyleneoxy group and an alkoxysilyl group. 3. The method according to claim 1 or 2,
Wherein m in the formula (X) is 2 and R ⁴ in the formula (X) is a divalent aliphatic hydrocarbon group which may have a hetero atom. 5. The method of claim 4,
M is 1 in the formula (X). 3. The method of claim 2,
The polybenzoxazole precursor is a mixture of a repeating unit A represented by the formula (1) wherein Y is a cyclic aliphatic group having 3 to 15 carbon atoms and a repeating unit A represented by the formula (1) wherein Y is a straight or branched And a repeating unit B represented by an aliphatic group. 3. The method of claim 2,
Wherein the polybenzoxazole precursor contains at least an aromatic group having 6 to 20 carbon atoms in the formula (1). 8. The method of claim 7,
The polybenzoxazole precursor contains the repeating unit A and the repeating unit B in a total amount of 70 mol% or more of the total repeating units in the polybenzoxazole precursor, and the repeating unit A and the repeating unit B Is in a molar ratio of 9: 1 to 3: 7. 3. The method according to claim 1 or 2,
Wherein the polybenzoxazole precursor is protected with the acid-decomposable group by 10 to 60% of the phenolic hydroxyl groups of all the repeating units of the polybenzoxazole precursor. A step of applying the photosensitive resin composition according to claim 1 or 2 to a substrate;
Removing the solvent from the applied photosensitive resin composition;
A step of exposing the photosensitive resin composition from which the solvent has been removed to actinic radiation;
A step of developing the exposed photosensitive resin composition with a developer,
And a step of thermally curing the developed photosensitive resin composition to obtain a cured film. 12. The method of claim 11,
And a step of exposing the developed photosensitive resin composition after the developing step and before the heat curing step. A cured film obtained by curing the photosensitive resin composition according to claim 1. 14. The method of claim 13,
A curing film which is an interlayer insulating film. A liquid crystal display device having the cured film according to claim 13 or 14. An organic electro luminescence display device having the cured film according to claim 13 or 14. A touch panel having the cured film according to claim 13 or 14. The method of claim 3,
R ⁴ in the formula (X) includes at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an alkyleneoxy group and an alkoxysilyl group. The method of claim 3,
The polybenzoxazole precursor is a mixture of a repeating unit A represented by the formula (1) wherein Y is a cyclic aliphatic group having 3 to 15 carbon atoms and a repeating unit A represented by the formula (1) wherein Y is a straight or branched And a repeating unit B represented by an aliphatic group. 5. The method of claim 4,
The polybenzoxazole precursor is a mixture of a repeating unit A represented by the formula (1) wherein Y is a cyclic aliphatic group having 3 to 15 carbon atoms and a repeating unit A represented by the formula (1) wherein Y is a straight or branched And a repeating unit B represented by an aliphatic group. 6. The method of claim 5,
The polybenzoxazole precursor is a mixture of a repeating unit A represented by the formula (1) wherein Y is a cyclic aliphatic group having 3 to 15 carbon atoms and a repeating unit A represented by the formula (1) wherein Y is a straight or branched And a repeating unit B represented by an aliphatic group. The method according to claim 6,
The polybenzoxazole precursor is a mixture of a repeating unit A represented by the formula (1) wherein Y is a cyclic aliphatic group having 3 to 15 carbon atoms and a repeating unit A represented by the formula (1) wherein Y is a straight or branched And a repeating unit B represented by an aliphatic group.