JP2015004000A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a positive photosensitive resin composition suitable for formation of an insulator layer, light-shielding separator or black matrix used in an organic light-emitting device or a display element; and a compound which has a function of reducing transmittance of a cured film in the visible light region while maintaining transmittance of a resin film before curing.SOLUTION: A resin composition contains (a) an amide acid represented by the general formula (1), and (b) a polyimide, polybenzoxazole, polyimide precursor or polybenzoxazole precursor. (In the general formula (1), Rrepresents a hydrogen atom or a C1-20 alkyl group; n is an integer between 1 and 3; and o is an integer between 1 and 4.)

Description

  The present invention relates to a resin composition using a compound that is colored by heat treatment. In more detail, a surface protective film and an interlayer insulating film of a semiconductor element, an insulating layer of an organic electroluminescence (hereinafter referred to as EL) element, a thin film transistor for driving a display device using the organic EL element (Thin Film Transistor). : Hereafter referred to as TFT) Suitable for applications such as substrate planarization film, circuit board wiring protection insulation film, solid-state image sensor on-chip microlens, various displays and solid-state image sensor planarization film, circuit board solder resist The present invention relates to a resin composition.

  A cured film obtained by curing a composition containing polyimide or benzoxazole is widely used for an insulating film, a protective film, a planarizing film, or the like of a semiconductor element or a display device. Among them, in a display device, for example, in applications such as an insulating layer of an organic EL display and a black matrix of a liquid crystal display, it is required to lower the transmittance of the cured film in order to improve contrast. In addition, in order to prevent malfunction due to light entering the driving TFT of the display element, leakage current, etc., the transmittance is also applied to the insulating layer of the organic EL display and the planarizing film provided on the TFT substrate of the organic EL display. Lowering is required.

  In the cured film, as a technique for reducing the transmittance in the visible light region larger than 400 nm, for example, as seen in black matrix materials for liquid crystal displays and RGB paste materials, carbon black, organic / inorganic pigments, The method of adding coloring agents, such as dye, is mentioned. Since the resin composition containing these colorants has absorption in an exposure wavelength region of 400 to 450 nm, it is difficult to use as a positive photosensitive resin composition that sensitizes light by reaching the bottom of the film, The use as a negative photosensitive resin composition which photocures a film | membrane from the surface is common.

  Examples of techniques for reducing the transmittance of a cured film in a positive photosensitive resin composition include, for example, an alkali-soluble resin, a quinonediazide compound, and a positive radiation resin composition containing a coloring composition such as a leuco dye and a developer. Product (for example, see Patent Document 1), photosensitive resin (see, for example, Patent Document 2) in which a heat-sensitive material that becomes black when heated is added in advance, an alkali-soluble resin, a quinonediazide compound, color by heating, A positive photosensitive resin composition comprising a thermochromic compound having an absorption maximum at 350 nm to 700 nm and a compound having no absorption at 350 nm to less than 500 nm and having an absorption maximum at 500 nm to 750 nm (see, for example, Patent Document 3) Before polyimide, polybenzoxazole, polyimide precursor or polybenzoxazole A resin composition characterized by containing a body, dihydroxynaphthalene, and a thermal crosslinking agent having a specific structure, and maintaining the transmittance of the resin film before curing while reducing the transmittance in the visible light region of the cured film (For example, see Patent Document 4). These are techniques for reducing the transmittance of a cured film while maintaining a high transmittance in the exposure wavelength region of the resin film before curing by using a color developing compound that develops color by energy such as heat. Therefore, both positive and negative photosensitivity can be imparted to the resin composition, and versatility is high. However, these techniques have not yet been sufficient for reducing the transmittance of the cured film.

JP 2008-122501 A JP-A-10-170715 JP 2004-326094 A WO2010 / 87238

  An object of this invention is to provide the resin composition which can further reduce the transmittance | permeability in the visible light area | region of a cured film, maintaining the transmittance | permeability of the resin film before hardening.

The present invention is as shown in the following 1 to 6.
1. A resin composition comprising (a) an amic acid represented by the general formula (1) and (b) polyimide, polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor.

(In the general formula (1), R ¹ is a 1-3 valent hydrocarbon group having 1 to 50 carbon atoms, -CH _2- of a 1-3 valent hydrocarbon group having 1 to 50 carbon atoms is -CO-, A group substituted by —NH—, —NHCO—, —O—, —S—, —SO ₂ —, —Si— or —Si (CH ₃ ) ₂ —; A group in which a hydrogen atom of a hydrocarbon group is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom or —COOR ¹ ′, or a 1 to 3 valent group having 1 to 50 carbon atoms The hydrogen atom of the group in which —CH ₂ — of the hydrocarbon group is substituted by —NH—, —NHCO—, —O— or —S— is a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom , is substituted by a chlorine atom or a -COOR ¹ ' Indicating the group .R ¹ 'represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms .R ² is a hydrogen atom or .n represents an alkyl group having 1 to 20 carbon atoms is an integer of 1 to 3, o is Represents an integer of 1 to 4.)
2. 2. The resin composition as described in 1 above, wherein R ^{1 of the} amic acid represented by the general formula (1) has at least one aromatic ring.
3. 2. The resin composition as described in 1 above, wherein R ^{1 of the} amic acid represented by the general formula (1) is any one of the structures represented by the following structural formulas.

(In the structural formula, J ¹ and J ² are a direct bond, —CO—, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, — _{C 3 F 6 -, - C} 13 H 8 -, - SO 2 -, - S -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 - _{, -C 6 H 4 -O-C} 6 H 4 -, - C 6 H 4 -C 3 H 6 -C 6 H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows the R ^{3 to} R ⁶ and R ⁸ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ represents a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms.)
4). (B) The polyimide, polybenzoxazole, polyimide precursor, or polybenzoxazole precursor contains the structural unit represented by the general formula (2) as a main component. The resin composition as described.

(R ⁹ and R ¹⁰ may be the same or different from each other, and a divalent to octavalent hydrocarbon group having 2 or more carbon atoms or a divalent to octavalent hydrocarbon group having 2 or more carbon atoms) is -CO - -, - -CH ₂ of COO -, - NH -, - NHCO -, - O -, - S -, - SO 2 -, - Si- or -Si _{(CH 3) 2} - is replaced by Or a hydrogen atom of a divalent to octavalent hydrocarbon group having 2 or more carbon atoms is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom or -COOR ⁹ ' R ⁹ ′ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, R ¹¹ and R ¹² may be the same or different, and a hydrogen atom or carbon number 1 may be present. Represents an alkyl group of ˜20, p and q are Each is an integer of 0 to 4, and r and s are each an integer of 0 to 2.)
5. Furthermore, (c) The photo-acid generator is contained, The resin composition in any one of said 1-4 characterized by the above-mentioned.
6). Furthermore, (d) the photoinitiator and (e) the compound which has 2 or more of ethylenically unsaturated bonds are contained, The resin composition in any one of said 1-4 characterized by the above-mentioned.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which can reduce the transmittance | permeability in the visible region of a cured film can be obtained, maintaining the transmittance | permeability of the resin film before hardening.

Cross section of TFT substrate Transmission spectrum before and after curing of the composition of Example 1 Transmission spectrum before and after curing of the composition of Comparative Example 2

  Hereinafter, the present invention will be described in detail.

<(A) Amic acid represented by general formula (1)>
The amic acid used in the resin composition of the present invention is represented by the general formula (1) and is an amic acid having an amide group or a carboxyl group.

In general formula (1), R ¹ is a 1 to 3 carbon group having 1 to 50 carbon atoms, and —CH ₂ — of the 1 to 3 carbon group having 1 to 50 carbon atoms is —CO—, — A group substituted by NH—, —NHCO—, —O—, —S—, —SO ₂ —, —Si— or —Si (CH ₃ ) ₂ —; A group in which a hydrogen atom of a hydrogen group is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom, or —COOR ¹ ′, or a 1-3 valent carbon atom having 1 to 50 carbon atoms A hydrogen atom of a group in which —CH ₂ — of the hydrogen group is substituted by —NH—, —NHCO—, —O— or —S— is a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, It is substituted by a chlorine atom or a -COOR ¹ ' A group. R ¹ ′ represents hydrogen or an alkyl group having 1 to 20 carbon atoms. R ² represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. n represents an integer of 1 to 3, o represents an integer of 1 to 4, and is preferably an integer of 2 to 4, more preferably an integer of 3 to 4, and most preferably 4.

The R ¹ in the amic acid represented by the general formula (1) preferably has at least one aromatic ring. As a result, the electron transition from the HOMO of the imide structure closed by the heat treatment or the occupied orbit near it to the LUMO or the empty orbit close to it, that is, CT absorption occurs at an energy corresponding to the visible light region. The transmittance decreases.

The R ¹ in the amic acid represented by the general formula (1) is preferably any one of structures represented by the following structural formula. Thereby, an amic acid with high productivity and high solubility in a general-purpose solvent can be synthesized.

(In the structural formula, J ¹ and J ² are a direct bond, —CO—, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, — _{C 3 F 6 -, - C} 13 H 8 -, - SO 2 -, - S -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 - _{, -C 6 H 4 -O-C} 6 H 4 -, - C 6 H 4 -C 3 H 6 -C 6 H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows the R ^{3 to} R ⁶ and R ⁸ represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁷ represents a hydrogen atom or a monovalent alkyl group having 1 to 20 carbon atoms.)
<Method for producing amic acid represented by general formula (1)>
The amic acid represented by the general formula (1) can be obtained by using a compound having an amino group and a compound having one acid anhydride group and, if necessary, an esterifying agent. In addition, it can be produced according to a known method for producing an amide acid or an amide ester compound.

<Compound with amino group>
The compound having an amino group used for the production of amic acid is a compound having at least one amino group, and monoamine, diamine, and triamine can be used.

<Monoamine>
As a preferable skeleton structure of monoamine, when a heterocyclic structure is included as a monocyclic aromatic compound, benzene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, furan, pyrrole, thiophene, indole, benzofuran, benzothiophene, imidazole, pyrazole, triazole, Examples include oxazole and thiazole.

  In addition, as the condensed polycyclic aromatic compound, including a heterocyclic structure, carbon condensed bicyclic systems such as pentalene, indene, naphthalene, azulene, heptalene, and octalen, as-indacene, s-indacene, biphenylene, acenaphthylene, fluorene, phenanthrene , Carbon condensed tricyclic systems such as anthracene, triindene, fluoranthene, acephenanthrylene, aceanthrylene, triphenylene, pyrene, chrysene, tetraphen, naphthacene and other carbon condensed tetracyclic systems, picene, perylene, pentaphene, pentacene, tetra Carbon condensed pentacyclic systems such as phenylene, condensed heterobicyclic systems such as benzofuran, benzothiophene, indole, benzimidazole, benzothiazole, purine, quinoline, isoquinoline, shinoline, quinoxaline, diben Furan, carbazole, acridine, phenanthroline and the like condensed heterocyclic tricyclic such.

Specific examples of monoamines include aniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, and 3-ethynyl. Aniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 4-amino Salicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminoterephthalic acid, 2-amino Benzophenone, 3-aminobenzophenone, 4-aminobenzophenone, 2-amino Benzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 4-aminobenzanilide 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-aminopyridine 4-carboxylic acid, 2-amino -3-hydroxypyridine, 2-aminopyridine-5-sulfonic acid, 3-aminothiophene, 4-aminoindole, 4-amino-N-methylindole, 5-aminoindole, 6-aminoindole, 5-amino-8 -Hydroxyquinoline, 4-amino-8-hydroxyquinoline, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1 -Hydroxy-6-aminonaphthalene, 1-hydroxy 5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8 -Aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1 -Carboxy-2-aminonaphthalene 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy- 3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-amino-7-mercaptonaphthalene, 2-mercapto-7-aminonaphthalene, 2-mercapto-6 -Aminonaphthalene, 2-mercapto-5 Aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 1-ethynyl-2-aminonaphthalene 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl- 8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-a Nonaphthalene, 3,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7 -Diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8-diethynyl-2-aminonaphthalene,
2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminoimidazole, 2-aminofluorene, 9-aminofluorene, 2-amino-9-fluorenone, 1-aminoanthracene, 2-aminoanthracene, 1-aminopyrene, 2-aminopyrimidine, 2-amino-4-hydroxypyrimidine, 2-amino-5-hydroxypyrimidine, 2-aminopyrimidine- 5-carboxylic acid, 2-amino-4,6-dihydroxypyrimidine, 4-aminopyrimidine, 4-amino-6-hydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 5-aminopyrimidine, 5-amino- 4,6-dihydroxypyrimidine, 2-amino 1,3,5 Triazine, although 2-amino-1,3,5-triazine-4,6-dithiol, and the like, but is not limited thereto.

<Diamine>
As a preferable skeleton structure of diamine, the following structure, or a part of these hydrogen atoms, an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, or an ester group having 1 to 20 carbon atoms. , A nitro group, a cyano group, a structure substituted with a fluorine atom or a chlorine atom, and the like.

^{However, J 3,} J ⁴ is a direct bond, -CO -, - COO -, - CONH -, - CH 2 -, - C 2 H 4 -, - O -, - C 3 H 6 -, - C 3 F _{6 -, - C 13 H 8} -, - SO 2 -, - S -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C _{6 H 4 -O-C 6 H} 4 -, - C 6 H 4 -C 3 H 6 -C 6 H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - shows a. R ^{13 to} R ¹⁵ represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and preferably a monovalent alkyl group having 1 to 20 carbon atoms.

  Specific diamines include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, and bis (3 -Hydroxy such as amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene Group-containing diamine, 3,5-diaminobenzoic acid, carboxyl group-containing diamine such as 3-carboxy-4,4′-diaminodiphenyl ether, sulfonic acid-containing diamine such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, dithio Hydroxyphenylenediamine, 3, 4 -Diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,4 ' -Diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2, 6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1, 4-bis (4-aminophenyl) Noxy) benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3, , 3′-diethyl-4,4′-diaminobiphenyl, 2,2 ′, 3,3′-tetramethyl-4,4′-diaminobiphenyl, 3,3 ′, 4,4′-tetramethyl-4, Examples include, but are not limited to, 4′-diaminobiphenyl, 2,2′-di (trifluoromethyl) -4,4′-diaminobiphenyl, and the like.

<Triamine>
As a preferable skeleton structure of triamine, a structure as shown below, or a part of these hydrogen atoms is an alkyl group having 1 to 20 carbon atoms, a fluoroalkyl group, a hydroxyl group, an alkoxyl group, or an ester group having 1 to 20 carbon atoms. , A nitro group, a cyano group, a structure substituted with a fluorine atom or a chlorine atom, and the like.

However, R ¹⁶ represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, and is preferably a monovalent alkyl group having 1 to 20 carbon atoms.

  Specific examples of the triamine include para-rose aniline, 1,2,4-triaminobenzene, 2,3,6-triaminopyridine, melamine, and 2,4,6-triaminopyrimidine. It is not limited to these.

<Compound with one acid anhydride group>
The compound having one acid anhydride group used for the production of amic acid is not particularly limited as long as it is a compound satisfying the following general formula (1) ′.

However, o shows the integer of 1-4.

  Specific examples include tetrafluorophthalic anhydride, 3-fluorophthalic anhydride, 4-fluorophthalic anhydride, and the like.

<Esterification agent>
Although it does not specifically limit as an esterifying agent, For example, N, N-dimethylformamide dimethyl acetal etc. are mentioned.

<Reaction conditions>
Amic acid can be obtained using a step of reacting a compound having at least an amino group with a compound having one acid anhydride group. The reaction is preferably performed at 0 to 100 ° C. for 0.2 to 20 hours.

<Reaction solvent>
The reaction solvent used for synthesizing the amic acid is not particularly limited as long as the amic acid compound can be synthesized. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N , N-dimethylacetamide, polar aprotic solvents such as dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether and other glycol ethers, acetone , Ketones such as methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate Propylene glycol monomethyl ether acetate, glycol ether acetate, esters such as 3-methyl-3-methoxybutyl acetate, alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, toluene, xylene Aromatic hydrocarbons and the like. Two or more of these may be contained. The content of the solvent is preferably 100 to 2000 parts by weight with respect to 100 parts by weight in total of the compound having an amino group and the compound having an acid anhydride group.

<Order of addition to reaction system>
There is no particular limitation on the order of adding the reaction raw materials to the reaction system. That is, a compound having an amino group and a compound having one acid anhydride group are simultaneously added to the reaction solvent, and a compound having one acid anhydride group is added after dissolving the compound having an amino group in the reaction solvent. Any method can be used, such as adding a compound having an amino group after dissolving a compound having one acid anhydride group in a reaction solvent.

<(B) Polyimide, polybenzoxazole, polyimide precursor or polybenzoxazole precursor>
The (b) polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor used in the present invention will be described. The polyimide is not particularly limited as long as it has an imide ring, and the polybenzoxazole is not particularly limited as long as it has a benzoxazole ring. Moreover, in the case of a polyimide precursor, if it is a precursor of the polyimide which has the said imide ring, it will not specifically limit, In the case of a polybenzoxazole precursor, if it is the precursor of the polybenzoxazole which has the said benzoxazole ring There is no particular limitation.

  In addition, the (b) polyimide, polybenzoxazole, polyimide precursor, and polybenzoxazole precursor used in the present invention is preferably a polyimide precursor or a polybenzoxazole precursor, and is represented by the general formula (2). More preferably, the main component is a structural unit.

(R ⁹ and R ¹⁰ may be the same or different from each other, and a divalent to octavalent hydrocarbon group having 2 or more carbon atoms or a divalent to octavalent hydrocarbon group having 2 or more carbon atoms) is -CO - -, - -CH ₂ of COO -, - NH -, - NHCO -, - O -, - S -, - SO 2 -, - Si- or -Si _{(CH 3) 2} - is replaced by Or a hydrogen atom of a divalent to octavalent hydrocarbon group having 2 or more carbon atoms is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom or -COOR ⁹ ' R ⁹ ′ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, R ¹¹ and R ¹² may be the same or different, and a hydrogen atom or carbon number 1 may be present. Represents an alkyl group of ˜20, p and q are Each is an integer of 0 to 4, and r and s are each an integer of 0 to 2.)
The general formula (2) represents a polyimide precursor having a hydroxyl group or a polybenzoxazole precursor, and due to the hydroxyl group, a polyimide precursor having no solubility in an alkaline aqueous solution and a polybenzoxazole precursor. Becomes better than the body.

The polyimide precursor or polybenzoxazole precursor is a resin having an amide bond in the main chain, and generally comprises an amine component and an acid component. A polyimide precursor or a polybenzoxazole precursor becomes the above-mentioned polyimide or polybenzoxazole by dehydrating and ring-closing by heat treatment or chemical treatment. The number of repetitions is preferably 10 to 100,000. Examples of the polyimide precursor include polyamic acid ester and polyisoimide, and polyamic acid ester is preferable. Examples of the polybenzoxazole precursor include polyhydroxyamide, polyaminoamide, polyamide, polyamideimide and the like, and polyhydroxyamide is preferable. From the viewpoint of solubility in an aqueous alkali solution, the polyimide precursor and the polybenzoxazole precursor are OR ¹⁷ , SO ₃ R ¹⁷ , CONR ¹⁷ R ¹⁸ , COOR ¹⁷ , SO ₂ NR ¹⁷ R ^{18 in the} acid residue or amine residue. It is preferable to have an acidic group or acidic group derivative such as, and more preferably have a hydroxyl group. R ¹⁷ and R ¹⁸ represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group in which a hydrogen atom of a hydrocarbon group having 1 to 20 carbon atoms is substituted with another atom. In addition, an acidic group refers to the case where R ¹⁷ or R ¹⁸ are all hydrogen atoms, and an acidic group derivative is a hydrocarbon group having 1 to 20 carbon atoms or a hydrocarbon having 1 to 20 carbon atoms in R ¹⁷ or R ^18. This refers to the case where a hydrogen atom of the group is substituted with another atom.

<Acid component>
Dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid can be used as the acid component used for the production of the polyimide precursor and the polybenzoxazole precursor.

  Preferred examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyl dicarboxylic acid, benzophenone dicarboxylic acid, and triphenyl dicarboxylic acid.

  Examples of the tricarboxylic acid include trimellitic acid, trimesic acid, diphenyl ether tricarboxylic acid, biphenyltricarboxylic acid and the like.

  Examples of tetracarboxylic acid include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3 ′ -Biphenyltetracarboxylic acid, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 2,2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) Hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxy) Phenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) sulfone, (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid , Aromatic tetracarboxylic acids such as 3,4,9,10-perylenetetracarboxylic acid, and aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and 1,2,3,4-cyclopentanetetracarboxylic acid. be able to.

In addition, the dicarboxylic acid, tricarboxylic acid, and tetracarboxylic acid exemplified above may be converted into acidic groups or acidic group derivatives such as OR ¹⁷ , SO ₃ R ¹⁷ , CONR ¹⁷ R ¹⁸ , COOR ¹⁷ , SO ₂ NR ¹⁷ R ¹⁸ , preferably It is more preferable to use one substituted with 1 to 4 hydroxyl group, sulfonic acid group, sulfonic acid amide group, sulfonic acid ester group or the like.

  These acids can be used as they are, or as acid anhydrides and active esters, alone or in combination of two or more.

  In addition, by using a silicon atom-containing tetracarboxylic acid such as dimethylsilanediphthalic acid or 1,3-bis (phthalic acid) tetramethyldisiloxane, adhesion to the substrate, oxygen plasma used for cleaning, etc., UV ozone Resistance to processing can be increased. These silicon atom-containing tetracarboxylic acids are preferably used in an amount of 1 to 30 mol% of the total acid components.

<Diamine>
A diamine can be used as the amine component used in the production of the polyimide precursor and the polybenzoxazole precursor.

Preferred examples of the diamine include bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis ( Such as 3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3-amino-4-hydroxy) biphenyl, bis (3-amino-4-hydroxyphenyl) fluorene, etc. Hydroxyl group-containing diamine, 3,5-diaminobenzoic acid, carboxyl group-containing diamine such as 3-carboxy-4,4′-diaminodiphenyl ether, sulfonic acid-containing diamine such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, Dithiohydroxyphenylenediamine, 3 4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3, 4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, 1,4-bis (4-aminophenoxy) benzene, benzine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxyphenyl) sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis {4- (4-aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy Benzene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-diethyl-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3 '-Diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4'-diaminobiphenyl, 3,3 ', 4,4'-tetramethyl-4,4' -Diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, or a compound in which a part of hydrogen atoms of these aromatic rings are substituted with an alkyl group or a halogen atom, or cyclohexyldiamine And aliphatic diamines such as methylenebiscyclohexylamine. Furthermore, these diamines are substituted with a group having 1 to 10 carbon atoms such as a methyl group or an ethyl group, a fluoroalkyl group having 1 to 10 carbon atoms such as a trifluoromethyl group, or a group such as F, Cl, Br or I May be. Further, the diamine exemplified above preferably has an acidic group or acidic group derivative such as OR ¹⁷ , SO ₃ R ¹⁷ , CONR ¹⁷ R ¹⁸ , COOR ¹⁷ , SO ₂ NR ¹⁷ R ^18, and preferably has a hydroxyl group. More preferred.

  These diamines can be used as they are or as the corresponding diisocyanate compound and trimethylsilylated diamine, either singly or in combination of two or more. In applications where heat resistance is required, it is preferable to use an aromatic diamine in an amount of 50 mol% or more of the total diamine.

  Further, by using a silicon atom-containing diamine such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane or 1,3-bis (4-anilino) tetramethyldisiloxane as the diamine component, adhesion to the substrate is achieved. And resistance to oxygen plasma used for cleaning and UV ozone treatment can be increased. These silicon atom-containing diamines are preferably used in an amount of 1 to 30 mol% of the total diamine component.

<End sealant>
The end of the polyimide precursor or polybenzoxazole precursor is preferably sealed with a monoamine, acid anhydride, acid chloride or monocarboxylic acid having a hydroxyl group, carboxyl group, sulfonic acid group or thiol group. Two or more of these may be used. By having the above-mentioned group at the terminal of the resin, the dissolution rate of the resin in the alkaline aqueous solution can be easily adjusted to a preferred range.

  Preferred examples of the monoamine include 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-amino. Naphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy -5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid 4-aminosalicylic acid, 5-aminosalicylic acid, -Aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol , 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, and the like.

  Preferred examples of the acid anhydride, acid chloride, and monocarboxylic acid include phthalic anhydride, maleic anhydride, nadic acid, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride and other acid anhydrides, 3-carboxyphenol 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7 Monocarboxylic acids such as carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, and Converted monoacid chloride compound, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 2,6-di Monoacid chloride compound in which only monocarboxyl group of dicarboxylic acids such as carboxynaphthalene is acid chloride, reaction of monoacid chloride compound with N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3-dicarboximide An active ester compound obtained by

  The content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid described above is preferably in the range of 0.1 to 60 mol% of the charged number of moles of acid component monomer or diamine component monomer. -50 mol% is more preferable. By setting it as such a range, the viscosity of the solution at the time of apply | coating a resin composition can be obtained, and the resin composition which had the outstanding film | membrane physical property can be obtained.

  Moreover, you may have a polymerizable functional group at the terminal of resin. Examples of the polymerizable functional group include an ethylenically unsaturated bond group, an acetylene group, a methylol group, and an alkoxymethyl group.

The end-capping agent introduced into the resin can be easily detected by the following method. For example, a resin having a terminal blocking agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR measurement. The end capping agent can be easily detected. Apart from this, it is possible to directly detect the resin into which the end-capping agent is introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

<(C) Photoacid generator>
By containing (c) a photoacid generator in the resin composition of the present invention, an acid is generated in the light irradiation part to increase the solubility of the light irradiation part in an alkaline aqueous solution, and the light irradiation part dissolves. The relief pattern can be obtained. Moreover, (c) By containing a photo-acid generator and an epoxy compound, the acid which generate | occur | produced in the light irradiation part accelerates | stimulates the reaction of an epoxy compound, and the negative type relief pattern which a light irradiation part becomes insoluble can be obtained. .

  (C) Examples of the photoacid generator include a quinonediazide compound, a sulfonium salt, a phosphonium salt, a diazonium salt, and an iodonium salt.

  The quinonediazide compound includes a polyhydroxy compound in which a sulfonic acid of quinonediazide is bonded with an ester, a polyamino compound in which a sulfonic acid of quinonediazide is bonded to a sulfonamide, and a sulfonic acid of quinonediazide in an ester bond and / or sulfone. Examples include amide-bonded ones. It is preferable that 50 mol% or more of the total functional groups of these polyhydroxy compounds and polyamino compounds are substituted with quinonediazide. Moreover, it is preferable to contain 2 or more types of (c) photo-acid generators, and a highly sensitive photosensitive resin composition can be obtained.

  In the present invention, as the quinonediazide, either a quinonediazide having a 5-naphthoquinonediazidesulfonyl group or a quinonediazide having a 4-naphthoquinonediazidesulfonyl group is preferably used. The 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. The 5-naphthoquinone diazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound or a 5-naphthoquinone diazide sulfonyl ester compound depending on the wavelength to be exposed. Further, it may contain a naphthoquinone diazide sulfonyl ester compound having a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, You may contain.

  Of the photoacid generators (c), sulfonium salts, phosphonium salts, and diazonium salts are preferred because they moderately stabilize the acid component generated by exposure. Of these, sulfonium salts are preferred.

  In the present invention, the content of the (c) photoacid generator is preferably 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin of the component (b) from the viewpoint of increasing sensitivity. Of these, the quinonediazide compound is preferably in the range of 3 to 40 parts by weight. The total amount of the sulfonium salt, phosphonium salt and diazonium salt is preferably in the range of 0.5 to 20 parts by weight. Furthermore, it can also contain a sensitizer etc. as needed.

<(D) Photopolymerization initiator and (e) Compound having two or more ethylenically unsaturated bonds>
The photosensitive resin composition of the present invention may contain (d) a photopolymerization initiator and (e) a compound having two or more ethylenically unsaturated bonds. An active radical generated in the light irradiation part advances radical polymerization of ethylenically unsaturated bonds, and a negative relief pattern in which the light irradiation part becomes insoluble can be obtained.

  (D) As a photopolymerization initiator, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 1-phenyl-1,2-propanedione-2- ( o-ethoxycarbonyl) oxime, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone -1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isop Pyrether, benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide , (4-benzoylbenzyl) trimethylammonium chloride, 2-hydroxy-3- (4-benzoylphenoxy) -N, N, N-trimethyl-1-propenaminium chloride monohydrate, 2-isopropylthioxanthone, 2,4 - Tylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy) -N, N, N- Trimethyl-1-propanaminium chloride, 2,4,6-trimethylbenzoylphenylphosphine oxide, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), 2,2'-bis (o-chlorophenyl) -4,5 4 ', 5'-tetraphenyl-1,2-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl 9,10-phenanthrenequinone, camphorquinone, methylphenylglyoxyester, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), diphenyl sulfide derivative, bis ( η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 4,4-bis (dimethylamino) benzophenone, 4 , 4-bis (diethylamino) benzophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 4-benzoyl-4-methylphenylketone, dibenzylketone, fluorenone, 2,3-diethoxyacetophenone, 2,2-dimethoxy -2-phenyl-2-phenylaceto Enone, 2-hydroxy-2-methylpropiophenone, p-t-butyldichloroacetophenone, benzylmethoxyethyl acetal, anthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, β-chloroanthraquinone, anthrone, benzanthrone, Dibenzsuberon, methyleneanthrone, 4-azidobenzalacetophenone, 2,6-bis (p-azidobenzylidene) cyclohexane, 2,6-bis (p-azidobenzylidene) -4-methylcyclohexanone, 2-phenyl-1,2- Butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, naphthalenesulfonyl chloride, quinolinesulfonyl chloride, N-fluoro Photoreducing dyes such as enylthioacridone, 4,4-azobisisobutyronitrile, benzthiazole disulfide, triphenylphosphine, carbon tetrabromide, tribromophenylsulfone, benzoyl peroxide and eosin, methylene blue and ascorbine The combination of reducing agents, such as an acid and a triethanolamine, etc. are mentioned. Two or more of these may be contained.

  In the present invention, the content of (d) the photopolymerization initiator is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the resin of component (b). If it is 0.1 parts by weight or more, sufficient radicals are generated by light irradiation, and the sensitivity is improved. Moreover, if it is 20 weight part or less, there will be no hardening of the light non-irradiation part by generation | occurrence | production of an excessive radical, and alkali developability will improve.

  (E) As a compound having two or more ethylenically unsaturated bonds, ethylene glycol dimethacrylate, ethylene glycol diacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, ethoxylated bisphenol A dimethacrylate, glycerin dimethacrylate, tripropylene glycol Acrylic monomers such as dimethacrylate, butanediol dimethacrylate, glycerin triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxylated isocyanuric acid triacrylate it can. Two or more of these may be contained.

  In the present invention, the content of the compound (e) having two or more ethylenically unsaturated bonds is preferably 1 part by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the component (b) resin. Moreover, 100 weight part or less is preferable and 50 weight part or less is more preferable.

  Moreover, you may contain 1-50 weight part of compounds which have only one ethylenically unsaturated bond for solubility adjustment etc. with respect to 100 weight part of resin of (b) component. Examples of such compounds are acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, dimethylacrylamide, dimethylaminoethyl methacrylate, acryloyl morphophore, 1-hydroxyethyl. α-chloroacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl α-chloroacrylate, 1-hydroxypropyl methacrylate, 1-hydroxypropyl acrylate, 1-hydroxypropyl α-chloroacrylate, 2-hydroxy Propyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl α-chloroacrylate, 3-hydroxy Propyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl α-chloroacrylate, 1-hydroxy-1-methylethyl methacrylate, 1-hydroxy-1-methylethyl acrylate, 1-hydroxy-1-methylethyl α-chloroacrylate 2-hydroxy-1-methylethyl methacrylate, 2-hydroxy-1-methylethyl acrylate, 2-hydroxy-1-methylethyl α-chloroacrylate, 1-hydroxybutyl methacrylate, 1-hydroxybutyl acrylate, 1-hydroxybutyl α-chloroacrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl α-chloroacrylate, 3-hydroxybutyl methacrylate 3-hydroxybutyl acrylate, 3-hydroxybutyl α-chloroacrylate, 4-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl α-chloroacrylate, 1-hydroxy-1-methylpropyl methacrylate, 1-hydroxy- 1-methylpropyl acrylate, 1-hydroxy-1-methylpropyl α-chloroacrylate, 2-hydroxy-1-methylpropyl methacrylate, 2-hydroxy-1-methylpropyl acrylate, 2-hydroxy-1-methylpropyl α-chloro Acrylate, 1-hydroxy-2-methylpropyl methacrylate, 1-hydroxy-2-methylpropyl acrylate, 1-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydride Xyl-2-methylpropyl methacrylate, 2-hydroxy-2-methylpropyl acrylate, 2-hydroxy-2-methylpropyl α-chloroacrylate, 2-hydroxy-1,1-dimethylethyl methacrylate, 2-hydroxy-1,1 -Dimethylethyl acrylate, 2-hydroxy-1,1-dimethylethyl α-chloroacrylate, 1,2-dihydroxypropyl methacrylate, 1,2-dihydroxypropyl acrylate, 1,2-dihydroxypropyl α-chloroacrylate, 2,3 -Dihydroxypropyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl α-chloroacrylate, 2,3-dihydroxybutyl methacrylate, 2,3-dihydroxybutyl acrylate 2,3-dihydroxybutyl α-chloroacrylate, p-hydroxystyrene, p-isopropenylphenol, phenethyl methacrylate, phenethyl acrylate, phenethyl α-chloroacrylate, N-methylol acrylamide, N-methylol methacrylamide, α-chloroacryl Acid, crotonic acid, 4-pentenoic acid, 5-hexenoic acid, 6-heptenoic acid, 7-octenoic acid, 8-nonanoic acid, 9-decanoic acid, 10-undecylene acid, brassic acid, ricinoleic acid, 2- (methacrylic acid) Examples include leuoxy) ethyl isocyanate, 2- (acryloyloxy) ethyl isocyanate, and 2- (α-chloroacryloyloxy) ethyl isocyanate.

<(F) Thermal crosslinking agent>
The resin composition of the present invention may further contain (f) a thermal cross-linking agent, and can impart positive or negative photosensitivity. (F) By containing a thermal crosslinking agent, the chemical resistance of the cured film can be improved.

  (F) As a thermal crosslinking agent, the thermal crosslinking agent represented by General formula (3) and the thermal crosslinking agent which has a structure represented by General formula (4) are preferable.

In the general formula (3), R ¹⁹ represents a divalent to tetravalent linking group. R ²⁰ is Cl, Br, I, F, 1 monovalent hydrocarbon group having 1 to 20 carbon atoms, -CH ₂ monovalent hydrocarbon group having 1 to 20 carbon atoms - is -CO -, - COO-, A group substituted by —NH—, —NHCO—, —O—, —S—, —SO ₂ —, —Si— or —Si (CH ₃ ) ₂ — or a monovalent hydrocarbon having 1 to 20 carbon atoms; It represents a hydrogen atom fluoroalkyl group group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a substituted group by a chlorine atom or -COOR ^21. R ²¹ represents hydrogen or an alkyl group having 1 to 20 carbon atoms. R ²² and R ²³ represent CH ₂ OR ²⁴ . R ²⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ²⁵ represents a hydrogen atom, a methyl group or an ethyl group. t represents an integer of 0 to 2, and u represents an integer of 2 to 4. A plurality of R ²⁰ , R ²² , R ²³ , R ²⁵ may be the same or different. Examples of linking group R ¹⁹ are shown below.

In the above formula, R ^{26 to} R ⁴⁶ are each a hydrogen atom, Cl, Br, I, F, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or —CH _{2 of a} monovalent hydrocarbon group having 1 to 20 carbon atoms. A group in which — is substituted by —CO—, —COO—, —NH—, —NHCO—, —O—, —S—, —SO ₂ —, —Si— or —Si (CH 3) ₂ —, or the number of carbon atoms; 1-20 monovalent hydrocarbon group hydrogen atom fluoroalkyl group, showing a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, been substituted by a chlorine atom or -COOR ^47. R ⁴⁷ represents hydrogen or an alkyl group having 1 to 20 carbon atoms.

^{_{-N (CH 2 OR 48) v}} (H) w (4)
In the general formula (4), R ⁴⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. v represents 1 or 2, and w represents 0 or 1. However, v + w is 1 or 2.

In the general formula (3), R ²² and R ²³ represent CH ₂ OR ²⁴ which is a thermal crosslinking group. R ²⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ²⁴ is preferably a monovalent hydrocarbon group having 1 to 4 carbon atoms because it retains moderate reactivity and is excellent in storage stability. Moreover, in the photosensitive resin composition containing a photoacid generator or a photopolymerization initiator, R ²⁴ is more preferably a methyl group or an ethyl group.

  The purity of the compound having the structure represented by the general formula (3) is preferably 75% or more, and more preferably 85% or more. If the purity is 85% or more, the storage stability is excellent, the crosslinking reaction of the resin composition is sufficiently performed, the colorability after curing is excellent, and the transmittance in the visible light region of the cured film can be further reduced. Moreover, since the unreacted group used as a water absorbing group can be decreased, the water absorption of a resin composition can be made small. Examples of the method for obtaining a high-purity thermal crosslinking agent include recrystallization and distillation. The purity of the thermal crosslinking agent can be determined by a liquid chromatography method.

  Preferable examples of the thermal crosslinking agent having a structure represented by the general formula (3) are shown below.

  Preferable examples of the thermal crosslinking agent having a structure represented by the general formula (4) are shown below.

  (F) The content of the thermal crosslinking agent is preferably 5 parts by weight or more and more preferably 10 parts by weight or more with respect to 100 parts by weight of the resin of component (b). Moreover, 120 weight part or less is preferable and 100 weight part or less is more preferable. If it is 5 weight part or more and 120 weight part or less, the intensity | strength of a cured film is high and it is excellent also in the storage stability of a resin composition.

<(G) Thermal acid generator>
The resin composition of the present invention may further contain (g) a thermal acid generator. (G) The thermal acid generator generates an acid by heating after development, which will be described later, and promotes a crosslinking reaction between the resin of the component (b) and the thermal crosslinking agent of the component (f). Promotes cyclization of the imide ring and oxazole ring. For this reason, the chemical resistance of the cured film is improved, and film loss can be reduced. (G) The acid generated from the thermal acid generator is preferably a strong acid. For example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid, and butanesulfonic acid. Is preferred. In the present invention, the thermal acid generator is preferably an aliphatic sulfonic acid compound represented by the general formula (5) or (6), and may contain two or more of these.

In the general formulas (5) and (6), R ^{49 to} R ⁵¹ represent an alkyl group having 1 to 10 carbon atoms or a monovalent aromatic group having 7 to 12 carbon atoms. The alkyl group and the aromatic group may be substituted, and examples of the substituent include an alkyl group and a carbonyl group.

  Specific examples of the compound represented by the general formula (5) include the following compounds.

  Specific examples of the compound represented by the general formula (6) include the following compounds.

  (G) From the viewpoint of further promoting the crosslinking reaction, the content of the thermal acid generator is preferably 0.1 parts by weight or more, and 0.3 parts by weight or more with respect to 100 parts by weight of the resin of the component (b). More preferably, 0.5 parts by weight or more is more preferable. On the other hand, from the viewpoint of electrical insulation of the cured film, 20 parts by weight or less is preferable, 15 parts by weight or less is more preferable, and 10 parts by weight or less is more preferable.

<(H) Filler>
The resin composition of the present invention can contain (h) a filler. (H) By containing a filler, when the resin composition of the present invention is used as a solder resist for a circuit board, it develops thixotropy in a process of applying and drying by screen printing, and keeps the pattern at a predetermined size. There is an effect to. Furthermore, the effect of suppressing shrinkage of thermosetting can be expected.

  (H) Examples of insulating fillers include calcium carbonate, silica, alumina, aluminum nitride, titanium oxide, silica-titanium oxide composite particles, etc., and silica, titanium oxide, silica-titanium oxide composite particles. Is preferred. Examples of the conductive filler include gold, silver, copper, nickel, aluminum, carbon and the like, and silver is preferable. You may contain 2 or more types of these according to a use.

  (H) Content of a filler becomes like this. Preferably it is the range of 5-500 weight part with respect to 100 weight part of (b) component. (H) The number average particle diameter of the filler is preferably 10 μm or less, and more preferably 2 μm or less. It is also preferable to use a mixture of two or more fillers having different number average particle diameters from the viewpoint of imparting thixotropy and stress relaxation.

  Further, by using (h) particles having a number average particle diameter of 100 nm or less as the filler, so-called nanoparticles, it becomes possible to adjust physical properties such as refractive index while maintaining light transmittance. In particular, by using high refractive index nanoparticles, high transmittance and high refractive index can be expressed simultaneously. By mixing such nanoparticles, it can be suitably used as a low-temperature curable optical thin film such as an on-chip microlens of a solid-state imaging device or a flattening film for various displays / solid-state imaging devices. Suitable particles for the above purpose include tin oxide-aluminum oxide composite particles, zirconium oxide-aluminum oxide composite particles, zirconium oxide-silicon oxide composite particles, tin oxide particles, zirconium oxide-tin oxide composite particles, titanium oxide particles, tin oxide. Examples thereof include titanium oxide composite particles, silicon oxide-titanium oxide composite particles, zirconium oxide-titanium oxide composite particles, and zirconium oxide particles. Moreover, you may coat | cover the particle | grain surface with another substance. The particles may be in the form of powder or sol, but is more preferably in the form of sol from the viewpoint of ease of dispersion. The number average particle diameter of the nanoparticles is preferably 50 nm or less, more preferably 30 nm or less from the viewpoint of transmittance.

  (H) The number average particle diameter of the filler can be measured with various particle counters. The average particle diameter of the nanoparticles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a method of directly measuring the particle size by a transmission electron microscope, or the like. The particle diameter obtained by these measurement methods may be a volume average or a mass average, but can be converted to a number average molecular weight by assuming that the particle shape is spherical.

<(I) Adhesion improving agent>
The resin composition of the present invention may contain (i) an adhesion improving agent. (I) As an adhesion improver, vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltri Silane coupling agents such as methoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds Examples thereof include compounds obtained by reacting an alkoxy group-containing silicon compound. Two or more of these may be contained. By containing these (i) adhesion improvers, when developing a photosensitive resin composition film, it is possible to improve adhesion with a base substrate such as a silicon wafer, ITO, SiO ₂ , silicon nitride or the like. it can. Further, resistance to oxygen plasma and UV ozone treatment used for cleaning or the like can be increased. (I) As for content of an adhesion improving agent, 0.1-10 weight part is preferable with respect to 100 weight part of resin of (b) component.

<(J) Adhesion improver>
The resin composition of the present invention may contain (j) an adhesion improver. (J) Examples of the adhesion improving agent include an alkoxysilane-containing aromatic amine compound, an aromatic amide compound, or an aromatic non-containing silane compound. Two or more of these may be contained. By containing these compounds, the adhesiveness with the base material after curing can be improved. Specific examples of the alkoxysilane-containing aromatic amine compound and aromatic amide compound are shown below. In addition, a compound obtained by reacting an aromatic amine compound and an alkoxy group-containing silicon compound may be used. For example, an aromatic amine compound and a group that reacts with an amino group such as an epoxy group or a chloromethyl group. The compound etc. which are obtained by making the alkoxysilane compound which has it react are mentioned.

  Non-aromatic silane compounds include vinyl silane compounds such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyl. Examples thereof include carbon-carbon unsaturated bond-containing silane compounds such as trimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  (J) As for content of an adhesion improving agent, 0.01-15 weight part is preferable with respect to 100 weight part of resin of (b) component.

<(K) Surfactant>
The resin composition of the present invention may contain (k) a surfactant and improve the wettability with the substrate.

  (K) Fluoro-based surfactants such as Florard (trade name, manufactured by Sumitomo 3M Co., Ltd.), MegaFac (trade name, manufactured by DIC Corporation), Sulflon (trade name, manufactured by Asahi Glass Co., Ltd.) Surfactant, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Corp.), Polyflow, Granol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (Bic Chemie) And an acrylic polymer surfactant such as Polyflow (trade name, manufactured by Kyoeisha Chemical Co., Ltd.).

<Solvent contained in resin composition>
The resin composition of the present invention preferably contains a solvent. As the solvent, polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, Propylene glycol monoethyl ether Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, glycol ethers such as diethylene glycol ethyl methyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene Such as glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate Le ethers, ethyl lactate, methyl lactate, diacetone alcohol, alcohols such as 3-methyl-3-methoxybutanol, toluene, and aromatic hydrocarbons such as xylene. Two or more of these may be contained. As for content of a solvent, 100-2000 weight part is preferable with respect to 100 weight part of resin of (a) component.

<Method for producing resin composition>
Next, the manufacturing method of the resin composition of this invention is demonstrated. For example, the resin composition can be obtained by dissolving the components (a) to (b) and, if necessary, the components (c) to (k) in a solvent. Examples of the dissolution method include stirring and heating. In the case of heating, the heating temperature is preferably set in a range not impairing the performance of the resin composition, and is usually room temperature to 80 ° C. In addition, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. In addition, for components that tend to generate bubbles when stirring and dissolving, such as surfactants and some adhesion improvers, by dissolving other components and adding them last, poor dissolution of other components due to the generation of bubbles Can be prevented.

  The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. Examples of the filter pore diameter include, but are not limited to, 0.5 μm, 0.2 μm, 0.1 μm, and 0.05 μm. Examples of the material for the filter include polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE), and polyethylene and nylon are preferable. When (h) a filler or an organic pigment is contained in the resin composition, it is preferable to use a filtration filter having a pore size larger than these particle sizes.

  Next, the manufacturing method of the cured film using the resin composition of this invention is demonstrated. The resin composition of the present invention is applied by spin coating, slit coating, dip coating, spray coating, printing, or the like to obtain a resin composition film. Prior to the application, the substrate on which the resin composition is applied may be pretreated with the above-described adhesion improving agent in advance. For example, a solution obtained by dissolving 0.5 to 20% by weight of an adhesion improver in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate, etc. Examples thereof include a method of treating the substrate surface by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, or steam treatment. If necessary, a reduced-pressure drying treatment can be performed, and then the reaction between the substrate and the adhesion improver can be advanced by a heat treatment at 50 ° C to 300 ° C.

  A cured film can be obtained by heat-treating the obtained resin composition film. For example, a method of heat treatment at 320 ° C. for 60 minutes, a method of heat treatment at 120 to 400 ° C. for 1 minute to 10 hours, a method of heat treatment at room temperature to about 100 ° C. with addition of a curing catalyst, ultrasonic waves or electromagnetic waves Examples of the method include a method of curing at a low temperature of about room temperature to 100 ° C. by treatment.

  When the resin composition of the present invention has photosensitivity, a negative or positive relief is obtained by partially irradiating the resin composition film with actinic rays such as ultraviolet rays and developing with a developer. A pattern can be obtained.

  The cured film obtained from the resin composition of the present invention is suitably used as an insulating film or protective film for wiring. For example, use of insulating films and protective films for printed circuit boards that form wiring with copper, aluminum, etc. on films and substrates such as polyimide and ceramics, and use of protective films for partially soldering wiring Is mentioned. Moreover, when a resin composition contains a conductive filler, it can also be used as a wiring material.

  In addition, the cured film obtained from the resin composition of the present invention is suitably used as a planarization film for a display device having a TFT-formed substrate, a planarization film, and a display element in this order. Examples of such a display device include a liquid crystal display device and an organic EL display device. An active matrix type display device has a flattening film on a substrate such as glass or various plastics, which has a TFT and a wiring located on a side portion of the TFT and connected to the TFT, covering the unevenness thereon. And a display element is provided over the planarization film. The display element and the wiring are connected through a contact hole formed in the planarization film. FIG. 1 shows a cross-sectional view of a TFT substrate. On the substrate 6, bottom-gate or top-gate TFTs 1 are provided in a matrix, and the insulating film 3 is formed so as to cover the TFTs 1. A wiring 2 connected to the TFT 1 is provided on the insulating film 3. Further, a planarizing film 4 is provided on the insulating film 3 so as to bury the wiring 2. A contact hole 7 reaching the wiring 2 is provided in the planarizing film 4. An ITO (transparent electrode) 5 is formed on the planarizing film 4 while being connected to the wiring 2 through the contact hole 7. Here, ITO5 becomes an electrode of a display element (for example, organic EL element). The organic EL element may be a top emission type that emits emitted light from the side opposite to the substrate 6 or a bottom emission type that extracts light from the substrate 6 side. In this manner, an active matrix organic EL display device in which each organic EL element is connected with the TFT 1 for driving the organic EL element is obtained.

  For example, in the case of an organic EL display device using a TFT having a semiconductor layer made of a metal oxide such as amorphous silicon, microcrystal silicon, or IGZO, a leak current or a photo-organic current is caused by a relatively high energy blue light emission. May cause an undesirable phenomenon. Since the cured film obtained from the resin composition of the present invention has an appropriate absorption around 450 nm, even in such an organic EL display device, generation of leakage current, photoinduced current, etc. is prevented, and stable driving / light emission is achieved. Characteristics are obtained.

  Further, the cured film obtained from the resin composition of the present invention includes a surface protective film for semiconductor devices such as LSI, an interlayer insulating film, an adhesive or an underfill agent for encapsulating a device in a package, and a cap agent for preventing copper migration It can be preferably used for applications such as an on-chip microlens for a solid-state image sensor and a flattening film for various displays and solid-state image sensors.

  Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. In addition, evaluation of the resin composition in an Example was performed with the following method.

(1) Synthesis evaluation of amic acid <proton NMR spectrum>
Amic acid was dissolved in deuterated dimethyl sulfoxide to prepare a sample having a concentration of 0.5% by weight. The proton NMR spectrum of amic acid was measured using an NMR spectrophotometer (manufactured by JEOL Datum Co., Ltd., EX-270).

(2) Coloring evaluation of resin composition <Evaluation of transmittance>
A resin composition (hereinafter referred to as varnish) was spin-coated on a 5 cm square glass substrate and prebaked at 120 ° C. for 2 minutes to prepare a prebaked film having a thickness of 3.0 μm. In addition, the varnish was spin-coated so as to have a film thickness of 3.0 μm, and an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd. was used for 60 minutes at 320 ° C. under a nitrogen stream (oxygen concentration of 20 ppm or less). A cured film was prepared by curing. The film thickness of the pre-baked film and the cured film was measured at a refractive index of 1.629 using Surfcom 1400D (manufactured by Tokyo Seimitsu Co., Ltd.). About the prebaked film | membrane and cured film which were obtained in this way, the ultraviolet-visible spectrophotometer MultiSpec-1500 (made by Shimadzu Corp.) was used, the transmission spectrum of wavelength 300nm -800nm was measured, and wavelength 400nm and 450nm The transmittance was measured. For each of the wavelengths of 400 nm and 450 nm, the transmittance change was determined by the following equation from the transmittance before curing (= pre-baked film) and after curing (= cured film). If the transmittance change is 20% or more, it can be judged as good, and if it is 30% or more, it can be judged as very good.
Change in transmittance (%) = transmittance before cure (%) − transmittance after cure (%)
Synthesis Example 1 Synthesis of hydroxyl group-containing diamine compound (a)
18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF) was added to 100 mL of acetone and propylene oxide (Tokyo). The product was dissolved in 17.4 g (0.3 mol) manufactured by Kasei Co., Ltd. and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

  30 g of the obtained white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated by confirming that the balloons did not squeeze any more. After completion of the reaction, the catalyst was filtered to remove the palladium compound as a catalyst, and the mixture was concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

Synthesis Example 2 Synthesis of amic acid compound (a-1)
Under a dry nitrogen stream, 6.05 g (0.01 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 was dissolved in 33 g of N-methylpyrrolidone (hereinafter referred to as NMP). To this, 4.62 g (0.021 mol) of 3,4,5,6-tetrafluorophenylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-1).

Synthesis Example 3 Synthesis of amic acid compound (a-2)
Under a dry nitrogen stream, 6.05 g (0.01 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 was dissolved in 43 g of NMP. Here, 3.32 g (0.02 mol) of 3-fluorophenylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, followed by stirring at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-2).

Synthesis Example 4 Synthesis of amic acid compound (a-3)
Under a dry nitrogen stream, 2.20 g (0.006 mol) of BAHF was dissolved in 15 g of NMP. To this was added 2.77 g (0.0126 mol) of 3,4,5,6 tetrafluorophenylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-3).

Synthesis Example 5 Synthesis of amic acid compound (a-4)
Under a dry nitrogen stream, 2.0 g (0.01 mol) of 4,4′-diaminodiphenyl ether was dissolved in 9.9 g of NMP. To this, 4.62 g (0.021 mol) of 3,4,5,6 tetrafluorophenylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-4).

Synthesis Example 6 Synthesis of amic acid compound (a-5)
Under a dry nitrogen stream, 0.93 g (0.01 mol) of aniline was dissolved in 5 g of NMP. 2.44 g (0.011 mol) of 3,4,5,6 tetrafluorophenylphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-5).

Synthesis Example 7 Synthesis of amic acid compound (a-6)
Under a dry nitrogen stream, 9.07 g (0.015 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 was dissolved in 45 g of NMP. To this, 4.67 g (0.0315 mol) of phthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-6).

Synthesis Example 8 Synthesis of amic acid compound (a-7)
Under a dry nitrogen stream, 9.07 g (0.015 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 was dissolved in 26 g of NMP. Here, 6.24 g (0.0315 mol) of 2,3-naphthalene anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added together with 10 g of NMP, and the mixture was stirred at 25 ° C. for 2 hours. The solution was poured into 1.5 L of water to obtain a white powder. The powder was collected by filtration and further washed with water three times. After washing, the white powder was dried with a vacuum dryer at 50 ° C. for 24 hours to obtain an amic acid compound represented by the following formula (a-7).

Synthesis Example 9 Synthesis of polyamic acid (Polymer B)
Under a dry nitrogen stream, 57.4 g (0.095 mol) of the hydroxyl group-containing diamine obtained in Synthesis Example 1 and 1,3-bis (3-aminopropyl) tetramethyldisiloxane (hereinafter referred to as SiDA) 1 .24 g (0.005 mol) was dissolved in 200 g of NMP. To this was added 31.0 g (0.1 mol) of 4,4′-oxydiphthalic anhydride (hereinafter referred to as ODPA), and the mixture was stirred at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of dimethylformamide dimethylacetal (manufactured by Mitsubishi Rayon Co., Ltd., hereinafter referred to as DFA) with 5 g of NMP was added dropwise over 10 minutes. After dropping, stirring was continued at 40 ° C. for 2 hours. After the completion of stirring, the solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. Further, it was washed with 2 L of water three times, and the collected polymer solid was dried with a vacuum dryer at 50 ° C. for 72 hours to obtain polyamic acid.

Synthesis Example 10 Synthesis of quinonediazide compound (c-1)
Under a dry nitrogen stream, 4,4 ′-[1- [4- [1- (4-hydroxyphenyl-1) -1-methylethyl] phenyl] ethylidene] bisphenol (manufactured by Honshu Chemical Industry Co., Ltd., hereinafter referred to as TrisP-) PA)) 21.22 g (0.05 mol) and 5-naphthoquinone diazide sulfonic acid chloride (Toyo Gosei Co., Ltd., NAC-5) 26.8 g (0.1 mol) 1,4-dioxane 450 g And brought to room temperature. Here, 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane was added dropwise so that the temperature in the system would not be 35 ° C. or higher. After dropping, the mixture was stirred at 40 ° C. for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration and further washed with 1 L of 1% aqueous hydrochloric acid. Thereafter, it was further washed twice with 2 L of water. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound represented by the following formula.

Synthesis Example 11 Synthesis of alkoxymethyl group-containing compound (f-1) (1) 1,1,1-tris (4-hydroxyphenyl) ethane (manufactured by Honshu Chemical Industry Co., Ltd., TrisP-HAP) 103.2 g (0 4 mol) was dissolved in a solution of 80 g (2.0 mol) of sodium hydroxide in 800 g of pure water. After complete dissolution, 686 g of 36-38 wt% formalin aqueous solution was added dropwise at 20-25 ° C. over 2 hours. Then, it stirred at 20-25 degreeC for 17 hours. This was neutralized by adding 98 g of sulfuric acid and 552 g of water, and allowed to stand for 2 days. Needle-like white crystals formed in the solution after standing were collected by filtration and washed with 100 mL of water. The white crystals were vacuum dried at 50 ° C. for 48 hours. When the dried white crystals were analyzed at 254 nm using high performance liquid chromatography manufactured by Shimadzu Corporation using ODS as the column and acetonitrile / water = 70/30 as the developing solvent, the starting material disappeared completely. The purity was found to be 92%. Furthermore, when it analyzed by NMR (the JEOL Co., Ltd. product, GX-270) using DMSO-d6 for a heavy solvent, it turned out that it is the trimethyl P-HAP hexamethylolated.

  (2) Next, the compound thus obtained was dissolved in 300 mL of methanol, 2 g of sulfuric acid was added, and the mixture was stirred at room temperature for 24 hours. To this solution, 15 g of an anionic ion exchange resin (Rumm and Haas, Amberlyst IRA96SB) was added and stirred for 1 hour, and the ion exchange resin was removed by filtration. Thereafter, 500 mL of ethyl lactate was added, and methanol was removed by a rotary evaporator to obtain an ethyl lactate solution. When this solution was allowed to stand at room temperature for 2 days, white crystals were formed. When the obtained white crystals were analyzed by high performance liquid chromatography, it was found to be a 99% pure TrisP-HAP hexamethoxymethyl compound (alkoxymethyl group-containing compound (A-1)) represented by the following formula. all right.

  The chemical structure of the compound TrisP-HAP (produced by Honshu Chemical Industry Co., Ltd.) having other phenolic hydroxyl groups used in the examples is as follows.

Example 1
10 g of the polyamic acid (Polymer B) obtained in Synthesis Example 9 was weighed, and 1 g of the amic acid compound (a-1) was dissolved in 40 g of γ-butyrolactone (hereinafter referred to as GBL) to obtain a varnish of a polyimide precursor composition. Got. The transmittance of the film before and after curing obtained using this varnish at 400 nm was 97% before curing and 40% after curing. As a result, the transmittance change was 57%. The transmittance at 450 nm was 98% before curing and 42% after curing. As a result, the transmittance change was 56%. The transmission spectrum before and after curing is shown in FIG.

Example 2
A varnish of the polyimide resin composition was obtained in the same manner as in Example 1 except that 1 g of the amic acid compound (a-2) was added instead of the amic acid compound (a-1) obtained in Synthesis Example 2. The transmittance of the film before and after curing obtained using this varnish at 400 nm was 97% before curing and 53% after curing. As a result, the transmittance change was 44%. The transmittance at 450 nm was 98% before curing and 82% after curing. As a result, the transmittance change was 16%.

Example 3
Instead of the amic acid compound (a-1) obtained in Synthesis Example 2, a varnish of a polyimide resin composition was obtained in the same manner as in Example 1 except that 1 g of the amic acid compound (a-3) was added. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 97% before curing and 28% after curing. As a result, the transmittance change was 69%. The transmittance at 450 nm was 98% before curing and 30% after curing. As a result, the transmittance change was 68%.

Example 4
In place of the amic acid compound (a-1) obtained in Synthesis Example 2, 1 g of the amic acid compound (a-4) was added and dissolved in 40 g of NMP instead of GBL 40 g. A varnish of the resin composition was obtained. The transmittance of the film before and after curing obtained using this varnish at 400 nm was 99% before curing and 35% after curing. As a result, the transmittance change was 64%. The transmittance at 450 nm was 99% before curing and 36% after curing. As a result, the transmittance change was 63%.

Example 5
A varnish of a polyimide resin composition was obtained in the same manner as in Example 1 except that 1 g of the amic acid compound (a-5) was added instead of the amic acid compound (a-1) obtained in Synthesis Example 2. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 97% before curing and 22% after curing. As a result, the transmittance change was 75%. The transmittance at 450 nm was 98% before curing and 21% after curing. As a result, the transmittance change was 77%.

Example 6
In the varnish produced in Example 1, 3 g of the quinonediazide compound (c-1) obtained in Synthesis Example 10 was dissolved to obtain a varnish of a polyimide precursor composition. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 97% before curing and 34% after curing. As a result, the transmittance change was 63%. The transmittance at 450 nm was 98% before curing and 51% after curing. As a result, the transmittance change was 47%.

Example 7
1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Ciba Specialty Chemicals Co., Ltd.) instead of the quinonediazide compound (c-1) obtained in Synthesis Example 10 )) (D) 0.1 g, ethylene oxide modified bisphenol A dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester BPE-100) (e) A varnish of the resin composition was obtained. The transmittance of the film before and after curing obtained using this varnish at 400 nm was 97% before curing and 40% after curing. As a result, the transmittance change was 57%. The transmittance at 450 nm was 98% before curing and 45% after curing. As a result, the transmittance change was 53%.

Example 8
A polyimide resin composition as in Example 6 except that 2 g of the alkoxymethyl group-containing compound (f-1) obtained in Synthesis Example 11 was added instead of the quinonediazide compound (c-1) obtained in Synthesis Example 10. The varnish was obtained. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 97% before curing and 46% after curing. As a result, the transmittance change was 51%. The transmittance at 450 nm was 98% before curing and 71% after curing. As a result, the transmittance change was 27%.

Example 9
A polyimide was prepared in the same manner as in Example 6 except that 0.50 g of a compound TrisP-HAP (produced by Honshu Chemical Industry Co., Ltd.) having a phenolic hydroxyl group was added instead of the quinonediazide compound (c-1) obtained in Synthesis Example 10. A varnish of the resin composition was obtained. The transmittance of the film before and after curing obtained with this varnish at 400 nm was 97% before curing and 32% after curing. As a result, the transmittance change was 65%. The transmittance at 450 nm was 98% before curing and 37% after curing. As a result, the transmittance change was 61%.

Comparative Example 1
A varnish of a polyimide resin composition was obtained in the same manner as in Example 1 except that the amic acid compound (a-1) obtained in Synthesis Example 2 was not added. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 99% before curing and 82% after curing. As a result, the transmittance change was 17%. The transmittance at 450 nm was 99% before curing and 96% after curing. As a result, the transmittance change was 3%.

Comparative Example 2
A varnish of the polyimide resin composition was obtained in the same manner as in Example 1 except that 1 g of the amic acid compound (a-6) was added instead of the amic acid compound (a-1) obtained in Synthesis Example 2. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 98% before curing and 76% after curing. As a result, the transmittance change was 22%. The transmittance at 450 nm was 99% before curing and 95% after curing. As a result, the change in transmittance was 4%. The transmission spectrum before and after curing is shown in FIG.

Comparative Example 3
A varnish of a polyimide resin composition was obtained in the same manner as in Example 1 except that 1 g of the amic acid compound (a-7) was added instead of the amic acid compound (a-1) obtained in Synthesis Example 2. The transmittance at 400 nm of the film before and after curing obtained using this varnish was 98% before curing and 78% after curing. As a result, the transmittance change was 20%. The transmittance at 450 nm was 98% before curing and 93% after curing. As a result, the change in transmittance was 5%.

  The compositions of Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1, and the evaluation results are shown in Table 2.

1 TFT
2 Wiring 3 Insulating film 4 Flattening film 5 ITO
6 Substrate 7 Contact hole 8 Insulating layer

Claims (6)

A resin composition comprising (a) an amic acid represented by the general formula (1) and (b) polyimide, polybenzoxazole, a polyimide precursor or a polybenzoxazole precursor.

(In the general formula (1), R ¹ is a 1-3 valent hydrocarbon group having 1 to 50 carbon atoms, -CH _2- of a 1-3 valent hydrocarbon group having 1 to 50 carbon atoms is -CO-, A group substituted by —NH—, —NHCO—, —O—, —S—, —SO ₂ —, —Si— or —Si (CH ₃ ) ₂ —; A group in which a hydrogen atom of a hydrocarbon group is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom or —COOR ¹ ′, or a 1 to 3 valent group having 1 to 50 carbon atoms The hydrogen atom of the group in which —CH ₂ — of the hydrocarbon group is substituted by —NH—, —NHCO—, —O— or —S— is a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom , is substituted by a chlorine atom or a -COOR ¹ ' Indicating the group .R ¹ 'represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms .R ² is a hydrogen atom or .n represents an alkyl group having 1 to 20 carbon atoms is an integer of 1 to 3, o is Represents an integer of 1 to 4.) 2. The resin composition according to claim 1, wherein R ^{1 of the} amic acid represented by the general formula (1) has at least one aromatic ring. 2. The resin composition according to claim 1, wherein R ^{1 of the} amic acid represented by the general formula (1) is any one of the structures represented by the following structural formulas.

(In the structural formula, J ¹ is a direct bond, —CO—, —COO—, —CONH—, —CH ₂ —, —C ₂ H ₄ —, —O—, —C ₃ H ₆ —, —C ₃ F _{6 -, - C 13 H 8} -, - SO 2 -, - S -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -O -, - C 6 H 4 -, - C _{6 H 4 -O-C 6 H} 4 -, - C 6 H 4 -C 3 H 6 -C 6 H 4 - or _{-C 6 H 4 -C 3 F 6} -C 6 H 4 - are shown .R ³ to R ^{6, R 8} is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, ^{R 7} represents a monovalent hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) The said (b) polyimide, polybenzoxazole, a polyimide precursor, or a polybenzoxazole precursor has the structural unit represented by General formula (2) as a main component, The any one of Claims 1-3 characterized by the above-mentioned. The resin composition described in 1.

(R ⁹ and R ¹⁰ may be the same or different from each other, and a divalent to octavalent hydrocarbon group having 2 or more carbon atoms or a divalent to octavalent hydrocarbon group having 2 or more carbon atoms) is -CO - -, - -CH ₂ of COO -, - NH -, - NHCO -, - O -, - S -, - SO 2 -, - Si- or -Si _{(CH 3) 2} - is replaced by Or a hydrogen atom of a divalent to octavalent hydrocarbon group having 2 or more carbon atoms is substituted by a fluoroalkyl group, a hydroxyl group, an alkoxyl group, a nitro group, a cyano group, a fluorine atom, a chlorine atom or -COOR ⁹ ' R ⁹ ′ represents hydrogen or an alkyl group having 1 to 20 carbon atoms, R ¹¹ and R ¹² may be the same or different, and a hydrogen atom or carbon number 1 may be present. Represents an alkyl group of ˜20, p and q are Each is an integer of 0 to 4, and r and s are each an integer of 0 to 2.)   Furthermore, (c) a photo-acid generator is contained, The resin composition in any one of Claims 1-4 characterized by the above-mentioned.   The resin composition according to any one of claims 1 to 4, further comprising (d) a photopolymerization initiator and (e) a compound having two or more ethylenically unsaturated bonds.

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