JP4456401B2 - Polybenzoxazole precursor - Google Patents

Description

  The present invention relates to a polybenzoxazole precursor and a method for producing the same. The present invention is also excellent in electrical insulation, heat resistance, adhesion to a substrate, mechanical strength, etc., and can form a film useful as a protective film or insulation film for circuit boards such as semiconductor elements or printed boards. The present invention relates to a coating composition.

  Furthermore, the present invention is a resist having excellent operational stability and high reliability for conductor image formation, in particular, a positive photosensitive resin composition suitable as an etching resist for producing a printed wiring board, and a pattern using the resin composition. It relates to a forming method.

  Conventionally, a polyimide resin excellent in heat resistance and mechanical properties has been used as a coating organic material for protecting and insulating a circuit board such as a semiconductor element or printed circuit board.

  In recent years, photosensitive polyimide resins excellent in heat resistance and mechanical properties are being used as organic materials for the purpose of circuit pattern formation, protection and insulation of electronic / electrical circuit boards such as semiconductor elements or printed circuit boards. . In such a photosensitive polyimide resin composition, a negative photosensitive polyimide resin composition in which an exposed portion is cured and insolubilized is disclosed (see, for example, Patent Document 1, Patent Document 2, etc.). However, negative photosensitive polyimide resin compositions have problems in sensitivity, resolution, and processability, and positive photosensitive polyimide resin compositions have been developed for the purpose of improving them (for example, patents). (Refer to Literature 3, Patent Literature 4, Patent Literature 5, etc.). However, in general, a polyimide resin has a high hygroscopic property and has a problem in terms of electrical characteristics. In particular, in recent years, it has not been possible to sufficiently meet the electrical characteristics required with the miniaturization of circuits and the speeding up of signals.

  On the other hand, polybenzoxazole resin has excellent electrical insulation in addition to heat resistance, mechanical strength, etc., so it is expected that it can be sufficiently applied to future applications for higher density and higher performance of electronic devices. Has been. Since the polybenzoxazole resin film has high heat resistance, excellent electrical properties, and fine workability, the possibility of use as a resin for interlayer insulation as well as for wafer coating has been studied.

  For example, Patent Document 6, Patent Document 7 and the like disclose a positive photosensitive resin composed of a polybenzoxazole precursor and a diazoquinone compound. The polybenzoxazole precursors used in these are generally prepared by reacting a dicarboxylic acid chloride with a suitable bis-o-aminophenol. However, since these reactions produce hydrogen chloride (HCl), it is generally necessary to add a soluble base such as pyridine or triethylamine to capture it, but the chloride formed thereby remains in the product. If so, it may adversely affect the semiconductor element and the electronic / electrical circuit. For example, it must be completely removed by an ion exchanger. However, it is difficult to obtain a high-purity polybenzoxazole precursor by the above-described method, and labor is required for purification and the cost is high.

  Therefore, the present inventors have proposed a new benzoxazole precursor obtained by reacting a bis-o-aminophenol compound with a dialdehyde compound (see Patent Document 8). The benzoxazole precursor is a high-purity novel polyoxazole precursor that does not contain an ionic by-product that adversely affects electrical properties, and can be manufactured at low cost because of its easy manufacturing method. is there. However, the novel polyoxazole precursor resin composition needs to be stored at a low temperature because the viscosity tends to increase during storage. The increase in viscosity is presumed to be due to the reaction between the unreacted aldehyde group and amino group at the end of the resin molecule to increase the molecular weight, and when the viscosity varies during storage, the coating conditions are changed each time to obtain the same film thickness. In addition, when a polybenzoxazole precursor whose viscosity has been increased by storage is used as a positive photosensitive resin composition, there is a problem that the development speed becomes slower than the initial stage. Since storage at low temperature is costly and not convenient, a polybenzoxazole precursor having good storage stability even at room temperature is desired.

  In order to prevent high molecular weight due to storage, the synthesis conditions of the polybenzoxazole precursor are changed, and the blending molar ratio of the raw material aldehyde compound and bis-o-aminophenol compound is blended in only one of the two, and the resin molecule ends When only the aldehyde group or only the o-aminophenol group remains, the polybenzoxazole coating obtained by coating the resin solution and heating at a high temperature of 300 ° C. or more becomes brittle and the practicality is lowered. It is presumed that this is because the groups at the resin molecule terminals do not react with each other, and the molecular weight does not increase until the film has tough physical properties during heating.

Japanese Patent Publication No.55-030207

JP 54-145794 A Japanese Patent Laid-Open No. 06-324493 Japanese Patent Laid-Open No. 07-179604 JP 2000-143980 A Japanese Examined Patent Publication No. 1-46862 Japanese Patent Application Laid-Open No. 07-281441 JP 2003-221444 A

  The object of the present invention is excellent in electrical insulation, heat resistance, mechanical strength, workability, etc., and in particular, forms a film useful as a protective film or insulating film for a circuit board such as a semiconductor element or a printed circuit board, and is stable in storage. It is to provide a polybenzoxazole precursor having excellent properties.

  Yet another object of the present invention is that it does not contain impurities such as chlorides that adversely affect semiconductor elements and electronic / electrical circuits, is inexpensive, has excellent heat resistance, mechanical properties, workability and electrical properties, and high resolution. It is an object of the present invention to provide a positive photosensitive resin composition capable of forming a circuit pattern.

As a result of intensive studies to achieve the above object, the present inventors have polymerized by heat at the molecular terminals of a polyoxazole precursor obtained by reacting a bis-o-aminophenol compound with a dialdehyde compound. the Rukoto organic group allowed Yes, further allowed have a specific monovalent organic group which can be converted to decompose hydrogen atoms by the action of an acid in the polyoxazole precursor having the can functional groups, electrical insulation, heat The present inventors have found that a polyoxazole precursor excellent in not only the property and mechanical strength but also the adhesion to the substrate and the workability can be obtained.

  Thus, the present invention provides a general formula (1)

In the formula, A ₁ represents a tetravalent aromatic group, N and OE ₁ bonded to A ₁ form a pair, and N and OE ₁ of each pair are bonded to adjacent carbons on the same aromatic ring. A ₂ represents a divalent organic group, and E ₁ is a t-butoxycarbonyl group, a t-butyl group, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, a trialkylsilyl group or an iso-propoxycarbonyl group. A polybenzoxazole precursor having a repeating unit represented by at least one group selected from the group , wherein n is a number from 2 to 300, wherein the molecular terminals of the precursor are polymerized by heat. The present invention provides a polybenzoxazole precursor characterized by having an organic group having a functional group.

  The present invention also provides a general formula (2)

In the formula, A ₁ represents a tetravalent aromatic group.
A bis-o-aminophenol compound (A) represented by
General formula (3)

In the formula, A ₂ represents a divalent organic group.
And at least one thermally polymerizable functional group-containing compound selected from the group consisting of a carboxylic acid anhydride having at least one functional group capable of being polymerized by heat, an aldehyde compound, and an amino compound (C) were reacted to obtain a polybenzoxazole precursor E ₁ is hydrogen in the above formula (I), further resulting the polybenzoxazole E ₁ precursor t- butoxycarbonyl group, t - butyl group, t-butoxycarbonyl methyl group, tetrahydropyranyl group, to claim 1, characterized that you substituted with at least one group selected from the group consisting of trialkylsilyl groups and iso- propoxycarbonyl group A method for producing the described polybenzoxazole precursor is provided.

  The present invention further provides a coating composition containing the polybenzoxazole precursor.

  The present invention further provides a positive photosensitive resin composition comprising the polybenzoxazole precursor and an acid generator.

  By providing an organic group having a functional group capable of polymerizing with heat at the molecular terminal of the polyoxazole precursor obtained by reacting a bis-o-aminophenol compound with a dialdehyde compound, electrical insulation, heat resistance and In addition to obtaining a polyoxazole precursor that is excellent not only in mechanical strength but also in adhesion to the substrate and processability, the polyoxazole precursor has high purity and does not contain ionic by-products. Since no cleaning is required, the manufacturing cost can be greatly reduced, which is extremely economical and useful.

  The polyoxazole precursor of the present invention has the general formula (1)

In the formula, A ₁ represents a tetravalent aromatic group, N and OE ₁ bonded to A ₁ form a pair, and N and OE ₁ of each pair are bonded to adjacent carbons on the same aromatic ring. A ₂ represents a divalent organic group, E ₁ represents a monovalent organic group that can be decomposed by the action of hydrogen or an acid and converted to a hydrogen atom, and n is a number from 2 to 300. A polybenzoxazole precursor having a repeating unit, wherein the molecular terminal of the precursor has an organic group having a functional group capable of being polymerized by heat. Here, E ₁ is a monovalent organic group that can be decomposed and converted to a hydrogen atom by the action of hydrogen or an acid. Examples of the monovalent organic group that can be decomposed and converted to a hydrogen atom by the action of an acid include: , T-butoxycarbonyl group, t-butyl group, t-butoxycarbonylmethyl group, tetrahydropyranyl group, trialkylsilyl group, iso-propoxycarbonyl group and the like.

  The polyoxazole precursor includes a bis-o-aminophenol compound (A), a dialdehyde compound (B), and a carboxylic acid anhydride having at least one functional group capable of being polymerized by heat, an aldehyde compound, and an amino compound. It is produced by reacting at least one heat-polymerizable functional group-containing compound (C) selected from the above. The manufacturing method will be described below.

Bis-o-aminophenol compound (A)
The bis-o-aminophenol compound (A) used as a starting material in the production of the polybenzoxazole precursor of the present invention is a compound represented by the following general formula (2).

In the formula, A ₁ represents a tetravalent aromatic group, NH ₂ group and OH group bonded to A ₁ form a pair, and NH ₂ group and OH group of each pair are adjacent carbons on the same aromatic ring. Is bound to.

The aromatic group is a carbocyclic or heterocyclic monocyclic or polycyclic ring containing at least one, preferably 1 to 3 heteroatoms selected from nitrogen, oxygen and sulfur atoms in the ring. In some cases, an aromatic group which may form a condensed ring is included. Specific examples of such an aromatic group A ₁ include those having the following structure.

In the formula, X and Y are each independently —CH ₂ —, —O—, —S—, —SO—, —SO ₂ —, —SO ₂ NH—, —CO—, —CO ₂ —, —NHCO—. , -NHCONH-, -C (CF ₃ ) _2- , -CF _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) (CH ₃ )-, -Si _{(R 21) 2 -, -} O-Si (R 21) 2 -O -, - Si (R 21) 2 -O-Si (R 22) 2 -, - (CH 2) a -Si (R 21) ₂ -O-Si (R ₂₂ ) _2- (CH ₂ ) _a- (where a is an integer from 0 to 6) and a direct bond, R _{1 to} R ₁₄ , R ₂₁ and R ₂₂ is independently H, F, an alkyl or alkoxyl group having 1 to 6 carbon atoms, or — (CF ₂ ) _b —CF ₃ or —O— (CF ₂ ) _b —CF ₃ (where b is 0 to 5). P and q are each an integer of 0 to 3.

Of these aromatic groups _{A 1,} in particular, the formulas (2-1) to (2-6), (2-10) to groups (2-12), more particularly (2-1), (2-4 ), (2-6) and (2-12) are preferred.

  Specific examples of the bis-o-aminophenol compound of the above formula (2) are as follows. These are merely examples and are not intended to be limiting.

  2,4-diamino-1,5-benzenediol, 2,5-diamino-1,4-benzenediol, 2,5-diamino-3-fluoro-1,4-benzenediol, 2,5-diamino-3 , 6-difluoro-1,4-benzenediol, 2,5-diamino-3,6-difluoro-1,4-benzenediol, 2,6-diamino-1,5-dihydroxynaphthalene, 1,5-diamino- 2,6-dihydroxynaphthalene, 2,6-diamino-3,7-dihydroxynaphthalene, 1,6-diamino-2,5-dihydroxynaphthalene, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3, 3'-diamino-4,4'-dihydroxybiphenyl, 2,3'-diamino-3,2'-dihydroxybiphenyl, 3,4'-diamino-4,3'-dihydroxy Biphenyl, 4,4′-diamino-3,3′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 2,3′-diamino-3,2′-dihydroxy-6,6′-trifluoromethylbiphenyl, 3,4′-diamino-4,3′-dihydroxy-6,6′-ditrifluoromethylbiphenyl, 4, 4′-diamino-3,3′-dihydroxy-5,5′-ditrifluoromethylbiphenyl, 3,3′-diamino-4,4′-dihydroxy-5,5′-ditrifluoromethylbiphenyl, 2,3 ′ -Diamino-3,2'-dihydroxy-5,5'-ditrifluoromethylbiphenyl, 3,4'-diamino-4,3'-dihydroxy-5,5'-ditrifluoromethylbiphenyl Bis (4-amino-3-hydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) methane, 3,4'-diamino-4,3'-dihydroxydiphenylmethane, bis (4-amino-3- Hydroxy-6-trifluoromethylphenyl) methane, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) methane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditri Fluoromethyldiphenylmethane, bis (4-amino-3-hydroxyphenyl) difluoromethane, bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxydiphenyldifluoromethane, bis (4-Amino-3-hydroxy-6-trifluoromethylphenyl) difluoromethane Bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) difluoromethane, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyldifluoromethane, bis (4 -Amino-3-hydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) ether, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis (4-amino-3-hydroxy-6- Trifluoromethylphenyl) ether, bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) ether, 3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl ether, Bis (4-amino-3-hydroxyphenyl) ketone, bis (3-amino-4-hydride) Xylphenyl) ketone, 3,4'-diamino-4,3'-dihydroxydiphenylketone, bis (4-amino-3-hydroxy-6-trifluoromethylphenyl), bis (3-amino-4-hydroxy-6- Trifluoromethylphenyl) ketone, 3,4′-diamino-4,3′-dihydroxy-6,6′-ditrifluoromethyldiphenylketone, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 2 , 2-bis (4-amino-3-hydroxyphenyl) propane, 2,2- (3,4'-diamino-4,3'-dihydroxydiphenyl) propane, 2,2-bis (3-amino-4-) Hydroxy-6-trifluoromethylphenyl) propane, 2,2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) propa 2,2- (3,4'-diamino-4,3'-dihydroxy-6,6'-ditrifluoromethyldiphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2- (3,4'-diamino-4,3'-dihydroxydiphenyl) hexafluoropropane, 2,2-bis ( 3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2,2- (3 , 4′-diamino-4,3′-dihydroxy-6,6′-ditrifluoromethyldiphenyl) hexafluoropropane, bis (4-amino -3-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone, 3,4'-diamino-4,3'-dihydroxydiphenylsulfone, bis (4-amino-3-hydroxyphenyl) sulfide, 4-amino-3-hydroxyphenyl 4-amino-3-hydroxybenzoate, 4-amino-3-hydroxyphenyl 4-amino-3-hydroxybenzoate, N- (4-amino-3-hydroxyphenyl) 4-amino- 3-hydroxybenzanilide, bis (4-amino-3-hydroxyphenyl) dimethylsilane, bis (3-amino-4-hydroxyphenyl) dimethylsilane, 3,4'-diamino-4,3'-dihydroxydiphenyl ether, bis (4-Amino-3-hydroxyphenyl) tetramethyldi Loxane, bis (3-amino-4-hydroxyphenyl) tetramethyldisiloxane, 2,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl, 2,4′-bis (3-amino-4-hydroxy) Phenoxy) biphenyl, 4,4′-bis (3-amino-4-hydroxyphenoxy) biphenyl, 2,4′-bis (3-amino-4-hydroxyphenoxy) biphenyl, 2,4′-bis [4- ( 4-amino-3-hydroxyphenoxy) phenyl] ether, 2,4′-bis (3-amino-4-hydroxyphenoxy) biphenyl, 4,4′-bis [4- (4-amino-3-hydroxyphenoxy) Phenyl] ether, 2,4′-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] ether, 2,4′-bis [4- (3-a No-4-hydroxyphenoxy) phenyl] ether, 4,4′-bis (4-amino-3-hydroxyphenoxy) benzophenone, 4,4′-bis (4-amino-3-hydroxyphenoxy) benzophenone, 4,4 '-Bis (3-amino-4-hydroxyphenoxy) benzophenone, 2,4'-bis (3-amino-4-hydroxyphenoxy) benzophenone, 2,2-bis (3-amino-4-hydroxy-5-tri Fluoromethylphenyl) propane, 2,4′-bis (4-amino-3-hydroxyphenoxy) octafluorobiphenyl, 2,4′-bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 4,4 ′ -Bis (3-amino-4-hydroxyphenoxy) octafluorobiphenyl, 2,4'-bis (3-a No-4-hydroxyphenoxy) octafluorobiphenyl, 4,4′-bis (4-amino-3-hydroxyphenoxy) octafluorobenzophenone, 4,4′-bis (4-amino-3-hydroxyphenoxy) octafluorobenzophenone 4,4′-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 2,4′-bis (3-amino-4-hydroxyphenoxy) octafluorobenzophenone, 2,2-bis (3-amino -4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino) -3-hydroxyphenoxy) phenyl] hexafluoropropane, 2,2-bi [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, 2,8-diamino-3,7-dihydroxydibenzofuran, 2,8-diamino-3,7-dihydroxyfluorene, 2,6-diamino -3,7-dihydroxyxanthene, 9,9-bis [4-amino-3-hydroxyphenyl] fluorene, 9,9-bis [3-amino-4-hydroxyphenyl] fluorene, 9,9-bis [3- Amino-4-hydroxyphenyl] fluorene and a compound represented by the following formula:

Such.

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

Dialdehyde compound (B)
The dialdehyde compound to be reacted with the bis-o-aminophenol compound of the above formula (2) according to the method of the present invention is represented by the general formula (3).

In the formula, A ₂ represents a divalent organic group.

  The above-mentioned divalent organic group is a carbocyclic or heterocyclic, saturated or unsaturated group containing at least 1, preferably 1 to 3, hetero atoms selected from nitrogen, oxygen and sulfur in the ring. Divalent groups which may be saturated and monocyclic or polycyclic and optionally form a condensed ring are included. Specific examples of such an organic group include those having the following structure.

In the formula, X and Y are each independently —CH ₂ —, —O—, —S—, —SO—, —SO ₂ —, —SO ₂ NH—, —CO—, —CO ₂ —, —NHCO—. , -NHCONH-, -C (CF ₃ ) _2- , -CF _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) (CH ₃ )-, -Si _{(R 21) 2 -, -} O-Si (R 21) 2 -O -, - Si (R 21) 2 -O-Si (R 22) 2 -, - (CH 2) a -Si (R 21) ₂ -O-Si (R ₂₂ ) _2- (CH ₂ ) _a- (where a is an integer from 0 to 6) and a direct bond, R _{1 to} R ₁₆ , R ₂₁ and R ₂₂ is independently H, F, an alkyl or alkoxyl group having 1 to 6 carbon atoms, or — (CF ₂ ) b—CF ₃ or —O— (CF ₂ ) b—CF ₃ (where b is 0 to 5). Z is —CH ₂ —, —C ₂ H ₄ — or —CH ₂ ═CH ₂ —, and p and q are each an integer of 0 to 3.

Among these organic groups _{A 2,} in particular, the formulas (3-1) to (3-8), to (3-12) (3-22), (3-25), to (3-27) to (3 -29) and (3-31) groups, more particularly the groups of formulas (3-1), (3-5), (3-7), (3-14) and (3-31) are preferred. .

  Specific examples of the dialdehyde compound of the above formula (3) are as follows. These are merely examples and are not intended to be limiting.

  Phthalaldehyde, isophthalaldehyde, terephthalaldehyde, 3-fluorophthalaldehyde, 4-fluorophthalaldehyde, 2-fluoroisophthalaldehyde, 4-fluoroisophthalaldehyde, 5-fluoroisophthalaldehyde, 2-fluoroterephthalaldehyde, 3-trifluoromethyl Phthalaldehyde, 4-trifluoromethylphthalaldehyde, 2-trifluoromethylisophthalaldehyde, 4-trifluoromethylisophthalaldehyde, 5-trifluoromethylisophthalaldehyde, 2-trifluoromethylterephthalaldehyde, 3,4,5,6 -Tetrafluorophthalaldehyde, 2,4,5,6-tetrafluoroisophthalaldehyde, 2,3,5,6-tetrafluoroterephthalaldehyde Pyridine-2,3-dialdehyde, pyridine-3,4-dialdehyde, pyridine-3,5-dialdehyde, pyrazine-2,3-dialdehyde, pyrazine-2,5-dialdehyde, pyrazine-2,6 -Dialdehyde, pyrimidine-2,4-dialdehyde, pyrimidine-4,5-dialdehyde, pyrimidine-4,6-dialdehyde, naphthalene-1,5-dialdehyde, naphthalene-1,6-dialdehyde, 2 , 6-dialdehyde, naphthalene-3,7-dialdehyde, 2,3,4,6,7,8-hexafluoronaphthalene-1,5-dialdehyde, 2,3,4,5,6,8- Hexafluoronaphthalene-1,6-dialdehyde, 1,3,4,5,7,8-hexafluoronaphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene -2,6-dialdehyde, 1,5-bis (trifluoromethyl) naphthalene-2,6-dialdehyde, 1-trifluoromethylnaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) ) Naphthalene-3,7-dialdehyde, 1-trifluoromethyl-2,4,5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1-bis (trifluoromethyl) methoxy-2,4 , 5,6,8-pentafluoronaphthalene-3,7-dialdehyde, 1,5-bis (trifluoromethyl) -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, 1, 5-bis [bis (trifluoromethyl) methoxy] -2,4,6,8-tetrafluoronaphthalene-3,7-dialdehyde, 2,2′-biphenyldialdehyde, , 4'-biphenyldialdehyde, 3,3'-biphenyldialdehyde, 6,6'-difluoro-3,4-biphenyldialdehyde, 4,4'-biphenyldialdehyde, 6,6'-difluoro-2 , 4′-biphenyldialdehyde, 6,6′-difluoro-3,3′-biphenyldialdehyde, 6,6′-difluoro-3,4′-biphenyldialdehyde, 6,6′-difluoro-4,4 '-Biphenyldialdehyde, 6,6'-ditrifluoromethyl-2,2'-biphenyldialdehyde, 6,6'-ditrifluoromethyl-2,4'-biphenyldialdehyde, 6,6'-ditrifluoromethyl −3,3′-biphenyldialdehyde, 6,6′-ditrifluoromethyl-3,4′-biphenyldialdehyde, 6,6′-ditrifluoromethyl-4,4′-bifu Enyldialdehyde, 2,4'-oxydibenzaldehyde, 3,3'-oxydibensaldehyde, 3,4'-oxydibenzaldehyde, 4,4'-oxydibenzaldehyde, 2,4'-di Formyldiphenylmethane, 3,3′-diformyldiphenylmethane, 3,4′-diformyldiphenylmethane, 4,4′-diformyldiphenylmethane, 2,4′-diformyldiphenyldifluoromethane, 3,3′-diformyldiphenyldifluoro Methane, 3,4'-diformyldiphenyldifluoromethane, 4,4'-diformyldiphenyldifluoromethane, 3,3'-diformyldiphenylsulfone, 3,4'-diformyldiphenylsulfone, 4,4'-di Formyldiphenylsulfone, 3,3′-diformyldiphenylsulfide, 3,4′-diformi Rudiphenyl sulfide, 4,4′-diformyl diphenyl sulfide, 3,3′-diformyl diphenyl ketone, 3,4′-diformyl diphenyl ketone, 4,4′-diformyl diphenyl ketone, 2,2-bis ( 3-formylphenyl) propane, 2,2-bis (4-formylphenyl) propane, 2,2- (3,4'-diformylphenyl) propane, 2,2- (3,4'-diformylphenyl) Propane, 2,2- (2,4′-diformylphenyl) propane, 2,2-bis (3-formylphenyl) hexafluoropropane, 2,2-bis (4-formylphenyl) hexafluoropropane, 2, 2- (2,4′-diformylphenyl) hexafluoropropane, 2,2- (3,4′-diformylphenyl) hexafluoropropane, 1,3- (3-diformylphenoxy) benzene, 1,4-bis (3-formylphenoxy) benzene, 1,4-bis (4-formylciphenoxy) benzene, 3,3 ′-[1,4-phenylenebis ( 1-methylethylidene)] bisbenzaldehyde, 3,4 ′-[1,4-phenylenebis (1-methylethylidene)] bisbenzaldehyde, 4,4 ′-[1,4-phenylenebis (1-methylethylidene)] Bisbenzaldehyde, 2,2-bis [4- (2-formylphenoxy) phenyl] propane, 2,2-bis [4- (3-formylphenoxy) phenyl] propane, 2,2-bis [4- (4- Formylphenoxy) phenyl] propane, 2,2-bis (4- [3-formylphenoxy] phenyl) hexafluoropropane, 2,2-bis ( -(4-formylphenoxy) phenyl) hexafluoropropane, bis (4- (3-formylphenoxy) phenyl) sulfide, bis (4- (4-formylphenoxy) phenyl) sulfide, bis (4- (3-formylphenoxy) ) Phenyl) sulfone, bis (4- (4-formylphenoxy) phenyl) sulfone, fluorene 2,6-diformylanthraquinone, fluorene-2,7-dialdehyde, 3,7-dibenzofurandaldehyde, 9,9-bis [4-Formylphenyl] fluorene, 9,9-bis [3-formylphenyl] fluorene, 9,9- (3,4'-diformylphenyl) fluorene, 9,9- (3,4'-diformylphenyl) ) Aromatic dialdehydes such as fluorene; and 1,4-cyclohexanedialdehyde, , 3-cyclohexanedialdehyde, bicyclo [2.2.1] heptane-2,5-dialdehyde, bicyclo [2.2.2] octane-2,5-dialdehyde, bicyclo [2.2.2 ] Oct-7-ene-2,5-dialdehyde, bicyclo [2.2.1] heptane-2,3-dialdehyde, bicyclo [2.2.1] hept-5-ene-2,3-dialdehyde Aldehyde, tricyclo [5.2.1.02,6] decane-3,4-dialdehyde, tricyclo [5.2.1.02,6] dec-4-ene-8,9-dialdehyde, perhydro Naphthalene-2,3-dialdehyde, perhydronaphthalene-1,4-dialdehyde, perhydronaphthalene-1,6-dialdehyde, perhydro-1,4-dimethananaphthalene-2,3-dialdehyde, perhydro- 1,4-me Nonaphthalene-2,7-dialdehyde, perhydro-1,4-methanonaphthalene-7,8-dialdehyde, perhydro-1,4: 5,8-dimethanonaphthalene-2,3-dialdehyde, perhydro-1 , 4: 5,8-dimethanonaphthalene-2,7-dialdehyde, perhydro-1,4: 5,8: 9,10-trimethanoanthracene-2,3-dialdehyde, 4,4′-diformyl Bicyclohexyl, 3,4'-oxydicyclohexanecarbaldehyde, 3,3'-diformyldicyclohexylmethane, 3,4'-diformyldicyclohexylmethane, 4,4'-diformyldicyclohexylmethane, 3,3'-di Formyldicyclohexylfluoromethane, 3,4'-diformyldicyclohexyldifluoromethane, 4,4'-diformyldicyclohexyl Rudifluoromethane, 3,3′-diformyldicyclohexylsulfone, 3,4′-diformyldicyclohexylsulfone, 4,4′-diformyldicyclohexylsulfone, 3,3′-diformyldicyclohexylsulfide, 3,4′-di Formyl dicyclohexyl sulfide, 4,4′-diformyl dicyclohexyl sulfide, 3,3′-diformyl dicyclohexyl ketone, 3,4′-diformyl dicyclohexyl ketone, 4,4′-diformyl dicyclohexyl ketone, 2,2-bis ( 3-formylcyclohexyl) propane, 2,2-bis (4-formylcyclohexyl) propane, 2,2-bis (3-formylcyclohexyl) hexafluoropropane, 2,2-bis (4-formylcyclohexyl) hexafluoropropane, 1,3 Bis (3-diformylcyclohexyl) benzene, 1,4-bis (3-formylcyclohexyl) benzene, 1,4-bis (4-formylcyclohexyl) benzene, 3,3 ′-(1,4-cyclohexylenebis ( 1-methylethylidene)) biscyclohexylsancarbaldehyde, 3,4 '-(1,4-cyclohexylenebis (1-methylethylidene)) biscyclohexylsancarbaldehyde, 4,4'-(1,4- Cyclohexylenebis (1-methylethylidene)) biscyclohexylsancarbaldehyde, 2,2-bis (4- (3-formylcyclohexyl) cyclohexyl) propane, 2,2-bis (4- (4-formylcyclohexyl) cyclohexyl ) Propane, 2,2-bis (4- (3-formylcyclohexyl) cyclohexyl) he Xafluoropropane, 2,2-bis (4- (4-formylphenoxy) cyclohexyl) hexafluoropropane, bis (4- (3-formylcyclohexyloxy) cyclohexyl) sulfide, bis (4- (4-formylcyclohexyloxy) Cyclohexyl) sulfide, bis (4- (3cyclohexyloxy) cyclohexyl) sulfone, bis (4- (4-formylcyclohexyloxy) cyclohexyl) sulfone, 2,2′-bicyclo [2.2.1] heptane-5,6 Alicyclic dialdehydes such as' -dialdehyde, 2,2'-bicyclo [2.2.1] heptane-6,6'-dialdehyde, 1,3-diformyladamantane; and a compound represented by the following formula :

Such.

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

Thermally polymerizable functional group-containing compound (C)
The thermally polymerizable functional group-containing compound (C) used in the production of the polybenzoxazole precursor of the present invention comprises a carboxylic acid anhydride having at least one functional group capable of being polymerized by heat, an aldehyde compound, and an amino compound. It is at least one compound selected from the group.

  The functional group that can be polymerized by heat is preferably at least one functional group selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, and benzocyclobutene.

  Examples of the carboxylic acid anhydride include 3-ethynylphthalic anhydride, vinylphthalic anhydride, maleic anhydride, 3-phenylethynylphthalic anhydride, 4-phenylethynylphthalic anhydride, and tetrahydroxyphthalic anhydride. , 5-norbornene-2,3-dicarboxylicsan anhydride and the like are preferable.

  Preferred examples of the aldehyde compound include 4- (2-phenyl-1-ynyl) benzaldehyde, 3-vinylbenzaldehyde, cinnamaldehyde, 4-oxobenzocyclobutene, and the like.

  Examples of the amino compound include 4- (3-aminophenyl) -2-methyl-3-butyn-2-ol, 3-ethynylaniline, 4-ethynylaniline, phenylethynylaniline, 4-aminostyrene, propargylamine, Preferred are 3-butene-1-amine, allylamine, 4-aminobenzocyclobutene and the like.

Production of Polybenzoxazole Precursor The polyoxazole precursor of the present invention is produced by reacting a bis-o-aminophenol compound (A), a dialdehyde compound (B) and a thermally polymerizable functional group-containing compound (C). can do.

Specific examples include the following production methods.
(I): a carboxylic acid anhydride having at least one functional group capable of being polymerized by heat at the terminal amino group after reacting the dialdehyde compound (B) with the bis-o-aminophenol compound (A) and / or Or the manufacturing method of the polybenzoxazole precursor which makes an aldehyde compound react.
(II): A polyaldehyde obtained by reacting a bis-o-aminophenol compound (A) with a dialdehyde compound (B) and then reacting an amino compound having at least one functional group capable of being polymerized by heat with a terminal aldehyde group. A method for producing a benzoxazole precursor.
(III): a bis-o-aminophenol compound (A) and a dialdehyde compound (B) and a carboxylic acid anhydride and / or an aldehyde compound having at least one functional group capable of being thermally polymerized at the terminal amino group at the same time A method for producing a polybenzoxazole precursor to be reacted.
(IV): A method for producing a polybenzoxazole precursor in which a bis-o-aminophenol compound (A) is simultaneously reacted with a dialdehyde compound (B) and an amino compound having at least one functional group capable of being polymerized by heat.
(V): After reacting a part of the bis-o-aminophenol compound (A) with a carboxylic acid anhydride and / or an aldehyde compound having at least one functional group capable of being polymerized by heat, a dialdehyde compound (B ) Is reacted with a polybenzoxazole precursor.
(VI): A polybenzo which is reacted with a bis-o-aminophenol compound (A) after reacting a part of the dialdehyde compound (B) with a primary amino compound having at least one functional group capable of being polymerized by heat. A method for producing an oxazole precursor.

  In the above production method, each reaction is usually at a temperature between room temperature and about 200 ° C., preferably at a temperature between room temperature and about 160 ° C., more preferably incompatible with water and having a boiling point of 100 ° C. to 180 ° C. A solvent such as toluene can be mixed at a blending ratio within a range in which the reactant does not precipitate, and can be performed in about 2 to 72 hours while performing reflux dehydration.

  The reaction between the bis-o-aminophenol compound (A) and the dialdehyde compound (B) is a Schiff base formation reaction and can be carried out by a method known per se. For example, bis-o-aminophenol compound (A) and dialdehyde compound (B) are converted into amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone and other ketones; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl lactate, methyl acetate Esters such as methanol, ethanol and propanol; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propanol; phenols containing aromatic groups such as phenol and cresol; alcohols containing aromatic groups such as benzyl alcohol; Class: Ethylene Glyco Glycols such as propylene glycol, or glycol ethers such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol and the like monoethers or diethers or esters of such monoethers; Cyclic ethers such as tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons such as toluene and xylene; and an inert solvent such as dimethyl sulfoxide. The reaction can be carried out at a temperature between 200 ° C., preferably 100 ° C. to about 160 ° C. for about 2 to 72 hours. These solvents can be used alone or in admixture of two or more as required.

  The mixing ratio of the bis-o-aminophenol compound (A) and the dialdehyde compound (B) is such that the dialdehyde compound (B) is 0.5 to 1.5 per mole of the bis-o-aminophenol compound (A). It is preferable to be in the range of mol, particularly 0.7 to 1.3 mol.

  Further, the thermally polymerizable functional group-containing compound (C) is 1.8 times to the absolute value of the difference between the number of moles of the bis-o-aminophenol compound (A) and the number of moles of the dialdehyde compound (B). It is preferable to blend in the range of 2.2 times the number of moles, especially 1.9 times to 2.1 times the number of moles. When the blending mole number of the bis-o-aminophenol compound (A) is equal to the blending mole number of the dialdehyde compound (B), the blending mole number of the bis-o-aminophenol compound (A) is 0.005 times to It is preferable to blend the thermally polymerizable functional group-containing compound (C) in the range of 0.5 times the number of moles.

In the polybenzoxazole precursor obtained as described above, among the repeating units represented by the general formula (1), E ₁ is hydrogen, but E ₁ is decomposed by the action of an acid. It may be a monovalent organic group that can be converted to a hydrogen atom.

Polybenzoxazole precursor E ₁ is a monovalent organic group which can be converted to decompose hydrogen atoms by the action of an acid, by replacing a hydrogen polybenzoxazole precursor E ₁ is hydrogen to E ₁ Conventionally known methods (see, for example, TW Greene, Protective Groups in Organic Synthesis, John Wiley &; Sons (1981)) can be used. Preferred examples of the organic group E ₁ include a t-butoxycarbonyl group, a t-butyl group, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, a trialkylsilyl group, and an iso-propoxycarbonyl group.

  The polybenzoxazole precursor of the present invention is generally 0.1 to 1.5 dl / g, preferably 0.2 to 0.8 dl / g, depending on the number (n) of repeating units of the general formula (1). It can have an intrinsic viscosity in the range of g. In addition, in this specification, an intrinsic viscosity is a value when it measures at 30 degreeC using an Ostwald viscometer.

  The polybenzoxazole precursor obtained as described above has at least one structure selected from the group represented by the following general formulas (1-1), (1-2) and (1-3). It is preferable that

In the formula, A ₁ represents a tetravalent aromatic group, N and OE ₁ bonded to A ₁ form a pair, and N and OE ₁ of each pair are bonded to adjacent carbons on the same aromatic ring. A ₂ represents a divalent organic group, E ₂ and E ₃ represent functional groups that can be polymerized by heat, and E ₁ is a monovalent organic that can be decomposed by the action of hydrogen or an acid and converted into a hydrogen atom. Represents a group, E ₄ represents a bond with a hydrogen group or a terminal group, and n is a number of 2 to 300.

Examples of E ₂ in the above general formula include the following.

In the formula, E ₅ represents hydrogen, an alkyl group, an alkoxyl group or an aromatic ring, and X represents a divalent organic group.

As the E _3, for example, are given below.

In the formula, E ₅ represents hydrogen, an alkyl group, an alkoxyl group or an aromatic ring, and X represents a divalent organic group.

Coating composition :
When the polybenzoxazole precursor of the present invention produced as described above is heated, the ring is closed, and the general formula (4)

In which A ₁ , A ₂ and n have the above-mentioned meanings,
And a polybenzoxazole resin having a functional group capable of being polymerized by heat at the molecular terminal and having excellent electrical insulation, heat resistance, mechanical strength, and the like.

  Therefore, the polybenzoxazole precursor of the present invention can be prepared by adding a solvent and / or various additives, for example, a surfactant, a coupling agent, and the like, if necessary, to provide an interlayer insulating film for a semiconductor and a protective layer. A coating composition useful for forming a film, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper-clad plate, a solder resist film, a liquid crystal alignment film and the like can be obtained.

  The solvent is not particularly limited as long as it dissolves the polybenzoxazole precursor of the present invention and additives used as necessary. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N Amides such as methyl-2-pyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α -Esters such as methyl-γ-butyrolactone, ethyl lactate, methyl acetate, ethyl acetate and butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propanol; containing aromatic groups such as phenol and cresol Phenolics; benzyl alcohol, etc. Group group-containing alcohols; glycols such as ethylene glycol and propylene glycol, or monoethers or diethers of these glycols such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol, or esters of such monoethers Examples include glycol ethers such as dicarboxylic acids; cyclic ethers such as dioxane and tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons; and dimethyl sulfoxide. These solvents can be used alone or in admixture of two or more as required.

  The content of the polybenzoxazole precursor of the present invention in the coating composition is not strictly limited and can be changed according to its use, etc. A range of 60% by weight, particularly 10 to 40% by weight, is preferred.

  There are no particular restrictions on the substrate to which the coating composition of the present invention can be applied. For example, a semiconductor material such as a silicon wafer or gallium arsenide, a metal, a metal oxide, a ceramic, a resin, or a copper foil is laminated. Examples of such coating methods include coating substrates, glass, and the like, and the coating composition is a coating method known per se such as spin coating, spray coating, roll coating, curtain flow coating, and printing. Can be applied.

  The formed coating is then dried and baked. The coating film thickness at that time is not strictly limited and can be changed according to the purpose of use, etc., but is usually about 0.1 to about 100 μm, preferably about 0.5 to about about 100 μm in dry film thickness. It can be in the range of 30 μm. The polybenzoxazole precursor film to be formed is usually pre-baked at a temperature of 80 to 190 ° C. for about 10 seconds to about 120 minutes as necessary, and then at a temperature of 200 to 500 ° C., preferably 250 to 400 ° C. By baking for about 10 to about 300 minutes, it can be changed to a polybenzoxazole resin film.

Positive photosensitive resin composition:
The polybenzoxazole precursor of the present invention can also be made into a positive photosensitive resin composition by combining with an acid generator, and can be used, for example, for pattern formation.

The acid generator is a photopolymerization initiator that generates an acid by light irradiation. A typical photoacid generator that can be used in combination with the polybenzoxazole precursor of the present invention is a photosensitive quinonediazide compound. In this case, E ₁ in the repeating unit represented by the general formula (1) of the polybenzooisazole precursor used at the same time is preferably hydrogen.

  The photosensitive quinonediazide compound is a photosensitive compound containing at least one quinonediazide unit in one molecule. For example, 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester 1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

  These quinonediazide sulfonate esters are known per se, for example polyhydroxybenzophenones such as tri- or tetrahydroxybenzophenone, gallate esters, dihydroxynaphthalene, 1- {1,1-bis (4-hydroxyphenyl) ethyl. } -4- {1- [4-Hydroxyphenyl] methylethyl} benzene and other polyphenolic hydroxyl group-containing compounds such as benzoquinone diazide sulfonic acid chloride, naphthoquinone diazide sulfonic acid chloride and the like and presence of weak alkali It can be obtained by carrying out a condensation reaction under this condition (see JP-A-5-53314).

  The quinonediazide sulfonic acid esters include, for example, a hydroxyl group-containing quinonediazide compound obtained by reacting quinonediazidesulfonic acid chloride with hydroxylamine, and a compound containing one or more carboxylic acid halide groups in one molecule (for example, , Halides such as chlorides and iodides of aromatic or alicyclic carboxylic acids such as isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid or hydrogenated products thereof; aliphatic carboxylic acids such as adipic acid, azelaic acid, sebacic acid, etc. A similar halide, etc.) at a ratio such that the hydroxyl group and the carboxylic acid halide group are in an equimolar ratio, or a ratio in which the number of moles of the carboxylic acid halide group is excessive with respect to the number of moles of the hydroxyl group. It can also manufacture by making it react. In this case, a photosensitive quinonediazide compound containing a carboxyl group can be produced by using a carboxylic acid halide group in a molar excess and changing the carboxylic acid halide group in the product to a carboxyl group (Japanese Patent Application Laid-Open No. Hei 5). -287222).

  Furthermore, a polymer containing a quinonediazide unit can be used as the photosensitive quinonediazide compound. For example, such a polymer can be obtained by reacting a hydroxyl group-containing quinonediazide compound obtained by reacting quinonediazidesulfonic acid chloride with hydroxylamine, an isocyanate. The quinonediazide unit is introduced into the polymer by reacting with the isocyanate group of the polymer having a group; the quinonediazide unit is introduced into the polymer by reacting the polymer having a hydroxyl group with the hydroxyl group-containing quinonediazide compound via the diisocyanate compound. Copolymerizing a monomer obtained by reacting the hydroxyl group of the quinonediazide compound with a monomer having an isocyanate group and another monomer; the hydroxyl group of the quinonediazide compound and the hydroxyl group of the monomer having a hydroxyl group; And the diiso A monomer obtained by reacting via Aneto compound and other monomers can be produced by a method such as copolymerizing. In this case, as the polymer into which the hydroxyl group-containing quinonediazide group is introduced, a polymer further having a carboxyl group is used, or at least of other monomers copolymerized with the monomer into which the hydroxyl group-containing quinonediazide group is introduced. By using a monomer having a carboxyl group as a part, a photosensitive quinonediazide polymer containing a carboxyl group can be obtained (see JP-A No. 64-90270).

  The quinonediazide polymer also includes, for example, a hydroxyl group-containing quinonediazide compound, a resin containing a carboxylic acid halide group such as carboxylic acid chloride (for example, a halogen of a polymerizable carboxylic acid such as (meth) acrylic acid chloride or crotonic acid chloride). A carboxyl group with a thionyl chloride copolymer, a copolymer of a polymerizable unsaturated monomer that does not contain functional groups reactive with acid halides, and a carboxyl group-containing acrylic resin, polyester resin, etc. The carboxylic acid halide group of the resin or the like and the hydroxyl group of the hydroxyl group-containing quinonediazide compound can be produced in an equimolar ratio or by reacting an excessive number of moles of carboxylic acid halide groups with respect to the number of moles of hydroxyl groups. When the number of moles of the carboxylic acid halide group is excessive, a photosensitive quinonediazide polymer containing a carboxyl group can be obtained by changing the carboxylic acid halide group to a carboxyl group (see JP-A-5-287222). ).

  Furthermore, the photosensitive quinonediazide polymer is obtained by reacting the hydroxyl group-containing quinonediazide compound with a polymerizable unsaturated monomer having a carboxylic acid halide group such as (meth) acrylic acid chloride, for example. It can also be produced by copolymerizing a quinonediazide compound with another unsaturated group-containing monomer. In this case, a photosensitive resin containing a carboxyl group can be obtained by using an unsaturated monomer having a carboxyl group as at least a part of other monomers to be copolymerized (Japanese Patent Laid-Open No. 4-53877). reference).

Acid generator The acid generator compound of the positive photosensitive composition of the present invention is a compound that generates an acid by light or heat, and using the generated acid as a catalyst, the hydroxyl group of the polybenzoxazole precursor (A). The protecting group that has blocked is removed to regenerate the hydroxyl group, and conventionally known compounds can be used as the radiation-sensitive or heat-sensitive acid generator compound.

  Examples of the photoacid generator compound include diazonium, phosphonium, sulfonium and iodonium salts: halogen compounds: organometallic / organic halogen combinations: strong acids such as benzoin and o-nitrobenzyl esters of toluenesulfonic acid: N-hydroxyamides and N-hydroxyimide sulfonates described in US Pat. No. 4,371,605 are included. Aryl naphthoquinone diazide-4-sulfonates are also included. Suitable photoacid generator compounds are diaryliodonium or triarylsulfonium salts.

  These are generally present in the form of salts of double metal halide ions such as tetrafluoroborate, hexafluoroantimonate, hexafluoroarsenate and hexafluorophosphate.

  Another effective group of photosensitive acid generators includes oligomers and polymers to which an anionic group having an aromatic onium acid generator as a positive counter ion is added. Examples of such polymers include those described in US Pat. No. 4,661,429 at column 9, lines 1-68 and column 10, lines 1-14. It is desirable to add a sensitizer to the system in order to adjust the spectral sensitivity to the available wavelengths of actinic radiation. This need depends on the requirements of the system and the particular photosensitive compound used. For example, in the case of iodonium and sulfonium salts that respond only to wavelengths below 300 nm, by using benzophenone and their derivatives, polycyclic aromatic hydrocarbons such as berylene, pyrene and anthracene, and their derivatives, It can be exposed to longer wavelengths. The decomposition of diaryliodonium and triarylsulfonium salts can also be photosensitized with bis- (pN, N-dimethylaminobenzylidene) -acetone. Sulphonium salts bonded to anthracene having a chain length of 3 to 4 atoms are effective light solubilizers. The compound described in MG.Tilley's doctoral dissertation, North Dakota State University, Fargo, ND (1988) [Diss. Abstr. Lnt. B, 49,8791 (1989): Chem. Abstr., 111, 39942u] , A preferred type of light solubilizer. Another suitable acid generator is ATASS, ie 3- (9-anthracenyl) propyl diphenylsulfonium hexafluoroantimonate. In this compound, anthracene and a sulfonium salt are bound together by a chain composed of three carbons.

  The amount of these sensitizers is 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight per 100 parts by weight of the benzotriazole precursor (A).

  Additional examples of acid generators that may be used here are diphenyliodonium tosylate, benzoin tosylate, and triarylsulfonium hexafluoroantimonate. In addition to the above, for example, iron-allene complexes, ruthenium allene complexes, silanol-metal chelate complexes, triazine compounds, diazide naphthoquinone compounds, sulfonate esters, sulfonate imide esters, halogen series Compounds and the like can be used. Further, acid generators described in JP-A-7-146552 and Japanese Patent Application No. 9-289218 can also be used.

  Examples of the compound used as the heat-sensitive acid generator include onium salts such as ammonium salts, phosphonium salts, sulfonium salts, phosphonium salts, selenium salts, and iodonium salts: diazonium: halogen compounds: organic metals / organic halogens. Combinations: Strong acids such as benzoin and o-nitrobenzyl esters of toluenesulfonic acid: and N-hydroxyamides and N-hydroxyimide sulfonates described in US Pat. No. 4,371,605. Aryl naphthoquinone diazide-4-sulfonates are also included. Another effective group of thermosensitive acid generators includes oligomers and polymers to which an anionic group having an aromatic onium acid generator as a positive counter ion is added. Examples of such polymers include the polymer amounts described in US Pat. No. 4,661,429 at column 9, lines 1-68 and column 10, lines 1-14. Another suitable thermosensitive acid generator is ATASS, ie, 3- (9-anthracenyl) propyl diphenylsulfonium hexafluoroantimonate. In this compound, anthracene and a sulfonium salt are bound together by a chain composed of three carbons. Additional examples of acid generators that may be used here are diphenyliodonium tosylate, benzoin tosylate, and triarylsulfonium hexafluoroantimonate. In addition to the thermal acid generators described above, for example, iron-allene complexes, ruthenium allene complexes, silanol-metal chelate complexes, triazine compounds, diazide naphthoquinone compounds, sulfonic acid esters, sulfonic acid Imidoesters and the like can be used. Further, JP-A-7-146552, Japanese Patent Application No. 9-289218, JP-A-10-204407, JP-A-1-96169, JP-A-2-1470, JP-A-2-255646, JP-A-2-268173, JP-A-3-11044, JP-A-3-115262, JP-A-4-1177, JP-A-4-327574, JP-A-4-308563, JP-A-4-308563 JP-A-4-328106, JP-A-5-132461, JP-A-5-132462, JP-A-5-140132, JP-A-5-140209, JP-A-5-140210, JP-A-5-140210. No. 170737, JP-A-5-230190, JP-A-5-230189, JP-A-6-271532, JP-A-6-2 No. 1544, JP-A-6-321897, JP-A-6-321195, JP-A-6-345726, JP-A-6-345733, JP-A-6-814754, JP-A-7-25852. JP-A-7-25863, JP-A-7-89909, JP-A-7-501581, and those described in International Publication No. 97/08141 can be used.

  Further, a heat-sensitive acid generator and a photothermal conversion dye can be used in combination. The photothermal conversion dye is a substance that absorbs light and generates heat, and conventionally known pigments or dyes can be used. Examples of the pigment include black pigments, yellow pigments, orange pigments, brown pigments, red pigments, purple pigments, blue pigments, green pigments, fluorescent pigments, metal powder pigments, and other polymer-bonded dyes. Specifically, insoluble azo pigments, azo lake pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, anthraquinone pigments, perylene and perinone pigments, thioindigo pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments In addition, quinophthalone pigments, dyed lake pigments, azine pigments, nitroso pigments, nitro pigments, natural pigments, fluorescent pigments, inorganic pigments, carbon black, and the like can be used.

  The particle diameter of the pigment is preferably in the range of 0.001 μm to 10 μm, more preferably in the range of 0.01 μm to 1 μm, and particularly preferably in the range of 0.05 μm to 1 μm. When the particle size of the pigment is less than 0.001 μm, it is not preferable from the viewpoint of stability and developability in the positive photosensitive composition, and when it exceeds 10 μm, it is not preferable from the viewpoint of uniformity of the image forming film layer. .

  Conventionally known dyes can be used as the dye. Specific examples include azo dyes, metal complex azo dyes, pyrazolone azo dyes, anthraquinone dyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methine dyes, and cyanine dyes.

  In the present invention, among these pigments or dyes, those that absorb infrared light or near infrared light are particularly preferable in that they are suitable for use in lasers that emit infrared light or near infrared light. Carbon black is suitably used as the pigment that absorbs such infrared light or near infrared light.

  As such carbon black, it is preferable to use carbon black for water-based inks described in JP-A No. 2002-241643. Since the carbon black for water-based ink is described in detail in the publication, it is replaced with a detailed description by a simple description in this specification.

Aqueous inks for carbon black, CTAB specific surface area of 140 m ² / g or more, the ratio tinting strength (Tint) is a 120% or more, DBP absorption 100cm ^3/100 g or more of the carbon black A and the DBP absorption 100cm ^{3 /} the carbon black B of less than 100 g, a: B is 70: 30-10: 90 carbon black were mixed in a weight ratio of oxidized, total carbon atoms and the total oxygen as measured by X-ray photoelectron spectroscopy It is characterized by being chemically modified so that the atomic ratio (oxygen bond energy strength / carbon bond energy strength) with atoms is 0.1 or more and the amount of hydrogen-containing surface functional groups is 3.0 μeq / m ² or more. Carbon black for water-based inks.

  Further, in the carbon black for water-based ink, the carbon black agglomerate average particle size Dupa 50% in a state dispersed in water has a particle aggregation property of 50 to 110 nm and the maximum particle size Dupa 99% of the agglomerate is 250 nm or less.

Further, the carbon black aqueous ink, CTAB specific surface area of 140 m ² / g or more, a ratio tinting strength (Tint) of 120% or more, a DBP absorption amount of 100 cm ³ / carbon black A and the DBP absorption of more than 100g is and 100100cm ³ / 100g less of the carbon black B, a: B is 70: 30-10: 90 carbon black were mixed in a weight ratio of oxidized with dispersed state in water was measured by X-ray photoelectron spectroscopy Chemical modification of the atomic ratio of all carbon atoms to all oxygen atoms (oxygen bond energy strength / carbon bond energy strength) to 0.1 or more and hydrogen-containing surface functional group amount to 3.0 μeq / m ² or more, After separation by filtration, the product is dispersed in an alkaline aqueous solution, and then the salt remaining in the dispersion is separated and purified.

  Examples of the dye that absorbs infrared light or near-infrared light include, for example, JP-A-58-125246, JP-A-59-84356, JP-A-59-202829, JP-A-60. Cyanine dyes described in JP-A-78787 etc., methine dyes described in JP-A-58-173696, JP-A-58-181690, JP-A-58-194595, etc. JP 58-112793, JP 58-224793, JP 59-48187, JP 59-73996, JP 60-52940, JP 60-63744. Naphthoquinone dyes described in Japanese Laid-Open Patent Publications, etc., squarylium dyes described in Japanese Patent Application Laid-Open No. 58-112792, etc., cyanine dyes described in British Patent 434,875, etc. It can gel.

  These pigments or dyes are 0.01 to 50% by weight, preferably 0.1 to 10% by weight, particularly preferably 0.5 to 10% by weight, based on the total solid content of the composition of the present invention. In this case, it can be added to the positive photosensitive resin composition at a ratio of preferably 3.1 to 10% by weight. When the added amount of the pigment or dye is less than 0.01% by weight, the sensitivity is lowered, and when it exceeds 50% by weight, the uniformity of the image forming film layer is lost and the durability of the image forming film layer is deteriorated.

  In addition to the polybenzoxazole precursor of the present invention and the above-mentioned photoacid generator, the positive photosensitive resin composition provided by the present invention may further include a surfactant, a fluidity regulator, Additives such as chelating agents can be included.

  The positive photosensitive resin composition can be prepared by mixing the above-described components as they are or in a solvent as necessary. The solvent that can be used in this case is not particularly limited as long as it can dissolve each component of the composition. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Amides; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone; γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, lactic acid Esters such as ethyl, methyl acetate, ethyl acetate and butyl acetate; aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and propanol; phenols containing aromatic groups such as phenol and cresol; aroma such as benzyl alcohol Group-containing alcohols; ethylene glycol Glycols such as propylene glycol, or glycol ethers such as methanol, ethanol, butanol, hexanol, octanol, benzyl alcohol, phenol, cresol and the like monoethers or diethers or esters of such monoethers; And cyclic ethers such as tetrahydrofuran; cyclic carbonates such as ethylene carbonate and propylene carbonate; aliphatic and aromatic hydrocarbons; and dimethyl sulfoxide. These solvents can be used alone or in admixture of two or more as required.

Formation of Pattern Formation of the pattern using the photosensitive resin composition described above can be performed, for example, as described below.

  First, a photosensitive resin composition on a substrate such as a semiconductor material silicon wafer, ceramics, gallium arsenide, aluminum plate for PS plate, printed circuit board laminated with copper foil, glass plate, resin, etc. Is applied by a coating method known per se, such as spin coating, spray coating, roll coating, curtain flow coating, and printing, and dried. The coating film thickness at that time is not strictly limited and can be changed according to the purpose of use of the formation pattern, etc., but is usually about 0.1 to about 50 microns in dry film thickness, particularly about 1 to A range of about 30 microns is suitable.

Next, the applied resist film is exposed and exposed to actinic rays such as ultraviolet rays through a pattern mask (for example, photographic positive). As the actinic ray used for exposure, a ray having a wavelength of 3,000 to 4,500 angstroms is generally suitable. Examples of such a light source that emits light include sunlight, a mercury lamp, a xenon lamp, and an arc lamp. The irradiation amount of actinic rays is usually 30 to 800 mJ / cm ² , preferably 50 to 500 mJ / cm ² . You may heat the film after exposure at the temperature of 50-140 degreeC as needed.

  After irradiation exposure with actinic rays, the coating film is developed. The development processing is usually performed by washing away the exposed portion of the coating film with an alkaline aqueous solution. Examples of the alkaline aqueous solution that can be used for this development process include alkaline aqueous solutions such as caustic soda, caustic potash, sodium metasilicate, and sodium carbonate; aqueous tetraalkylammonium salts such as tetramethylammonium hydroxide; amine compounds such as triethylamine, diethanolamine, and dimethylethanolamine An aqueous solution is exemplified.

  Further, when the substrate can be etched, the pattern film can be obtained by removing the exposed substrate portion with an appropriate etching agent.

  The obtained polybenzoxazole precursor pattern film is usually formed into a polybenzoxazole resin pattern film by baking at a temperature of 200 to 500 ° C., preferably 250 to 400 ° C. for about 10 minutes to about 300 minutes. Can do.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. Hereinafter, both “parts” and “%” are based on weight.

Production of polybenzoxazole precursor
Reference example 1
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .595 g (4.44 mmol), 0.103 g (0.88 mmol) of 4-ethynylaniline, 3 ml of ethyl lactate and 2 ml of toluene were added, and the mixture was refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution under reduced pressure to obtain a terminal unsaturated capped polybenzoxazole precursor solution (A1) having a solid content of 31% and a viscosity of 750 mPa · s. The precursor had a number average molecular weight of about 4,000. To confirm the synthesized product, the terminal unsaturated capped polybenzoxazole precursor solution (A1) is reprecipitated into a small amount of 100 ml of a toluene mixed solution, and the precipitate is filtered and dried under reduced pressure to obtain a polybenzoxazole precursor solid. Obtained by IR analysis and 1H-NMR analysis. As a result, in the IR analysis ^{chart, 2981cm -1 (CH), 1766cm} -1 (C = O), 1653cm -1 (C = N) absorption peaks were observed ^{1600cm -1 (Ar), 1H-} NMR analysis In the (DMSO-d6) chart, a carbon-carbon triple bond was confirmed at δ = 3.81, and poly at δ = 8.47, δ = 8.04, δ = 7.58, δ = 7.37, δ = 7.29-7.14 and δ = 1.30. A spectrum peak indicating an azomethine structure was observed.

Reference example 2
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .563 g (4.20 mmol), 4-ethynylaniline 0.0468 g (0.40 mmol), ethyl lactate 3 ml and toluene 2 ml were added, and the mixture was refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution by distillation under reduced pressure to obtain a terminal unsaturated capped polybenzoxazole precursor solution (A2) having a solid content of 34% and a viscosity of 2,700 mPa · s. The precursor had a number average molecular weight of about 6,000.

Reference example 3
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .563 g (4.12 mmol), 4-ethynylaniline 0.0515 g (0.20 mmol), ethyl lactate 11 ml and toluene 6.5 ml were added, and the mixture was refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution by vacuum distillation to obtain a terminal unsaturated capped polybenzoxazole precursor solution (A3) having a solid content of 26% and a viscosity of 140 mPa · s. The precursor had a number average molecular weight of about 8,000.

Reference example 4
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .482 g (3.60 mmol), 5-norbornene-2,3-dicarboxylic acid anhydride 0.131 g (0.80 mmol), N-methyl-2-pyrrolidone 3 ml and toluene 2 ml were added and refluxed for 5 hours under nitrogen filling. It was. Toluene was distilled off from the resulting solution by vacuum distillation to obtain a terminally unsaturated capped polybenzoxazole precursor solution (A4) having a solid content of 32% and a viscosity of 80 mPa · s. The precursor had a number average molecular weight of about 4,000.

Reference Example 5
The same procedure as in Reference Example 4 was carried out except that N-methyl-2-pyrrolidone was changed to ethyl lactate to obtain a terminally unsaturated capped polybenzoxazole precursor solution (A5) having a solid content of 32% and a viscosity of 530 mPa · s. The precursor had a number average molecular weight of about 3,500.

Reference Example 6
In a 50 ml round bottom flask equipped with a Dean-Stark water separator and condenser, 1.464 g (4 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 5-norbornene-2,3-dicarboxylic acid 0.131 g (0.80 mmol) of acid anhydride, 3 ml of ethyl lactate and 3 ml of toluene were added, and the mixture was refluxed for 2 hours under nitrogen filling. To this reaction mixture, 0.482 g (3.60 mmol) of isophthalaldehyde was added, and the mixture was further refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution by vacuum distillation to obtain a terminal unsaturated capped polybenzoxazole precursor solution (A6) having a solid content of 34% and a viscosity of 80 mPa · s. The precursor had a number average molecular weight of about 4,000.

Reference Example 7
The same procedure as in Reference Example 6 was conducted except that 0.137 g (0.80 mmol) of 3-ethynylphthalic anhydride was used in place of the 5-norbornene-2,3-carboxylic acid anhydride of Reference Example 6, and the solid content was 32. % And a terminally unsaturated capped polybenzoxazole precursor solution (A7) having a viscosity of 300 mPa · s. The precursor had a number average molecular weight of about 4,000.

Example 9
0.098 g (0.8 mmol) of N, N-dimethylaminopyridine dissolved in 2 ml of N-methylpyrrolidone in 6.5 g (4 mmol) of the polybenzoxazole precursor solution (A1) obtained in Reference Example 1 and di-tert -2.18 g (10 mmol) of butyl dicarbonate was added and stirred at room temperature for 1 hour. The solution was reprecipitated into 100 ml of a mixed solution of water: methanol volume ratio = 1: 1, and the precipitate was filtered out to obtain a polybenzoxazole precursor solution (A9) having a solid content of 42% and protecting the phenol group. . The precursor had a number average molecular weight of about 6,000.

Comparative Reference Example 1
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .482 g (3.60 mmol), N-methyl-2-pyrrolidone (3 ml) and toluene (2 ml) were added, and the mixture was refluxed for 5 hours under nitrogen filling. From the resulting solution by distilling off the toluene by vacuum distillation to give Po Li benzoxazole precursor solution having a solid content of 34% and a viscosity of 80 mPa · s to (A10). The precursor had a number average molecular weight of about 3500.

Comparative Reference Example 2
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .536 g (4.00 mmol), 11 ml of ethyl lactate and 6.5 ml of toluene were added, and the mixture was refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution under reduced pressure to obtain a polybenzoxazole precursor solution (A11) having a solid content of 33% and a viscosity of 90 mPa · s. The precursor had a number average molecular weight of about 3,500.

Comparative Reference Example 3
To a 50 ml round bottom flask equipped with a Dean-Stark water separator filled with toluene and a condenser tube, 1.464 g (4.00 mmol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 0 .595 g (4.44 mmol), 3 ml of ethyl lactate and 2 ml of toluene were added, and the mixture was refluxed for 5 hours under nitrogen filling. Toluene was distilled off from the resulting solution by vacuum distillation to obtain a polybenzoxazole precursor solution (A12) having a solid content of 35% and a viscosity of 980 mPa · s. The precursor had a number average molecular weight of about 9,000.

Reference Example 10
The polybenzoxazole precursor solution (A1) obtained in Reference Example 1 is coated on quartz with a spin coater to form a 3 μm thin film, preheated at 100 ° C. for 3 minutes, and the IR spectrum of the resulting coating is obtained. It was measured. Next, the quartz having the coating film was heated at an ambient temperature of 300 ° C. for 1 hour and then cooled, and the IR spectrum of the obtained coating film after heating was measured. In comparison of the IR analysis chart of the film before and after heating, the absorption is reduced to from polyazomethine around 3382cm ^-1 and 1627cm ^-1 after heating, the 1554Cm ^-1 from polybenzoxazole appeared is confirmed in Reference The polybenzoxazole formation by heating of the polybenzoxazole precursor obtained in Example 1 was confirmed.

Positive photosensitive resin composition
Reference Example 11
A photosensitizer (2,3,4-tris [1-oxy-2-diazonaphthoquinone-) having a solid content of 30% dissolved in ethyl lactate was added to 0.25 g of the polybenzoxazole precursor solution (A1) obtained in Reference Example 1. 4-sulfonyl] benzophenone) solution (0.111 g) was placed in a light-shielded sample bottle and stirred for 30 minutes. Thereafter, the insoluble matter was removed through a 0.5 micron PKFE filter to obtain a positive photosensitive resin composition (I).

The obtained positive photosensitive resin composition (I) is dropped on a glass plate, a 10 μm thin film is prepared with an applicator, preheated at 100 ° C. for 3 minutes, and then heated at 300 ° C. for 1 hour. Heated. The obtained coating film was peeled off from the glass plate, and the mechanical strength of the cured film was subjected to a tensile test using a tensile tester “EZ-Test” manufactured by Shimadzu Corporation. As a result, the breaking strength was 125 MPa and the breaking elongation was 8%. Next, the positive photosensitive resin composition (I) was dropped onto a silicon wafer, and spin was performed for 30 seconds using a spin coater at a slope of 5 seconds and 2,000 rpm. Thereafter, prebaking was performed at 120 ° C. for 5 minutes to obtain a polyazomethine film having a thickness of 3.0 μm. Next, it was covered with a pattern mask, irradiated with 500 mJ / cm ² of g-line by a UV irradiation apparatus, and developed with a 2.38% tetramethylammonium hydroxide aqueous solution. As a result, a good pattern with a thickness of 2.8 μm and a width of 6 μm was obtained.

  Further, after measuring the initial viscosity of the positive photosensitive resin composition (I) with a Gardner viscometer, it was put into a 20 ml glass bottle, put in a tin can filled with dry silica gel, and sealed at room temperature for 3 months. I left it for a while. The viscosity after 3 months of storage was measured with a Gardner viscometer. As a result, it was confirmed that there was no change in viscosity at the initial stage and three months after storage.

Reference Example 12-1 7 and Comparative Reference Example 4-6
Except that the polybenzoxazole precursor solution and the photosensitive material shown in the following Table 1 in the same manner as in Reference Example 11 to create a positive photosensitive resin composition, except that the heating temperature shown in Table 1 and the Reference Example 11 Similarly, a film was prepared, and the breaking strength (MPa) and elongation at break (%) were measured, and the pattern formability and storage were evaluated.

The results are shown in Table 1 below. In all the reference examples, positive patterns were obtained and good mechanical properties were exhibited. On the other hand, the viscosity of the positive photosensitive resin composition was not changed in the storage examples in Reference Examples 12 to 17 and Comparative Reference Examples 1 and 2, but the positive type of Comparative Reference Example 3 was used. It was confirmed that the photosensitive resin composition thickened.

The photosensitive agents P1 and P2 in Table 1 have the following contents.
P1: 2,3,4-tris [1-oxy-2-diazonaphthoquinone-4-sulfonyl] benzophenone.
P2: 1- {1,1-bis (4-hydroxyphenyl) ethyl} -4- {1- [4-hydroxyphenyl] methylethyl} benzene.

Example 19
0.25 g of the polybenzoxazole precursor solution (A9) protected with the t-butoxycarbonyl group obtained in Example 9 and the iminosulfonate compound “NAI-105” (trade name, manufactured by Midori Chemical Co., N- (trifluoro) Methylsulfonyloxy) -1,8-naphthalenedicarboximide) 0.0278 g and N-methylpyrrolidone 0.5 ml were placed in a light-shielded sample bottle and stirred for 30 minutes. Thereafter, insoluble matters were removed through a PTFE filter of 0.5 μm to obtain a positive photosensitive resin composition (II).

The obtained positive photosensitive resin composition (II) was dropped on a silicon wafer, and a spin for 5 seconds and a spin of 2,000 rpm were performed for 30 seconds using a spin coater. Thereafter, preheating was performed at 120 ° C. for 5 minutes to obtain a polyazomethine film having a thickness of 2.0 μm. The coated silicon wafer substrate is left in a dark place at 23 ° C. for one day and then covered with a pattern mask, and irradiated with 300 mJ / cm ² of g-line by a UV irradiation device, and 2.38% tetramethylammonium hydroxide aqueous solution Developed. As a result, a good pattern with a thickness of 1.8 μm and a width of 6 μm was obtained. When the pattern film obtained above was heated on a hot plate at 300 ° C. for 1 hour, the film thickness was 1.1 μm, and no deformation of the pattern was observed. In addition, IR analysis of the film before and after heating showed that absorption derived from polyazomethine near 3382 cm ⁻¹ and 1627 cm ⁻¹ decreased and absorption near 1554 cm ⁻¹ derived from polybenzoxazole appeared. Polybenzoxazolization of polyazomethine, which is a precursor of polybenzoxazole, was confirmed. The obtained positive photosensitive resin composition (II) was dropped on a glass plate, a 10 μm thin film was prepared with an applicator, preheated at 100 ° C. for 3 minutes, and then heated at 300 ° C. for 1 hour. . The obtained coating film was peeled off from the glass plate, and the mechanical strength of the cured film was subjected to a tensile test using a tensile tester “EZ-Test” manufactured by Shimadzu Corporation. As a result, the breaking strength was 120 MPa, and the breaking elongation was 8%.

  In addition, after measuring the initial viscosity of the positive photosensitive resin composition (II) with a Gardner viscometer, it was put into a 20 ml glass bottle, which was put in a tin can containing dry silica gel and sealed at room temperature for 3 months. I left it for a while. The viscosity after 3 months of storage was measured with a Gardner viscometer. As a result, it was confirmed that there was no change in viscosity at the initial stage and three months after storage.

Claims (21)

General formula (1)

In the formula, A ₁ represents a tetravalent aromatic group, N and OE ₁ bonded to A ₁ form a pair, and N and OE ₁ of each pair are bonded to adjacent carbons on the same aromatic ring. A ₂ represents a divalent organic group, and E ₁ is a t-butoxycarbonyl group, a t-butyl group, a t-butoxycarbonylmethyl group, a tetrahydropyranyl group, a trialkylsilyl group or an iso-propoxycarbonyl group. Represents at least one group selected from the group consisting of : n is a number from 2 to 300,
A polybenzoxazole precursor having a repeating unit represented by the above, wherein the molecular terminal of the precursor has an organic group having a functional group capable of being polymerized by heat. The polybenzoxazole precursor according to claim 1, wherein the functional group capable of being polymerized by heat is at least one functional group selected from the group consisting of a carbon-carbon double bond, a carbon-carbon triple bond, and benzocyclobutene. . A ₁ is

In the formula, X and Y are each independently —CH ₂ —, —O—, —S—, —SO—, —SO ₂ —, —SO ₂ NH—, —CO—, —CO ₂ —, —NHCO—. , -NHCONH-, -C (CF ₃ ) _2- , -CF _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) (CH ₃ )-, -Si _{(R 21) 2 -, -} O-Si (R 21) 2 -O -, - Si (R 21) 2 -O-Si (R 22) 2 -, - (CH 2) a -Si (R 21) ₂ -O-Si (R ₂₂ ) _2- (CH ₂ ) _a- (where a is an integer from 0 to 6) and a direct bond, R _{1 to} R ₁₄ , R ₂₁ and R ₂₂ is independently H, F, an alkyl or alkoxyl group having 1 to 6 carbon atoms, or — (CF ₂ ) _b —CF ₃ or —O— (CF ₂ ) _b —CF ₃ (where b is 0 to 5). P and q are each an integer of 0 to 3,
The polybenzoxazole precursor according to claim 1 selected from the group consisting of: A ₁ has the formula (2-1) to (2-6) and (2-10) to polybenzoxazole precursor according to claim 1 is a group selected from (2-12). A ₂ is

In the formula, X and Y are each independently —CH ₂ —, —O—, —S—, —SO—, —SO ₂ —, —SO ₂ NH—, —CO—, —CO ₂ —, —NHCO—. , -NHCONH-, -C (CF ₃ ) _2- , -CF _2- , -C (CH ₃ ) _2- , -CH (CH ₃ )-, -C (CF ₃ ) (CH ₃ )-, -Si _{(R 21) 2 -, -} O-Si (R 21) 2 -O -, - Si (R 21) 2 -O-Si (R 22) 2 -, - (CH 2) a -Si (R 21) ₂ -O-Si (R ₂₂ ) _2- (CH ₂ ) _a- (where a is an integer from 0 to 6) and a direct bond, R _{1 to} R ₁₆ , R ₂₁ and R ₂₂ are each independently H, F, an alkyl or alkoxyl group having 1 to 6 carbon atoms, or — (CF ₂ ) _b —CF ₃ or —O— (CF ₂ ) _b —CF ₃ (where b is 0 to 5). Z represents —CH ₂ —, —C ₂ H ₄ — or —CH ₂ ═CH ₂ —, and p and q are each an integer of 0 to 3,
The polybenzoxazole precursor according to claim 1 selected from the group consisting of: A ₂ is represented by formulas (3-1) to (3-8), (3-12) to (3-22), (3-25), (3-27) to (3-29) and (3-31). The polybenzoxazole precursor according to claim 1, which is a group selected from: The polybenzoxazole precursor has the following general formula

In the formula, A ₁ represents a tetravalent aromatic group, N and OE ₁ bonded to A ₁ form a pair, and N and OE ₁ of each pair are bonded to adjacent carbons on the same aromatic ring. A ₂ represents a divalent organic group, E ₂ and E ₃ represent a functional group capable of being polymerized by heat, E ₁ represents a t-butoxycarbonyl group, a t-butyl group, a t-butoxycarbonylmethyl group, E ₄ represents at least one group selected from the group consisting of a tetrahydropyranyl group, a trialkylsilyl group and an iso-propoxycarbonyl group , E ₄ represents a bond with a hydrogen group or a terminal group, and n is a number from 2 to 300. Is,
The polybenzoxazole precursor of Claim 1 shown by these. E ₂ is

In the formula, E ₅ represents hydrogen, an alkyl group, an alkoxyl group or an aromatic ring, and X represents a divalent organic group.
The polybenzoxazole precursor according to claim 7, which is selected from the group consisting of: E ₃ is

In the formula, E ₅ represents hydrogen, an alkyl group, an alkoxyl group or an aromatic ring, and X represents a divalent organic group.
The polybenzoxazole precursor according to claim 7, which is selected from the group consisting of: General formula (2)

In the formula, A ₁ represents a tetravalent aromatic group, NH ₂ group and OH group bonded to A ₁ form a pair, and NH ₂ group and OH group of each pair are adjacent carbons on the same aromatic ring. Bound to the
A bis-o-aminophenol compound (A) represented by
General formula (3)

In the formula, A ₂ represents a divalent organic group.
And at least one thermally polymerizable functional group-containing compound selected from the group consisting of a carboxylic acid anhydride having at least one functional group capable of being polymerized by heat, an aldehyde compound, and an amino compound (C) reacting a, E ₁ is to obtain a polybenzoxazole precursor is hydrogen in the general formula (1) according to claim 1, further resulting E ₁ of the polybenzoxazole precursor t- butoxycarbonyl group, t- butyl group, t-butoxycarbonyl methyl group, tetrahydropyranyl group, and wherein that you substituted with at least one group selected from the group consisting of trialkylsilyl groups and iso- propoxycarbonyl group The manufacturing method of the polybenzoxazole precursor of Claim 1. The method for producing a polybenzoxazole precursor according to claim 10, wherein the bis-o-aminophenol compound (A) is reacted with the dialdehyde compound (B) and then thermally functionalized to the terminal amino group. A method for producing a polybenzoxazole precursor comprising reacting a carboxylic acid anhydride having at least one group and / or an aldehyde compound. In the manufacturing method of the polybenzoxazole precursor of Claim 10, after making a dialdehyde compound (B) react with a bis-o-aminophenol compound (A), it is the function which can superpose | polymerize with a terminal aldehyde group with a heat | fever. A method for producing a polybenzoxazole precursor comprising reacting an amino compound having at least one group. The method for producing a polybenzoxazole precursor according to claim 10, wherein the bis-o-aminophenol compound (A) has at least one functional group capable of being thermally polymerized to the dialdehyde compound (B) and the terminal amino group. The manufacturing method of the polybenzoxazole precursor which makes the carboxylic acid anhydride and / or aldehyde compound which have it react simultaneously. The method for producing a polybenzoxazole precursor according to claim 10, wherein a dialdehyde compound (B) and an amino compound having at least one functional group capable of being polymerized by heat are simultaneously added to the bis-o-aminophenol compound (A). A method for producing a polybenzoxazole precursor to be reacted. The method for producing a polybenzoxazole precursor according to claim 10, wherein a part of the bis-o-aminophenol compound (A) has a carboxylic acid anhydride and / or an aldehyde having at least one functional group capable of being polymerized by heat. A method for producing a polybenzoxazole precursor, in which a dialdehyde compound (B) is reacted after reacting the compound. In the manufacturing method of the polybenzoxazole precursor of Claim 10, after making the primary amino compound which has at least 1 the functional group which can superpose | polymerize with a part of dialdehyde compound (B) react, it is bis-o. -The manufacturing method of the polybenzoxazole precursor with which an aminophenol compound (A) is made to react. A coating composition comprising the polybenzoxazole precursor according to any one of claims 1 to 9. A positive photosensitive resin composition comprising the polybenzoxazole precursor according to any one of claims 1 to 9 and an acid generator. The positive photosensitive resin composition according to claim 18 , wherein the acid generator is contained within a range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the polybenzoxazole precursor. The positive photosensitive resin composition according to claim 18 , wherein the positive photosensitive resin composition further contains a solvent. A step of coating the positive photosensitive resin composition according to claim 18 on a substrate, forming a positive photosensitive coating on the substrate, exposing the positive photosensitive coating through a pattern mask, and A pattern forming method comprising sequentially performing the steps of developing the exposed positive photosensitive film with a basic developer.