JP2007212602A - Positive photosensitive resin precursor composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive photosensitive resin precursor composition having such high ductility that it can be sufficiently used even in a semiconductor device which requires high reliability. <P>SOLUTION: The positive photosensitive resin precursor composition comprises (a) a polymer capable of forming an imide ring, an oxazole ring or another cyclic structure by heating and having both terminal structures represented by X, (b) a polymer capable of forming an imide ring, an oxazole ring or another cyclic structure upon heating and having both terminal structures represented by Y, (c) a quinonediazide compound and (d) a solvent, wherein X and Y are organic groups capable of forming -X-Y- bond by heating. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a positive photosensitive resin precursor composition. More specifically, the present invention relates to a positive photosensitive resin precursor composition suitable for a surface protective film of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, etc., in which a portion exposed to ultraviolet rays is dissolved in an alkali developer. .

  The positive heat-resistant resin precursor composition in which the exposed part is dissolved by development includes quinone diazide added to polyamic acid, quinone diazide added to a soluble polyimide having a hydroxyl group, and quinone diazide to a polyamide having a hydroxyl group. And the like were known.

  However, the addition of quinonediazide to normal polyamic acid has the problem that the desired pattern cannot be obtained in most cases because the solubility of the carboxyl group of the polyamic acid is higher than the dissolution inhibiting effect of quinonediazide on alkali. It was. In addition, the addition of a soluble polyimide resin having a hydroxyl group in the main chain has less problems as described above, but the structure is limited to make it soluble, and the solvent resistance of the resulting polyimide resin The problem was a bad point. When a quinonediazide is added to a polyamide resin having a hydroxyl group, the structure is limited in order to obtain solubility, and therefore the solvent resistance of the resin obtained after heat treatment is inferior.

  Therefore, in order to control the alkali solubility of the polyamic acid, a polyamic acid derivative in which the carboxyl group of the polyamic acid is protected with an ester group has been developed. When naphthoquinone diazide was added to this polyamic acid derivative, a desired pattern could be formed. However, the polymer had a large molecular weight, so the solubility in an alkaline developer was low, and the sensitivity was low and unsuitable for practical use. . Therefore, a technique for controlling the molecular weight by end-capping the polymer to ensure solubility in an alkaline developer was studied, and sensitivity was improved (for example, see Patent Documents 1 to 13).

On the other hand, heat resistant resin precursor compositions using these end group-containing polymers have insufficient mechanical properties after curing due to their low molecular weight, and their use has been limited. From these situations, examples in which heat-reactive substituents are introduced into the polymer ends and crosslinked at the time of thermosetting to improve the film properties (for example, see Patent Documents 14 to 24), examples in which a chain extender is added (For example, see Patent Document 25) and the like have been tried and the practical range has been widened, but for applications that require high reliability such as in-vehicle semiconductors, the mechanical properties, in particular, the degree of elongation is insufficient. The actual situation is that a non-photosensitive resin precursor composition having high elongation is used for the application.
JP-A-11-143070 Japanese Patent Laid-Open No. 11-249306 JP 2001-033963 A JP 2001-125263 A JP 2001-174996 A JP 2001-183835 A JP 2002-012665 A JP 2002-020484 A JP 2002-053664 A JP 2002-303977 A JP 2003-337415 A JP 2004-206032 A JP 2004-302430 A WO99 / 54787 pamphlet JP 2001-235860 A JP 2001-329061 A JP 2002-221794 A JP 2002-284875 A JP 2003-241377 A JP 2003-248314 A JP 2004-157248 A JP 2004-077551 A JP 2004-132994 A JP 2004-212678 A JP 2003-330167 A

  The above-described conventional technology has a problem in that, since sufficient elongation cannot be ensured, a problem occurs when used in a semiconductor device that requires high reliability. An object of the present invention is to provide a positive photosensitive resin precursor composition having high elongation that can be sufficiently used even in a semiconductor device requiring high reliability.

  That is, the present invention relates to (a) a polymer whose main component is a structure represented by the general formula (1) and / or (2), (b) a structure represented by the general formula (3) and / or (4). A positive photosensitive resin precursor composition comprising: (c) a quinonediazide compound; and (d) a solvent.

(In the formula, R ¹ and R ² are divalent to octavalent organic groups having two or more carbon atoms, R ³ and R ⁴ may be the same as or different from each other, and may be hydrogen or C 1-20. R ⁵ and R ⁶ represent a single bond or an organic group having 1 to 20 carbon atoms, X and Y represent an organic group capable of forming an —X—Y— bond by heating, and n represents 10 to 10. In the range of 100,000, l and m are integers of 0 to 2, p and q are integers of 0 to 4, provided that p + q> 0.

  According to the present invention, it is possible to obtain a positive photosensitive resin precursor composition that can be developed with an aqueous alkaline solution and not only has excellent resolution and sensitivity but also has excellent elongation after curing.

  (A) a polymer mainly composed of a structure represented by the general formula (1) and / or (2) used in the positive photosensitive resin precursor composition of the present invention, (b) a general formula (3) and The polymer having the structure represented by (4) as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst, and is preferably a polyimide precursor. Examples thereof include polyamic acid, polyamic acid ester, and polyhydroxyamide of a polybenzoxazole precursor. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved. Here, the main component is 50 mol% or more of n structural units of the structure represented by the general formula (1) and / or (2) or the general formula (3) and / or (4). It means having. Preferably it is 70 mol% or more, and more preferably 90 mol% or more.

In the general formulas (1) to (4), R ¹ represents a divalent to octavalent organic group having 2 or more carbon atoms, and represents an acid structural component. Examples of acids in which R ¹ is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. And so on. The acid R ¹ is trivalent, trimellitic acid, tricarboxylic acids such as trimesic acid, pyromellitic acid as the acid R ¹ is tetravalent, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid And tetracarboxylic acids such as Moreover, acids having a hydroxyl group such as hydroxyphthalic acid and hydroxytrimellitic acid can also be used. These acid components may be used alone or in combination of two or more, but it is preferable to use 1 to 40 mol% of tetracarboxylic acid as a copolymer.

R ¹ is preferably a trivalent to octavalent organic group having two or more carbon atoms containing an aromatic ring from the viewpoint of heat resistance, and is a trivalent or tetravalent organic group having 6 to 30 carbon atoms. Groups are more preferred. Specifically, it is preferable that R ¹ (COOR ³ ) _m (OH) _p in the general formulas (1) to (4) has a structure as shown in the general formula (7).

In the above formula, R ⁷ and R ⁹ may be the same or different and each represents a divalent to tetravalent organic group having 2 to 20 carbon atoms, and R ⁸ is a trivalent to hexavalent group having 3 to 20 carbon atoms. Represents an organic group, and R ¹⁰ and R ¹¹ may be the same or different and represent hydrogen or an organic group having 1 to 20 carbon atoms. o and t are integers of 0 to 2, and r is an integer of 1 to 4. However, o + t ≦ 2.

R ⁷ and R ⁹ are more preferably those containing an aromatic ring from the viewpoint of the heat resistance of the resulting polymer, and among them, particularly preferred structures include trimellitic acid, trimesic acid, naphthalene tricarboxylic acid residue and the like. .

R ⁸ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Furthermore, the r hydroxyl groups are preferably located adjacent to the amide bond. As such an example, bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-hydroxy-4-aminophenyl) hexafluoropropane containing a fluorine atom, bis ( 3-amino-4-hydroxyphenyl) propane, bis (3-hydroxy-4-aminophenyl) propane, 3,3′-diamino-4,4′-dihydroxybiphenyl, 3,3′-dihydroxy-4,4 ′ Examples include diaminobiphenyl, 2,4-diamino-phenol, 2,5-diaminophenol, and 1,4-diamino-2,5-dihydroxybenzene having an amino group bonded thereto.

Further, R ¹⁰ and R ¹¹ in the general formula (7) may be the same or different, and represent hydrogen or an organic group having 1 to 20 carbon atoms. When the number of carbon atoms exceeds 20, the solubility in an alkaline developer is lowered, which is not preferable. o and t represent integers of 0 to 2, but are preferably selected from integers of 1 to 2. However, o + t ≦ 2. R represents an integer of 1 to 4. When r is 5 or more, the chemical resistance of the resulting heat-resistant resin film is lowered, which is not preferable.

  Of the structures represented by the general formula (7), examples of preferred structures include the structures shown below, but are not limited thereto.

In addition, in the general formulas (1) to (4), the structural component of the acid represented by R ¹ is a tetracarboxylic acid having no hydroxyl group as long as the solubility in alkali, the photosensitive performance, and the heat resistance are not impaired. It is also possible to copolymerize using a dicarboxylic acid. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, diphenylethertetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and diesters in which two carboxyl groups are methyl or ethyl groups. Compounds, aliphatic tetracarboxylic acids such as butanetetracarboxylic acid and cyclopentanetetracarboxylic acid, diester compounds in which two carboxyl groups are methyl or ethyl groups, terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid And aromatic dicarboxylic acids such as adipic acid and the like. These are preferably a copolymer of 50 mol% or less of the acid component, more preferably 30 mol% or less. When the copolymerization is carried out in an amount larger than 50 mol%, the amount of the component not having a hydroxyl group becomes excessive, so that the solubility in alkali and the photosensitivity may be impaired.

In general formulas (1) to (4), R ² represents a divalent to octavalent organic group having two or more carbon atoms, and represents a structural component of diamine. Among these, those having an aromatic group are preferred from the viewpoint of the heat resistance of the obtained polymer. Specific examples of diamines include bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol having no fluorine atom, Compounds such as dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid, and R ² (COOR ⁴ ) _l (OH) _{q in} the general formulas (1) to (4) are any of the general formulas (8) to (10). The structure shown by can be mentioned.

R ¹² and R ^{14 in} the general formula (8) may be the same or different, and represent a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and R ¹³ is a divalent organic group having 2 to 30 carbon atoms. Indicates a group. u and v represent 1 or 2. R ¹⁵ and R ^{17 in} the general formula (9) may be the same or different and represent a divalent organic group having 2 to 20 carbon atoms, and R ¹⁶ is a trivalent to hexavalent organic group having 3 to 20 carbon atoms. Indicates a group. w shows the integer of 1-4. R ^{18 in the} general formula (10) represents a divalent organic group having 2 to 20 carbon atoms, and R ¹⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms. x shows the integer of 1-4.

In the general formula (8), R ¹² and R ¹⁴ represent a trivalent to tetravalent organic group having 2 to 20 carbon atoms, and those having an aromatic ring are preferable from the viewpoint of heat resistance of the resulting polymer. . Specific examples of —R ¹² (OH) _u — and —R ¹⁴ (OH) _v — include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (Hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like can be mentioned. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹³ represents a divalent organic group having 2 to 30 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, an aromatic divalent group is preferable, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group can also be used.

In the general formula (9), R ¹⁵ and R ¹⁷ represent a divalent organic group having 2 to 20 carbon atoms. A divalent group having an aromatic ring is preferable from the heat resistance of the obtained polymer, and examples thereof include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group and the like can also be used. R ¹⁶ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the obtained polymer. Specific examples of —R ¹⁶ (OH) _w — include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, Examples thereof include a bis (hydroxyphenyl) propane group, a bis (hydroxyphenyl) sulfone group, a hydroxydiphenyl ether group, and a dihydroxydiphenyl ether group. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

In the general formula (10), R ¹⁸ represents a divalent organic group having 2 to 20 carbon atoms. From the heat resistance of the resulting polymer, a divalent group having an aromatic ring is preferable. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, and a diphenylsulfone group. In addition, an aliphatic cyclohexyl group can also be used. R ¹⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the heat resistance of the resulting polymer. Specific examples of —R ¹⁹ (OH) _x — include hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, Examples thereof include bis (hydroxyphenyl) propane group, bis (hydroxyphenyl) sulfone group, hydroxydiphenyl ether group, and dihydroxydiphenyl ether group. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

  Moreover, u and v of General formula (8) show 1 or 2, w of General formula (9) and x of General formula (10) show the integer of 1-4.

  Among the structures represented by the general formula (8), examples of preferred structures include the structures shown below, but are not limited thereto.

  Further, among the structures represented by the general formula (9), examples of preferable structures include the structures shown below, but are not limited thereto.

  Of the structures represented by the general formula (10), examples of preferred structures include the structures shown below, but are not limited thereto.

  Other diamine components may be copolymerized in the range of 1 to 40 mol% with respect to the diamine represented by the general formulas (8), (9), and (10). Examples include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone or their fragrances. Examples thereof include compounds in which the aromatic ring is substituted with an alkyl group or a halogen atom, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, and the like. If such an aliphatic diamine component is copolymerized in excess of 40 mol%, the heat resistance of the resulting polymer is lowered, so care must be taken.

R ³ and R ^{4 in the} general formulas (1) to (4) may be the same or different and represent hydrogen or an organic group having 1 to 20 carbon atoms. From the viewpoint of solution stability of the resulting photosensitive resin precursor solution, R ³ and R ⁴ are preferably organic groups, but hydrogen is preferable from the viewpoint of solubility in an aqueous alkali solution. In the present invention, hydrogen atoms and organic groups can be mixed. By adjusting the amounts of hydrogen and organic groups of R ³ and R ^4, the dissolution rate with respect to the aqueous alkali solution is changed, so that a photosensitive resin precursor composition having an appropriate dissolution rate can be obtained by this adjustment. it can. As a preferable range, 10% to 90% of R ³ and R ⁴ are each a hydrogen atom. When the number of carbon atoms in R ³ and R ⁴ exceeds 20, it will not dissolve in the alkaline aqueous solution. From the above, R ³ and R ⁴ preferably contain at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are hydrogen atoms.

  In the general formulas (1) to (4), l and m represent the number of carboxyl groups, and represent an integer of 0 to 2. More preferably, it is 1 or 2. P and q of General formula (1)-(4) show the integer of 0-4, and it is p + q> 0. In the general formulas (1) to (4), n represents the number of repeating structural units of the polymer and is in the range of 10 to 100,000. If n is less than 10, the solubility of the polymer in an alkaline developer becomes too high, and the contrast between the exposed area and the unexposed area cannot be obtained, and a desired pattern may not be formed. Moreover, even if the polymer terminal forms an -X-Y- bond by heating, the increase in molecular weight is small, so that it is difficult to obtain the improvement in elongation, which is an effect of the present invention. On the other hand, if n is larger than 100,000, the solubility of the polymer in the alkaline developer becomes too small, the exposed portion is not dissolved, and a desired pattern cannot be formed. Thus, n is in the range of 10 to 100,000, more preferably in the range of 20 to 1000, and most preferably in the range of 20 to 100, from the viewpoint of the solubility of the polymer in an alkaline developer and the improvement in elongation. It is a range.

  N in the general formulas (1) to (4) can be easily calculated by measuring the weight average molecular weight (Mw) by gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering method, or the like. When the molecular weight of the repeating unit is M and the weight average molecular weight of the polymer is Mw, n = Mw / M.

Furthermore, in order to improve the adhesion to the substrate, an aliphatic group having a siloxane structure may be copolymerized with R ¹ and R ² in the general formulas (1) to (4) as long as the heat resistance is not lowered. Good. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.

  X in the general formulas (1) and (2) and Y in the general formulas (3) and (4) each represent an end group of the polymer, and an organic group capable of forming an -X-Y- bond by heat curing. By containing the polymer of component (a) having an X group at the terminal and the polymer of component (b) having a Y group at the terminal, it has excellent solubility in an alkaline developer during pattern formation, Since these end groups are directly bonded, the molecular chain is extended, so that the positive photosensitive resin precursor composition of the present invention exhibits excellent mechanical properties after thermosetting. In the case of a resin composition containing a compound having a crosslinkable group (Patent Documents 14 to 24), since it binds to an unspecified part of the polymer chain, molecular chain elongation may be impaired. In the case of a polymer having a specific terminal group, the polymer ends can be bonded to each other to efficiently extend the molecular chain, and the mechanical properties are dramatically improved.

  Content ratio (a) of polymer of component (a) represented by general formula (1) and / or (2) and polymer of component (b) represented by general formula (3) and / or (4) ) :( b) is preferably in the range of 20:80 to 80:20 (weight ratio). By mixing and using the polymer of the component (a) and the polymer of the component (b) in this range, a sufficient elongation improving effect can be obtained by the -XY bond generated after thermosetting. For these reasons, the content ratio (a) :( b) of the polymer of the component (a) and the polymer of the component (b) is more preferably in the range of 30:70 to 70:30 (weight ratio). The range of 60-60: 40 is more preferable.

  General formulas (1) and (3) indicate the case where a monoamino compound is used at the terminal, and general formulas (2) and (4) indicate a monoacid anhydride, monocarboxylic acid, monoacid chloride compound, or monoactivity at the terminal. The case where an ester compound is used is shown. Since the effect is expressed if the terminal X and Y groups are bonded by heating, any combination of the general formula (1) and / or (2) and the general formula (3) and / or (4) Even in the case, it is preferably used.

R ⁵ and R ^{6 in the} general formulas (1) to (4) represent a single bond or an organic group having 1 to 20 carbon atoms, and those having an aromatic ring are preferable from the viewpoint of heat resistance of the obtained polymer. . Specific examples include a phenyl group, a diphenyl group, a naphthyl group, a diphenylhexafluoropropane group, a diphenylpropane group, a diphenylsulfone group, and a diphenyl ether group. In addition, aliphatic groups such as a cyclohexyl group and a cyclooctyl group can also be used.

The bond formed by heating X in the general formula (1) or (2) and Y in the general formula (3) or (4) is a urea bond, an amide bond or a sulfonamide bond from the viewpoint of heat resistance of the film after curing. It is preferable that Specific examples of -X forming such a bond include -NR ²⁰ R ²¹ , and -Y having a structure represented by -NCO, -COOR ²² , -SO ₂ R ^23. Can do. Here, R ²⁰ , R ²¹ , R ²² , and R ²³ each independently represent hydrogen or an organic group having 1 to 10 carbon atoms.

Examples in which —NH—R ⁵ —X in the general formula (1) is represented by —NH—R ⁵ —NR ²⁰ R ²¹ include methyl hydrazine, acetyl hydrazine, methylsulfonyl hydrazine, 2-methylaminoaniline, 3- Methylaminoaniline, 4-methylaminoaniline, 2-dimethylaminoaniline, 3-dimethylaminoaniline, 4-dimethylaminoaniline, 2-ethylaminoaniline, 3-ethylaminoaniline, 4-ethylaminoaniline, 2-diethylaminoaniline 3-diethylaminoaniline, 4-diethylaminoaniline, 2-aminoacetanilide, 3-aminoacetanilide, 4-aminoacetanilide, 2-aminomethylsulfonanilide, 3-aminomethylsulfonanilide, 4-aminomethylsulfonanilide, N- (2-aminophenyl) -N′-methylurea, N- (3-aminophenyl) -N′-methylurea, N- (4-aminophenyl) -N′-methylurea, 1-amino-2-methylaminonaphthalene, 1-amino-3-methylaminonaphthalene, 1-amino-4-methylaminonaphthalene, 1-amino-5-methylaminonaphthalene, 2-amino-6-methylaminonaphthalene, 1-amino-2-dimethylaminonaphthalene, 1-amino-3-dimethylaminonaphthalene, 1-amino-4-dimethylaminonaphthalene, 1-amino-5-dimethylaminonaphthalene, 2-amino-6-dimethylaminonaphthalene, 1-amino-2-acetaminonaphthalene, 1-amino-3-acetaminonaphthalene, 1-amino-4-acetaminonaphthalene, -Amino-5-acetaminonaphthalene, 2-amino-6-acetaminonaphthalene, 1-amino-2-methylsulfoneaminonaphthalene, 1-amino-3-methylsulfoneaminonaphthalene, 1-amino-4-methylsulfonamino Examples include, but are not limited to, naphthalene, 1-amino-5-methylsulfoneaminonaphthalene, 2-amino-6-methylsulfoneaminonaphthalene, and the like. Of these, 2-aminoacetanilide, 3-aminoacetanilide, 4-aminoacetanilide, 2-aminomethylsulfonanilide, 3-aminomethylsulfonanilide, 4-amino from the standpoints of solution stability and solubility in an aqueous alkali solution. Methylsulfonanilide is preferably used.

Examples in which —CO—R ⁵ —X in the general formula (2) is represented by —CO—R ⁵ —NR ²⁰ R ²¹ include 2-acetylaminophthalic anhydride, 3-acetylaminophthalic anhydride, and the like. Monocarboxylic anhydrides, monoacetyl acids such as 2-acetylaminobenzoic acid, 3-acetylaminobenzoic acid and 4-acetylaminobenzoic acid, and monoacid chloride compounds in which these carboxyl groups are converted to acid chlorides. However, it is not limited to these.

As an example in which —NH—R ⁶ —Y in the general formula (3) is represented by —NH—R ⁶ —NCO, —NH—R ⁶ —COOR ²² , —NH—R ⁶ —SO ₂ R ²³ , 2-amino Phenyl isocyanate, 3-aminophenyl isocyanate, 4-aminophenyl isocyanate, 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, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4 -Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, methyl 2-aminonicotinate, methyl 4-aminonicotinate, methyl 5-aminonicotinate, methyl 6-aminonicotinate, methyl 4-aminosalicylate, 5- Methyl aminosalicylate, methyl 6-aminosalicylate, 3-amino-O Methyl toluic acid, methyl 2-aminobenzoate, methyl 3-aminobenzoate, methyl 4-aminobenzoate, methyl 2-aminobenzenesulfonate, methyl 3-aminobenzenesulfonate, methyl 4-aminobenzenesulfonate, etc. For example, but not limited to. Of these, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-O-toluic acid, 2-aminobenzoic acid, Aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, methyl 4-aminosalicylate, methyl 5-aminosalicylate, methyl 6-aminosalicylate, 3 -Methyl amino-O-toluic acid, methyl 2-aminobenzoate, methyl 3-aminobenzoate, methyl 4-aminobenzoate, methyl 2-aminobenzenesulfonate, methyl 3-aminobenzenesulfonate, 4-aminobenzene Methyl sulfonate is preferably used.

As an example in which —CO—R ⁶ —Y in the general formula (4) is represented by —CO—R ⁶ —NCO, —CO—R ⁶ —COOR ²² , —CO—R ⁶ —SO ₂ R ²³ , phthalic anhydride , Maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, acid anhydrides such as trimellitic anhydride, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxy Monocarboxylic acids such as benzenesulfonic acid and monoacid chloride compounds in which these carboxyl groups are acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3 -Dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene and 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole and N-hydroxy-5 Examples include, but are not limited to, active ester compounds obtained by reaction with norbornene-2,3-dicarboximide.

  The introduction ratio of the monoamine compound used for the terminal blocking agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent ranges from 0.1 to 100 mol% with respect to the diamine component. Preferably, it is 5-90 mol% especially preferably.

The end-capping agent introduced into the polymer can be easily detected by the following method. For example, by dissolving a polymer having an end capping agent dissolved in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the polymer, this is measured by gas chromatography (GC) or NMR measurement, The end capping agent can be easily detected. In addition, the polymer component into which the end-capping agent is introduced can be easily detected directly by pyrolysis gas chromatograph (PGC), infrared spectrum and ¹³ C NMR spectrum measurement.

  In the present invention, the polymer of component (a) may be composed of only the structure represented by the general formula (1) and / or (2), or may contain other polymers. The polymer of the component (b) may be composed of only the structure represented by the general formula (3) and / or (4), or may contain other polymers.

  The polymer having the structure represented by the general formula (1) or (3) as a main component is synthesized by the following method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound and a monoamino compound used for terminal blocking at a low temperature, a diester is obtained by tetracarboxylic dianhydride and an alcohol, Thereafter, a method of reacting a diamine compound, a monoamino compound and a condensing agent, a method of obtaining a diester by tetracarboxylic dianhydride and an alcohol, and then converting the remaining dicarboxylic acid to an acid chloride and reacting with the diamine compound or the monoamino compound. and so on. Polyhydroxyamide can also be used in place of polyamic acid as a heat-resistant polymer precursor similar to polyamic acid. In the case of polyhydroxyamide, it can be obtained by a production method in which a bisaminophenol compound, a dicarboxylic acid, and a monoamino compound are subjected to a condensation reaction. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a method of adding a bisaminophenol compound or monoamino compound to this, or a bisaminophenol compound or monoamino added with a tertiary amine such as pyridine. There is a method of dropping a dicarboxylic acid dichloride solution into a compound solution.

  The polymer having the structure represented by the general formula (2) or (4) as a main component is synthesized by the following method. In the case of polyamic acid or polyamic acid ester, for example, a method of reacting a tetracarboxylic dianhydride and a diamine compound and a monoacid anhydride used for terminal blocking at a low temperature, a diester is formed by tetracarboxylic dianhydride and alcohol. Diamine compound, a method of reacting in the presence of a monocarboxylic acid and a condensing agent, a diester is obtained by tetracarboxylic dianhydride and an alcohol, and then the remaining dicarboxylic acid is converted into an acid chloride, and the diamine compound, monoacid chloride is obtained. There is a method of reacting with a compound. In the case of polyhydroxyamide, it can be obtained by a production method in which a bisaminophenol compound and a dicarboxylic acid, a monocarboxylic acid or dicarboxylic acid anhydride used for end-capping are subjected to a condensation reaction. Specifically, a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid, and a bisaminophenol compound is added thereto, or a solution of a bisaminophenol compound added with a tertiary amine such as pyridine is added to a dicarboxylic acid. There is a method of dropping a solution of a dichloride or monoacid chloride compound.

  The polymer having the structure represented by any one of the general formulas (1) to (4) as a main component is polymerized by the above method, and then poured into a large amount of water or a methanol / water mixture to precipitate. It is desirable to filter, dry and isolate. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved.

  The positive photosensitive resin precursor composition of the present invention contains (c) a quinonediazide compound. The quinonediazide compound is a compound in which a sulfonic acid of quinonediazide is bonded to a polyhydroxy compound with an ester, a compound in which a sulfonic acid of quinonediazide is bonded to a polyamino compound, and a sulfonamide of quinonediazide to a polyhydroxypolyamino compound Examples include those that are combined. Although all the functional groups of these polyhydroxy compounds and polyamino compounds may not be substituted with quinonediazide, it is preferable that 50 mol% or more of the entire functional groups are substituted with quinonediazide. If it is less than 50 mol%, the solubility in an alkali developer becomes too high, and a contrast with an unexposed portion cannot be obtained, and a desired pattern may not be obtained. By using such a quinonediazide compound, a positive photosensitive resin precursor composition sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet ray, is obtained. be able to.

  Polyhydroxy compounds are Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, BisP-PZ, BisP-IPZ, BisOCP -IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR- PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A 2,6-dimethoxymethyl-4-t-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A , Bisphenol E, methylene bisphenol, BisP-AP (trade name, Honshu Manufactured by Manabu Kogyo Co.) and the like, but not limited to.

  Polyamino compounds are 1,4-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenyl. Although sulfide etc. are mentioned, it is not limited to these.

  Examples of the polyhydroxypolyamino compound include 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 3,3'-dihydroxybenzidine, but are not limited thereto.

  In the present invention, quinonediazide is preferably a 5-naphthoquinonediazidesulfonyl group or a 4-naphthoquinonediazidesulfonyl group. 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. In addition, a naphthoquinone diazide sulfonyl ester compound in which 4-naphthoquinone diazide sulfonyl group and 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be obtained, or 4-naphthoquinone diazide sulfonyl ester compound and 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  The molecular weight of the quinonediazide compound is preferably 300 to 1500. When the molecular weight is 1500 or less, the quinonediazide compound is sufficiently thermally decomposed in the heat treatment after pattern formation, and a cured film having excellent heat resistance, mechanical properties, and adhesiveness can be obtained. More preferably, it is 350-1200.

  Further, the content of the (c) quinonediazide compound is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight based on 100 parts by weight of the total of the polymer of the component (a) and the polymer of the component (b). The range is parts by weight.

  The quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazide sulfonyl chloride and a phenol compound in the presence of triethylamine. Examples of the method for synthesizing a phenol compound include a method in which an α- (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.

  The positive photosensitive resin precursor composition of the present invention contains (d) a solvent. Solvents include polar aprotic solvents such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, etc. Ethers, acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol and other ketones, ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate and other esters, toluene, xylene and other aromatic hydrocarbons alone, Or it can be mixed and used. The content of the solvent used in the present invention is preferably from 50 to 2000 parts by weight, particularly preferably from 100 to 1500 parts by weight, based on 100 parts by weight of the total of the polymer of component (a) and the polymer of component (b).

  The positive photosensitive resin precursor composition of the present invention further contains (e) at least one silane compound selected from compounds represented by the following general formula (5) or (6) and vinylsilane compounds. Is preferred. Such a silane compound can be a component for improving adhesion to the substrate.

Ar ¹ and Ar ^{2 in the} general formulas (5) and (6) represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. Specific examples include, but are not limited to, a phenyl group, a naphthalene group, a biphenyl group, a triazine group, and a pyridine group.

R ²⁶ , R ²⁷ , R ³⁴ , R ³⁵ , R ⁴² and R ⁴³ in the general formulas (5) and (6) may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms. Specific examples of the organic group having 1 to 4 carbon atoms include hydrocarbon such as methyl group, ethyl group and propyl group, and carbonyl group such as acetyl group. If the number of carbon atoms is 5 or more, the film shrinkage during curing becomes large, so care must be taken. R ²⁸ , R ³⁶ and R ⁴¹ may be the same or different, each represents an organic group having 1 to 6 carbon atoms, and R ^{29 to} R ³³ and R ^{37 to} R ⁴⁰ may be the same or different, A hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group is represented. Further, at least one of R ^{29 to} R ³³ and R ^{37 to} R ⁴⁰ has an alkoxy group having 1 to 6 carbon atoms. a, d, f, and h are integers of 1 or more, and b, c, e, and g are integers of 0 or more. However, 1 ≦ a + b ≦ 4, 1 ≦ d + e ≦ 4, 1 ≦ g + h ≦ 4. Specific examples of the hydrocarbon group include, but are not limited to, a methyl group, an ethyl group, and a propyl group. Specific examples of the alkoxy group include, but are not limited to, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and an isobutoxy group. If the hydrocarbon group or alkoxy group has 7 or more carbon atoms, the film shrinkage at the time of curing will increase, so care must be taken. Preferable specific examples of this compound include the following structures, but are not limited thereto.

  Among them, the structure shown below is more preferable.

  Examples of the vinyl silane compound include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl trichloro silane, vinyl tris (β-methoxy ethoxy) silane, etc. In addition to this, 3-methacryloxypropyl trimethoxy silane, 3- Carbon-carbon unsaturated bond-containing silane compounds such as acryloxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane can also be used. Vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  The compound represented by the general formula (5) or (6) and the vinylsilane compound may be used alone or in combination, and in any case, good adhesion to various substrates is exhibited.

  The compound represented by the general formula (5) or (6) and the vinylsilane compound are each 0.001 to 30 parts by weight with respect to 100 parts by weight of the total of the polymer of the component (a) and the polymer of the component (b). It is preferable to contain. Within this range, a sufficient adhesion improving effect can be obtained while maintaining the heat resistance of the composition. More preferably, it is 0.005-20 weight part, More preferably, it is 0.01-15 weight part.

  Moreover, when using the said component (e) in this invention, it is preferable to add the said component (e) to the composition after completion | finish of superposition | polymerization of a polymer. When a compound corresponding to the component (e) is added at the time of polymer polymerization, it may be incorporated into the polymer main chain by a covalent bond in the polymer and the adhesion effect may be reduced. Also, when reprecipitating the polymer, the unreacted product of the above compound is removed at the time of reprecipitation, so that the adhesion effect is lowered, and gelation is caused by condensation of alkoxy groups. It is preferable to add the component (e) when redissolving in a solvent or after redissolving.

  The positive photosensitive resin precursor composition of the present invention may contain (f) a photoacid generator selected from sulfonium salts, phosphonium salts, and diazonium salts. By containing the photoacid generator, a decrease in sensitivity due to standing after exposure can be reduced. Since the resin composition obtained from the photosensitive resin precursor composition of the present invention is used as a permanent film, it is not environmentally preferable that phosphorus or the like remains, and it is necessary to consider the color tone of the film. Of these, sulfonium salts are preferably used. Among the sulfonium salts, a triarylsulfonium salt represented by the general formula (11) is particularly preferable.

In the formula, each R ²⁴ may be the same or different, and represents hydrogen or an organic group having 1 to 20 carbon atoms. R ²⁵ represents an organic group having 1 to 20 carbon atoms. α, β, and γ each represent an integer of 0 to 5.

  Specific examples of the triarylsulfonium salt represented by the general formula (11) are shown below, but are not limited thereto.

  In the positive photosensitive resin precursor composition of the present invention, the content of the photoacid generator used as the component (f) is 100 parts by weight in total of the polymer of the component (a) and the polymer of the component (b). The amount is preferably 0.01 to 50 parts by weight. More preferably, it is the range of 0.05-10 weight part.

  The positive photosensitive resin precursor composition of the present invention may further contain (g) an alkoxymethyl group-containing compound. By containing this compound, the remaining film rate at the time of curing is improved, and a good pattern shape can be obtained. The alkoxymethyl group-containing compound is preferably a compound having a phenolic hydroxyl group and / or a compound containing a urea organic group.

  Examples of compounds having a phenolic hydroxyl group include, but are not limited to, the following compounds.

  Examples of the alkoxymethyl compound having a urea-based organic group include, but are not limited to, the following compounds.

  By containing these compounds that exhibit thermal crosslinkability, the resulting photosensitive resin precursor composition hardly dissolves in the alkali developer before exposure, and easily dissolves in the alkali developer upon exposure. The film loss due to development is small, and development can be performed in a short time. In addition, the shrinkage after curing is reduced.

  (G) The content of the alkoxymethyl group-containing compound is preferably 0.5 to 50 parts by weight, more preferably 100 parts by weight in total of the polymer of the component (a) and the polymer of the component (b). It is in the range of 3 to 40 parts by weight.

  Moreover, the compound which has a phenolic hydroxyl group can be contained for the purpose of improving the sensitivity of the said photosensitive resin precursor composition as needed.

  Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, BisP-EZ. Bis26X-CP, BisP-PZ, BisP-IPZ, BisCR-IPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakis P-DO-BPA), TrisP-HAP, TrisP -PA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26 -OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR -PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.).

  Among these, compounds having a phenolic hydroxyl group preferably used in the present invention include, for example, Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisOCHP-Z, BisP-MZ, BisP- PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methylenetris-FR-CR, BisRS-26X, BIP-PC, BIR-PC, BIR-PTBP, BIR -BIPC-F etc. are mentioned. Among these, particularly preferred compounds having a phenolic hydroxyl group include, for example, Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P, BIR-PC, BIR-PTBP, BIR- BIPC-F. By containing the compound having a phenolic hydroxyl group, the obtained resin precursor composition hardly dissolves in the alkali developer before exposure, and easily dissolves in the alkali developer upon exposure. There is little decrease, and development is easy in a short time.

  The content of such a compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 parts per 100 parts by weight in total of the polymer of component (a) and the polymer of component (b). It is in the range of ˜40 parts by weight.

  Further, if necessary, for the purpose of improving the coatability between the photosensitive precursor composition and the substrate, surfactants, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, Ketones such as methyl isobutyl ketone and ethers such as tetrahydrofuran and dioxane may be contained. Further, inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.

  Further, in order to improve the adhesion to a base substrate such as a silicon wafer, the base substrate can be pretreated with the component (e). In this case, a solution obtained by dissolving 0.5 to 20% by weight of the component (e) in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, or diethyl adipate Is subjected to surface treatment by spin coating, dipping, spray coating, steam treatment or the like. Depending on the case, reaction of a board | substrate and said (e) component is advanced by applying the temperature of 50 to 300 degreeC after that.

  Next, a method for forming a heat-resistant resin pattern using the positive photosensitive resin precursor composition of the present invention will be described.

  The photosensitive resin precursor composition is applied onto the substrate. As the substrate, a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, ITO, or the like is used, but not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and slit die coating. Further, the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

  Next, the substrate coated with the photosensitive resin precursor composition is dried to obtain a photosensitive resin precursor composition film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like in the range of 50 ° C. to 150 ° C. for 1 minute to several hours.

  Next, the photosensitive resin precursor composition film is exposed to actinic radiation through a mask having a desired pattern. As the actinic radiation used for exposure, there are ultraviolet rays, visible rays, electron beams, X-rays and the like. In the present invention, it is preferable to use i rays (365 nm), h rays (405 nm), and g rays (436 nm) of a mercury lamp. .

  In order to form a heat-resistant resin pattern from the photosensitive resin precursor composition film, the exposed portion may be removed using a developer after exposure. The developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone, dimethylacrylamide, methanol, ethanol, Alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone may be added singly or in combination. Good. After development, rinse with water. Here, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing treatment.

  After development, a temperature of 200 ° C. to 500 ° C. is applied to convert it to a heat resistant resin film. This heat treatment is carried out for 5 minutes to 5 hours by selecting the temperature and increasing the temperature stepwise or by selecting a certain temperature range and continuously increasing the temperature. As an example, heat treatment is performed at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each. Alternatively, a method such as linearly raising the temperature from room temperature to 400 ° C. over 2 hours may be mentioned.

  The heat-resistant resin film formed from the positive photosensitive heat-resistant precursor composition of the present invention includes a semiconductor passivation film, a protective film for a semiconductor element, an interlayer insulating film for multilayer wiring for high-density mounting, and an insulation for an organic electroluminescent element. It is suitably used for applications such as layers.

  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 photosensitive resin precursor composition in an Example was performed with the following method.

(1) Evaluation of pattern processability Production of photosensitive resin precursor film A photosensitive resin precursor composition (hereinafter referred to as varnish) was applied on a 6-inch silicon wafer so that the film thickness after pre-baking was 8 μm, Subsequently, the photosensitive resin precursor film | membrane was obtained by prebaking for 3 minutes at 120 degreeC using the hotplate (Tokyo Electron Co., Ltd. coating development apparatus Mark-7).

Film thickness measurement method Using Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the film after pre-baking and development is measured at a refractive index of 1.629, and the cured film is measured at a refractive index of 1.773. did.

Exposure The reticle from which the pattern was cut was set in an exposure machine (i-line stepper DSW-8000 manufactured by GCA), and the photosensitive resin precursor film was exposed with i-line by changing the exposure time at an intensity of 365 nm.

Development Using a developing device of Mark-7 manufactured by Tokyo Electron Ltd., a 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed on the exposed film for 10 seconds at 50 revolutions. Then, it was allowed to stand for 70 seconds at 0 rotation, rinsed with water at 400 rotation, and shaken and dried for 10 seconds at 3000 rotation.

Calculation of Sensitivity After exposure and development, an exposure time for forming a 50 μm line and space pattern (1L / 1S) in a one-to-one width (hereinafter referred to as an optimal exposure time) was determined.

Calculation of resolution The minimum pattern size at the optimum exposure time was taken as the resolution.

(2) Evaluation of mechanical properties Production of heat-resistant resin film On a 6-inch silicon wafer, varnish was applied so that the film thickness after pre-baking would be 10 μm, and then hot plate (Coating and developing device Mark manufactured by Tokyo Electron Ltd.) The photosensitive resin precursor film | membrane was obtained by prebaking for 3 minutes at 120 degreeC using -7). Thereafter, the photosensitive resin precursor film developed by the above-described method was manufactured using an inert oven INH-21CD manufactured by Koyo Thermo System Co., Ltd., under nitrogen flow (oxygen concentration of 20 ppm or less) at 140 ° C. for 30 minutes. Thereafter, the temperature was raised to 350 ° C. over 1 hour, and heat treatment was performed at 350 ° C. for 1 hour to produce a heat-resistant resin film (cured film).

Preparation of measurement sample A heat-resistant resin film (cured film) prepared on a silicon wafer was immersed in 47% hydrofluoric acid at room temperature for 7 minutes, washed with water, and carefully peeled from the silicon wafer. The peeled cured film was cut into a strip shape having a width of 1 cm and a length of about 9 cm with a single blade to obtain a measurement sample.

Measurement The Tensylon RTM-100 manufactured by Orientec was set with the measurement sample at an initial sample length of 50 mm, and a tensile test was performed at a tensile speed of 50 mm / min. Measurement was performed at n = 12, and the average value of the top five points of the maximum stress, elastic modulus, and elongation obtained was obtained.

(3) Measurement of weight average molecular weight The molecular weight of the polymer was measured under the following conditions using GPCModel 510 manufactured by Waters Co., Ltd., and the weight average molecular weight (Mw) was calculated using a calibration curve of standard polystyrene.
Column: TSK-GELα2500, TSK-GELα40000 (manufactured by Tosoh Corporation)
Developing solvent: N-methylpyrrolidone (NMP)
LiCl 0.05 mol / L, H ₃ PO ₄ 0.05 mol / L
Flow rate: 0.4 mL / min.

(4) Evaluation of Adhesion with Substrate After 10-row and 10-column grid cuts were cut into the cured film at intervals of 2 mm, after 100 hours of pressure cooker test (PCT) treatment, peeling with cello tape (registered trademark) Tested. In the peeling test, the number of peeling was less than 10 as good and 10 or more as bad. The PCT treatment was performed under a saturation condition of 121 ° C. and 2 atm.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride (a) In a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) 34.2 g (0.3 mol) of allyl glycidyl ether was dissolved in 100 g of gamma butyrolactone and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of gamma butyrolactone was added dropwise so that the temperature of the reaction solution did not exceed 0 ° C. After completion of dropping, the reaction was carried out at 0 ° C. for 4 hours. This solution was concentrated with a rotary evaporator and charged into 1 L of toluene to obtain a hydroxyl group-containing acid anhydride (a).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (b) 18.3 g (0.05 mol) of BAHF was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, and cooled to -15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was added dropwise thereto. After completion of dropping, the mixture was reacted 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 solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon 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 (b). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of hydroxyl group-containing diamine (c) 2-Amino-4-nitrophenol (15.4 g, 0.1 mol) was dissolved in acetone (50 mL) and propylene oxide (30 g, 0.34 mol). Cooled down. A solution prepared by dissolving 11.2 g (0.055 mol) of isophthalic acid chloride in 60 mL of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration.

  This precipitate was dissolved in 200 mL of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any further at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After completion of the stirring, the palladium compound was removed by filtration, and the solution was concentrated to half by a rotary evaporator. Ethanol was added thereto for recrystallization to obtain a hydroxyl group-containing diamine (c) crystal.

Synthesis Example 4 Synthesis of Hydroxyl Group-Containing Diamine (d) 2-Amino-4-nitrophenol 15.4 g (0.1 mol) was dissolved in acetone 100 mL and propylene oxide 17.4 g (0.3 mol), and −15 Cooled to ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 4-nitrobenzoyl chloride in 100 mL of acetone was gradually added dropwise thereto. After completion of dropping, the reaction was carried out at −15 ° C. for 4 hours. Thereafter, the precipitate formed by returning to room temperature was collected by filtration. Thereafter, a hydroxyl group-containing diamine (d) crystal was obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (e) Under a dry nitrogen stream, BisP-RS (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 16.10 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 26.86 g (0.1 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. Here, 10.12 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. It stirred at 30 degreeC after dripping for 2 hours. The triethylamine salt was filtered and the filtrate was poured into water. Thereafter, the deposited precipitate was collected by filtration. This precipitate was dried with a vacuum dryer to obtain a quinonediazide compound (e).

Synthesis Example 6 Synthesis of quinonediazide compound (f) TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 15.31 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 40. 28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (f) was obtained in the same manner as in Synthesis Example 5 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 7 Synthesis of quinonediazide compound (g) TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 21.22 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl chloride 26. 86 g (0.10 mol) and 13.43 g (0.05 mol) of 4-naphthoquinone diazide sulfonyl chloride were dissolved in 450 g of 1,4-dioxane and brought to room temperature. A quinonediazide compound (g) was obtained in the same manner as in Synthesis Example 5 using 12.65 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 8 Synthesis of quinonediazide compound (h) In a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A and 26.86 g (0.1 mol) of 4-naphthoquinonediazidesulfonyl acid chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. A quinonediazide compound (h) was obtained in the same manner as in Synthesis Example 5 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 9 Synthesis of Polymer A 4.4 g (0.022 mol) of 4,4′-diaminophenyl ether (DAE), 1,3-bis (3-aminopropyl) tetramethyldisiloxane (SiDA) under a dry nitrogen stream ) 1.24 g (0.005 mol) was dissolved in 50 g of N-methyl-2-pyrrolidone (NMP). 21.4 g (0.030 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, 1.12 g (0.006 mol) of 4-aminomethylsulfonanilide was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.06 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer A. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 35000. Since the molecular weight of the repeating unit of polymer A was about 920, polymer A having a repeating number n of about 38 was obtained.

Synthesis Example 10 Synthesis of Polymer B The end-capping agent of Synthesis Example 9 was changed from 1.12 g (0.006 mol) of 4-aminomethylsulfonanilide to 0.82 g (0.006 mol) of 3-aminobenzoic acid. Produced polymer B (Mw = 31000, n = about 34) in the same manner as in Synthesis Example 9.

Synthesis Example 11 Synthesis of Polymer C 13.6 g (0.0225 mol) of hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 was dissolved in 50 g of NMP under a dry nitrogen stream. 17.5 g (0.025 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and reacted at 40 ° C. for 2 hours. Thereafter, 0.75 g (0.005 mol) of 4-aminoacetanilide was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer C. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 28000. Since the molecular weight of the repeating unit of the polymer C is about 1320, the polymer C having a repeating number n of about 21 was obtained.

Synthesis Example 12 Synthesis of Polymer D Synthesis was performed except that the end-capping agent of Synthesis Example 11 was changed from 0.75 g (0.005 mol) of 4-aminoacetanilide to 0.68 g (0.005 mol) of 4-aminobenzoic acid. In the same manner as in Example 11, polymer D (Mw = 30000, n = about 23) was obtained.

Synthesis Example 13 Synthesis of Polymer E Under a dry nitrogen stream, 13.2 g (0.035 mol) of the hydroxyl group-containing diamine compound (c) obtained in Synthesis Example 3 and 1.24 g (0.005 mol) of SiDA were dissolved in 50 g of NMP. I let you. 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid anhydride (ODPA) 13.9 g (0.045 mol) was added together with 21 g of NMP and reacted at 20 ° C. for 1 hour, then at 50 ° C. for 2 hours. Reacted. Thereafter, 1.50 g (0.010 mol) of 3-aminoacetanilide was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 2 hours, and then 14.7 g (0.1% of N, N-dimethylformamide diethyl acetal). Mol) was diluted with 5 g of NMP over 10 minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer E. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 20000. Since the molecular weight of the repeating unit of the polymer E is about 690, a polymer E having a repeating number n of about 29 was obtained.

Synthesis Example 14 Synthesis of Polymer F Synthesis was performed except that the end-capping agent in Synthesis Example 13 was changed from 1.50 g (0.010 mol) of 3-aminoacetanilide to 1.66 g (0.010 mol) of methyl 4-aminosalicylate. In the same manner as in Example 13, Polymer F (Mw = 17000, n = about 25) was obtained.

Synthesis Example 15 Synthesis of Polymer G Under a dry nitrogen stream, the hydroxyl group-containing diamine compound (d) obtained in Synthesis Example 4 (6.08 g, 0.025 mol), DAE 4.51 g (0.0225 mol), and SiDA 0.62 g (0.0025 mol) was dissolved in 70 g of NMP. Here, 24.99 g (0.035 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 and 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) 4. 41 g (0.010 mol) was added at room temperature together with 25 g of NMP, and the mixture was stirred at room temperature for 1 hour and then at 50 ° C. for 2 hours. Thereafter, 2.04 g (0.010 mol) of 3-acetylaminophthalic anhydride was added as a terminal blocking agent, and the mixture was further reacted at 50 ° C. for 2 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer G. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 23000. Since the molecular weight of the repeating unit of the polymer G is about 840, a polymer G having a repeating number n of about 27 was obtained.

Synthesis Example 16 Synthesis of Polymer H The end-capping agent of Synthesis Example 15 was changed from 2.04 g (0.010 mol) of 3-acetylaminophthalic anhydride to 1.92 g (0.010 mol) of trimellitic anhydride. Otherwise in the same manner as in Synthesis Example 15, polymer H (Mw = 25000, n = about 30) was obtained.

Synthesis Example 17 Synthesis of Polymer I Under a dry nitrogen stream, 13.90 g (0.023 mol) of hydroxyl group-containing diamine (b) obtained in Synthesis Example 2 and 0.50 g (0.002 mol) of SiDA were dissolved in 50 g of NMP. It was. 12.86 g (0.018 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 30 g of NMP, and the mixture was reacted at 60 ° C. for 2 hours. Next, 2.87 g (0.014 mol) of 2-acetylaminophthalic anhydride is added as an end-capping agent, and after completion of the reaction, the solution is poured into 2 L of water, and the polymer solid precipitate is collected by filtration. It was. The polymer solid was dried in a vacuum dryer at 80 ° C. for 20 hours to obtain polymer I. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 15000. Since the molecular weight of the repeating unit of Polymer I is about 840, Polymer I having a repeating number n of about 18 was obtained.

Synthesis Example 18 Synthesis of Polymer J The end-capping agent of Synthesis Example 17 was changed from 2.87 g (0.014 mol) of 2-acetylaminophthalic anhydride to 2.69 g (0.014 mol) of trimellitic anhydride. Otherwise in the same manner as in Synthesis Example 17, Polymer J (Mw = 13000, n = about 15) was obtained.

Synthesis Example 19 Synthesis of Polymer K 19.70 g (0) of a dicarboxylic acid derivative obtained by reacting 1 mol of diphenyl ether-4,4′-dicarboxylic acid (DEDC) with 2 mol of 1-hydroxybenzotriazole in a dry nitrogen stream. 0.040 mol) and 18.31 g (0.050 mol) of BAHF were dissolved in 200 g of NMP and stirred at 75 ° C. for 12 hours. Next, 4.08 g (0.020 mol) of 2-acetylaminophthalic anhydride dissolved in 30 g of NMP was added as a terminal blocking agent, and the mixture was further stirred at 75 ° C. for 12 hours to complete the reaction. After the completion of the reaction, the solution was put into 3 L of a solution of water / methanol = 3/1, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer K. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 16000. Since the molecular weight of the repeating unit of polymer K is about 620, polymer K having a repeating number n of about 26 was obtained.

Synthesis Example 20 Synthesis of Polymer L The end-capping agent of Synthesis Example 19 was changed from 4.08 g (0.020 mol) of 2-acetylaminophthalic anhydride to 3.84 g (0.020 mol) of trimellitic anhydride. Otherwise in the same manner as in Synthesis Example 19, Polymer L (Mw = 13000, n = about 21) was obtained.

Synthesis Example 21 Synthesis of Polymer M Dicarboxylic acid derivative obtained by reacting 0.8 mol of terephthalic acid (TPA), 0.2 mol of isophthalic acid (IPA) and 2 mol of 1-hydroxybenzotriazole in a dry nitrogen stream 16.01 g (0.040 mol) and 12.82 g (0.035 mol) of BAHF were dissolved in 200 g of NMP and stirred at 75 ° C. for 12 hours. Next, 1.50 g (0.010 mol) of 3-aminoacetanilide dissolved in 20 g of NMP was added as a terminal blocking agent, and the mixture was further stirred at 75 ° C. for 12 hours to complete the reaction. After the completion of the reaction, the solution was put into 3 L of a solution of water / methanol = 3/1, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain a polymer M. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 14000. Since the molecular weight of the repeating unit of the polymer M is about 530, the polymer M having a repeating number n of about 26 was obtained.

Synthesis Example 22 Synthesis of Polymer N Synthesis was performed except that the end-capping agent in Synthesis Example 21 was changed from 1.50 g (0.010 mol) of 3-aminoacetanilide to 1.66 g (0.010 mol) of methyl 4-aminosalicylate. In the same manner as in Example 21, polymer N (Mw = 15000, n = about 28) was obtained.

Synthesis Example 23 Synthesis of Polymer O In a dry nitrogen stream, 3.00 g (0.015 mol) of DAE was dissolved in 50 g of NMP. 21.4 g (0.030 mol) of the hydroxyl group-containing acid anhydride (a) obtained in Synthesis Example 1 was added thereto together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 40 ° C. for 2 hours. . Thereafter, 5.58 g (0.030 mol) of 4-aminomethylsulfonanilide was added as a terminal blocking agent, and the mixture was further reacted at 40 ° C. for 2 hours. Thereafter, a solution obtained by diluting 7.14 g (0.060 mol) of N, N-dimethylformamide dimethylacetal with 5 g of NMP was added dropwise over 10 minutes. After dropping, the mixture was stirred at 40 ° C. for 3 hours. After completion of the reaction, the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration. The polymer solid was dried with a vacuum dryer at 80 ° C. for 20 hours to obtain polymer O. When the weight average molecular weight (Mw) was measured as described above, it was Mw = 6000. Since the molecular weight of the repeating unit of the polymer O is about 920, a polymer O having a repeating number n of about 6 was obtained.

Synthesis Example 24 Synthesis of Polymer P The end-capping agent in Synthesis Example 23 was changed from 5.58 g (0.030 mol) of 4-aminomethylsulfonanilide to 4.10 g (0.030 mol) of 3-aminobenzoic acid. In the same manner as in Synthesis Example 23, a polymer N (Mw = 5000, n = about 5) was obtained.

Synthesis Example 25 Synthesis of Polymer Q The end-capping agent of Synthesis Example 9 was changed from 1.12 g (0.006 mol) of 4-aminomethylsulfonanilide to 0.70 g (0.006 mol) of 4-ethynylaniline. Polymer Q (Mw = 34000, n = about 37) was obtained in the same manner as in Synthesis Example 9.

Synthesis Example 26 Synthesis of Polymer R Synthesis Example except that the end-capping agent in Synthesis Example 11 was changed from 0.75 g (0.005 mol) of 4-aminoacetanilide to 0.54 g (0.005 mol) of 3-aminophenol. In the same manner as in Example 11, polymer R (Mw = 31000, n = about 23) was obtained.

Synthesis Example 27 Synthesis of Polymer S Synthesis Example except that the terminal blocking agent of Synthesis Example 13 was changed from 1.50 g (0.010 mol) of 3-aminoacetanilide to 1.33 g (0.010 mol) of 4-allylaniline. In the same manner as in Example 13, a polymer S (Mw = 21000, n = about 30) was obtained.

Synthesis Example 28 Synthesis of Polymer T Polymer T (Mw = 25000, n = about 30) was obtained in the same manner as in Synthesis Example 15 except that the end capping agent was not used in Synthesis Example 15.

Synthesis Example 29 Synthesis of Polymer U The end-capping agent of Synthesis Example 17 was changed from 2.87 g (0.014 mol) of 2-acetylaminophthalic anhydride to 2.30 g (0.014 mol) of nadic anhydride. In the same manner as in Synthesis Example 17, Polymer L (Mw = 15000, n = about 18) was obtained.

Synthesis Example 30 Synthesis of Polymer V Polymer V (Mw = 13,000, n = about 21) was obtained in the same manner as in Synthesis Example 19 except that the end capping agent was not used in Synthesis Example 19.

  Table 1 shows the polymer compositions of Synthesis Examples 9 to 30.

  The compounds having a phenolic hydroxyl group, the photoacid generator, and the thermally crosslinkable compound (alkoxymethyl group-containing compound) used in each Example and Comparative Example are shown below.

Example 1
5 g of the polymer A solid obtained in Synthesis Example 9 and 5 g of the polymer B solid obtained in Synthesis Example 10 were weighed, and 2 g of the quinonediazide compound (e) obtained in Synthesis Example 5 and 0.1 g of vinyltrimethoxysilane were measured. It was made to melt | dissolve in NMP30g and the varnish of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 2
5 g of the polymer C obtained in Synthesis Example 11 and 5 g of the polymer D obtained in Synthesis Example 12 were weighed, and 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6 and Bis-Z (trade name, Honshu) Chemical Industry Co., Ltd.) 1.5 g and m-aminophenyltrimethoxysilane 0.2 g were dissolved in GBL 30 g to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 3
5 g of the polymer E obtained in Synthesis Example 13 and 5 g of the polymer F obtained in Synthesis Example 14 were weighed, and 1.6 g of the quinonediazide compound (g) obtained in Synthesis Example 7 was dissolved in 30 g of NMP. The varnish of the conductive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 4
4 g of the polymer G obtained in Synthesis Example 15 and 6 g of the polymer H obtained in Synthesis Example 16 were weighed, 2.5 g of the quinonediazide compound (h) obtained in Synthesis Example 8, and WPAG-350 (trade name) , Wako Pure Chemical Industries, Ltd.) 0.2 g, Thermally crosslinkable compound Nicarax MX-290 (trade name, manufactured by Sanwa Chemical Co., Ltd.) 1.5 g, m-acetylaminophenyltrimethoxysilane 0.5 g It was made to melt | dissolve in NMP30g and the varnish of the photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 5
6 g of the polymer I obtained in Synthesis Example 17 and 4 g of the polymer J obtained in Synthesis Example 18 were weighed, 2 g of the quinonediazide compound (e) obtained in Synthesis Example 5, TrisP-PA (trade name, Honshu, Japan) Chemical Industry Co., Ltd.) (1.5 g) and 3,3′-diacetylaminodiphenyltetramethoxydisiloxane (0.5 g) were dissolved in GBL (30 g) to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 6
6 g of the polymer K obtained in Synthesis Example 19 and 4 g of the polymer L obtained in Synthesis Example 20 were weighed, and 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6 was dissolved in 30 g of GBL. A benzoxazole precursor composition varnish was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 7
The solid 5 g of polymer M obtained in Synthesis Example 21 and the solid 5 g of polymer N obtained in Synthesis Example 22 were weighed, and 2 g of the quinonediazide compound (g) obtained in Synthesis Example 7 and WPAG-567 (trade name, Japanese) Kogure Pharmaceutical Co., Ltd. (0.01 g), thermally crosslinkable compound DMOM-PC (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 1 g, p-aminophenyltrimethoxysilane 0.5 g was dissolved in GBL 30 g for photosensitivity. A varnish of a conductive polybenzoxazole precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 8
5 g of the polymer A solid obtained in Synthesis Example 9 and 5 g of the polymer H solid obtained in Synthesis Example 16 were weighed, 2 g of the quinonediazide compound (f) obtained in Synthesis Example 6, TrisP-HAP (trade name, Honshu) 1 g of Chemical Industry Co., Ltd., 3 g of DMOM-PTBP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 1.5 g of thermally crosslinkable compound Nicarak MX-270 (trade name, manufactured by Sanwa Chemical Co., Ltd.) A varnish of a photosensitive polyimide precursor composition was obtained by dissolving together with 20 g of GBL and 10 g of ethyl lactate. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 9
The procedure was carried out except that 4 g of the polymer F obtained in Synthesis Example 14 and 6 g of the polymer G obtained in Synthesis Example 15 were used as polymers, and 0.5 g of 3.3′-diaminodiphenyltetramethoxydisiloxane was added. In the same manner as in Example 3, a varnish of a photosensitive polyimide precursor composition was obtained. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Example 10
3 g of the polymer A solid obtained in Synthesis Example 9 as the polymer, 3 g of the polymer B solid obtained in Synthesis Example 10, 2 g of the polymer G solid obtained in Synthesis Example 15, and the polymer H obtained in Synthesis Example 16 A varnish of a photosensitive polyimide precursor composition was obtained in the same manner as in Example 4 except that 2 g of the above solid was used. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 1
Using 5 g of the solid polymer O obtained in Synthesis Example 23 and 5 g of the polymer P solid obtained in Synthesis Example 24 as the polymer, except that vinyltrimethoxysilane was not added, a varnish was obtained in the same manner as in Example 1, As described above, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed.

Comparative Example 2
A varnish was obtained in the same manner as in Example 1 except that 10 g of the polymer Q solid obtained in Synthesis Example 25 was used as the polymer and no vinyltrimethoxysilane was added. As described above, pattern processability evaluation and mechanical property evaluation The adhesion with the substrate was evaluated.

Comparative Example 3
Using 10 g of the polymer R solid obtained in Synthesis Example 26 as a polymer, except that m-aminophenyltrimethoxysilane was not added, a varnish was obtained in the same manner as in Example 2, and as described above, pattern workability evaluation was performed. Mechanical property evaluation and adhesion evaluation with a substrate were performed.

Comparative Example 4
A varnish was obtained in the same manner as in Example 3 except that 10 g of the polymer S solid obtained in Synthesis Example 27 was used as the polymer. As described above, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed. Went.

Comparative Example 5
10 g of the polymer T solid obtained in Synthesis Example 28 was measured as a polymer, and 2.5 g of the quinonediazide compound (h) obtained in Synthesis Example 8 was dissolved in 30 g of NMP to obtain a varnish of a photosensitive polyimide precursor composition. . Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 6
A varnish was obtained in the same manner as in Example 5 except that 10 g of the polymer U obtained in Synthesis Example 29 was used as the polymer, and 3,3′-diacetylaminodiphenyltetramethoxydisiloxane was not used. Pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed.

Comparative Example 7
A varnish was obtained in the same manner as in Example 6 except that 10 g of the polymer V solid obtained in Synthesis Example 30 was used as the polymer. As described above, pattern processability evaluation, mechanical property evaluation, and adhesion evaluation with the substrate were performed. Went.

Comparative Example 8
Amide acid compound obtained by reacting 1.6 g of the quinonediazide compound (g) obtained in Synthesis Example 7 with 1 mol of 4,4′-diaminodiphenyl ether and 2 mol of ODPA with 10 g of the polymer T obtained in Synthesis Example 28 0.5 g was dissolved in 10 g of NMP to obtain a varnish of a photosensitive polyimide precursor composition. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

Comparative Example 9
Amide acid compound obtained by reacting 2.0 g of the quinonediazide compound (g) obtained in Synthesis Example 7 with 1 mol of 4,4′-diaminodiphenyl ether and 2 mol of ODPA with 10 g of the polymer V obtained in Synthesis Example 30 0.5 g was dissolved in 10 g of GBL to obtain a varnish of a photosensitive polybenzoxazole precursor composition. Using the obtained varnish, pattern workability evaluation, mechanical property evaluation, and adhesion evaluation with a substrate were performed as described above.

  The compositions and evaluation results of Examples 1 to 10 and Comparative Examples 1 to 9 are shown in Tables 2 to 3.

Claims (3)

(A) A polymer having a structure represented by the general formula (1) and / or (2) as a main component, and (b) a structure represented by the general formula (3) and / or (4) as a main component. A positive photosensitive resin precursor composition comprising a polymer, (c) a quinonediazide compound, and (d) a solvent.

(In the formula, R ¹ and R ² are divalent to octavalent organic groups having two or more carbon atoms, R ³ and R ⁴ may be the same as or different from each other, and may be hydrogen or C 1-20. R ⁵ and R ⁶ represent a single bond or an organic group having 1 to 20 carbon atoms, X and Y represent an organic group capable of forming an —X—Y— bond by heating, and n represents 10 to 10. In the range of 100,000, l and m are integers of 0 to 2, p and q are integers of 0 to 4, provided that p + q> 0. X in the general formulas (1) and (2) is represented by —NR ²⁰ R ²¹ , and Y in the general formulas (3) and (4) is represented by —NCO, —COR ²² or —SO ₂ R ^23. The positive photosensitive resin precursor composition according to claim 1. ^(However, R 20 ^{to R 23} represents a hydrogen or an organic group having 1 to 10 carbon atoms independently.) 3. The method according to claim 1, further comprising at least one silane compound selected from (e) a compound represented by the general formula (5), a compound represented by the general formula (6), and a vinylsilane compound. A positive photosensitive resin precursor composition.

(In the formula, Ar ¹ and Ar ² represent an aromatic ring having 6 or more carbon atoms or an aromatic heterocyclic structure having 2 or more carbon atoms. R ²⁶ , R ²⁷ , R ³⁴ , R ^35. , R ⁴² and R ⁴³ may be the same or different and each represents hydrogen or an organic group having 1 to 4 carbon atoms, and each of R ²⁸ , R ³⁶ and R ⁴¹ may be the same or different and has 1 carbon atom. R ^{29 to} R ³³ , R ^{37 to} R ⁴⁰ may be the same or different and each represents a hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or phenyl And at least one of R ^{29 to} R ³³ and R ^{37 to} R ⁴⁰ is an alkoxy group having 1 to 6 carbon atoms, a, d, f, and h are integers of 1 or more, b, c, e , G represents an integer of 0 or more, provided that 1 ≦ a + B ≦ 4, 1 ≦ d + e ≦ 4, 1 ≦ g + h ≦ 4)