JP2006047627A - Photosensitive resin precursor composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin precursor composition having high sensitivity, high resolution, low water absorption and small shrinkage in a film state. <P>SOLUTION: The composition contains a polymer essentially comprising a structural unit expressed by general formula (1), a compound having a phenolic hydroxyl group, and a quinone diazide compound. In formula (1), each of R<SP>1</SP>and R<SP>2</SP>represents a ≥2C organic group having the valency of 2 to 8, each of R<SP>3</SP>and R<SP>4</SP>represents a hydrogen atom or an organic group, m ranges from 10 to 100,000, k and l represent integers 0 to 4, n and o represent integers 0 to 4 satisfying k+l>0 or n+o>0. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a positive photosensitive resin precursor composition suitable for a surface protective film, an interlayer insulating film, and the like of a semiconductor element, wherein a portion exposed to ultraviolet rays is dissolved in an alkaline aqueous solution.

  As the positive heat-resistant resin precursor composition in which the exposed part is dissolved by alkali development, naphthoquinone diazide added to polyamic acid, naphthoquinone diazide added to soluble polyimide having hydroxyl group, and hydroxyl group A material obtained by adding naphthoquinonediazide to polyamide has been known.

  However, in the case where naphthoquinone diazide is added to normal polyamic acid, the solubility of the carboxyl group of the polyamic acid is higher than the dissolution inhibiting effect of naphthoquinone diazide on alkali, so the desired pattern cannot be obtained in most cases. There was a problem. 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. However, when the naphthoquinone diazide is added to this polyamic acid derivative, the dissolution inhibition effect of naphthoquinone diazide on the alkali becomes very large, and a desired pattern can be obtained, but there is a problem that it causes a great decrease in sensitivity. there were. On the other hand, it has been studied to add various compounds having phenolic hydroxyl groups to those obtained by adding naphthoquinonediazide to this polyamic acid derivative.

  As a resin composition using a compound having a phenolic hydroxyl group, a form in which a photosensitive diazoquinone compound and a compound having a phenolic hydroxyl group are added to polyamide (see Patent Documents 1 to 5), a quinonediazide compound esterified to polyimide and phenol There are a form in which a compound having a functional hydroxyl group is added (see Patent Document 6), and a polymer and indophenol as a dissolution accelerator (see Patent Document 7). However, since the thermal decomposition temperature of these phenolic hydroxyl group-containing compounds is lower than that of the polymer, there is a drawback that the film thickness after curing becomes thin.

On the other hand, the resin composition having a small shrinkage after development and after curing includes those obtained by adding a filler to an alkali-soluble resin (see Patent Documents 8 to 9). It was necessary to carry out with a diamond mill or the like. In addition, there is a product using a compound containing a phenolic hydroxyl group that promotes dissolution and an alkoxymethyl group that crosslinks with the polymer in one molecule (see Patent Documents 10 to 12). Since the functional hydroxyl group remains, the water absorption rate of the cured film increases.
JP-A-9-302221 (pages 1 to 6) JP-A-11-65107 (pages 1-5, 9-12) JP-A-11-102069 (pages 1-3, 12-19) Japanese Patent Application Laid-Open No. 11-109620 (1-2 pages, 5 pages, 15-18 pages) JP-A-11-242338 (pages 1-3, 11-19) JP 2001-64507 A (pages 1 to 4) JP 2002-88066 A (1-5 pages) JP 2001-142209 A (pages 1 to 4) JP 2002-202593 A (pages 1 to 10) Japanese Patent Laid-Open No. 2001-312051 (pages 1 to 3) Japanese Patent Laid-Open No. 2001-312063 (pages 1 to 3) JP 2002-221794A (pages 1 to 3)

  An object of the present invention is to provide a photosensitive resin precursor composition capable of obtaining a film having good sensitivity, a small film shrinkage rate, and a low water absorption rate.

  That is, the present invention includes (a) a polymer having a structural unit represented by general formula (1) as a main component, (b) a compound having a phenolic hydroxyl group represented by general formula (2), and (c). A photosensitive resin precursor composition comprising a quinonediazide compound.

(Wherein R ¹ and R ² are divalent to octavalent organic groups having two or more carbon atoms, R ³ and R ⁴ are hydrogen, or an organic group having 1 to 20 carbon atoms; m is 10; To 100000, k and l are integers from 0 to 4, n and o are integers from 0 to 4, provided that k + l> 0 or n + o> 0.)

(Wherein R ⁵ represents a divalent to octavalent organic group having an aromatic ring, and R ⁶ represents a divalent to tetravalent group having two or more carbon atoms and having a thermal crosslinking group containing an unsaturated bond. R ⁷ represents an organic group having 1 to 15 carbon atoms, p represents an integer of 1 to 4, and q represents an integer of 1 to 4.)

  According to the present invention, it is possible to obtain a photosensitive resin precursor composition that can be developed with an aqueous alkali solution, ensures high sensitivity and high resolution, and has a small film shrinkage and water absorption.

  In the present invention, the polymer having the structural unit represented by the general formula (1) 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. With the ring structure, the heat resistance and solvent resistance are dramatically improved.

  The general formula (1) represents a polyamide having a hydroxyl group, a polyamic acid, and a polyamic acid ester. Due to the presence of this hydroxyl group, the solubility in an alkaline aqueous solution is better than that having no hydroxyl group. . In particular, among the hydroxyl groups, phenolic hydroxyl groups are more preferable than solubility in an aqueous alkali solution.

(Wherein R ¹ and R ² are divalent to octavalent organic groups having two or more carbon atoms, R ³ and R ⁴ are hydrogen, or an organic group having 1 to 20 carbon atoms; m is 10; To 100000, k and l are integers from 0 to 4, n and o are integers from 0 to 4, provided that k + l> 0 or n + o> 0.)
In addition, when the fluorine atom is contained in the general formula (1) by 10% by weight or more, water repellency appears moderately at the interface of the film when developing with an alkaline aqueous solution, so that the penetration of the interface can be suppressed. However, when the fluorine atom content exceeds 20% by weight, the solubility in an alkaline aqueous solution is lowered, the organic solvent resistance of a polymer having a cyclic structure by heat treatment is lowered, and the solubility in fuming nitric acid is lowered. There is. Therefore, the fluorine atom is preferably contained in an amount of 10% by weight to 20% by weight.

In the general formula (1), R ¹ (COOR ³ ) _k (OH) _n represents a structural component of acid dianhydride. This acid dianhydride is preferably a divalent to octavalent organic group having 2 or more carbon atoms containing an aromatic ring and having 1 to 4 hydroxyl groups, and has 6 to 30 carbon atoms. The trivalent or tetravalent organic group is more preferable. Specifically, a structure as shown in the following general formula (3) is preferable.

R ⁸ and R ¹⁰ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms, R ⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms having a hydroxyl group, R ¹¹ , R ¹² represents hydrogen or an organic group having 1 to 20 carbon atoms. r and t are integers from 0 to 2, and s is an integer from 1 to 4.

R ⁸ and R ¹⁰ are preferably those containing an aromatic ring from the heat resistance of the resulting polymer. Among them, particularly preferred structures include trimellitic acid, trimesic acid, naphthalene tricarboxylic acid residues and the like. . Further, the hydroxyl group is 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, among the compounds in which R ¹ (COOR ³ ) _k (OH) _n in the general formula (1) is represented by the general formula (3), examples of preferred compounds include the structures shown below. It is not limited.

In addition, a part of R ¹ (COOR ³ ) _k (OH) _n may be modified with a tetracarboxylic acid or dicarboxylic acid having no hydroxyl group within a range that does not impair the solubility in alkali, photosensitive performance, and heat resistance. it can. Examples of this include aromatic tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, diphenyl ether tetracarboxylic acid, and diphenylsulfone tetracarboxylic acid, and two carboxyl groups thereof as methyl or ethyl groups. Diester 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, naphthalene dicarboxylic acid Examples thereof include aromatic dicarboxylic acids such as acids, and aliphatic dicarboxylic acids such as adipic acid. When using a compound having a hydroxyl group for the component containing R ² , the hydroxyl group is not necessarily required for the component containing R ¹ , and the above-described tetracarboxylic acid and dicarboxylic acid can be used as the component containing R ¹ . Here, the modification is preferably 50 mol% or less of the acid component, more preferably 30 mol% or less. If the modification exceeds 50 mol%, the alkali solubility and photosensitivity may be impaired.

In general formula (1), the part containing R ² represents the structural component of diamine. Among these, as a preferable example of R ² (COOR ⁴ ) _l (OH) _o , those having aromaticity and having a hydroxyl group are preferable from the heat resistance of the obtained polymer, and also having a carboxyl group. Also good. Specific examples include bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, diaminophenol, dihydroxybench having no fluorine atom. Examples thereof include compounds such as gin and those represented by the general formulas (4), (5), and (6).

In formula (4), R ¹³ and R ¹⁵ represent a C 2-20 trivalent to hexavalent organic group having a hydroxyl group, and R ¹⁴ represents a C 2-30 divalent to tetravalent organic group. , R ¹⁶ , R ¹⁷ and R ¹⁸ represent hydrogen or an organic group having 1 to 20 carbon atoms. u and v represent integers from 0 to 2, and c, d, and e represent integers from 0 to 2.

R ¹⁹ and R ^{21 in} the general formula (5) represent a divalent to tetravalent organic group having 2 to ²⁰ carbon atoms, R ²⁰ represents a trivalent to octavalent organic group having 3 to ²⁰ carbon atoms, R ²² , R ²³ and R ²⁴ represent hydrogen or an organic group having 1 to 20 carbon atoms. w represents an integer from 1 to 4, and f, g, and h represent integers from 0 to 2 .

R ^{25 in the} general formula (6) represents a divalent to tetravalent organic group having 2 to 20 carbon atoms, R ²⁶ represents a trivalent to octavalent organic group having 3 to 20 carbon atoms, R ²⁷ , R ²⁸ represents hydrogen or an organic group having 1 to 20 carbon atoms. x represents an integer from 0 to 4, and i and j represent integers from 0 to 2.

In the general formula (4), R ¹³ and R ¹⁵ represent trivalent to hexavalent organic groups having 2 to 20 carbon atoms, and those having an aromatic ring are preferable from the viewpoint of heat resistance of the resulting polymer. . Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxy Phenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used. R ¹⁴ represents a divalent to tetravalent 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. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, a diphenylsulfone group, These include those having up to two carboxyl groups substituted, but in addition to these, aliphatic cyclohexyl groups and the like can also be used.

In the general formula (5), R ¹⁹ and R ²¹ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms. From the viewpoint of the heat resistance of the resulting polymer, an aromatic divalent group is preferable. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, a diphenylsulfone group, Examples thereof include those substituted with up to 2 carboxyl groups, and aliphatic cyclohexyl groups and the like can also be used. R ²⁰ represents a trivalent to octavalent organic group having 3 to 20 carbon atoms, and preferably has an aromatic ring from the viewpoint of the heat resistance of the obtained polymer. Specifically, 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.

In the general formula (6), R ²⁵ represents a divalent to tetravalent organic group selected from 2 to 20 carbon atoms. From the heat resistance of the resulting polymer, an aromatic divalent group is preferable. Examples of such a group include a phenyl group, a biphenyl group, a diphenyl ether group, a diphenylhexafluoropropane group, a diphenylpropane group, a diphenylsulfone group, and the like. In addition to the above, those having up to 2 carboxyl groups can be mentioned, but in addition to this, an aliphatic cyclohexyl group and the like can also be used. R ²⁶ represents a trivalent to octavalent organic group selected from 3 to 20 carbon atoms, and those having an aromatic ring are preferred from the viewpoint of the heat resistance of the resulting polymer. Specifically, hydroxyphenyl group, dihydroxyphenyl group, hydroxynaphthyl group, dihydroxynaphthyl group, hydroxybiphenyl group, dihydroxybiphenyl group, bis (hydroxyphenyl) hexafluoropropane group, bis (hydroxyphenyl) propane group, bis (hydroxy Phenyl) sulfone group, hydroxydiphenyl ether group, dihydroxydiphenyl ether group and the like. In addition, aliphatic groups such as a hydroxycyclohexyl group and a dihydroxycyclohexyl group can also be used.

Specific examples of R ² (COOR ⁴ ) _l (OH) _o in the general formula (1) represented by the general formula (4) are shown below.

A specific example in which R ² (COOR ⁴ ) ₁ (OH) _o in the general formula (1) is represented by the general formula (5) is shown below.

A specific example in which R ² (COOR ⁴ ) ₁ (OH) _o in the general formula (1) is represented by the general formula (6) is shown below.

1 to 40 mol% of R ² (COOR ⁴ ) _l (OH) _{o in} the general formula (1) can be modified with other diamine components. Examples of these are phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone, or these Examples include compounds in which the aromatic ring is substituted with an alkyl group or a halogen atom. Moreover, aliphatic cyclohexyl diamine, methylene bis cyclohexyl amine, etc. are mentioned, However, When such diamine component is copolymerized exceeding 40 mol%, the heat resistance of the polymer obtained will fall. When a compound having a hydroxyl group as the R ¹ component is used, a hydroxyl group is not necessarily required as the R ² component, and the above-described diamine having no hydroxyl group can be used.

R < ³ >, R < ⁴ > of General formula (1) represents hydrogen or a C1-C20 organic group. These are preferably organic groups from the viewpoint of the stability of the obtained positive photosensitive resin precursor solution, but hydrogen is preferable from the viewpoint of the solubility of the aqueous alkali solution. In the present invention, a hydrogen atom and an alkyl group can be mixed. By controlling the amounts of hydrogen and organic groups of R ³ and R ^4, the dissolution rate in the aqueous alkali solution is changed. By this adjustment, a positive photosensitive resin precursor composition having an appropriate dissolution rate is obtained. be able to. As a preferable range, 10% to 90% of R ³ and R ⁴ are each a hydrogen atom. If the number of carbon atoms exceeds 20, it is not preferable because it does not dissolve in the alkaline aqueous solution. From these points, 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 formula (1), k and l represent the number of carboxyl groups and represent integers from 0 to 4. M in the general formula (1) represents the number of repeating structural units of the polymer of the present invention, and is in the range of 10 to 100,000.

  Polyhydroxyamide can also be used as the structural unit represented by the general formula (1). As a method for producing such a polyhydroxyamide, it can be obtained, for example, by subjecting a bisaminophenol compound and a dicarboxylic acid 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 dichloride solution.

  When using polyhydroxyamide, a positive photosensitive heat-resistant resin precursor that can be removed with an alkaline aqueous solution by adding a photosensitizer such as naphthoquinonediazide sulfonate to the polyhydroxyamide solution. A composition can be obtained.

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 formula (1) within a range that does not decrease the heat resistance. Specifically, examples of the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like. The polymer of (a) contained in the photosensitive resin precursor composition may consist only of the structural unit represented by the general formula (1), or a copolymer or blend with other structural units. It may be the body. In that case, the content rate of the structural unit represented by General formula (1) becomes like this. Preferably it is 80 mol% or more, More preferably, it is 90 mol% or more. The type and amount of structural units used for copolymerization or blending are preferably selected within a range that does not impair the heat resistance of the polyimide polymer obtained by the final heat treatment.

  The polymer having the structural unit represented by the general formula (1) in the present invention is synthesized by a known method. For example, a method of reacting a tetracarboxylic dianhydride and a diamine compound at a low temperature, a method of obtaining a diester from a tetracarboxylic dianhydride and an alcohol, and then reacting in the presence of an amine and a condensing agent, a tetracarboxylic acid The diester can be obtained from dianhydride and alcohol, and then the remaining dicarboxylic acid can be acid chloride and synthesized with an amine.

In the present invention, the compound having a phenolic hydroxyl group represented by the general formula (2) of (b) crosslinks the unsaturated bonds of the compound represented by the general formula (2) by heating, and the oxazole ring. It is a compound that forms. The phenolic hydroxyl group of the compound represented by the general formula (2) gives moderate alkali solubility to the polymer and improves the sensitivity of the composition. In addition, after heating, the R ⁵ (OH) _p (NHCO) moiety becomes a ring structure by oxazole ring closure and becomes a crosslinked structure by reaction of unsaturated bonds, thereby improving the mechanical properties of the cured film and improving the shrinkage rate. The Furthermore, since the phenolic hydroxyl group is taken into the oxazole ring obtained by the oxazole ring closure reaction during curing and does not remain after curing, the water absorption rate of the cured film is reduced.

R ⁵ represents a divalent to hexavalent organic group having an aromatic ring, and R ⁶ represents a divalent to tetravalent organic group having a thermal crosslinking group having two or more carbon atoms and containing an unsaturated bond. R ⁷ represents an organic group having 1 to 15 carbon atoms. P represents an integer of 1 to 4, and q represents an integer of 1 to 4.

R ⁵ in the above general formula (2) preferably has an aromatic ring from the viewpoint of heat resistance and has 1 to 4 hydroxyl groups from the viewpoint of alkali solubility. The solubility becomes larger than necessary, and an appropriate residual film cannot be obtained. From such a viewpoint, p is more preferably 1 to 2. In addition, since R ⁵ (OH) _p (NHCO) is ring-closed with oxazole during curing, the heat resistance of the cured film is improved and the effect of suppressing water absorption is achieved. Therefore, it is desirable that the hydroxyl group and an amide group is located at the ortho position of the aromatic ring portion of R ^5.

Specific examples of R ⁵ (OH) _p satisfying such conditions include bis (amino-hydroxy-phenyl) hexafluoropropane, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine, hydroxy-diaminopyrrole, Examples of the compound include hydroxy-diaminopyridine, diaminophenol, and dihydroxybenzidine. Among these, bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom is most preferable.

  Moreover, although q in General formula (2) shows the integer of 1-4, More preferably, q is 1 or 2.

R ⁶ represents a component having a thermal crosslinking group containing an unsaturated bond. When this portion is crosslinked by itself during curing, the mechanical properties of the cured film are improved and the shrinkage rate is improved. By simultaneously obtaining the shrinkage rate improving effect and the water absorption inhibiting effect, the physical properties of the cured film are dramatically improved. That is, the shrinkage after curing is preferably 30% or less, more preferably 25% or less, and the water absorption is preferably 1% or less. By adding the compound having a phenolic hydroxyl group represented by (2) to the varnish, these preferable values can be achieved simultaneously. Specific examples of R ⁶ include maleic acid, acetylenedicarboxylic acid, norbornene dicarboxylic acid, cyclohexene dicarboxylic acid, ethynyl phthalic acid, phenylethynyl phthalic acid and the like, but are not limited thereto.

R ⁷ represents an organic group having 1 to 15 carbon atoms, and specifically, a structure represented by the following general formula (8) or (9) is preferable.

R ^{29 in the} general formula (8) represents an organic group having 1 to 15 carbon atoms. R ^{30 in the} general formula (9) represents hydrogen or an organic group having 1 to 9 carbon atoms. Moreover, y shows the integer of 1-4.

R ²⁹ in the general formula (8) represents an organic group having 1 to 15 carbon atoms, but in order not to reduce alkali solubility, an organic group having 1 to 6 carbon atoms is particularly preferable, and methyl is more preferable. Group, ethyl group, or tert-butyl group.

R ³⁰ in the general formula (9) represents hydrogen or an organic group having 1 to 9 carbon atoms, preferably hydrogen or an organic group having 1 to 6 carbon atoms, more preferably hydrogen, a methyl group, or ethyl. Or a tert-butyl group.

  Further, y represents an integer of 1 to 4, but y is preferably 1 or 2 from the viewpoint of moderate alkali solubility. Such compounds are 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminocresol, 3-aminocresol, 4-aminocresol, 2-amino-4-ethylphenol, 3-amino-4- Examples include ethylphenol, 2-amino-4-tert-butylphenol, 4-aminoresorcinol, but are not limited thereto.

As described above, R ⁷ preferably has a structure represented by the general formula (8) or (9). Among the compounds having the structure represented by the general formula (9), for example, 2-aminophenol In such a case, since the aromatic ring of the R ⁶ part has a hydroxyl group at the ortho position of the amide group, the oxazole ring can also be closed at that part. That is, in the molecule, there are oxazole moieties at two positions of the R ⁵ portion and the R ⁶ portion, and a compound having excellent heat resistance and low water absorption than the compound having the structure represented by the general formula (8) is obtained. be able to. For these reasons, it is more preferable to use a compound having a structure represented by the general formula (9) and an orthoaminophenol type compound.

  Examples of the compound having a phenolic hydroxyl group represented by the general formula (2) in the present invention include compounds having the following structure.

  The addition amount of the compound having a phenolic hydroxyl group is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer.

  As the quinonediazide compound added to the present invention, a compound in which a sulfonic acid of naphthoquinonediazide is bonded with an ester to a compound having a phenolic hydroxyl group is preferably used. The quinonediazide compound can be used alone or in combination of two or more. By adding a quinonediazide compound, the film obtained from the composition forms a positive type that can be developed with an alkaline aqueous solution, the film loss of the unexposed area after development is greatly reduced, and a good pattern is developed in a short time. You can get it in time.

  The compounds having a phenolic hydroxyl group used here are naphthol, tetrahydroxybenzophenone, gallic acid methyl ester, bisphenol A, methylene bisphenol, TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BisP-AP (product) Name, manufactured by Honshu Chemical Industry Co., Ltd.), TrisP-HAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BisRS-2P, BisPG-26X , BisOC-OCHP, BisP-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCHP, Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP (above, trade name, Honshu) Made by Chemical Industry Co., Ltd. , BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F (above, trade name, manufactured by Asahi Organic Materials Co., Ltd.), etc. These include, but are not limited to, 5-naphthoquinone diazide sulfonyl ester compounds and 4-naphthoquinone diazide sulfonyl ester compounds of compounds having a phenolic hydroxyl group. Moreover, the compound which esterified the compound which has the phenolic hydroxyl group represented by (b) general formula (2) used for this invention by 5-naphthoquinone diazide sulfonyl ester compound and 4-naphthoquinone diazide sulfonyl group can also be used preferably. .

  The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-line region of the mercury lamp and is suitable for i-line exposure, and the 5-naphthoquinone diazide sulfonyl ester compound has absorption extended to the g-line region of the mercury lamp. Suitable for exposure. In the present invention, both a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound can be preferably used, but depending on the wavelength of exposure, a 4-naphthoquinone diazide sulfonyl ester compound, a 5-naphthoquinone diazide sulfonyl ester compound. It is more preferable to select. Further, a naphthoquinone diazide sulfonyl ester compound in which a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group are used in the same molecule can be used, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.

  The (c) quinonediazide compound used in the present invention can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinonediazidesulfonic acid compound, and can be synthesized by a known method.

  Moreover, when the molecular weight of the esterified naphthoquinone diazide compound exceeds 1500, the heat resistance of the resulting film is lowered, the mechanical properties are lowered, or the adhesiveness is lowered due to the naphthoquinone diazide compound remaining after curing. May cause problems. From such a viewpoint, the molecular weight of a preferable esterified quinonediazide compound is 300 to 1500. More preferably, it is 350-1200. The amount of the esterified quinonediazide compound added is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight with respect to 100 parts by weight of the polymer (a). .

  The photosensitive resin precursor composition of the present invention includes a surfactant, ethyl lactate, propylene glycol monomethyl ether acetate, etc., for the purpose of improving the coatability between the photosensitive resin precursor composition and the substrate, if necessary. These esters, alcohols such as ethanol, ketones such as cyclohexanone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane may be mixed. In addition, inorganic particles such as silicon dioxide and titanium dioxide, or polyimide powder can be added.

  Furthermore, in order to improve the adhesiveness with a base substrate such as a silicon wafer, a silane coupling agent, a titanium chelating agent or the like is added to the varnish of the photosensitive resin precursor composition by 0.5 to 10% by weight, Can also be pretreated with such a chemical solution.

  When added to the varnish, 0.5 to 10% by weight of a silane coupling agent such as methylmethacryloxydimethoxysilane or 3-aminopropyltrimethoxysilane, a titanium chelating agent or an aluminum chelating agent with respect to the polymer (a) in the varnish. % Addition method is preferably used.

When the substrate is treated, the above coupling agent is added to a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diethyl adipate and the like in an amount of 0.5 to 20% by weight. A method of surface-treating the dissolved solution by spin coating, dipping, spray coating, steam treatment or the like is preferably used. Depending on the case, the method of advancing reaction of a board | substrate and the said coupling agent by applying the temperature from 50 to 300 degreeC after that is preferably used.
In the present invention, the solvent used for producing the varnish is a polar aprotic solvent such as N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Ethers such as tetrahydrofuran, dioxane and propylene glycol monomethyl ether, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone and cyclohexanone, esters such as ethyl acetate, propylene glycol monomethyl ether acetate and ethyl lactate, aromatic carbonization such as toluene and xylene Solvents such as hydrogen can be used alone or in combination.

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

  The photosensitive resin precursor composition is applied onto the substrate. A silicon wafer, ceramics, gallium arsenide, or the like is used as the substrate, but is not limited thereto. Examples of the coating method include spin coating using a spinner, spray coating, roll coating, and the like, which can be used without any particular limitation. 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 at a temperature 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. The actinic rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but it is preferable to use i-rays (365 nm), h-rays (405 nm), and g-rays (436 nm) of mercury lamps.

  The formation of the heat-resistant resin pattern is achieved by removing the exposed portion of the photosensitive resin precursor composition film using a developer after exposure. Developers include tetramethylammonium aqueous solution, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethyl An aqueous solution of a compound showing alkalinity such as aminoethyl 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 100 ° C. to 500 ° C. is applied to convert to a heat resistant resin film. This heat treatment is preferably carried out stepwise at a certain level of temperature, or 5 minutes to 5 hours while continuously raising the temperature by selecting a certain temperature range. As an example, a method of performing heat treatment at 130 ° C., 200 ° C., and 350 ° C. for 30 minutes each, or a method of linearly increasing the temperature from room temperature to 400 ° C. over 2 hours can be mentioned.

  The application of the heat-resistant resin film formed using the photosensitive resin precursor composition of the present invention is not particularly limited, but preferably bumps such as semiconductor buffer coat film, flip chip, wafer level CSP (chip size package), etc. It is used for applications such as protective films and interlayer insulation films for multilayer wiring for high-density mounting.

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

Preparation of photosensitive polyimide precursor film A photosensitive resin precursor composition (hereinafter referred to as varnish) was applied on a 6-inch silicon wafer so as to have a film thickness of 14 μm after pre-baking, and then hot plate (Tokyo Electron Limited). Using Mark-7), prebaking was performed at 120 ° C. for 2 minutes to obtain a photosensitive resin precursor film.

Method for measuring film thickness Using a Lambda Ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd., the refractive index was measured at 1.64.

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 i-line exposure was performed by changing the exposure time at an intensity of 365 nm.

Development A 2.38% aqueous solution of tetramethylammonium hydroxide was sprayed for 10 seconds at 50 revolutions using a Mark-7 developing device manufactured by Tokyo Electron Ltd. Then, it was allowed to stand for 50 seconds at 0 rotation, and again sprayed with a 2.38% aqueous solution of tetramethylammonium hydroxide for 10 seconds at 50 rotations. Thereafter, the plate was allowed to stand for 50 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 optimum exposure time) was determined. 900 msec or less is considered good.

Calculation of Resolution After exposure and development, the minimum pattern size in the optimum exposure time for forming a 50 μm line-and-space pattern (1L / 1S) in a 1: 1 width was taken as the resolution.

Calculation of shrinkage rate The produced photosensitive resin precursor film was subjected to an inert oven INH-21CD manufactured by Koyo Lindberg Co., Ltd., under a nitrogen stream (oxygen concentration 20 ppm or less) at 140 ° C. for 30 minutes, and then 320 ° C. The temperature was raised to 1 hour and then heat treated at 320 ° C. for 1 hour to produce a cured film. The shrinkage rate is calculated according to the following formula, and 30% or less is considered good.
Shrinkage rate (%) = (film thickness after pre-baking−film thickness after curing) / film thickness after pre-baking × 100.

Calculation of water absorption rate The dry weight of the cured film was weighed and subsequently immersed in water for 24 hours. Then, the moisture of the surface was wiped off, the weight of the film was weighed, and the weight was calculated according to the following formula. 1% or less is considered good.
Water absorption (%) = weight of membrane in dry state / weight of membrane after water immersion for 24 hours × 100.

Synthesis Example 1 Synthesis of hydroxyl group-containing acid anhydride Under dry nitrogen flow, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (BAHF) and allyl glycidyl ether 34.2 g (0.3 mol) was dissolved in 100 g of gamma butyrolactone (GBL) and cooled to −15 ° C. To this, 22.1 g (0.11 mol) of trimellitic anhydride chloride dissolved in 50 g of GBL 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 the following acid anhydride (1).

Synthesis Example 2 Synthesis of hydroxyl group-containing diamine compound (2) 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. Next, 30 g of the white solid was placed in a 300 mL stainless steel autoclave, dispersed in 250 mL of methyl cellosolve, and 2 g of 5% palladium-carbon 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 the following diamine compound (2). The obtained solid was used for the reaction as it was.

Synthesis Example 3 Synthesis of Hydroxyl Group-Containing Diamine (3) 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 and recrystallization was performed to obtain crystals of the following diamine (3).

Synthesis Example 4 Synthesis of hydroxyl group-containing diamine (4) 15.4 g (0.1 mol) of 2-amino-4-nitrophenol was dissolved in 100 mL of acetone and 17.4 g (0.3 mol) of propylene oxide, 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, the following diamine (4) crystals were obtained in the same manner as in Synthesis Example 2.

Synthesis Example 5 Synthesis of quinonediazide compound (5) Under a dry nitrogen stream, BisPG-26X (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), 19.71 g (0.05 mol) and 5-naphthoquinonediazidesulfonyl acid chloride 56 g (0.05 mol) and 14.14 g (0.05 mol) of 4-naphthoquinone diazide sulfonyl chloride were 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. After dropping, the mixture was stirred at 30 ° C. 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 the following quinonediazide compound (5). Here, the ratio in the formula is a molar ratio.

Synthesis Example 6 Synthesis of quinonediazide compound (6) In a dry nitrogen stream, 19.72 g (0.05 mol) of BIR-PTBP (trade name, manufactured by Asahi Organic Materials Co., Ltd.) and 4-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 inside of the system would not be 35 ° C. or higher, and then stirred at 30 ° C. 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 the following quinonediazide compound (6). The ratio in the formula is a molar ratio.

Synthesis Example 7 Synthesis of quinonediazide compound (7) In a dry nitrogen stream, 7.21 g (0.05 mol) of 2-naphthol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl chloride were added to 1,4-dioxane. Dissolved in 450 g and brought to room temperature. Here, 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane was used, and the following quinonediazide compound (7) was obtained in the same manner as in Synthesis Example 6.

Synthesis Example 8 Synthesis of quinonediazide compound (8) Under a dry nitrogen stream, 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. The following quinonediazide compound (8) was obtained in the same manner as in Synthesis Example 6 using 15.18 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 9 Synthesis of quinonediazide compound (9) In a dry nitrogen stream, 6.81 g (0.05 mol) of 4-isopropylphenol and 13.43 g (0.05 mol) of 5-naphthoquinonediazidesulfonyl acid chloride were added to 1,4- Dissolved in 450 g of dioxane and brought to room temperature. The following quinonediazide compound (9) was obtained in the same manner as in Synthesis Example 6 using 5.06 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 10 Synthesis of quinonediazide compound (10) Under a dry nitrogen stream, 11.41 g (0.05 mol) of bisphenol A (trade name BPA, manufactured by Honshu Chemical Industry Co., Ltd.) and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (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 used, and the following quinonediazide compound (10) was obtained in the same manner as in Synthesis Example 6.

Synthesis Example 11 Synthesis of quinonediazide compound (11) Under a dry nitrogen stream, 24.2 g (0.05 mol) of benzene-1,2,3-tri (carboxy) tris-((2-hydroxyphenyl) amide) and 5- Naphthoquinonediazide sulfonyl chloride 40.28 g (0.15 mol) was dissolved in 450 g of 1,4-dioxane and brought to room temperature. The following quinonediazide compound (11) was obtained in the same manner as in Synthesis Example 6 using 10.12 g of triethylamine mixed with 50 g of 1,4-dioxane.

Synthesis Example 12 Synthesis of quinonediazide compound (12) In a dry nitrogen stream, 17.42 g (0.05 mol) of N, N′bis- (2-hydroxyphenyl) -terephthalimide and 26.86 g of 5-naphthoquinonediazidesulfonyl acid chloride (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 used, and the following quinonediazide compound (12) was obtained in the same manner as in Synthesis Example 6.

Synthesis Example 13 Synthesis of Compound (13) Having Phenolic Hydroxyl Group Under dry nitrogen flow, 2,2-bis (3-amino-4-phenoxy) hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) 18.3 g (0 .05 mol) was dissolved in 100 g of N-methyl-2-pyrrolidone (NMP). Then, 16.4 g (0.1 mol) of norbornene dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for 2 hours. Furthermore, 38.3 g (0.1 mol) of (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl (Tokyo Chemical Industry Co., Ltd.) and 2-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.9 g (0.1 mol) was added and allowed to stir for 2 hours. After completion of the reaction, the solution was poured into 1 L of water to collect a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a compound (13) having the following phenolic hydroxyl group.

Synthesis Example 14 Synthesis of Compound (14) Having Phenolic Hydroxyl Group Under dry nitrogen flow, 2,2-bis (3-amino-4-phenoxy) hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) 18.3 g (0 .05 mol) was dissolved in 100 g of NMP. Then, 16.4 g (0.1 mol) of norbornene dicarboxylic acid anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred for 2 hours. Thereafter, a solution obtained by diluting 27 g (0.2 mol) of N, N-dimethylformamide dimethylacetal with 20 g of NMP was added dropwise over 10 minutes, and the mixture was stirred for 2 hours. After completion of the reaction, 24 g (0.4 mol) of acetic acid was added together with 18 g of NMP and stirred at 20 ° C. for 1 hour. This solution was poured into 2 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a compound (14) having the following phenolic hydroxyl group.

Synthesis Example 15 Synthesis of Compound (15) Having Phenolic Hydroxyl Group 2,2-bis (3 instead of 2,2-bis (3-amino-4-phenoxy) hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) -Amino-4-phenoxy) Propane (manufactured by Tokyo Chemical Industry Co., Ltd.) 11.7 g (0.05 mol) and the same method as in Synthesis Example 13 except that 3-aminophenol is used instead of 2-aminophenol The following compound (15) having the phenolic hydroxyl group was obtained.

Synthesis Example 16 Synthesis of Compound (16) Having Phenolic Hydroxyl Group Oxabis (3-amino-4) instead of 2,2-bis (3-amino-4-phenoxy) hexafluoropropane (manufactured by Tokyo Chemical Industry Co., Ltd.) -Phenol) (Tokyo Kasei Co., Ltd.) 12.9 g (0.05 mol) was used instead of norbornene dicarboxylic acid anhydride (Tokyo Kasei Co., Ltd.) and cyclohexene dicarboxylic acid anhydride (Tokyo Kasei Co., Ltd.) The compound (16) having the following phenolic hydroxyl group was obtained in the same manner as in Synthesis Example 13 except that 15.2 g (0.1 mol) was used.

Synthesis Example 17 Synthesis of Compound (17) Having Phenolic Hydroxyl Group 2,2-bis (3 instead of 2,2-bis (3-amino-4-phenoxy) hexafluoropropane (Tokyo Chemical Industry Co., Ltd.) -Amino-4-phenoxy) propane (Tokyo Kasei Co., Ltd.) 11.7 g (0.05 mol) was used instead of N, N-dimethylformamide dimethyl acetal 32.6 g of N, N-dimethylformamide diethyl acetal A compound (17) having the following phenolic hydroxyl group was obtained in the same manner as in Synthesis Example 14 except that (0.2 mol) was used.

Example 1
Under a dry nitrogen stream, 5.01 g (0.025 mol) of 4,4′-diaminophenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 50 g of NMP. Dissolved. To this, 21.4 g (0.03 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1 was added together with 14 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours. Thereafter, a solution prepared 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 50 ° C. for 3 hours. Thereafter, 18 g (0.3 mol) of acetic acid was added together with 18 g of NMP and stirred at 20 ° C. for 1 hour. This solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a white solid.

  10 g of the obtained white solid was measured, 2 g of the quinonediazide compound (5) obtained in Synthesis Example 5, 2 g of the compound (13) having a phenolic hydroxyl group obtained in Synthesis Example 13, and 1 g of vinyltrimethoxysilane were obtained by 30 g of GBL. The varnish A of the photosensitive polyimide precursor composition was obtained.

Example 2
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the hydroxyl group-containing diamine (2) obtained in Synthesis Example 2 was dissolved in 50 g of NMP. 17.5 g (0.025 mol) of the hydroxy group-containing acid anhydride obtained in Synthesis Example 1 was added thereto together with 30 g of pyridine, and the mixture was reacted at 60 ° C. for 6 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 a white solid. 10 g of the obtained white solid was measured, 2 g of the quinonediazide compound (8) obtained in Synthesis Example 8, 2 g of the compound (14) having a phenolic hydroxyl group obtained in Synthesis Example 14, and 1 g of vinyltrimethoxysilane. It was made to melt | dissolve in GBL30g and the varnish B of the photosensitive polyimide precursor composition was obtained.

Example 3
Under a dry nitrogen stream, 17 g (0.045 mol) of the hydroxyl group-containing diamine compound (3) obtained in Synthesis Example 3 and 1.24 g (0.005) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Mol) was dissolved in 50 g of NMP. To this, 12.4 g (0.04 mol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic anhydride was added together with 21 g of NMP, and reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 2 hours. . To this, 0.98 g (0.01 mol) of maleic anhydride was added, stirred for 2 hours at 50 ° C., and then a solution obtained by diluting 14.7 g (0.1 mol) of N, N-dimethylformamide diethyl acetal with 5 g of NMP was added. It was added dropwise over a period of minutes. After dropping, the mixture was stirred at 50 ° C. for 3 hours. Thereafter, 24 g (0.4 mol) of acetic acid was added together with 18 g of NMP, followed by stirring at 20 ° C. for 1 hour. This solution was poured into 2 L of water, and a precipitate of polymer solid was collected by filtration. The polymer solid was dried with a vacuum dryer at 50 ° C. for 20 hours to obtain a white solid. 10 g of the obtained white solid was measured, 2 g of the quinonediazide compound (9) obtained in Synthesis Example 9, 2 g of the compound (16) having a phenolic hydroxyl group obtained in Synthesis Example 16, and 1 g of vinyltrimethoxysilane. It was made to melt | dissolve in GBL30g and the varnish C of the photosensitive polyimide precursor composition was obtained.

Example 4
Under a dry nitrogen stream, 6.08 g (0.025 mol) of the hydroxyl group-containing diamine compound (4) obtained in Synthesis Example 4 and 4.51 g (0.0225 mol) of 4,4′-diaminodiphenyl ether and 1,3 -0.62 g (0.0025 mol) of bis (3-aminopropyl) tetramethyldisiloxane was dissolved in 70 g of NMP. Here, 24.99 g (0.035 mol) of hydroxyl group-containing acid anhydride (1) obtained in Synthesis Example 1, 4.41 g of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (0) .015 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. Next, a solution obtained by diluting 17.6 g (0.2 mol) of glycidyl methyl ether with 10 g of NMP was added and stirred at 70 ° C. for 6 hours to obtain a polymer solution. 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 a white solid. 10 g of the obtained white solid was measured, 2 g of the quinonediazide compound (10) obtained in Synthesis Example 10, 2 g of the compound (17) having a phenolic hydroxyl group obtained in Synthesis Example 17, and 1 g of vinyltrimethoxysilane. It was made to melt | dissolve in GBL30g and the varnish D of the photosensitive polyimide precursor composition was obtained.

Example 5
Under a dry nitrogen stream, 18.3 g (0.05 mol) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 50 g of NMP and 26.4 g (0.3 mol) of glycidyl methyl ether. The temperature of the solution was cooled to -15 ° C. A solution prepared by dissolving 7.38 g (0.025 mol) of diphenyl ether dicarboxylic acid dichloride and 5.08 g (0.025 mol) of isophthalic acid dichloride in 25 g of GBL was added dropwise so that the internal temperature did not exceed 0 ° C. After completion of the dropwise addition, stirring was continued for 6 hours at -15 ° C. After completion of the reaction, the solution was poured into 3 L of water to collect a white precipitate. The precipitate was collected by filtration, washed 3 times with water, and then dried for 20 hours in a vacuum dryer at 80 ° C. to obtain a white polymer solid. 10 g of the obtained polymer solid was measured, 2 g of the quinonediazide compound (5) obtained in Synthesis Example 5, 2 g of the compound (16) having a phenolic hydroxyl group obtained in Synthesis Example 16, and 1 g of vinyltrimethoxysilane were combined with gamma butyrolactone. Varnish E of the photosensitive polyimide precursor composition was obtained by dissolving in 30 g.

Example 6
The same method as in Example 1 except that 2 g of the quinonediazide compound (12) instead of the quinonediazide compound (5) and 2 g of the compound (17) having a phenolic hydroxyl group are dissolved instead of the compound (13) having a phenolic hydroxyl group. The varnish F of the photosensitive polyimide precursor composition was obtained.

Example 7
The same method as in Example 4 except that 2 g of the quinonediazide compound (6) instead of the quinonediazide compound (10) and 2 g of the compound (15) having a phenolic hydroxyl group are dissolved instead of the compound (17) having a phenolic hydroxyl group. The varnish G of the photosensitive polyimide precursor composition was obtained.

Example 8
The same method as in Example 5 except that 2 g of the quinonediazide compound (8) instead of the quinonediazide compound (5) and 1 g of the compound (14) having a phenolic hydroxyl group are dissolved instead of the compound (16) having a phenolic hydroxyl group. The varnish H of the photosensitive polyimide precursor composition was obtained.

Example 9
Under a dry nitrogen stream, 15.1 g (0.025 mol) of the diamine compound (3) obtained in Synthesis Example 3, 4.5 g (0.0225 mol) of 4,4′-diaminodiphenyl ether and 1,3-bis ( 0.62 g (0.0025 mol) of 3-aminopropyl) tetramethyldisiloxane was dissolved in 100 g of GBL. To this was added 16.1 g (0.050 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride together with 33 g of GBL at room temperature, and the mixture was allowed to react at room temperature for 1 hour and then at 50 ° C. for 4 hours. A solution was obtained. In 50 g of the obtained polymer solution, 7.6 g of the quinonediazide compound (11) obtained in Synthesis Example 11 and 7.6 g of the compound (13) having a phenolic hydroxyl group obtained in Synthesis Example 13 were dissolved to be photosensitive. A varnish I of a polyimide precursor composition was obtained.

Example 10
In a dry nitrogen stream, 19 g (0.095 mol) of 4,4′-diaminodiphenyl ether and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were dissolved in 350 g of GBL. . 71.4 g (0.1 mol) of the acid anhydride obtained in Synthesis Example 1 was added together with 40 g of GBL, reacted at 20 ° C. for 1 hour, and then reacted at 50 ° C. for 4 hours to obtain a polymer solution (24). It was. Photopolymer polyimide is obtained by adding 20 g of the quinonediazide compound (12) obtained in Synthesis Example 12 and 20 g of the compound having a phenolic hydroxyl group (15) obtained in Synthesis Example 15 together with 10 g of GBL to 50 g (24) of the obtained polymer solution. Varnish J of the precursor composition was obtained.

Comparative Example 1
2 g of quinonediazide compound (7) instead of quinonediazide compound (5), compound Bis-RS-2P having a phenolic hydroxyl group represented by the following chemical formula instead of compound (13) having phenolic hydroxyl group (trade name, Honshu Chemical Industry) Varnish K of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 1 except that 1 g was added.

Comparative Example 2
Example 2 except that 0.8 g of a compound Bis-RS-3P (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) having a phenolic hydroxyl group shown below is dissolved instead of the compound (14) having a phenolic hydroxyl group The varnish L of the photosensitive polyimide precursor composition was obtained by the same method.

Comparative Example 3
Varnish M of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 3 except that 0.8 g of Bis-RS-3P was dissolved instead of the compound (16) having a phenolic hydroxyl group.

Comparative Example 4
Varnish N of the photosensitive polyimide precursor composition was prepared in the same manner as in Example 1 except that 2 g of the quinonediazide compound (7) was dissolved in place of the quinonediazide compound (5) and the compound (13) having a phenolic hydroxyl group was not added. Got.

Comparative Example 5
Instead of the quinonediazide compound (8), 2 g of the quinonediazide compound (7) and 1 g of TrisP-PA (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) shown below are dissolved instead of the compound (14) having a phenolic hydroxyl group. Except for the above, a photosensitive polyimide precursor composition varnish O was obtained in the same manner as in Example 2.

Comparative Example 6
1.6 g of quinonediazide compound (9) instead of quinonediazide compound (8), BisP-AP represented by the following chemical formula instead of compound (14) having a phenolic hydroxyl group (trade name, manufactured by Honshu Chemical Industry Co., Ltd.) 0 Varnish P of the photosensitive polyimide precursor composition was obtained in the same manner as in Example 2 except that 0.8 g was dissolved.

Claims (3)

(A) a polymer containing as a main component a structural unit represented by general formula (1), (b) a compound having a phenolic hydroxyl group represented by general formula (2), and (c) a quinonediazide compound. The photosensitive resin precursor composition characterized by the above-mentioned.

(Wherein R ¹ and R ² are divalent to octavalent organic groups having two or more carbon atoms, R ³ and R ⁴ are hydrogen, or an organic group having 1 to 20 carbon atoms; m is 10; To 100000, k and l are integers from 0 to 4, n and o are integers from 0 to 4, provided that k + l> 0 or n + o> 0.)

(Wherein R ⁵ represents a divalent to octavalent organic group having an aromatic ring, and R ⁶ represents a divalent to tetravalent group having two or more carbon atoms and having a thermal crosslinking group containing an unsaturated bond. R ⁷ represents an organic group having 1 to 15 carbon atoms, p represents an integer of 1 to 4, and q represents an integer of 1 to 4.) The photosensitive resin precursor composition according to claim 1, wherein the R ¹ (COOR ³ ) _k (OH) _n portion of the general formula (1) has a structure represented by the general formula (3).

(Wherein R ⁸ and R ¹⁰ represent a divalent to tetravalent organic group having 2 to 20 carbon atoms, R ⁹ represents a trivalent to hexavalent organic group having 3 to 20 carbon atoms, R ¹¹ , R ¹² represents hydrogen or an organic group having 1 to 20 carbon atoms, r and t are integers from 0 to 2, and s is an integer from 1 to 4. ^2. The photosensitive according to claim 1, wherein R ² (COOR ⁴ ) ₁ (OH) _o in the general formula (1) has at least one of the structures represented by the general formulas (4) to (6). Resin precursor composition.

(In the formula, R ¹³ and R ¹⁵ represent a C 2-20 trivalent to hexavalent organic group having a hydroxyl group, R ¹⁴ represents a C 2-30 divalent to tetravalent organic group, and R ¹⁶ , R ¹⁷ and R ¹⁸ represent hydrogen or an organic group having 1 to 20 carbon atoms, u and v represent an integer of 0 to 2, and c, d and e represent an integer of 0 to 2.)

(Wherein R ¹⁹ and R ²¹ represent a divalent to tetravalent organic group having 2 to ²⁰ carbon atoms, R ²⁰ represents a trivalent to octavalent organic group having 3 to ²⁰ carbon atoms, R ²² , R ²³ and R ²⁴ represent hydrogen or an organic group having 1 to 20 carbon atoms, w represents an integer of 1 to 4, and f, g, and h represent integers of 0 to 2.)

(In the formula, R ²⁵ represents a divalent to tetravalent organic group having 2 to 20 carbon atoms, R ²⁶ represents a trivalent to octavalent organic group having 3 to 20 carbon atoms, and R ²⁷ and R ²⁸ represent Hydrogen or an organic group having 1 to 20 carbon atoms, x represents an integer from 0 to 4, and i and j represent integers from 0 to 2.