KR20180076327A - Polyimide resin and positive photosensitive resin composition - Google Patents

Abstract

The present invention provides polyimide resin, which is used as base resin for a positive photosensitive resin composition having excellent balance between pattern development properties, a linear expansion coefficient, substrate adhesion, toughness, and metal corrosion-resistance, and a positive photosensitive resin composition using the polyimide resin. Here, the polyimide resin is able to include: a repetitive unit having a carboxyl group of no less than 5 mole% to no more than 20 mole%; and a repetitive unit having a phenolic hydroxyl group of no less than 80 mole% to no more than 95 mole% (but, the sum of the repetitive unit having the carboxyl group and the repetitive unit having the phenolic hydroxyl group is 100 mole%).

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyimide resin and a positive photosensitive resin composition,

The present invention relates to a polyimide resin and a positive photosensitive resin composition.

In general, a positive type photoresist includes one type of novolak type resin soluble in an aqueous alkali and a photosensitive quinone diazide in alkali to reduce the solubility. When the photoresist is irradiated with ultraviolet light, quinonediazide is photoexcited to convert the structure into carboxylic acid, and the solubility of the quinone diazide in alkali is increased in the exposed region. Therefore, when an aqueous alkali development is carried out, a positive photoresist relief structure is obtained. Since the positive photoresist exhibits inherently high image resolution, it is known that the positive photoresist is more advantageous in the miniaturization process than the negative photoresist.

In recent years, from the viewpoints of high density and high integration, there has been a demand for a pattern developing property of a conventional photoresist or a reliability that can be used as a permanent film after curing, in interlayer insulating materials such as a flexible wiring board and a semiconductor integrated circuit formed from such positive type photoresist .

As an example of the positive type photoresist, there is a photosensitive polyimide composition comprising a photoacid generator as in Patent Document 1 and a solvent-soluble polyimide exhibiting positive photosensitivity in the presence of the photoacid generator .

WO 99/019771

In applications such as interlayer insulating materials, mechanical strength (toughness) is required to withstand bending due to difference in linear expansion coefficient from other materials constituting the substrate. However, in terms of mechanical strength and pattern developability, there is generally a trade-off, and it has been required to solve this trade-off. In addition, since the interlayer insulating material is in direct contact with the metal wiring, an effect of preventing metal corrosion is also required, and the technique described in Patent Document 1 does not satisfy all these requirements.

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances and has as its object to provide a polyimide resin which is used as a base resin of a positive photosensitive resin composition excellent in balance of pattern developability, And to provide a positive photosensitive resin composition using a mid resin.

In order to solve the above problems, the present inventors conducted intensive studies. As a result, it has been found that the above problems can be solved by a polyimide resin, a positive photosensitive resin composition containing the polyimide resin and a photoacid generator, and the present invention has been accomplished.

That is, the present invention relates to a resin composition comprising a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less and a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (provided that a repeating unit having a carboxyl group, And the sum of the repeating units having a hydroxyl group is 100 mol%).

The present invention also relates to a positive photosensitive resin composition comprising the polyimide resin and a photoacid generator in an amount of 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the polyimide resin.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyimide resin which is used as a base resin of a positive photosensitive resin composition excellent in balance of pattern developability, linear expansion coefficient, substrate adhesion, toughness and metal corrosion resistance, and a positive photosensitive A resin composition is provided.

Fig. 1 is an infrared absorption spectrum of Polymer Compound 1 obtained in Example 1. Fig.
2 is an infrared absorption spectrum of Polymer Compound 2 obtained in Example 2. Fig.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. Unless otherwise noted, the operations and physical properties are measured at room temperature (20 DEG C or higher and 25 DEG C or lower) / relative humidity 40% RH or higher and 60% RH or lower.

The present invention relates to a resin composition containing a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less and a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (provided that a repeating unit having a carboxyl group, And the total of the repeating units contained is 100 mol%).

The present invention also relates to a positive photosensitive resin composition comprising the polyimide resin and a photoacid generator in an amount of 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the polyimide resin.

The polyimide resin and the positive photosensitive resin composition of the present invention having such a structure are excellent in balance of pattern development property, linear expansion coefficient, substrate adhesion property, toughness and metal corrosion resistance. In addition, the cured film obtained from the positive photosensitive resin composition is excellent in balance of pattern developability, linear expansion coefficient, substrate adhesion, toughness and metal corrosion resistance.

The reason why the effects are obtained by the polyimide resin and the positive photosensitive resin composition of the present invention is unknown. However, even if the molecular weight is low, a relatively weak crosslinking structure is formed due to hydrogen bonding between the molecules of the polyimide resin, And that the alkali developability is improved by having a carboxyl group. On the other hand, this reason is based on speculation, and the present invention is not limited at all for this reason.

Hereinafter, the constituent components of the polyimide resin and the positive photosensitive resin composition of the present invention will be described in detail. On the other hand, the positive photosensitive resin composition of the present invention is also simply referred to as a composition.

 [Polyimide resin]

The polyimide resin of the present invention contains a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less and a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (provided that the repeating unit having a carboxyl group, And the total of the repeating units having a phenolic hydroxyl group is 100 mol%).

When the content of the carboxyl group-containing repeating unit is less than 5 mol%, at least one of the pattern developing property, toughness and metal corrosion resistance is lowered. On the other hand, when it exceeds 20 mol%, the metal corrosion resistance is lowered and it is difficult to dissolve in solvents and the like, so that the desired positive photosensitive resin composition may not be produced.

The content of the carboxyl group-containing repeating unit is preferably 5 mol% or more and 13 mol% or less, and more preferably 5 mol% or more and 10 mol% or less (provided that the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group The total of repeating units is 100 mol%).

In addition, when the content of the repeating unit having a phenolic hydroxyl group is less than 80 mol%, the metal corrosion resistance is lowered, and it is difficult to dissolve in a solvent or the like, so that a desired positive photosensitive resin composition may not be produced. On the other hand, when it exceeds 95 mol%, the pattern developability, toughness and metal corrosion resistance deteriorate.

The content of the repeating unit having a phenolic hydroxyl group is preferably 87 mol% or more and 95 mol% or less, and more preferably 90 mol% or more and 95 mol% or less (provided that the repeating unit having a carboxyl group and the phenolic hydroxyl group Is 100 mol%).

On the other hand, the content of the repeating unit having a carboxyl group and the content of the repeating unit having a phenolic hydroxyl group can be calculated by analyzing the finally obtained polyimide resin by 1 H-NMR or IR.

The total amount of the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group in the polyimide resin of the present invention is preferably from 70 mol% to 100 mol%, more preferably from 80 mol% to 100 mol% Or less, more preferably 90 mol% or more and 100 mol% or less.

The repeating unit having a carboxyl group is preferably a repeating unit represented by the following general formula (1), and the repeating unit containing a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (2).

In the general formulas (1) and (2), R ₁ represents, independently of each other, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may contain an ether bond or an ester bond, An arylene group having 6 to 20 carbon atoms which may contain an ester bond.

Examples of the straight chain, branched or cyclic alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a 2-methylpropylene group, N-hexylene group, n-octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopentylene group, cyclopentylene group , A cyclohexylene group, a methylcyclohexylene group, a dimethylcyclohexylene group, a cycloheptylene group, a 1-ethylcyclopentylene group, a cyclooctylene group, a cyclononylene group, a cyclodecylene group, a bicyclodesylene group, And a cyclohexanedimethylene group.

Examples of the arylene group having 6 to 20 carbon atoms include, for example, phenylene group, biphenylene group, naphthylene group, terphenylene group and anthranylene group.

The alkylene group and the arylene group may contain an ether bond or an ester bond. Examples of the alkylene group or the arylene group containing an ether bond or an ester bond include groups represented by the following formulas. In the following formulas, Ph 'represents a phenylene group.

From the viewpoint of further improving the effect of the present invention, the repeating unit having a carboxyl group represented by the general formula (1) is a repeating unit represented by the following general formula (3) and is a repeating unit having a phenolic hydroxyl group represented by the general formula The unit is preferably a repeating unit represented by the following general formula (4).

The repeating unit represented by the general formula (3) is preferably a repeating unit obtained by reacting 1,3-dihydro-1,3-dioxo-5-isobenzofuranocarboxylic acid-1,4-phenylene ester with methylenebisaminobenzoic acid Structure. The repeating unit represented by the general formula (4) can be obtained by reacting 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester with 2,2- 3-amino-4-hydroxyphenyl) hexafluoropropane.

The method for producing the polyimide resin of the present invention is not particularly limited. For example, tetracarboxylic acid can be obtained by reacting an anhydride with a diamine compound containing a carboxyl group and a diamine compound containing a phenolic hydroxyl group (polycondensation).

More specifically, the tetracarboxylic acid includes an anhydride, a diamine compound containing a carboxyl group, a diamine compound containing a phenolic hydroxyl group, and, if necessary, other diamine compounds containing no carboxyl group and phenolic hydroxyl group (Method A) in which a polyimide precursor is obtained by reacting a tetracarboxylic acid anhydride with a diamine compound (hereinafter also referred to as a monomer) to obtain a polyimide precursor and then imidizing the obtained polyimide precursor (Method A) And a method of synthesizing a polyimide resin (Method B).

Examples of the tetracarboxylic acid dianhydride include, for example, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2 , 2 ', 3,3'-biphenyltetracarboxylic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzophenonetetracarboxylic acid Oxydiphthalic acid dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bicyclo [2,2,2] octo- Tetraacetic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 5,5'-methylene-bis (anthranilic acid), pyromellitic acid (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-di (tert-butyldicyclohexylphenyl) propane dianhydride, 2,2- Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, this (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester , 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, 1,2,5,6-naphthalene tetra Carboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride Bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane dianhydride, 2,2- , Bis (4- (3,4-dicarboxybenzoyloxy) phenyl) hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4'- Dicarboxyphenoxy) biphenyl dianhydride, cyclobutane tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5,6-cyclohexane La-carboxylic acid are anhydrides, 5- (2,5-dioxo-tetrahydro-3-plastic carbonyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid include the anhydrides and the like.

These tetracarboxylic acid dianhydrides may be used alone or in combination of two or more.

Of these tetracarboxylic acid dianhydrides, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester is preferable.

Examples of the diamine compound containing a carboxyl group include, for example, methylene bisaminobenzoic acid, 2,5-diamino benzoic acid, 3,5-diamino benzoic acid, 4,4 '- (3,3'-dicarboxy) Minibiphenyl, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether, and the like. These diamine compounds containing carboxyl groups may be used alone or in combination of two or more.

Of these diamine compounds containing carboxyl groups, methylene bisaminobenzoic acid is preferred.

Examples of the diamine compound containing a phenolic hydroxyl group include 3,3'-dihydroxybenzidine, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'- Diamino-3,3'-dihydroxybiphenyl, 3,3'-diamino-4,4'-dihydroxydiphenylsulfone, 4,4'-diamino-3,3'-dihydroxy (3-amino-4-hydroxyphenyl) methane, 2,2-bis- (3-amino-4-hydroxyphenyl) propane, 2,2- Amino-3-hydroxyphenyl) methane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, -Amino-3-hydroxyphenyl) propane, 4,4'-diamino-3,3'-dihydroxybenzophenone, 3,3'-diamino-4,4'-dihydroxybenzophenone, 4 , 4'-diamino-3,3'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenyl ether, 1,4-diamino- Dihydroxybenzene, 1,3-di And the like can be furnace-2,4-dihydroxy-benzene, and 1,3-diamino-4,6-dihydroxy-benzene. These diamine compounds containing a phenolic hydroxyl group may be used singly or in combination of two or more.

Of these diamine compounds containing a phenolic hydroxyl group, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable, and 2,2-bis ) Hexafluoropropane is more preferable.

The polyimide resin of the present invention may contain, in addition to the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group, a repeating unit having a carboxyl group and a phenolic hydroxyl group, Of repeating units. Such arbitrary repeating units may be formed from other diamine compounds not containing a carboxyl group and a phenolic hydroxyl group. Examples of such diamine compounds include 4,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'- Diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfone, 3'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, , 4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone , 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) Di (3-aminophenyl) propane, 2- (3-aminophenyl) -2- , 3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- -Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) - 1- (4-aminophenyl) -1-phenylethane, 1, 3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, Benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, ) Benzene, 1,3-bis (3-amino- alpha, alpha -dimethylbenzyl) benzene, 1,3-bis (3-amino-a, -trifluoromethylbenzyl) benzene, 1,4-bis (4-amino- alpha, -dimethylbenzyl) benzene, Benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis Bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-amyl-α, (4-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) ] Ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) 4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- Bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- Bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- , 1,1,3,3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) Benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4- (3- (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -?,? - dimethylbenzyl] benzene, 1,4-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- Amino- [alpha], [alpha] -dimethylbenzyl) phenoxy] diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, -Diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino- (P-aminophenyl) -6,6'-bisbenzoxazole, 2- (p-aminophenyl) benzooxazole, Aminophenyl) -4-aminobenzamide, N, N'-bis (4-aminophenyl) terephthalamide, 4-aminophenyl- Ah And the like can be mentioned furnace benzoate, 2,2'-dimethyl-biphenyl-4,4'-diamine. These other diamine compounds may be used alone or in combination of two or more.

In Method A (a method of imidizing a polyimide precursor), a method for synthesizing a polyimide precursor is not particularly limited, and a known method can be employed.

For example, first, a diamine compound containing a carboxyl group, a diamine compound containing a phenolic hydroxyl group, and other diamine compounds not containing a carboxyl group and a phenolic hydroxyl group, which are used as needed, are dissolved in a solvent to obtain a solution, A solution of the polyimide precursor can be obtained by slowly adding a tetracarboxylic acid dianhydride to the solution and a substantially equivalent amount of the diamine compound used and continuing the stirring. The monomer concentration at this time is not particularly limited, but is preferably 5 mass% or more and 50 mass% or less, and more preferably 10 mass% or more and 40 mass% or less.

The solvent used in synthesizing the polyimide precursor is not particularly limited as long as it can sufficiently dissolve the monomer and the polyimide precursor. For example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam and hexamethylphosphoric triamide; Sulfone type solvents such as sulfolane, dimethyl sulfoxide, dimethyl sulfone, tetramethylene sulfone, and dimethyl tetramethylene sulfone; Phenolic solvents such as cresol, phenol, and xylenol; Diglycidic solvents such as diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme) and tetraglyme; lactone solvents such as? -butyrolactone,? -valerolactone,? -valerolactone,? -caprolactone and? -caprolactone; Ketone solvents such as isophorone, cyclopentanone, cyclohexanone, and 3,3,5-trimethylcyclohexanone; Aromatic hydrocarbon solvents such as benzene, toluene and xylene; Other solvents such as pyridine, ethylene glycol, dioxane, and tetramethylurea; And the like. These solvents may be used alone or in combination of two or more.

The reaction temperature is not particularly limited, but is preferably -10 ° C to 80 ° C, more preferably 0 ° C to 40 ° C. The reaction time is not particularly limited, but is preferably 0.5 to 150 hours, more preferably 3 to 24 hours.

The solution of the polyimide precursor thus obtained can be supplied to the subsequent imidization reaction without isolation of the polyimide precursor, or after adjustment of the concentration. The polyimide precursor may also be isolated by dropping a solution of the polyimide precursor in a large amount of water or a poor solvent such as methanol, precipitating the polyimide precursor, filtering, washing and drying the polyimide precursor.

The method for imidizing the polyimide precursor is not particularly limited, and for example, a known chemical imidation method or a heat imidation method may be employed. Among them, the chemical imidation method is more advantageously used because it does not need to be heated excessively and the lowering of the molecular weight of the polyimide resin can be suppressed.

The chemical imidation method can be carried out, for example, by dropping an organic acid anhydride and an organic base into the solution while stirring a solution of the polyimide precursor. Examples of the solvent for the solution of the polyimide precursor include the same solvents as the solvent for the synthesis of the polyimide precursor. Examples of the organic acid anhydride include acetic anhydride, propionic anhydride, maleic anhydride, and phthalic anhydride. Among them, acetic anhydride is suitably used from the standpoint of ease of removal after the reaction but from the viewpoint of cost. The amount of the organic acid anhydride to be used is not particularly limited, but is preferably 1 equivalent or more and 10 equivalents or less, and more preferably 2 or more and 5 equivalents or less, of the theoretical dehydration amount of the polyimide precursor.

Examples of the organic base include heterocyclic compounds such as pyridine and picoline; Tertiary amines such as triethylamine and N, N-dimethylaniline; And the like. The amount of the organic base to be used is not particularly limited, but is preferably 0.1 equivalents or more and 2 equivalents or less, more preferably 0.2 equivalents or more and 1.5 equivalents or less, based on the organic acid anhydride.

The reaction temperature of the chemical imidation method is not particularly limited, but is preferably 0 ° C or more and 130 ° C or less, and more preferably 20 ° C or more and 110 ° C or less. The reaction time is not particularly limited, but is preferably 0.5 hour to 48 hours, more preferably 1 hour to 24 hours.

The thermal imidation method can be performed, for example, by heating a solution of the polyimide precursor to a temperature at which the dehydration ring-closure reaction occurs. When heating, a method of raising the temperature up to one step to the maximum temperature or a method of raising the temperature in multiple steps may be used.

Examples of the solvent for the solution of the polyimide precursor include the same solvents as the solvent for the synthesis of the polyimide precursor. In the thermal imidation method, the reaction temperature is not particularly limited, but is preferably 130 deg. C or higher and 450 deg. C or lower, and more preferably 300 deg. C or higher and 400 deg. C or lower. The reaction time is not particularly limited, but is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 5 hours.

The reaction can be carried out in an inert gas such as nitrogen, argon, or in air or in air. In the reaction system, toluene, xylene, or the like may be added to azeotropically distill an organic base such as? -Picoline or the like as a catalyst or water as a by-product.

Further, the isolated polyimide precursor may be thermally imidized by heating as it is. The reaction temperature is not particularly limited, but is preferably 200 or more and 400 or less, and more preferably 250 or more and 300 or less. The reaction time is not particularly limited, but is preferably 0.5 hour to 48 hours, more preferably 1 hour to 24 hours.

The reaction can be carried out in an inert gas such as nitrogen, argon, or air, or in air. From the viewpoint of preventing coloring, the reaction is preferably carried out in a vacuum or an inert gas.

When the polyimide is synthesized by the method B (a method of synthesizing a polyimide directly from an anhydride and a diamine of tetracarboxylic acid), for example, the reaction conditions of the method for synthesizing the polyimide precursor in the method A are changed , A polyimide can be directly synthesized from an anhydride and a diamine compound of tetracarboxylic acid.

The solvent used for the reaction includes the same solvents as those shown as the solvent for synthesizing the polyimide precursor. Among them, an amide-based solvent and a phenol-based solvent are preferable. The reaction temperature is not particularly limited, but is preferably 130 or more and 250 or less, and more preferably 140 or more and 200 or less. The reaction time is not particularly limited, but is preferably 0.5 hour to 48 hours, more preferably 1 hour to 24 hours. In the reaction system, toluene, xylene, or the like may be added to azeotropically distill an organic base such as? -Picoline or the like as a catalyst or water as a by-product.

The polyimide can be precipitated by carrying out the reaction according to the method 1 or 2 and dropping the solution of the obtained polyimide into a large amount of poor solvent. Further, the polyimide powder can be obtained by subjecting the precipitated polyimide to freeness, washing, drying and the like.

The poor solvent is not particularly limited as long as it does not dissolve the polyimide. However, it is preferable that the solvent has a high affinity with the reaction solvent or the chemical imidizing agent, and water can be efficiently removed by drying. Alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; Ketone solvents such as acetone; Ester solvents such as ethyl acetate; These mixed solvents; And so on.

The weight average molecular weight (Mw) of the polyimide resin of the present invention is not particularly limited, but is preferably 40,000 or more, and more preferably 45,000 or more from the viewpoint of ensuring mechanical properties. The upper limit of the weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 80,000 or less.

The molecular weight distribution (Mw / Mn) of the polyimide resin of the present invention is preferably 1.5 or more and 5 or less.

The weight average molecular weight and molecular weight distribution of the polyimide resin can be controlled by, for example, changing the type and composition of the monomer, and the conditions at the time of synthesis. On the other hand, the weight average molecular weight and the molecular weight distribution of the polyimide resin are values in terms of polystyrene obtained by gel permeation chromatography, and more specifically, can be measured by the method described in the examples.

 (Positive photosensitive resin composition)

The positive photosensitive resin composition of the present invention preferably contains the above-described polyimide resin of the present invention and a photoacid generator in an amount of 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the polyimide resin. The polyimide resin may be used alone or in combination of two or more. Since the polyimide resin has been described in detail above, the photoacid generator and other components will be described below.

 [Photo acid generators]

Examples of the photoacid generator used in the positive photosensitive resin composition of the present invention include quinone diazide compounds, onium salts, and halogen-containing compounds. Among them, a quinone diazide compound is preferable from the viewpoints of solvent solubility, storage stability, high sensitivity and the like. The photoacid generators may be used alone or in combination of two or more.

Examples of the onium salt include iodonium salt, sulfonium salt, phosphonium salt, ammonium salt, diazonium salt and the like, but it is preferable to use a compound selected from the group consisting of diaryliodonium salt, triarylsulfonium salt and trialkylsulfonium salt The onium salt selected is preferred.

The halogen-containing compound includes, for example, a haloalkyl group-containing hydrocarbon compound, and trichloromethyl triazine is preferable from the viewpoint of high sensitivity.

As the quinone diazide compound, a naphthoquinone diazide compound (hereinafter also referred to as an NQD compound) is preferable, and among them, a compound having a 1,2-naphthoquinone diazide structure is preferable. The compound having a 1,2-naphthoquinone diazide structure is preferably a 1,2-naphthoquinonediazide-4-sulfonic acid ester of a polyhydroxy compound, and a 1,2-naphtho Quinone diazide-5-sulfonic acid ester, and the like.

The NQD compound may be a commercially available product or a synthetic product. In the case of synthesis, it is also possible to use a naphthoquinonediazide sulfonic acid compound as a chlorosulfonic acid or thionylsulfonyl chloride according to a conventional method, and to react the obtained naphthoquinonediazide sulfonyl chloride with a polyhydroxy compound . For example, when a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride are reacted with dioxane, acetone , Tetrahydrofuran and the like in the presence of a basic catalyst such as triethylamine, esterification is carried out, and the obtained product is washed with water and dried to obtain an NQD compound.

From the standpoint of securing contrast to the i-line exposure, preferred photo acid generators are at least one selected from the group consisting of the compounds represented by the following general formulas 5 to 10.

In the general formulas 5 to 10, each R independently represents a hydrogen atom, a group represented by the following general formula (11), or a group represented by the following general formula (12).

The content of the photoacid generator in the composition of the present invention is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 5 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the polyimide resin. Within this range, contrast at the time of development and good mechanical characteristics can be satisfied.

 [Crosslinking agent]

The composition of the present invention preferably contains a crosslinking agent. By including the crosslinking agent, mechanical strength and substrate adhesion can be improved. These crosslinking agents may be used alone or in combination of two or more. The crosslinking agent may be a commercially available product or a synthetic product.

As the crosslinking agent, there can be used an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound having an N-position substituted with a methylol group and / or an alkoxymethyl group, and an allyl compound.

Of these crosslinking agents, compounds in which the N-position is substituted with a methylol group and / or an alkoxymethyl group are preferable from the viewpoint of chemical resistance after thermosetting.

Specific examples of the compound in which the N position is substituted with a methylol group and / or an alkoxymethyl group include melamine resin, benzoguanamine resin, glycoluril resin, hydroxyethylene urea resin, urea resin, glycol urea resin, alkoxymethylated melamine resin , Alkoxymethylated benzoguanamine resins, alkoxymethylated glycoluril resins, and alkoxymethylated urea resins.

The alkoxymethylated melamine resin, the alkoxymethylated benzoguanamine resin, the alkoxymethylated glycoluril resin, and the alkoxymethylated urea resin may be prepared by reacting the methylol group of a known methylol melamine resin, a methylol benzoguanamine resin, or a methylol urea resin with an alkoxymethyl group . Examples of the alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, and a butoxymethyl group.

Examples of commercially available products of the compound in which the N position is substituted with a methylol group and / or an alkoxymethyl group include Cymel (registered trademark) 300, 301, 303, 370, 325, 327, 701, 266, 267, (Manufactured by Nippon Synthetic Industries Co., Ltd.), NIKARAK (registered trademark) MX-270, -280, -290, NIKARAK MS- 11, NIKARAK MW-30, -100, -300, -390, and -750 (manufactured by SANWA CHEMICAL CO., LTD.).

The content of the crosslinking agent in the composition is preferably 5 parts by mass or more and 25 parts by mass or less, more preferably 7 parts by mass or more and 20 parts by mass or less, based on 100 parts by mass of the polyimide resin.

 [Novolac resin]

The composition of the present invention preferably comprises a novolak resin. By including the novolak resin, developability and resolution are improved. As the novolac resin, a known novolac resin can be suitably selected and used. Specific examples thereof include phenol novolak resins, cresol novolac resins, t-butylphenol novolak resins, dicyclopentadiene cresol novolak resins, dicyclopentadiene phenol novolak resins, xylenes denatured phenol novolak resins, Resin, tetrakisphenol novolak resin, bisphenol A novolac resin, and poly-p-vinylphenol resin.

These novolak resins may be used alone or in combination of two or more. The novolac resin may be a commercially available product or a synthetic product. Examples of commercially available products include TR4020G and TR4080G (manufactured by Asahi Organic Materials Industry Co., Ltd., cresol novolak resin).

The content of the novolak resin in the composition is preferably 5 parts by mass or more and 50 parts by mass or more, more preferably 10 parts by mass or more and 40 parts by mass or less, based on 100 parts by mass of the polyimide resin.

 [Surfactants]

The composition of the present invention preferably contains a surfactant. By including the surfactant, the coating property of the composition, the in-plane uniformity of the coating film, smoothness and the like are improved.

The surfactant is preferably a nonionic surfactant. Specific examples thereof include fluorinated surfactants such as perfluoroalkylpolyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorinated organosiloxane compounds. have. S-141, S-145, KH-10, KH (trade name, manufactured by Sumitomo 3M Limited), FLORAD (registered trademark) FC-430, FC-431 and FC- -20, KH-30, KH-40 (manufactured by AGC SEIMI CHEMICAL CO., LTD.), Unidyne DS-401, DS-4031 and DS-451 (manufactured by Daikin Industries, F-8151 (manufactured by DIC Corporation), X-70-092 and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The addition amount of the surfactant is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 3 parts by mass or less, based on 100 parts by mass of the polyimide resin.

 [Other additives]

The composition of the present invention may contain other additives such as a colorant, a filler, a photosensitizer, an alkali dissolution accelerator, an adhesion aid, a defoaming agent, and a leveling agent to such an extent that the photosensitivity is not affected.

 [Method of producing positive-type photosensitive resin composition]

The method for producing the composition of the present invention is not particularly limited and usually can be obtained by stirring and mixing the above components. An organic solvent may be appropriately used for improving the coating property. The mixing method is not particularly limited. For example, in a room shielded with ultraviolet light, it may be sufficiently stirred and mixed at room temperature (20 or more and 40 or less) until the liquid becomes homogeneous. After stirring and mixing, filtration may be performed.

Examples of the organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol 1-monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, ethylene glycol dimethyl Ethers such as ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propyl acetate , Acetates such as butyl acetate, isobutyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate and butyl lactate, acetone, methyl ethyl ketone, Ketones such as methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, , Alcohols such as butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol and diacetone alcohol, 2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and gamma -butyrolactone.

Among them, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, cyclohexanone, 1-methoxy-2-propanol,? -Butyrolactone, and N- Lt; / RTI > and at least one member selected from the group consisting of lauridol.

The amount of the organic solvent to be added is not particularly limited, but may be an amount in which each component is uniformly dispersed or dissolved, and the composition of the present invention shows a liquid or paste phase suitable for each application. Usually, The total amount of the components other than the solvent) is 10% by mass or more and 90% by mass or less.

 [Cured film, patterned cured film]

By using the composition of the present invention, a cured film or a cured film having a pattern (patterned cured film) can be produced.

A preferred method of producing a cured film using the positive photosensitive resin composition of the present invention includes a step of coating a positive photosensitive resin composition on a substrate and drying to form a resin film and a step of heat treating the obtained resin film.

The method for producing a cured film having a pattern using the positive photosensitive resin composition of the present invention is preferably a method including the following steps:

(a) a step of forming a photosensitive resin layer made of the positive photosensitive resin composition of the present invention on a substrate,

(b) exposing the photosensitive resin layer,

(c) removing the exposed portion with a developing solution to obtain a pattern, and

(d) heating the pattern.

Hereinafter, the present method will be described.

 (a) a step of forming a photosensitive resin layer on a substrate

In this step, the composition of the present invention is coated on a substrate by spin coating using a spin coater, or a coater such as a die coater or a roll coater. Thereafter, this is dried using an oven or a hot plate, preferably at a temperature of not less than 50 but not more than 140 to remove the solvent to form a photosensitive resin layer. From the viewpoint of obtaining a coating film having a uniform film thickness, a spin coating method using a spin coater is preferable.

The substrate may be at least one selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymer, polyimide, epoxy resin, polyphenylene sulfide, and polyvinylidene chloride A substrate comprising a material is preferred. The substrate may have a single-layer structure or a multi-layer structure of two or more layers.

 (b) a step of exposing the photosensitive resin layer

Then, ultraviolet rays (i-line (wavelength: 365 nm), h-line (wavelength: 405 nm), g-line (wavelength: 436 nm), and the like were formed by using a mask aligner or a stepper with a photosensitive resin layer obtained in the above- Directly irradiating and exposing active energy lines such as lines and electron beams. The photomask may be a pattern obtained by cutting out a desired pattern.

The wavelength of the active energy ray used for exposure is preferably 190 nm or more and 500 nm or less. Further, the active energy beam irradiation amount is preferably 100mJ / cm ² or more than 3,000mJ / cm ^2.

Further, heat treatment (post-exposure baking) may be performed after exposure. By performing baking after exposure, the curing reaction caused by the acid generated from the photoacid generator can be promoted. The conditions for baking after exposure differ depending on the composition of the composition, the content of each component, the thickness of the photosensitive resin layer, and the like. For example, it is preferable that the baking is performed for not less than 70 minutes but not more than 150 minutes for not less than 1 minute and not more than 60 minutes.

 (c) a step of removing the exposed portion with a developer to obtain a pattern

Subsequently, the development can be carried out by selecting from a dipping method, a paddle method, a rotary spraying method, or the like. By the development, the uncured composition can be eluted and removed from the photosensitive resin layer to obtain a pattern. Examples of the developer include inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, organic amines such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide , And if necessary, an aqueous solution containing an appropriate amount of a water-soluble organic solvent such as methanol, ethanol or the like or a surfactant can be used. Of these, tetramethylammonium hydroxide aqueous solutions are preferred. The concentration of the tetramethylammonium hydroxide aqueous solution is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less.

After development, the pattern may be washed with pure water or the like.

 (d) a step of heating the pattern

Subsequently, the obtained pattern is cured by heating to form a patterned cured film. By heating, the cross-linking density of the composition can be increased, the remaining volatile components can be removed, and adhesion to the substrate, heat resistance and strength can be improved. As the heating apparatus, a hot oven, a hot plate, a vertical furnace, a belt conveyor, a pressure oven, or the like can be used. As the heating method, hot air, infrared rays, or heating by electromagnetic induction may be used. The heating temperature is preferably 280 or less, more preferably 120 or more and 280 or less, and still more preferably 160 or more and 250 or less. The heating time is preferably from 15 minutes to 8 hours, more preferably from 15 minutes to 4 hours. The atmosphere of the heat treatment process can be selected from the atmosphere or an inert atmosphere such as nitrogen.

The cured film or patterned cured film thus obtained includes a cured product of the composition of the present invention. The glass transition point of the cured product is preferably 200 or more and 350 or less from the viewpoints of securing the shape stability of the material during the solder reflow process and ensuring flexibility at room temperature. The glass transition point can be controlled by the composition of the polyimide resin, the composition of the positive photosensitive resin composition, and the like. The glass transition point of the cured product can be measured by the method described in the examples.

The film thickness of the cured film or the patterned cured film is preferably 5 占 퐉 or more and 20 占 퐉 or less.

The present invention relates to a method of manufacturing a semiconductor device comprising at least one kind selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymer, polyimide, epoxy resin, polyphenylene sulfide, A printed wiring board comprising a substrate including a material and a cured film having a pattern including a cured product of the composition of the present invention.

 [Electronic parts]

The electronic component according to the present invention is a cured film or a patterned cured film formed from the above-described positive photosensitive resin composition of the present invention, that is, a cured film or patterned cured film containing a cured product of the positive photosensitive resin composition of the present invention . Examples of electronic components include semiconductor devices, multilayer wiring boards, and various electronic devices.

Specifically, the cured film or the patterned cured film can be used as a surface protective film or an interlayer insulating film of an electronic part such as a semiconductor device, an interlayer insulating film of a multilayer wiring board, or the like. The electronic component according to the present invention is not particularly limited, except that it has a surface protective film, an interlayer insulating film, or the like formed using the above positive photosensitive resin composition, and can have various structures and structures.

[Example]

Hereinafter, the present invention will be described with reference to examples and comparative examples. However, the technical scope of the present invention is not limited to the following embodiments.

 (Example 1)

To a separable flask equipped with a stopper-attached water quantifying device, a thermometer, and a stirrer to which a reflux condenser was connected, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- (5 mol%) of methylene bisaminobenzoic acid, 48.4 g (45 mol%) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 67.4 g And 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25) for 20 hours. Again, 200 g of toluene was added to the reaction solution, and the mixture was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, subjected to re-precipitation and filtration, and the resulting white solid was dried under reduced pressure at 60 for 10 hours to obtain 105.0 g of a polymer compound (polyimide resin) 1.

The molecular weight of Polymer Compound 1 was measured by gel permeation chromatography (manufactured by Nippon Bunko KK, LC-2000Plus, column: KF-603x1, KF-606x1) (Mw) of 40,500, number average molecular weight (Mn) of 12400 and Mw / Mn of 3.26.

The chemical shift of ¹ H-NMR of the obtained polymer compound 1 was as follows, the content of the repeating unit having a carboxyl group was 10 mol%, and the content of the repeating unit having a phenolic hydroxyl group was 90 mol% .

@ ¹ H-NMR (300 MHz, DMSO-d6) .delta.3.17 (s, 0.2H, -CH2-), 6.6-8.7 (m, 16H, Ar-H), 10.54 (s, 1.8H, Ar-OH).

The infrared absorption spectrum of the obtained polymer compound 1 is shown in Fig. As also apparent from Fig. 1, it can be seen that the absorption peak exists in the C = O stretching vibration of 1722cm ^-2, and the stretching vibration of the OH 3080cm ^-2.

 (Example 2)

To a separable flask equipped with a stopper-attached water quantifying device, a thermometer, and a stirrer to which a reflux condenser was connected, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarbane- (2.5 mol%) of methylene bisaminobenzoic acid, 51.1 g (47.5 mol%) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, And 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25) for 20 hours. Again, 200 g of toluene was added to the reaction solution, and the mixture was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, reprecipitated and filtered, and the obtained white solid was dried under reduced pressure at 60 for 10 hours to obtain 102.5 g of a macromolecule compound (polyimide resin) 2.

The molecular weight of Polymer Compound 2 measured in the same manner as in Example 1 was 58,800 in terms of polystyrene, the number average molecular weight (Mn) was 12,400, and Mw / Mn was 4.76.

The chemical shift of ¹ H-NMR of the obtained Polymer Compound 2 was as follows, the content of the repeating unit having a carboxyl group was 5 mol%, and the content of the repeating unit having a phenolic hydroxyl group was 95 mol% Respectively.

@ ¹ H-NMR (300 MHz, DMSO-d6) .delta.3.17 (s, 0.1H, -CH2-), 6.6-8.7 (m, 16H, Ar-H), 10.54 (s, 1.9H, Ar-OH).

The infrared absorption spectrum of the obtained polymer compound 2 is shown in Fig. As also it is apparent from Figure 2, it can be seen that the absorption peak exists in the C = O stretching vibration of ^1718cm-2, and the OH stretching vibration of 3092cm ^-2.

 (Comparative Example 1)

(50 mol%) of ethylene glycol bisanhydrotrimellitate, 2,2-bis (3-amino-4-methoxyphenyl) propane dianhydride was added to a separable flask equipped with a thermometer and a stirrer, (50 mol%) and 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25) for 20 hours. Again, 200 g of toluene was added to the reaction solution, and the mixture was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, reprecipitated and filtered, and the obtained white solid was dried under reduced pressure at 60 for 10 hours to obtain 92.0 g of a polymer compound containing no recurring unit having a carboxyl group Mid resin) 3 was obtained.

Polymer Compound 3 measured in the same manner as in Example 1 had a weight average molecular weight (Mw) of 40200, a number average molecular weight (Mn) of 16,300 and Mw / Mn of 2.47 in terms of polystyrene.

 (Comparative Example 2)

To a separable flask equipped with a stopper-attached water quantifying device, a thermometer, and a stirrer to which a reflux condenser was connected, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- (50 mol%) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 450 g of N-methyl-2-pyrrolidone And the mixture was reacted at room temperature (25) for 20 hours. Again, 180 g of toluene was added to the reaction solution, which was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, reprecipitated and filtered, and the obtained white solid was dried under reduced pressure at 60 for 10 hours to obtain 91.5 g of a polymer compound containing no repeating unit having a carboxyl group Mid resin) 4 was obtained.

Polymer Compound 4, which was measured in the same manner as in Example 1, had a weight average molecular weight (Mw) of 160,000, a number average molecular weight (Mn) of 34500 and Mw / Mn of 4.64 in terms of polystyrene.

 (Comparative Example 3)

To a separable flask equipped with a stopper-attached water quantifying device, a thermometer, and a stirrer to which a reflux condenser was connected, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- (25 mol%) of methylene bisaminobenzoic acid, 26.9 g (25 mol%) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, And 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25) for 20 hours. Again, 200 g of toluene was added to the reaction solution, and the mixture was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, reprecipitated and filtered, and the resulting white solid was dried under reduced pressure at 60 ° C for 10 hours to obtain a polymer having a content of a repeating unit having 90.3 g of a carboxyl group of 50 mol% (Polyimide resin) 5 having a content of a repeating unit having a phenolic hydroxyl group of 50 mol%.

Polymer Compound 5, which was measured in the same manner as in Example 1, had a weight average molecular weight (Mw) of 58,800, a number average molecular weight (Mn) of 5,400 and Mw / Mn of 10.84 in terms of polystyrene.

 (Comparative Example 4)

To a separable flask equipped with a stopper-attached water quantifying device, a thermometer, and a stirrer to which a reflux condenser was connected, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- (50 mol%), 42.0 g (50 mol%) of methylenebisaminobenzoic acid and 540 g of N-methyl-2-pyrrolidone were added and reacted at room temperature (25) for 20 hours. Again, 200 g of toluene was added to the reaction solution, and the mixture was heated using an oil bath until the internal temperature reached 145, and the azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained was added to methanol, reprecipitation and filtration were carried out, and the resulting white solid was dried under reduced pressure at 60 for 10 hours to obtain 90.6 g of a macromolecule compound containing no phenolic hydroxyl group (polyimide resin ) 6 was obtained. However, since the resulting polymeric compound 6 was insoluble in an organic solvent, it was impossible to measure the molecular weight and prepare a positive photosensitive resin composition.

 (Preparation of composition)

Using the polymer compounds 1 to 5 synthesized above, a photosensitive resin composition was prepared according to the formulations shown in Table 1 below. Each component was stirred and mixed at 25 to 6 hours, and then filtered through a filtration membrane having a pore size of 5 mu m.

On the other hand, the following photo acid generators, crosslinking agents, novolak resins, and surfactants were used. In the following Table 1, - indicates that the component is not used.

Photoacid generator: 6,4'- (1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol 6-diazo-5,6-dihydro- 5-oxo-1-naphthalenesulfonic acid ester (a compound represented by the general formula 7 and R is a compound represented by the general formula 5), TS 200 manufactured by Toyo Synthetic Ind. Co.,

Crosslinking agent 1: Nicarac (registered trademark) MX-270 (manufactured by Sanwa Chemical Co., Ltd.)

Crosslinking agent 2: Nikarac (registered trademark) MX-390 (manufactured by Sanwa Chemical Co., Ltd.)

Novolac resin: Cresol novolak resin TR4020G (manufactured by Asahi Organic Materials Industry Co., Ltd.)

Surfactant: Surflon (registered trademark) S-141 (manufactured by AGC Seiyam Chemical Co., Ltd.)

 (Pattern formation)

The positive photosensitive resin composition obtained above was applied to a silicon wafer (Φ200mm Cu Blanket wafer made by Advantech Co., Ltd.) or a glass fiber reinforced epoxy multi-layer plate (MCL-E-700G made by Hitachi Chemical Co., Ltd.) Spin coating method. After application, drying was carried out using a hot plate at 120 for 5 minutes. After drying, a positive type photomask having a test pattern (through-hole and line-and-space pattern of 15 mu m) formed thereon was placed on the resulting coating film and irradiated with an ultraviolet ray irradiator (Maskarisliner M- Lamp, 250 W) was used to irradiate ultraviolet light having a wavelength of 365 nm at an irradiation dose at which a pattern was obtained.

As the developing solution, 2.38 mass% of tetramethylammonium hydroxide aqueous solution was used.

The coated film after irradiation with ultraviolet rays was immersed in the solution (liquid temperature 25) at the development time shown in Table 2, then washed with pure water, dried on a hot plate, and then dried in an inert oven at an oxygen concentration of 10 ppm or less , And heat treatment for 200 hours was performed to obtain a patterned cured film. The film thickness of the obtained patterned cured film was 10 占 퐉.

The ultraviolet irradiation amounts and development times of Examples 3 to 7 and Comparative Examples 5 to 7 are shown in Table 2 below.

 [evaluation]

(Reliability test (metal corrosion resistance))

In the high-temperature reliability test, the copper-plated silicon wafer obtained by the above pattern formation was allowed to stand in an oven at 150 atmosphere, and after 100 hours, after 250 hours, after 500 hours, and after 1000 hours , And the presence or absence of corrosion at the contact portion between the resist and the copper foil was observed with an optical microscope. The evaluation criteria are as follows, and it is practical if it is more than:

◎: No corrosion even when left for 500 hours or more

&Amp; cir &: corrosion occurred in 250 hours to less than 500 hours

B: Corrosion occurred in 100 hours or more and less than 250 hours

X: Corrosion occurred in less than 100 hours.

The thermal shock test was carried out in the same manner as in the above-mentioned pattern formation, except that a copper-plated silicon wafer and glass fiber-reinforced epoxy multilayer boards each having a hole pattern of 2 mm, 1 mm, 500 micron, (25) 15 minutes, 125 15 minutes, room temperature (25) 15 minutes using a cold / impact tester (TSA-101S-W made by Espec Co., Ltd.) Min was checked for the occurrence of cracks by an optical microscope in each of 100 cycles (after 100 hours), 250 cycles (after 250 hours), and 500 cycles (after 500 hours). The evaluation criteria are as follows. On the other hand, the tendency of occurrence of cracks in the copper-plated silicon wafer and the glass fiber-reinforced epoxy multilayer board was the same:

◎: Crack was not observed even when left for 500 hours

&Amp; cir &: Crack occurred in 250 hours or more and less than 500 hours

X: Cracks occurred in less than 250 hours.

 (Evaluation of peel strength (substrate adhesion)) [

A copper-plated silicon wafer substrate having a pattern of 1 mm in width and 1 mm in the same operation as the pattern formation was left in a high-temperature, high-humidity bath at 85 85% RH for 100 hours. Thereafter, the SAICAS (registered trademark) DN (manufactured by Dai-ichi Wintech Co., Ltd.) was subjected to a cutting peel test using a BN blade having a width of 1 mm, and the peel strength was determined. The peel strength is preferably 1.2 kgf / cm or more.

 (Preparation of Cured Film for Fracture Elongation, Toughness, Linear Expansion Coefficient, and Glass Transition Point Measurement)

The composition of each of the Examples and Comparative Examples was applied on a polytetrafluoroethylene (PTFE) film having a thickness of 50 탆, dried for 30 minutes on an 80 hot plate, and for 5 minutes in an oven of 130 air atmosphere, And the heat treatment for 200 hours was performed in the following inert oven. Thus, a cured film (thickness: 15 mu m) of the composition was obtained.

 (Measurement of elongation at break and toughness)

The cured film obtained above was cut into a rectangular shape with a width of 5 mm and subjected to a tensile test at a height of 20 mm and a speed of 0.1 mm / sec using a universal tester (Stable Micro System, Texture Analyzer TA.TXplus) (Elongation at break), and the area under the stress-strain curves were measured. On the other hand, the area under the stress-strain curve is defined as toughness in this specification. The breaking elongation is preferably 6% or more and 10% or less.

In addition, the toughness is preferably 6mJ / mm ³ or less than 10mJ / mm ^3.

 (Measurement of linear expansion coefficient)

The cured film obtained above was measured at a temperature raising rate of 10 / min and at a room temperature (25) to 200 using a thermomechanical analysis (TMA) apparatus (EXSTAR6000TMA / SS6100, manufactured by Seiko Instruments Inc.) The linear expansion coefficient was calculated from the TMA curve in the region of not less than 100. The coefficient of linear expansion is preferably 50 ppm or less.

 (Measurement of glass transition point)

The cured film obtained above was measured for the storage elastic modulus (E ') and the loss (E') in a temperature range from 23 to 400 using a dynamic viscoelasticity measurement (DMA) device (EXSTAR DMA7100, manufactured by Hitachi High- The elastic modulus E "was measured, and the temperature at which the loss factor defined by the ratio E" / E '= tan δ took the peak value was defined as the glass transition point.

The evaluation results of the respective properties are shown in Table 3 below.

As apparent from Tables 2 and 3, it can be seen that the positive photosensitive resin compositions of Examples 3 to 7 are excellent in balance of pattern development property, linear expansion coefficient, substrate adhesion property, toughness and metal corrosion resistance. Particularly, the positive photosensitive resin compositions of Examples 4 to 6 including a crosslinking agent had improved peel strength (substrate adhesion), and the positive photosensitive resin composition of Example 6 containing a novolac resin had a shortened developing time .

On the other hand, the positive photosensitive resin compositions of Comparative Examples 5 to 7 exhibited low resistance to metal corrosion particularly during a cold / heat shock, and the balance between pattern development property, linear expansion coefficient, substrate adhesion property, toughness and metal corrosion resistance have.

Claims (14)

And a repeating unit having a carboxyl group in an amount of 5 mol% to 20 mol% and a repeating unit having a phenolic hydroxyl group in an amount of 80 mol% to 95 mol%
Wherein the total of the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group is 100 mol%.
The method according to claim 1,
The repeating unit having a carboxyl group is a repeating unit represented by the following general formula (1)
The repeating unit having a phenolic hydroxyl group is a repeating unit represented by the following general formula (2): polyimide resin:

In the general formulas (1) and (2), R ₁ represents, independently of each other, a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms which may contain an ether bond or an ester bond, An arylene group having 6 to 20 carbon atoms which may contain an ester bond.
3. The method of claim 2,
The repeating unit having a carboxyl group represented by the general formula (1) is a repeating unit represented by the following general formula (3)
The repeating unit having a phenolic hydroxyl group represented by the general formula (2) is a repeating unit represented by the following general formula (4).

The method according to claim 1,
A polyimide resin having a weight average molecular weight of 40,000 or more.
A polyimide resin composition comprising the polyimide resin according to claim 1,
1 to 50 parts by mass of a photoacid generator based on 100 parts by mass of the polyimide resin.
6. The method of claim 5,
Wherein the photoacid generator is at least one selected from the group consisting of compounds represented by the following general formulas 5 to 10:

In the general formulas 5 to 10, each R independently represents a hydrogen atom, a group represented by the following formula 11, or a group represented by the following formula 12:

6. The method of claim 5,
Further comprising a crosslinking agent in an amount of 5 parts by mass or more and 25 parts by mass or less based on 100 parts by mass of the polyimide resin.
6. The method of claim 5,
Further comprising a novolak resin in an amount of 10 parts by mass or more and 40 parts by mass or less based on 100 parts by mass of the polyimide resin.
6. The method of claim 5,
A positive-working photosensitive resin composition, further comprising a surfactant.
6. The method of claim 5,
Propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, cyclohexanone, 1-methoxy-2-propanol, gamma -butyrolactone, and N- A positive photosensitive resin composition comprising at least one solvent.
A cured product of the positive photosensitive resin composition according to claim 5.
12. The method of claim 11,
A cured product having a glass transition point of 200 or more and 350 or less.
A cured film having a pattern comprising a cured product according to claim 11 and having a film thickness of 5 占 퐉 or more and 20 占 퐉 or less.
At least one material selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymer, polyimide, epoxy resin, polyphenylene sulfide, and polyvinylidene chloride A substrate;
A printed wiring board comprising the cured film having the pattern according to claim 13.

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