JP6961342B2 - Polyimide resin and positive photosensitive resin composition - Google Patents

Description

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

Generally, positive photoresists contain a type of novolak resin that is soluble in aqueous alkali and photosensitive quinonediazide that reduces this solubility in alkali. When this photoresist is irradiated with ultraviolet light, quinonediazide is photoexcited to convert its structure into a carboxylic acid, increasing its solubility in alkali in the exposed region. Therefore, a positive photoresist relief structure can be obtained by performing aqueous alkaline development. Positive photoresists are known to be advantageous in the miniaturization process as compared to negative photoresists because they exhibit inherently high image resolution.

In recent years, interlayer insulating materials such as flexible wiring boards and semiconductor integrated circuits formed from such positive photoresists have a pattern developability higher than that of conventional photoresists from the viewpoint of high density and high integration. There is a need for reliability that can be used as a permanent film after curing.

An example of a positive photoresist includes a photoacid generator as in Patent Document 1 and a solvent-soluble polyimide that exhibits positive photosensitivity in the presence of the photoacid generator. There is a polyimide composition.

International Publication No. 99/019771

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

The present invention has been made in view of the above circumstances, and is used as a base resin for a positive photosensitive resin composition having an excellent balance of pattern developability, linear expansion coefficient, substrate adhesion, toughness, and metal corrosion resistance. An object of the present invention is to provide a polyimide resin to be prepared and a positive photosensitive resin composition using the polyimide resin.

The present inventors have conducted diligent research in order to solve the above problems. As a result, they have found that the above-mentioned problems can be solved by the polyimide resin and the positive photosensitive resin composition containing the polyimide resin and the photoacid generator, and have completed the present invention.

That is, the present invention comprises a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less, a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (however, a repeating unit having a carboxyl group). And a repeating unit having a phenolic hydroxyl group (total of 100 mol%) is contained in the polyimide resin.

Further, the present invention is a positive photosensitive resin composition containing the polyimide resin and a photoacid generator of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyimide resin.

According to the present invention, a polyimide resin used as a base resin of a positive photosensitive resin composition having an excellent balance of pattern developability, coefficient of linear expansion, substrate adhesion, toughness, and metal corrosion resistance, and this polyimide resin are used. The positive photosensitive resin composition used is provided.

It is an infrared absorption spectrum of the polymer compound 1 obtained in Example 1. It is an infrared absorption spectrum of the polymer compound 2 obtained in Example 2.

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

The present invention includes a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less, a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (however, a repeating unit having a carboxyl group). It is a polyimide resin containing 100 mol% of the total with the repeating unit having a phenolic hydroxyl group.

Further, the present invention is a positive photosensitive resin composition containing the polyimide resin and a photoacid generator of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyimide resin.

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

The details of why the above effect can be obtained by the polyimide resin and the positive photosensitive resin composition of the present invention are unknown, but even if the molecular weight is low, the crosslinked structure is relatively weak due to the hydrogen bonds between the molecules of the polyimide resin. It is considered that this is due to the fact that the mechanical properties are improved by forming the resin and that the alkali developability is improved by having a carboxyl group. It should be noted that this reason is speculative, and the present invention is not limited to this reason.

Hereinafter, the constituent components of the polyimide resin of the present invention and the positive photosensitive resin composition will be described in detail. 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 includes a repeating unit having a carboxyl group of 5 mol% or more and 20 mol% or less, a repeating unit having a phenolic hydroxyl group of 80 mol% or more and 95 mol% or less (however, a repeating unit having a carboxyl group). The total of the unit and the repeating unit having a phenolic hydroxyl group is 100 mol%).

If the content of the repeating unit having a carboxyl group is less than 5 mol%, at least one of pattern developability, toughness and metal corrosion resistance is reduced. On the other hand, if it exceeds 20 mol%, the metal corrosion resistance is lowered and it becomes difficult to dissolve in a solvent or the like, so that the desired positive photosensitive resin composition may not be produced.

The content of the repeating unit having a carboxyl group is preferably 5 mol% or more and 13 mol% or less, more preferably 5 mol% or more and 10 mol% or less (however, the repeating unit having a carboxyl group and phenolic properties. The total with the repeating unit having a hydroxyl group is 100 mol%).

Further, 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 becomes difficult to dissolve in a solvent or the like, so that the desired positive photosensitive resin composition is produced. There are things you can't do. On the other hand, if it exceeds 95 mol%, the pattern developability, toughness and metal corrosion resistance are lowered.

The content of the repeating unit having a phenolic hydroxyl group is preferably 87 mol% or more and 95 mol% or less, more preferably 90 mol% or more and 95 mol% or less (however, the repeating unit having a carboxyl group and phenol. The total with the repeating unit having a sex hydroxyl group is 100 mol%).

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, IR or the like. ..

The total amount of the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group is preferably 70 mol% or more and 100 mol% or less with respect to all the repeating units in the polyimide resin of the present invention, and is preferably 80. It is more preferably mol% or more and 100 mol% or less, and 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. preferable.

In the general formula 1 and the general formula 2, R ₁ is a linear, branched, or cyclic alkylene group having 1 or more and 10 or less carbon atoms, which may independently contain an ether bond or an ester bond, respectively. It is an arylene group having 6 to 20 carbon atoms which may contain an ether bond or an ester bond.

Examples of linear, branched or cyclic alkylene groups having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, n-butylene group, 2-methylpropylene group and pentylene group. , 2,2-Dimethylpropylene group, 2-Ethylpropylene group, n-hexylene group, n-heptylene group, n-octylene group, 2-ethylhexylene group, nonylene group, decylene group, cyclopropylene group, cyclopentylene Group, cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group, cycloheptylene group, 1-ethylcyclopentylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, bicyclodecylene group, norbornylene group, cyclohexanedimethylene The group is mentioned.

Examples of the arylene group having 6 or more and 20 or less carbon atoms include a phenylene group, a biphenylene group, a naphthylene group, a terphenylene group, an anthranylene group and the like.

The above alkylene group and arylene group may contain an ether bond or an ester bond. Examples of an alkylene group or an arylene group containing an ether bond or an ester bond include a group represented by the following formula. In the following formula, 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 above general formula 1 is a repeating unit represented by the following general formula 3 and is represented by the above general formula 2. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula 4.

The repeating unit represented by the above general formula 3 is obtained by reacting 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester with methylenebisaminobenzoic acid. It has the resulting structure. The repeating units represented by the above general formula 4 are 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4-phenylene ester and 2,2-bis (3-amino). It has a structure obtained by reacting with -4-hydroxyphenyl) hexafluoropropane.

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

More specifically, tetracarboxylic dianhydride, a diamine compound containing a carboxyl group, a diamine compound containing a phenolic hydroxyl group, and optionally other diamine compounds not containing a carboxyl group and a phenolic hydroxyl group ( Hereinafter, these compounds may be referred to as monomers) to obtain a polyimide precursor, and then the obtained polyimide precursor is imidized to synthesize a polyimide resin (method A), or tetracarboxylic. Examples thereof include a method (method B) of directly synthesizing a polyimide resin from the acid dianhydride and the diamine compound.

Examples of tetracarboxylic acid dianhydrides include, for example, 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride, 2 , 2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride Anhydride, 3,3'-oxydiphthalic hydride, 4,4'-oxydiphthalic hydride, bis (3,4-dicarboxyphenyl) sulfonate dianhydride, bicyclo [2,2,2] octo- 7-En-2,3,5,6-tetracarboxylic acid dianhydride, 1,2,3,4-butanetetracarboxylic acid dianhydride, 5,5'-methylene-bis (anthranic acid), Pyromellitic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) 2,3-Dicarboxyphenyl) methane dianhydride, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 1,3-dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid- 1,4-Phenylene ester, 4- (2,5-dioxo tetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, 1,2,5,6 -Naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 2,3,5,6-pyridinetetracarboxylic acid dianhydride, 3,4,9,10-perylene Tetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane Dianhydride, 2,2-bis (4- (3,4-dicarboxybenzoyloxy) phenyl) Hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4'-bis ( 3,4-dicarboxyphenoxy) biphenyl dianhydride, cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic hydride, 2,3,5,6-cyclohexyl Examples thereof include santetracarboxylic dianhydride and 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride. These tetracarboxylic dianhydrides can be used alone or in admixture of two or more.

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

Examples of diamine compounds containing a carboxyl group include methylenebisaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,4'-(3,3'-dicarboxy). Examples thereof include diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminodiphenyl ether and the like. These carboxyl group-containing diamine compounds can be used alone or in admixture of two or more.

Among these diamine compounds containing a carboxyl group, methylenebisaminobenzoic acid is preferable.

Examples of diamine compounds containing phenolic hydroxyl groups include, for example, 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'-dihydroxydiphenylsulfone, bis (3-amino-4-hydroxyphenyl) methane, 2, 2-Bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) Hexafluoropropane, bis (4-amino-3-hydroxyphenyl) methane, 2,2-bis (4-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- Examples thereof include 2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, and 1,3-diamino-4,6-dihydroxybenzene. These diamine compounds containing phenolic hydroxyl groups can be used alone or in combination of two or more.

Among these diamine compounds containing phenolic hydroxyl groups, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane is preferable, and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoro Propane is more preferred.

From the viewpoint of improving heat resistance, chemical resistance, adjusting development performance, etc., the polyimide resin of the present invention has a carboxyl group and a phenolic hydroxyl group in addition to the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group. It may have any repeating unit that does not have. Such arbitrary repeating units can be formed from other diamine compounds that do not contain carboxyl groups and phenolic hydroxyl groups. Examples of such a diamine compound include 4,4'-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 3,3'-diamino. Diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenylsulfone, 3,4'-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) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2-di (3-amino) Phenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2-( 3-Aminophenyl) -2- (4-Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1-phenylethane, 1, 1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis (3-aminophenoxy) benzene , 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) ) Benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-) Amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1 , 4-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α) , Α-Ditrifluoromethylbenzene Benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2,6- Bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl , Bis [4- (3-aminophenoxy) phenyl] ketone, Bis [4- (4-aminophenoxy) phenyl] ketone, Bis [4- (3-aminophenoxy) phenyl] sulfide, Bis [4- (4- (4- (4- (4- (4- (4- (4- (4- (4- (4-Aminophenoxy)) phenyl] Aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-Aminophenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2 , 2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1 , 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-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy)] ) -Α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy)- α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl] Diphenyl ether, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] Diphenylsulfone, 4,4'-bis [4- (4-aminophenoxy) phenyl Noxy] Diphenylsulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenyloxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3 , 3'-diamino-4-biphenoxybenzophenone, 5-amino-2- (p-aminophenyl) benzoxazole, 2,2'-di (p-aminophenyl) -6,6'-bisbenzoxazole, 2 -(4-Aminophenyl) -6-aminobenzoxazole, N- (4-aminophenyl) -4-aminobenzamide, N, N'-bis (4-aminophenyl) terephthalamide, 4-aminophenyl-4- Aminobenzoate, 2,2'-dimethylbiphenyl-4,4'-diamine and the like can be mentioned. These other diamine compounds can be used alone or in combination of two or more.

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

For example, first, a diamine compound containing a carboxyl group and a diamine compound containing a phenolic hydroxyl group, and another diamine compound containing no carboxyl group and a phenolic hydroxyl group, which are used as needed, were dissolved in a solvent to obtain a solution. Then, under stirring, substantially the same amount of tetracarboxylic acid dianhydride as the diamine compound used was gradually added to this solution, and the stirring was continued to react to obtain a solution of the polyimide precursor. Can be done. The monomer concentration at this time is not particularly limited, but is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.

The solvent used for synthesizing the polyimide precursor is not particularly limited as long as it sufficiently dissolves the monomer and the polyimide precursor. For example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, hexamethylphosphate triamide; sulfolane, dimethylsulfoxide, dimethylsulfone, tetramethylene. Sulfur-containing solvents such as sulfone and dimethyltetramethylene sulfone; phenolic solvents such as cresol, phenol and xylenol; diglyme-based solvents such as diethylene glycol dimethyl ether (diglime), triethylene glycol dimethyl ether (triglime) and tetraglime; γ-butyrolactone, lactone-based solvents such as γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone; ketone solvents such as isophorone, cyclopentanone, cyclohexanone, 3,3,5-trimethylcyclohexanone; benzene, toluene, xylene Such as aromatic hydrocarbon solvents; other solvents such as pyridine, ethylene glycol, dioxane, tetramethylurea; and the like. These solvents can be used alone or in admixture of two or more.

The reaction temperature is not particularly limited, but is preferably −10 ° C. or higher and 80 ° C. or lower, and more preferably 0 ° C. or higher and 40 ° C. or lower. The reaction time is also not particularly limited, but is preferably 0.5 hours or more and 150 hours or less, and more preferably 3 hours or more and 24 hours or less.

The obtained solution of the polyimide precursor can be subjected to the next imidization reaction as it is or after adjusting the concentration without isolating the polyimide precursor. Further, the polyimide precursor can be isolated by dropping a solution of the polyimide precursor into a large amount of water or a poor solvent such as methanol to precipitate the polyimide precursor, and filtering, washing, and drying the polyimide precursor.

The method for imidizing the polyimide precursor is not particularly limited, and for example, a known chemical imidization method or thermal imidization method can be adopted. Among them, the chemical imidization method is more preferably used because it is not necessary to overheat and the decrease in the molecular weight of the polyimide resin can be suppressed.

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

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 used is not particularly limited, but is preferably 0.1 equivalent or more and 2 equivalents or less, and more preferably 0.2 equivalent or more and 1.5 equivalent or less with respect to the organic acid anhydride.

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

The thermal imidization method can be carried out, for example, by heating a solution of the polyimide precursor to a temperature at which a dehydration ring closure reaction occurs. When heating, either a method of raising the temperature to the maximum temperature in one step 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 those similar to those shown as the solvent for synthesizing the polyimide precursor. In the thermal imidization method, the reaction temperature is not particularly limited, but is preferably 130 ° C. or higher and 450 ° C. or lower, and more preferably 300 ° C. or higher and 400 ° C. or lower. The reaction time is also not particularly limited, but is preferably 0.1 hour or more and 24 hours or less, and more preferably 0.5 hours or more and 5 hours or less.

The reaction can be carried out in vacuum, in an inert gas such as nitrogen or argon, or in air. Toluene, xylene, or the like may be added to the reaction system in order to azeotropically distill off an organic base such as γ-picoline or water as a by-product.

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

The reaction can be carried out in vacuum, in an inert gas such as nitrogen or argon, or in air, but is preferably carried out in vacuum or in an inert gas because it can prevent coloring.

When synthesizing polyimide by method B (a method of directly synthesizing polyimide from tetracarboxylic acid dianhydride and diamine), for example, by changing the reaction conditions of the method for synthesizing a polyimide precursor in method A, tetracarboxylic acid. Polyimide can be directly synthesized from the dianhydride and the diamine compound.

Examples of the solvent used in the reaction include the same as those shown as the solvent for synthesizing the polyimide precursor. Of these, amide-based solvents and phenol-based solvents are preferable. The reaction temperature is not particularly limited, but is preferably 130 ° C. or higher and 250 ° C. or lower, and more preferably 140 ° C. or higher and 200 ° C. or lower. The reaction time is also not particularly limited, but is preferably 0.5 hours or more and 48 hours or less, and more preferably 1 hour or more and 24 hours or less. Toluene, xylene, or the like may be added to the reaction system in order to azeotropically distill off an organic base such as γ-picoline or water as a by-product.

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

The poor solvent is not particularly limited as long as it does not dissolve polyimide, but water; methanol, ethanol, because it has a high affinity with a reaction solvent and a chemical imidizing agent and can be efficiently removed by drying. Alcohol-based solvents such as n-propanol and isopropanol; ketone-based solvents such as acetone; ester-based solvents such as ethyl acetate; mixed solvents thereof; and the like are preferably used.

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 the molecular weight distribution of the polyimide resin can be controlled, for example, by changing the type and composition of the monomer, the conditions at the time of synthesis, and the like. The weight average molecular weight and the molecular weight distribution of the polyimide resin are polystyrene-equivalent values obtained by gel permeation chromatography, and more specifically, they can be measured by the method described in Examples.

(Positive Photosensitive Resin Composition)
The positive photosensitive resin composition of the present invention preferably contains the polyimide resin of the present invention and a photoacid generator of 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the polyimide resin. The polyimide resin can 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.

[Photoacid generator]
Examples of the photoacid generator used in the positive photosensitive resin composition of the present invention include quinonediazide compounds, onium salts, halogen-containing compounds and the like. Of these, quinonediazide compounds are preferable from the viewpoints of solvent solubility, storage stability, high sensitivity and the like. The photoacid generator 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, and onium selected from the group consisting of diaryliodonium salt, triarylsulfonium salt and trialkylsulfonium salt. Salt is preferred.

Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds, and trichloromethyltriazine is preferable from the viewpoint of increasing sensitivity.

As the quinone diazide compound, a naphthoquinone diazide compound (hereinafter, also referred to as “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 comprises a polyhydroxy compound of 1,2-naphthoquinone diazide-4-sulfonic acid ester and a polyhydroxy compound of 1,2-naphthoquinone diazide-5-sulfonic acid ester. It is preferably at least one compound selected from the group.

As the NQD compound, a commercially available product or a synthetic product may be used. In the case of synthesis, it is obtained by converting a naphthoquinone diazide sulfonic acid compound into a sulfonyl chloride with chlorsulfonic acid or thionyl chloride according to a conventional method, and subjecting the obtained naphthoquinone diazido sulfonyl chloride to a condensation reaction with a polyhydroxy compound. For example, a polyhydroxy compound and a predetermined amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride or 1,2-naphthoquinonediazide-4-sulfonyl chloride in a solvent such as dioxane, acetone, tetrahydrofuran, etc. The NQD compound can be obtained by reacting in the presence of a basic catalyst to carry out esterification, washing the obtained product with water, and drying it.

From the viewpoint of ensuring contrast in i-line exposure, a preferable photoacid generator is at least one selected from the group consisting of compounds represented by the following chemical formulas 5 to 10.

In the above general formulas 5 to 10, R is independently 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, and 5 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyimide resin. Is preferable. Within this range, both contrast during development and good mechanical properties can be achieved at the same time.

[Crosslinking agent]
The composition of the present invention preferably contains a cross-linking agent. By containing a cross-linking agent, mechanical strength and substrate adhesion can be improved. The cross-linking agent can be used alone or in combination of two or more. Further, as the cross-linking agent, a commercially available product or a synthetic product may be used.

As the cross-linking agent, an aromatic compound having a methylol group and / or an alkoxymethyl group, a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, an allyl compound and the like can be used.

Among these cross-linking agents, a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group is preferable from the viewpoint of chemical resistance after thermosetting.

More specifically, as a compound in which the N-position is substituted with a methylol group and / or an alkoxymethyl group, a melamine resin, a benzoguanamine resin, a glycol uryl resin, a hydroxyethylene urea resin, a urea resin, a glycol urea resin, an alkoxymethylated melamine. Examples thereof include resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycol uryl resins, and alkoxymethylated urea resins.

Alkoxymethylated melamine resins, alkoxymethylated benzoguanamine resins, alkoxymethylated glycol uryl resins, and alkoxymethylated urea resins are known methylolated melamine resins, methylolated benzoguanamine resins, or alkoxymethyl groups of methylol groups of methylolated urea resins. It can be obtained by converting to. Examples of the type of this alkoxymethyl group include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a butoxymethyl group and the like.

Examples of commercially available compounds in which the N-position is substituted with a methylol group and / or an alkoxymethyl group include, for example, Cymel® 300, 301, 303, 370, 325, 327, 701, 266, 267, 238. , 1141, 272, 202, 1156, 1158, 1123, 1170, 1174, UFR65, 300 (all manufactured by Nippon Cytec Industries Co., Ltd.), Nicarak (registered trademark) MX-270, 280, -290, Nikarak MS-11. , Nicarac MW-30, -100, -300, -390, -750 (manufactured by Sanwa Chemical Co., Ltd.) and the like.

The content of the cross-linking agent in the composition is preferably 5 parts by mass or more and 25 parts by mass or less, and more preferably 7 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyimide resin.

[Novolak resin]
The composition of the present invention preferably contains a novolak resin. The inclusion of novolak resin improves developability and resolution. As the novolak resin, a known novolak resin can be appropriately selected and used. Specifically, for example, phenol novolac resin, cresol novolac resin, t-butylphenol novolak resin, dicyclopentadiene cresol novolac resin, dicyclopentadienephenol novolak resin, xylylene-modified phenol novolac resin, tetrakisphenol novolac resin, bisphenol A novolac resin. , Poly-p-vinylphenol resin and the like.

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

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

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

The surfactant is preferably nonionic, and specifically, a fluorine-based surfactant such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, and fluorine-containing organosiloxane compound. Can be mentioned. Examples of commercially available products include Florard (registered trademark) "FC-430", "FC-431", "FC-4430" (all manufactured by Sumitomo 3M Co., Ltd.), Surflon (registered trademark) "S-141", "S-145", "KH-10", "KH-20", "KH-30", "KH-40" (all manufactured by AGC Seimi Chemical Co., Ltd.), Unidyne "DS-401", "DS- 4031 "," DS-451 "(above, manufactured by Daikin Industries, Ltd.), Megafuck (registered trademark)" F-8151 "(above, manufactured by DIC Corporation)," X-70-092 "," X-70 " −093 ”(above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

The amount of the surfactant added is preferably 0.05 parts by mass or more and 5 parts by mass or less, and more preferably 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polyimide resin.

[Other additives]
The composition of the present invention, if necessary, adds other colorants, fillers, photosensitizers, alkali dissolution accelerators, adhesion aids, defoamers, leveling agents, etc. to the extent that it does not affect the photosensitive characteristics. The agent can be added.

[Manufacturing method of positive photosensitive resin composition]
The method for producing the composition of the present invention is not particularly limited, and can usually be obtained by stirring and mixing the above components. An organic solvent may be appropriately used to improve the coatability. The mixing method is also not particularly limited. For example, the mixture may be sufficiently stirred and mixed at room temperature (20 ° C. or higher and 40 ° C. or lower) in a room shielded from ultraviolet light until the inside of the liquid becomes uniform. Filtration may be performed after stirring and mixing.

Examples of the above organic solvent include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol 1-monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl. Ethers, ethers such as ethylene glycol dibutyl ether and tetrahydrofuran, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate (propylene glycol 1-monomethyl ether 2-acetate), propyl acetate, butyl acetate, isobutyl acetate, 3-methoxybutyl Ethers such as acetate, 3-methyl-3-methoxybutyl acetate, methyl lactate, ethyl lactate, butyl lactate, acetone, methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 2 − Ketones such as heptanone, butyl alcohol, isobutyl alcohol, pentanol, 4-methyl-2-pentanol, 3-methyl-2-butanol, 3-methyl-3-methoxybutanol, diacetone alcohol and other alcohols , N-Methyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, γ-butyrolactone and the like.

Among them, from the viewpoint of solubility, it was selected from the group consisting of propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, cyclohexanone, 1-methoxy-2-propanol, γ-butyrolactone, and N-methyl-2-pyrrolidone. At least one type is preferable.

The amount of the organic solvent added is not particularly limited, but may be any amount as long as each component is uniformly dispersed or dissolved and the composition of the present invention exhibits a liquid or paste suitable for each application. It is preferable to contain the solvent in a range in which the amount of the solid content (all components other than the solvent) in the composition of the present invention is 10% by mass or more and 90% by mass.

[Cured film, pattern cured film]
Using the composition of the present invention, a cured film or a cured film having a pattern (pattern cured film) can be produced.

A preferred method for producing a cured film using the positive photosensitive resin composition of the present invention is a step of applying the positive photosensitive resin composition on a substrate and drying it to form a resin film, and forming the obtained resin film. Includes a step of heat treatment.

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) A step of exposing the photosensitive resin layer,
(C) A step of removing an exposed portion with a developing solution to obtain a pattern, and (d) a step of heating the pattern.

Hereinafter, this method will be described.

(A) Step of Forming a Photosensitive Resin Layer on a Substrate In this step, the composition of the present invention is applied onto a substrate by rotation coating using a spin coater or by a coater such as a die coater or a roll coater. Then, this is dried using an oven or a hot plate at a temperature of preferably 50 ° C. or higher and 140 ° C. or lower to remove the solvent to form a photosensitive resin layer. From the viewpoint of obtaining a coating film having a uniform film thickness, a rotary coating method using a spin coater is preferable.

The substrate is 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, polyvinylidene sulfide, and polyvinylidene chloride. A substrate containing the above is preferable. The substrate may have a single-layer structure or a multi-layer structure having two or more layers.

(B) Step of exposing the photosensitive resin layer Next, the photosensitive resin layer obtained above is exposed to ultraviolet rays (i-ray (wavelength 365 nm), h) using a mask aligner or a stepper via a photomask. Directly irradiates and exposes active energy rays such as rays (wavelength 405 nm), g-rays (wavelength 436 nm), X-rays, and electron beams. The photomask may be one in which a desired pattern is hollowed out.

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

Further, heat treatment (baking after exposure) may be performed after exposure. By baking after exposure, the curing reaction by the acid generated from the photoacid generator can be promoted. The conditions for baking after exposure vary depending on the composition of the composition, the content of each component, the thickness of the photosensitive resin layer, etc., but for example, heating at 70 ° C. or higher and 150 ° C. or lower for 1 minute or more and 60 minutes or less is possible. preferable.

(C) Step of removing the exposed portion with a developing solution to obtain a pattern Next, development can be performed by selecting from a method such as a dipping method, a paddle method, and a rotary spray method. By development, the uncured composition can be eluted and removed from the photosensitive resin layer to obtain a pattern. The developing solution includes inorganic alkalis such as sodium hydroxide, sodium carbonate, sodium silicate and aqueous ammonia, organic amines such as ethylamine, diethylamine, triethylamine and triethanolamine, tetramethylammonium hydroxide and tetrabutylammonium hydroxide. An aqueous solution of a quaternary ammonium salt or the like and, if necessary, a water-soluble organic solvent such as methanol or ethanol or an aqueous solution to which an appropriate amount of a surfactant is added can be used. Among these, an aqueous solution of tetramethylammonium hydroxide is preferable. 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) Step of heating the pattern Subsequently, the obtained pattern is heated to cure it to form a pattern cured film. By heating, the crosslink density of the composition can be increased, the remaining volatile components can be removed, and the adhesion to the substrate, heat resistance, strength and the like can be improved. As the heating device, an oven furnace, a hot plate, a vertical furnace, a belt conveyor furnace, a pressure oven, or the like can be used, and as a heating method, hot air, infrared rays, heating by electromagnetic induction, or the like may be used. The heating temperature is preferably 280 ° C. or lower, more preferably 120 ° C. or higher and 280 ° C. or lower, and further preferably 160 ° C. or higher and 250 ° C. or lower. The heating time is preferably 15 minutes or more and 8 hours or less, and more preferably 15 minutes or more and 4 hours or less. Further, the atmosphere of the heat treatment step can be selected from either the atmosphere or the inert atmosphere such as nitrogen.

The cured film or pattern cured film thus obtained contains a cured product of the composition of the present invention. The glass transition point of the cured product is preferably 200 ° C. or higher and 350 ° C. or lower from the viewpoint of ensuring the shape stability of the material during the solder reflow process and ensuring the 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. Further, the glass transition point of the cured product can be measured by the method described in Examples.

The film thickness of the cured film or the pattern cured film is preferably 5 μm or more and 20 μm or less.

The present invention is at least one material selected from the group consisting of copper, aluminum, titanium nitride, tantalum, tantalum nitride, silicon, silicon nitride, liquid crystal polymers, polyimides, epoxy resins, polyvinylidene sulfide, and polyvinylidene chloride. Provided is a printed wiring board comprising a substrate containing the above and a cured film having a pattern containing a cured product of the composition of the present invention.

[Electronic components]
The electronic component according to the present invention is a cured film or pattern cured film formed from the above-mentioned positive photosensitive resin composition of the present invention, that is, a cured film containing a cured product of the positive photosensitive resin composition of the present invention. It has a pattern cured film. Examples of electronic components include semiconductor devices, multilayer wiring boards, various electronic devices, and the like.

Specifically, the cured film or pattern cured film can be used as a surface protective film or an interlayer insulating film of an electronic component 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, etc. formed by using the positive photosensitive resin composition, and can have various configurations and structures. ..

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 examples.

(Example 1)
1,3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4- Phenylene ester 67.4 g (50 mol%), methylene bisaminobenzoic acid 4.2 g (5 mol%), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 48.4 g (45 mol%) ), And 540 g of N-methyl-2-pyrrolidone were added and reacted at room temperature (25 ° C.) for 20 hours. Further, 200 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an 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 ° C. for 10 hours to obtain 105.0 g of a polymer compound (15.0 g). Polyimide resin) 1 was obtained.

The molecular weight of the polymer compound 1 was measured by gel permeation chromatography (LC-2000Plus manufactured by JASCO Corporation, column KF-603 x 1 and KF-606 x 1 manufactured by Showa Denko Co., Ltd.) and found to be polystyrene. In terms of conversion, the weight average molecular weight (Mw) was 40500, the number average molecular weight (Mn) was 12400, and Mw / Mn = 3.26.

^{The chemical shift of 1} H-NMR of the obtained polymer compound 1 is as follows, the content of the repeating unit having a carboxyl group is 10 mol%, and the content of the repeating unit having a phenolic hydroxyl group is as follows. Was confirmed to be 90 mol%.
^{1 1} H-NMR (300 MHz, DMSO-d ₆ ) δ 3.17 (s, 0.2H, -CH _2- ), 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 apparent from FIG. 1, it can be seen that the absorption peak at 3080cm ^-2 of 1722 cm ^-2, and OH stretching vibration of C = O stretching vibration is present.

(Example 2)
1,3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic-1,4-phenylene in a separable flask equipped with a water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer. Ester 67.4 g (50 mol%), methylene bisaminobenzoic acid 2.1 g (2.5 mol%), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 51.1 g (47. 5 mol%) and 540 g of N-methyl-2-pyrrolidone were added and reacted at room temperature (25 ° C.) for 20 hours. Further, 200 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an 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 ° C. for 10 hours to obtain 102.5 g of a polymer compound (12.5 g). Polyimide resin) 2 was obtained.

The molecular weight of the polymer compound 2 measured in the same manner as in Example 1 was 58800 in terms of polystyrene, weight average molecular weight (Mw) was 58800, number average molecular weight (Mn) was 12400, and Mw / Mn = 4.76.

^{The chemical shift of 1} H-NMR of the obtained polymer compound 2 is as follows, the content of the repeating unit having a carboxyl group is 5 mol%, and the content of the repeating unit having a phenolic hydroxyl group is contained. The amount was confirmed to be 95 mol%.
^{1 1} H-NMR (300 MHz, DMSO-d ₆ ) δ 3.17 (s, 0.1H, -CH _2- ), 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 apparent from FIG. 2, it can be seen that the absorption peak at 3092cm ^-2 of 1718 cm ^-2, and OH stretching vibration of C = O stretching vibration is present.

(Comparative Example 1)
In a separable flask equipped with a water meter with a cock connected to a reflux condenser, a thermometer, and a stirrer, 63.4 g (50 mol%) of ethylene glycol bisamhydrotrimeritate, 2,2-bis ( 56.6 g (50 mol%) of 3-amino-4-hydroxyphenyl) hexafluoropropane and 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25 ° C.) for 20 hours. Further, 200 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained is added to methanol, reprecipitated and filtered, and the obtained white solid is dried under reduced pressure at 60 ° C. for 10 hours to have 92.0 g of carboxyl groups. A polymer compound (polyimide resin) 3 containing no repeating unit was obtained.

The molecular weight of the polymer compound 3 measured in the same manner as in Example 1 was 40200 in terms of polystyrene, weight average molecular weight (Mw) was 40200, number average molecular weight (Mn) was 16300, and Mw / Mn = 2.47.

(Comparative Example 2)
1,3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4- 55.6 g (50 mol%) of phenylene ester, 44.4 g (50 mol%) of 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and 450 g of N-methyl-2-pyrrolidone were added. The reaction was carried out at room temperature (25 ° C.) for 20 hours. Further, 180 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained is added to methanol, reprecipitated and filtered, and the obtained white solid is dried under reduced pressure at 60 ° C. for 10 hours to have 91.5 g of carboxyl groups. A polymer compound (polyimide resin) 4 containing no repeating unit was obtained.

The molecular weights of the polymer compound 4 measured in the same manner as in Example 1 were a weight average molecular weight (Mw) of 160000, a number average molecular weight (Mn) of 34500, and Mw / Mn = 4.64 in terms of polystyrene.

(Comparative Example 3)
1,3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4- Phenylene ester 67.4 g (50 mol%), methylene bisaminobenzoic acid 21.0 g (25 mol%), 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane 26.9 g (25 mol%) ), And 540 g of N-methyl-2-pyrrolidone were added and reacted at room temperature (25 ° C.) for 20 hours. Further, 200 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an azeotropic dehydration reaction of toluene-water was carried out for 5 hours. The reaction solution thus obtained is added to methanol, reprecipitated and filtered, and the obtained white solid is dried under reduced pressure at 60 ° C. for 10 hours to have 90.3 g of carboxyl groups. A polymer compound (polygonide resin) 5 having a repeating unit content of 50 mol% and a repeating unit having a phenolic hydroxyl group having a content of 50 mol% was obtained.

The molecular weight of the polymer compound 5 measured in the same manner as in Example 1 was 58800 in terms of polystyrene, weight average molecular weight (Mw) was 58800, number average molecular weight (Mn) was 5400, and Mw / Mn = 10.84.

(Comparative Example 4)
1,3-Dihydro-1,3-dioxo-5-isobenzofurancarboxylic acid-1,4- 67.4 g (50 mol%) of phenylene ester, 42.0 g (50 mol%) of methylenebisaminobenzoic acid, and 540 g of N-methyl-2-pyrrolidone were added, and the mixture was reacted at room temperature (25 ° C.) for 20 hours. Further, 200 g of toluene was added to the reaction solution, and the mixture was heated to an internal temperature of 145 ° C. using an oil bath, and an 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 ° C. for 10 hours to obtain 90.6 g of phenolic hydroxyl groups. A polymer compound (polyimide resin) 6 not contained was obtained. However, since the obtained polymer compound 6 was insoluble in an organic solvent, it was not possible 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 formulation shown in Table 1 below. The preparation was carried out by stirring and mixing each component at 25 ° C. for 6 hours and then filtering through a filtration membrane having a pore size of 5 μm.

The following photoacid generators, cross-linking agents, novolak resins, and surfactants were used. In addition, "-" in Table 1 below indicates that the component was not used.

Photoacid generator: 6-diazo-5,6-dihydro-5-oxo of 1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol -1-naphthalene sulfonic acid ester (compound having a structure of general formula 7 and R of general formula 5), manufactured by Toyo Synthetic Industry Co., Ltd., TS200
Crosslinking agent 1: Nicarac (registered trademark) MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
Crosslinking agent 2: Nicarac (registered trademark) MX-390 (manufactured by Sanwa Chemical Co., Ltd.)
Novolac resin: Cresol Novolac resin TR4020G (manufactured by Asahi Organic Materials Industry Co., Ltd.)
Surfactant: Surflon (registered trademark) S-141 (manufactured by AGC Seimi Chemical Co., Ltd.)

(Pattern formation)
A silicon wafer (manufactured by Advantech Toyo Co., Ltd., Φ200 mm Cu Blanket wafer) or a glass fiber reinforced epoxy multilayer plate (manufactured by Hitachi Kasei Co., Ltd., MCL) obtained by subjecting the above-mentioned positive photosensitive resin composition to a copper-plated silicon wafer having a diameter of 200 mm. -E-700G) was applied by a spin coating method. After coating, it was dried at 120 ° C. for 5 minutes using a hot plate. After drying, a positive photomask on which a test pattern (15 μm through hole and line and space pattern) is formed is placed on the obtained coating film, and an ultraviolet irradiation device (Mikasa, mask aligner M-1S type) is placed. , Ultra-high pressure mercury lamp, 250 W) was used to irradiate ultraviolet rays having a wavelength of 365 nm at an irradiation amount at which a pattern could be obtained.

A 2.38% by mass tetramethylammonium hydroxide aqueous solution was used as the developing solution. The coating film after irradiation with ultraviolet rays is immersed in this liquid (liquid temperature 25 ° C.) for the development time shown in Table 2 below, washed with pure water, dried on a hot plate, and has an oxygen concentration of 10 ppm or less. A pattern-cured film was obtained by heat-treating at 200 ° C. for 1 hour using an inert oven. The film thickness of the obtained pattern cured film was 10 μm.

The ultraviolet irradiation amount and development time 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 left in an oven in an air environment of 150 ° C., and after 100 hours, 250 hours, 500 hours, and 1000. After the end of the time, the presence or absence of corrosion of the contact portion between the resist and the copper foil was observed with an optical microscope. The evaluation criteria are as follows, and if it is △ or more, it is practical:
⊚: No corrosion was observed even after being left for 500 hours or more. ○: Corrosion occurred in 250 hours or more and less than 500 hours. Δ: Corrosion occurred in 100 hours or more and less than 250 hours. ×: Corrosion occurred in less than 100 hours. bottom.

The thermal shock test is a copper-plated silicon wafer and a glass fiber reinforced epoxy multilayer in which hole-shaped patterns having side lengths of 2 mm, 1 mm, 500 microns, and 200 microns are produced by the same method as the above pattern formation. Using a thermal shock tester (TSA-101SW manufactured by Espec Co., Ltd.) that can set each plate to -70 ° C or higher and 125 ° C or lower, -55 ° C for 15 minutes, normal temperature (25 ° C) for 15 minutes, Cracks occur after 100 cycles (after 100 hours), 250 cycles (after 250 hours), and 500 cycles (500 hours), respectively, with 125 ° C. for 15 minutes and normal temperature (25 ° C.) for 15 minutes as one cycle. The presence or absence of this was observed with an optical microscope. The evaluation criteria are as follows, and if it is ○ or higher, it is practical. The tendency of cracks to occur in the copper-plated silicon wafer and the glass fiber reinforced epoxy multilayer plate was the same:
⊚: No crack was observed even after being left for 500 hours. ◯: Crack occurred in 250 hours or more and less than 500 hours. ×: Crack occurred in less than 250 hours.

(Evaluation of peel strength (adhesion to substrate))
A copper-plated silicon wafer substrate having a 1 mm square pattern formed by the same operation as the above pattern formation was left in a high-temperature and high-humidity tank at 85 ° C. and 85% RH for 100 hours. Then, a cutting peeling test using a BN blade having a width of 1 mm was carried out at SAICAS (registered trademark) DN (manufactured by Daipla Wintes Co., Ltd.) to determine the peeling strength. The peel strength is preferably 1.2 kgf / cm or more.

(Preparation of cured film for measuring elongation at break, toughness, coefficient of linear expansion, and glass transition point)
The compositions of each Example and Comparative Example are applied onto a 50 μm thick polytetrafluoroethylene (PTFE) film and dried on a hot plate at 80 ° C. for 30 minutes and in an oven at 130 ° C. in an air environment for 5 minutes. After that, heat treatment was performed at 200 ° C. for 1 hour in an inert oven having an oxygen concentration of 10 ppm or less. As a result, a cured film (thickness 15 μm) of the composition was obtained.

(Measurement of elongation at break and toughness)
The cured film obtained above is cut into strips with a width of 5 mm, and a tensile test is performed using a universal testing machine (Texture Analyzer TA.TXplus manufactured by Table Micro System) at a chuck width of 20 mm and a speed of 0.1 mm / sec. Then, the elongation to the breaking point (breaking elongation) and the area at the bottom of the stress-strain curve were measured. The area of the lower part of the stress-strain curve is defined as toughness in this specification. The elongation at break is preferably 6% or more and 10% or less. Further, it is preferable that the toughness is 6 mJ / mm ³ or more 10 mJ / mm ³ or less.

(Measurement of coefficient of linear expansion)
The cured film obtained above was subjected to a thermomechanical analysis (TMA) apparatus (EXSTAR6000TMA / SS6100 manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min and from room temperature (25 ° C.) to 200 ° C. In two cycles, the coefficient of linear expansion was calculated from the TMA curve in the region of 50 ° C. or higher and 100 ° C. or lower in the second cycle. The coefficient of linear expansion is preferably 50 ppm / ° C. or less.

(Measurement of glass transition point)
The cured film obtained above was subjected to a temperature range of 5 ° C./min and 23 ° C. to 400 ° C. using a dynamic elastic modulus measurement (DMA) device (EXSTAR DMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.). Then, the storage elastic modulus (E') and the loss elastic modulus (E'') are measured, and the temperature at which the loss coefficient defined as the ratio E'' / E'= tan δ takes a peak value is defined as the glass transition point. Defined and measured.

The evaluation results of each physical property are shown in Table 3 below.

As is clear from Tables 2 and 3, the positive photosensitive resin compositions of Examples 3 to 7 have an excellent balance of pattern developability, coefficient of linear expansion, substrate adhesion, toughness, and metal corrosion resistance. You can see that. In particular, the positive photosensitive resin compositions of Examples 4 to 6 containing a cross-linking agent have improved peel strength (graft adhesion), and the positive photosensitive resin compositions of Example 6 containing a novolak resin have been developed. You can see that the time is shortened.

On the other hand, the positive photosensitive resin compositions of Comparative Examples 5 to 7 have low metal corrosion resistance especially at the time of thermal impact, and have pattern developability, coefficient of linear expansion, substrate adhesion, toughness, and metal corrosion resistance. It can be seen that the balance is reduced.

Claims (13)

Repeating units having a carboxyl group of 5 mol% or more and 20 mol% or less,
Repeating units having 80 mol% or more and 95 mol% or less of phenolic hydroxyl groups,
(However, the total of the repeating unit having a carboxyl group and the repeating unit having a phenolic hydroxyl group is 100 mol%)
Here, 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.

(In the general formula 1 and the general formula 2, R ₁ is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, which may independently contain an ether bond or an ester bond. Alternatively, it is an arylene group having 6 to 20 carbon atoms which may contain an ether bond or an ester bond).
Including polyimide resin. The repeating unit having a carboxyl group represented by the above general formula 1 is a repeating unit represented by the following general formula 3.
The polyimide resin according to claim 1, wherein 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 polyimide resin according to claim 1 or 2, wherein the weight average molecular weight is 40,000 or more. The polyimide resin according to any one of claims 1 to 3 and
With respect to 100 parts by mass of the polyimide resin, 1 part by mass or more and 50 parts by mass or less of a photoacid generator
A positive photosensitive resin composition containing. The positive photosensitive resin composition according to claim 4, wherein the photoacid generator is at least one selected from the group consisting of compounds represented by the following general chemical formulas 5 to 10.

In the above general formulas 5 to 10, R is independently a hydrogen atom, a group represented by the following general formula 11, or a group represented by the following general formula 12.

The positive photosensitive resin composition according to claim 4 or 5, further comprising a cross-linking agent of 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the polyimide resin. The positive photosensitive resin composition according to any one of claims 4 to 6, further comprising a novolak resin of 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyimide resin. The positive photosensitive resin composition according to any one of claims 4 to 7, further comprising a surfactant. Contains at least one solvent selected from the group consisting of propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, cyclohexanone, 1-methoxy-2-propanol, γ-butyrolactone, and N-methyl-2-pyrrolidone. , The positive photosensitive resin composition according to any one of claims 4 to 8. A cured product of the positive photosensitive resin composition according to any one of claims 4 to 9. The cured product according to claim 10, wherein the glass transition point is 200 ° C. or higher and 350 ° C. or lower. A cured film having a pattern, which comprises the cured product according to claim 10 or 11, and has a film thickness of 5 μm or more and 20 μm or less. With a substrate containing 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 cured film having the pattern according to claim 12,
A printed wiring board.

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