JP5492793B2 - Polyamide amic acid, polyamide imide and photosensitive resin composition - Google Patents

Description

  The present invention relates to a novel polyamide amic acid, a polyamide imide derived therefrom, and a photosensitive resin composition using the same.

  Aromatic polyamideimide resin produced from aromatic diisocyanate and trimellitic anhydride can be synthesized by a simple process that does not generate harmful impurities such as halogen during production, and it also has heat resistance, mechanical strength, electrical properties, and chemical resistance. It is known as an excellent plastic (see Patent Documents 1 to 6). A specific tetracarboxylic dianhydride is known as a raw material for aromatic polyamideimide, and this anhydride is obtained by a method of reacting with diamine using trimellitic anhydride chloride. (See Patent Document 7)

However, in the above method, chlorine is generated as an impurity at the time of manufacture, so that it cannot be used as an electric / electronic material without removing the impurity. In order to increase the purity so that it can be used for electrical and electronic materials, a purification step using water or alkali is essential, but the purification step is performed because the tetracarboxylic dianhydride is decomposed at that time. I can't. That is, a method for producing the tetracarboxylic dianhydride, which is a raw material for aromatic polyamideimide, usable for electrical and electronic materials has not been known.
Moreover, an aromatic polyamide-imide resin precursor that can be used as a resist composition is not known.

JP-A-3-157429 JP-A-5-59174 JP-A-6-322060 Japanese Patent No. 2844744 Japanese Patent No. 3097704 Japanese Patent No. 3183305 JP 2000-26445 A

  The problem to be solved by the present invention is to develop an aromatic polyamideimide resin precursor that can be used as a resist composition, and an aromatic polyamideimide resin that can be used as a resist composition in which harmful impurities such as halogens are not generated during the production. It is the development of a precursor manufacturing method.

  The gist of the present invention for solving the above problems is as follows.

[1] Condensation product (A) of diisocyanate and trimellitic anhydride selected from tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and / or ortho-tolidine diisocyanate, and diamine (B) Polyamide amic acid obtained by reacting.
[2] The polyamide amic acid according to [1], wherein the molar ratio of diisocyanate and trimellitic anhydride is 1.02: 2 to 1.5: 2.
[3] The polyamide amic acid according to [1] or [2], wherein the solid content acid value is 50 to 240 mg · KOH / g.
[4] A polyamide amic acid having a weight average molecular weight of 5,000 to 150,000 in the polyamic acid according to [1] to [3].
[5] A polyamideimide derived from the polyamideamic acid according to any one of [1] to [4].
[6] A photosensitive resin composition comprising the polyamide amic acid according to any one of [1] to [4], a compound having a photoreactive group, and a photoinitiator.

  According to the present invention, since the carboxylic acid is contained in the skeleton while having the heat resistance, mechanical strength, electrical properties, and chemical resistance that are the characteristics of the conventional polyamideimide, the binder of the photoresist and the epoxy resin Thus, it is possible to obtain a polyamideamic acid which is an aromatic polyamideimide resin precursor suitable for applications such as a curing agent.

  Hereinafter, the polyamideamic acid and polyamideimide of the present invention will be described in detail. In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

  The polyamide amic acid in the present invention has an amide group that has no possibility of becoming an imide group in the skeleton (there is no carboxyl group at the adjacent site) and can become an imide group by heating (the carboxyl group at the adjacent site). Is defined as a macromolecular organic compound that also has an amide group. Therefore, polyamideimide is obtained by heating the polyamide amic acid.

  The polyamide amic acid of the present invention is a condensate obtained by reacting a diisocyanate selected from tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and / or ortho-tolidine diisocyanate with trimellitic anhydride. It can be obtained by reacting (A) with diamine (B).

  The condensate (A) of the present invention is obtained by dissolving diisocyanate and trimellitic anhydride in a solvent and heating.

  The diisocyanate is selected from tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and / or ortho-tolidine diisocyanate. You may mix and use 2 or more types of diisocyanate from the above. Tolylene diisocyanate includes 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate. In the present invention, either 2,4-substituted product or 2,6-substituted product should be used as a single component. Alternatively, it can be used as a mixture of 2,4-substituted and 2,6-substituted. When used as a mixture, the mixing ratio is arbitrary.

  As a compound having a carboxylic acid and an acid anhydride in one molecule to be reacted with diisocyanate, trimellitic anhydride is used.

  The molar ratio of diisocyanate and trimellitic anhydride is preferably 1.02: 2 to 1.5: 2. The molar ratio of diisocyanate and trimellitic anhydride is more preferably 1.1: 2 to 1.5: 2. When the amount of diisocyanate is less than this ratio, a high molecular weight compound cannot be obtained when the produced condensate (A) is reacted with diamine. Moreover, when there are more diisocyanates than this ratio, carboxylic acid content in the polyamide amic acid obtained by making the produced | generated condensate (A) and diamine react is too small, and does not make the effect of this invention.

As a solvent used when synthesizing the condensate (A), it is sufficient if it is inactive with respect to diisocyanate and trimellitic anhydride and has solubility. N-methyl-2-pyrrolidone, N, N'-dimethylformamide, N, N'-dimethylacetamide and the like are preferably used because of their moderate solubility and boiling point in the raw material. Also good. Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene and tetramethylbenzene, aliphatic hydrocarbon solvents such as hexane, octane and decane, and mixtures thereof, petroleum ether, white Examples include gasoline and solvent naphtha.

Examples of ester solvents include alkyl acetates such as ethyl acetate, propyl acetate, and butyl acetate, cyclic esters such as γ-butyrolactone, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Mono- or polyalkylene glycol monoalkyl ether monoacetates such as triethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, adipine Polyesters of polycarboxylic acids such as dialkyl acids Kind, and the like.

Examples of ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, and triethylene glycol diethyl ether. Glycol ethers, and cyclic ethers such as tetrahydrofuran.

  Examples of the ketone solvent include acetone, methyl ethyl ketone, cyclohexanone, and isophorone.

  As a reaction condition for synthesizing the condensate (A), it is preferable to react by stirring at a reaction temperature of 80 to 150 ° C. for 1 to 8 hours. 2-4 hours are more preferable at the temperature of 100-130 degreeC.

In the synthesis reaction of the condensate (A), the carboxylic acid of trimellitic anhydride reacts preferentially with the isocyanate group, and the anhydride group remains after completion of the reaction. Therefore, by confirming the disappearance of 2275 cm ^{−1 and} the remaining 1860 cm ^{−1 in} the IR spectrum, it is judged that the reaction has proceeded appropriately.

  When the diisocyanate and trimellitic anhydride are reacted at a molar ratio specified by the present invention, a solvent solution of the condensate (A) in which all terminal groups are acid anhydrides is obtained. The polyamide amic acid of the present invention is obtained by reacting the condensate (A) with the diamine (B).

  As the diamine (B), an aromatic diamine or an aliphatic diamine can be selected depending on the purpose. In order to obtain a polyamide amic acid having a high glass transition point and a low linear expansion coefficient comparable to those of known aromatic polyamideimides, para-phenylenediamine, meta-phenylenediamine, 4,4′-diaminobenzanilide, 2 2,2'-dimethylbenzidine, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-oxydianiline, 3,4'-oxydianiline, and other diamines having a rigid skeleton are used. It ’s fine. When it is desired to obtain elongation and flexibility, 1,8-octamethylenediamine, 1,6-hexamethylenediamine, 4,7,10-trioxatridecane-1,13-diamine, 4,9-di- Oxadodecane-1,12-diamine, 1,3-bis- (4-aminophenoxy) benzene, and 1,3-bis- (3-aminophenoxy) benzene may be used. Other bisanilines such as 4,4 ′-[1,4-phenylenebis (1-methylidene)] bisaniline depending on purposes; 2,4′-diaminodiphenylmethane; 4,4′-diaminodiphenyl sulfide, 3,4 Diaminodiphenyl sulfides such as' -diaminodiphenyl sulfide; diaminodiphenyl sulfones such as 4,4'-diaminodiphenylsulfone and 3,4'-diaminodiphenylsulfone; diaminonaphthalenes such as 1,5-diaminonaphthalene; Various diamines such as 4-bis (β-amino-t-butyl) toluene and bis (p-β-amino-t-butylphenyl) ether can be used. Two or more kinds of diamines may be used in combination.

  As long as the effects of the present invention are not impaired, other tetrabasic dianhydrides other than the condensate (A) can be used together as a raw material for the polyamide amic acid. Other tetrabasic acid dianhydrides include 3,3′4,4′-biphenyltetracarboxylic acid, pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3, Oxydiphthalic dianhydrides such as 3′4,4′-oxydiphthalic dianhydride, 2,2′3,3′-oxydiphthalic dianhydride, 3,3′4,4′-benzophenone tetracarboxylic acid, 2 , 3,4,5-thiophenetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) sulfonic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride may be mentioned, and these tetrabasic dianhydrides may be used alone or in combination within a range not impairing the effects of the present invention. Can do.

  After completion of the synthesis reaction of the condensate (A), the polyamide amic acid of the present invention is obtained by adding a predetermined amount of the diamine (B) and, if necessary, other tetrabasic dianhydrides to the reaction solution and reacting them. Can do. A solvent may be added as necessary for viscosity adjustment.

  After adding diamine (B), it is made to react at the temperature of 0-100 degreeC for 0.5 to 15 hours. 1-10 hours are more preferable at 30-90 degreeC. After completion of the reaction, the preferred embodiment of the present invention is to use the polyamide amic acid of the present invention as it is as a solvent solution.

  As the amount of diamine (B), when the amount of diisocyanate is x mol, the amount of trimellitic anhydride is y mol, and the amount of other tetrabasic dianhydrides is z mol, 0.8 × (z + y− x) to 1.2 × (z + y−x) is preferable.

  The weight average molecular weight of the polyamide amic acid of the present invention is 5,000 to 150,000. 10,000 to 120,000 is more preferable, and 30,000 to 100,000 is more preferable. By keeping the weight average molecular weight within the range of the present invention, a compound having physical properties suitable for use as a binder for a photoresist is obtained. The weight average molecular weight of the polyamide amic acid of the present invention is such that the amount of diisocyanate is x mol, the amount of trimellitic anhydride is y mol, the amount of other tetrabasic dianhydrides is z mol, and the amount of diamine (B). When a mole, it can be controlled by adjusting the ratio of (x + a) :( y + z).

  The amide amic acid of the present invention has a solid content acid value (based on JIS K5601-2-1: 1999) of 50 to 240 mg · KOH / g. More preferably, it is 100-240 mg * KOH / g, More preferably, it is 120-240 mg * KOH / g. When the solid content acid value at this time is within this range, the polyamide amic acid of the present invention is soluble in alkali and is suitable for use as a photoresist. By controlling the molar ratio of diisocyanate and trimellitic anhydride and using other tetrabasic acid dianhydrides, the acid value of the polyamide amic acid of the present invention is controlled within the above range according to the purpose. Can do.

  The polyamide-imide of the present invention is obtained by applying the polyamide-amic acid solvent solution obtained by the above-described method to a substrate such as a film, a glass substrate or a copper foil and heating. As heating conditions, it is desirable to heat at 80 to 400 ° C. for 5 minutes to 8 hours. It is more preferable to heat at 200 to 375 ° C. for 30 minutes to 5 hours. A heating mode in which the heating temperature is gradually increased from a low temperature to a high temperature in order to prevent foaming accompanying the evaporation of the solvent is one of the preferred embodiments of the present invention.

After heating, a cured film having excellent heat resistance, mechanical strength, electrical properties, and chemical resistance can be obtained. As physical properties of the cured film, the linear expansion coefficient is desirably 10 to 60 [10 ⁻⁶ / ° C.]. More preferably, it is 15-45 [10 < ^-6 > / degreeC]. The cured film obtained from the polyamide amic acid of the present invention having a linear expansion coefficient in the above range has little warpage and internal stress when laminated with various substrates such as metal, glass, and silicon for semiconductors. preferable.

  Moreover, 200-400 degreeC is preferable and, as for the glass transition temperature of a cured film, More preferably, it is 250-350 degreeC. When the glass transition temperature is in the above range, it is suitable as a resin for electrical and electronic materials having excellent heat resistance, particularly solder heat resistance.

  As a preferable uniform body of the present invention, the photosensitive resin composition of the present invention obtained by mixing a predetermined amount of a compound having a photoreactive group and a photoinitiator into the polyamide amic acid of the present invention can be mentioned.

Specific examples of the compound having a photoreactive group that can be used in the present invention include so-called reactive oligomers such as radical-reactive acrylates, cation-reactive other epoxy compounds, and vinyl compounds sensitive to both. Is mentioned.

Examples of acrylates that can be used include monofunctional (meth) acrylates, polyfunctional (meth) acrylates, other epoxy acrylates, polyester acrylates, urethane acrylates, and the like.

Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate monomethyl ether, Examples include phenylethyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. As polyfunctional (meth) acrylates, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, nonanediol di (meth) acrylate, glycol di (meth) acrylate, Diethylene di (meth) acrylate, polyethylene glycol di (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate, polypropylene glycol di (meth) acrylate, adipic acid epoxy di (meth) acrylate, bisphenol ethylene oxide di (meth) acrylate, hydrogen Ε-Caprola of bisphenol ethylene oxide (meth) acrylate, bisphenol di (meth) acrylate, and neopent glycol hydroxybivalate Tone adduct di (meth) acrylate, poly (meth) acrylate, dipentaerythritol poly (meth) acrylate, reaction product of dipentaerythritol and ε-caprolactone, trimethylolpropane tri (meth) acrylate, triethylolpropane tri ( (Meth) acrylate and its ethylene oxide adduct, pentaerythritol tri (meth) acrylate and its ethylene oxide adduct, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and its ethylene oxide adduct, etc. Is mentioned.

Examples of vinyl compounds that can be used include vinyl ethers, styrenes, and other vinyl compounds. Examples of vinyl ethers include ethyl vinyl ether, propyl vinyl ether, hydroxyethyl vinyl ether, and ethylene glycol divinyl ether. Examples of styrenes include styrene, methyl styrene, and ethyl styrene. Other vinyl compounds include triallyl isocyanurate and trimethallyl isocyanurate.

Furthermore, as so-called reactive oligomers, urethane acrylate having a functional group capable of acting on active energy rays and a urethane bond in the same molecule, and similarly a functional group capable of acting on active energy rays and an ester bond in the same molecule. Examples thereof include polyester acrylate, epoxy acrylate derived from an epoxy resin, and epoxy acrylate having a functional group capable of acting on active energy rays in the same molecule, and a reactive oligomer in which these bonds are used in combination.

The cation reactive monomer is not particularly limited as long as it is generally a compound having an epoxy group. For example, glycidyl (meth) acrylate, methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4, -epoxycyclohexanecarboxylate (manufactured by Union Carbide) "Syracure UVR-6110" etc.), 3,4-epoxycyclohexylethyl-3,4-epoxycyclohexanecarboxylate, vinylcyclohexene dioxide (such as "ELR-4206" manufactured by Union Carbide), limonene dioxide (Daicel Chemical) “Celoxide 3000” manufactured by Kogyo Co., Ltd.), allyl cyclohexylene dioxide, 3,4, -epoxy-4-methylcyclohexyl-2-propylene oxide, 2- (3,4-epoxy Cycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4-epoxycyclohexyl) adipate (such as “Syracure UVR-6128” manufactured by Union Carbide), bis (3 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexyl) ether, bis (3,4-epoxycyclohexylmethyl) ether, bis (3,4-epoxycyclohexyl) diethylsiloxane and the like.

Of these, as the compound having a photoreactive group, radically curable acrylates are most preferable. In the case of the cationic type, the carboxylic acid of the polyamide amic acid and the epoxy react with each other, so that it is necessary to use a two-component mixed type.

Examples of the photoinitiator include radical photopolymerization initiators and cationic photopolymerization initiators.

Examples of the radical photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy 2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxyhexylphenyl ketone, 2-methyl-1- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholino-propan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as xanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethyl Benzophenones such as aminobenzophenone; known general radical photoinitiators such as phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide Is mentioned.

As cationic photopolymerization initiators, Lewis acid diazonium salt, Lewis acid iodonium salt, Lewis acid sulfonium salt, Lewis acid phosphonium salt, other halides, triazine initiator, borate initiator, And other photoacid generators.

Examples of the diazonium salt of Lewis acid include p-methoxyphenyldiazonium fluorophosphonate, N, N-diethylaminophenyldiazonium hexafluorophosphonate (Sun Shine SI-60L / SI-80L / SI-100L, etc., manufactured by Sanshin Chemical Industry Co., Ltd.) and the like. Examples of Lewis acid iodonium salts include diphenyliodonium hexafluorophosphonate and diphenyliodonium hexafluoroantimonate. Examples of Lewis acid sulfonium salts include triphenylsulfonium hexafluorophosphonate (Cyracure UVI-6990 manufactured by Union Carbide). ), Triphenylsulfonium hexafluoroantimonate (Cyracure UVI-697 manufactured by Union Carbide) 4) and the like, and examples of the phosphonium salt of Lewis acid include triphenylphosphonium hexafluoroantimonate.

In addition, as a triazine-based initiator having a halogen, 2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4′-methoxyphenyl) -6-triazine ( Panchim Triazine A, etc.), 2,4-trichloromethyl- (4′-methoxystyryl) -6-triazine (Panchim Triazine PMS etc.), 2,4-trichloromethyl- (pipronyl) -6-triazine ( Triazine PP manufactured by Panchim), 2,4-trichloromethyl- (4′-methoxynaphthyl) -6-triazine (Triazine B manufactured by Panchim), 2 [2 ′ (5 ″ -methylfuryl) ethylidene]- 4,6-bis (trichloro Chill) -s-triazine (manufactured by Sanwa Chemical Co., etc.), manufactured by 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine (Sanwa Chemical Co.) and the like can be used. In addition, 2,2,2-trichloro- [1-4 ′-(dimethylethyl) phenyl] ethanone (eg, Trigonal PI manufactured by AKZO), 2.2-dichloro-1--4- (phenoxyphenyl) ethanone (Sandoz) (Sandray 1000 manufactured) and α, α, α-tribromomethylphenyl sulfone (such as BMPS manufactured by Steel Manufacturing Chemical Co., Ltd.) can be used as long as there is no problem.

Examples of the borate initiator include NK-3876 and NK-3881 manufactured by Nippon Photosensitizer, and other photoacid generators include 9-phenylacridine, 2,2′-bis (o-chlorophenyl)- 4,4 ′, 5,5′-tetraphenyl-1,2-biimidazole (such as biimidazole manufactured by Kurokin Kasei Co., Ltd.), 2,2-azobis (2-amino-propane) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) V50, etc.), 2,2-azobis [2- (imidazolin-2-yl) propane] dihydrochloride (VA044 manufactured by Wako Pure Chemical Industries, Ltd.), [eta-5-2-4- (cyclopentadecyl) (1,2 , 3,4,5,6, eta)-(methylethyl) -benzene] Iron (II) hexafluorophosphonate (Irga manufactured by Ciba Geigy) cure 261), bis (y5-cyclopentadienyl) bis [2,6-difluoro-3- (1H-py-1-yl) phenyl] titanium (CGI-784 manufactured by Ciba Geigy) and the like. .

In addition, an azo initiator such as azobisisobutyronitrile, a peroxide radical initiator sensitive to heat such as benzoyl peroxide, and the like may be used in combination. Further, both radical and cationic initiators may be used in combination. One type of initiator can be used alone, or two or more types can be used in combination.

The photosensitive resin composition of the present invention contains 5 to 60% by weight of a compound having a photoreactive group and 0.5 to 7% by weight of a photoinitiator with respect to 100% by weight of polyamideamic acid in the composition. Is preferred. If necessary, other components may be contained up to about 100% by weight.

  The photosensitive resin composition of the present invention can contain various additives such as an antifoaming agent, a rheology control agent, a flame retardant, and a filler as long as the effects of the present invention are not impaired.

  Thus, although the photosensitive resin composition can be obtained, a method for forming a solder resist film or an insulating film on the surface of a metal or a metal laminate using these photosensitive resin compositions is already known. It can be easily applied using an applicator, roll coater, screen coating, bar coater or the like. The applied photosensitive resin composition becomes a photosensitive film by volatilizing the organic solvent, but drying may be performed by a known method, for example, using a dryer such as a hot air dryer, far infrared ray, near infrared ray, etc. A photosensitive film can be obtained by drying at 150 ° C. for 3 to 120 minutes. The film thickness of the photosensitive film is suitably 5 to 200 μm, preferably 15 to 100 μm. If the film thickness is less than 5 μm, the insulation reliability is poor, and if it exceeds 200 μm, the exposure sensitivity is lowered and development time is required.

  The photosensitive resin composition of the present invention is coated and dried on a colorless and transparent film such as polyethylene, polypropylene, polyester, etc., and after obtaining a photosensitive film, it is photosensitized by thermocompression bonding to the surface of a metal or metal laminate. It can also be used as a conductive film. The said photosensitive film is obtained by apply | coating by a well-known method, such as a reverse roll coater, a gravure roll coater, a comma coater, a curtain coater, and subsequent drying on the film | membrane with a film thickness of 10-100 micrometers mentioned above. Drying is preferably performed at a temperature of 50 to 120 ° C., more preferably 60 to 100 ° C. for 3 to 120 minutes with a dryer using hot air drying, far infrared rays, or near infrared rays. If the film thickness is less than 5 μm, the insulation reliability is poor, and if it exceeds 200 μm, the exposure sensitivity is lowered and development time is required.

In addition, in order to obtain a photosensitive film | membrane using the said photosensitive film, it heat-presses by the pressure of 1-5 kgf / cm < ² >, heating at 40-150 degreeC by well-known methods, such as a flat plate press and a roll press. Good to do.

  The photosensitive film thus obtained is exposed using a normal photomask. Examples of the actinic rays used at this time include ultraviolet rays, electron beams, and X-rays. Among these, ultraviolet rays are more preferable. Examples of the light source include low-pressure mercury lamps, high-pressure mercury lamps, and ultra-high pressures. Examples include mercury lamps and halogen lamps.

  When developing using a developing solution after exposure, an immersion method or a spray method can be used. As the developer, an alkaline aqueous solution such as an aqueous sodium hydroxide solution, an aqueous sodium carbonate solution, or an aqueous tetrahydroammonium hydroxide solution is used. After development, it is desirable to rinse with water or an acidic aqueous solution such as dilute hydrochloric acid or dilute sulfuric acid. The pattern obtained by development is then converted into a polyamideimide pattern by heat treatment. The heat treatment is desirably performed at 80 to 400 ° C. for 5 minutes to 8 hours. It is more preferable to heat at 200 to 375 ° C. for 30 minutes to 5 hours. In order to prevent foaming due to evaporation of the solvent, a heating mode in which the heating temperature is gradually increased from a low temperature to a high temperature is one of preferred embodiments.

Hereinafter, the present invention will be described in detail by way of representative examples, but the present invention is not limited thereto. The measurement and evaluation described in Examples and Comparative Examples were performed by the following methods.
-Measurement of acid value It measured by the method according to JISK0070: 1992.

-Molecular weight measurement It measured on GPC (gel permeation chromatography) on condition of the following. Model: TOSOH HLC-8220 GPC Column: TSKGEL Super AWM-H Eluent: 30 mmol / L lithium bromide and 1 wt% acetic acid dissolved in NMP (N-methyl-2-pyrrolidone) Outflow rate: 0.6 ml Temperature per minute: 40 ° C. detector: differential refractometer molecular weight standard: polystyrene

・ Measurement of glass transition point and thermal expansion coefficient A sample of 4mm (width) x 30μm (thickness) was measured with SMA NanoTechnology TMA / SS6100 under a load of 3g and a heating rate of 10 ° C / min. did. As the linear expansion coefficient, a value between 100 ° C. and 200 ° C. was used.

-Evaluation of the test sample in Example 7 (Table 2) Evaluation 1 (pencil hardness test): The method described in JIS-K-5405 was used.
Evaluation 2 (Adhesiveness after cross-cutting): The method described in JIS-K-5405 was used.
Evaluation 3 (solvent resistance test): The crosscut described in JIS-K-5405 was immersed in acetone at room temperature for 12 hours, and the remaining amount of the grid was counted.
Evaluation 4 (Acid Resistance Test): The crosscut described in JIS-K-5405 was immersed in a 10 wt% hydrochloric acid aqueous solution at 60 ° C. for 12 hours, and the remaining amount of the grid was counted.
Evaluation 5 (alkali resistance test): The crosscut described in JIS-K-5405 was immersed in a 10 wt% sodium hydroxide aqueous solution at 60 ° C. for 12 hours, and the remaining amount of the grid was counted.
Evaluation 6 (Peel strength): In a test sample formed on a gloss of 1 ounce rolled copper foil, the copper foil was then etched to a width of 2 mm, and the film and the 2 mm width copper foil were peeled off at an angle of 90 °. The strength was Peel strength (Kg / cm).
Evaluation 7 (solder heat resistance): A test sample formed on a 1 ounce rolled copper foil gloss was floated on molten solder held at 260 ± 5 ° C. for 5 seconds with the photosensitive film surface facing up, and the film swelled The presence or absence of cracks was confirmed. (According to JPCA-BM02)

Example 1
A stirrer, a reflux condenser, and a nitrogen introducing tube were installed in a 500 ml separable flask, and 41.44 g of ortho-tolidine diisocyanate (manufactured by Nippon Soda Co., Ltd.) and trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) in a nitrogen atmosphere. 21 g was dissolved in 210.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Thereafter, 12.15 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) was added and reacted at 80 ° C. for 6 hours to obtain 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 2
A stirrer, a reflux condenser, and a nitrogen inlet tube are installed in a 500 ml separable flask, and under a nitrogen atmosphere, 32.40 g of tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) and trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) 59. 56 g was dissolved in 210.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Then, 14.42 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) was added and reacted at 80 ° C. for 6 hours to obtain 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 3
A 500 ml separable flask was equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube. Under a nitrogen atmosphere, 40.22 g of 4,4'-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) and trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.) 51.47 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan) was dissolved in 210.0 g. After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Thereafter, 12.46 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) was added and reacted at 80 ° C. for 6 hours to obtain 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 4
A 500 ml separable flask was equipped with a stirrer, reflux condenser, and nitrogen inlet tube. Under a nitrogen atmosphere, 36.39 g of 1,5-naphthalene diisocyanate (Mitsui Chemical Polyurethane) and trimellitic anhydride (Mitsubishi Gas Chemical) ) 55.43 g was dissolved in 210.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan Ltd.). After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Thereafter, 13.42 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) was added and reacted at 80 ° C. for 6 hours to obtain 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 5
A stirrer, a reflux condenser, and a nitrogen introduction tube were installed in a 500 ml separable flask, and 41.64 g of ortho-tolidine diisocyanate (manufactured by Nippon Soda Co., Ltd.) and trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) were placed under a nitrogen atmosphere. 45 g was dissolved in 210.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Thereafter, 11.78 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) was added and reacted at 80 ° C. for 6 hours to obtain 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 6
A stirrer, a reflux condenser, and a nitrogen inlet tube were installed in a 500 ml separable flask, and under a nitrogen atmosphere, ortho-tolidine diisocyanate (Nippon Soda Co., Ltd.) 14.50 g and trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.) 17. 57 g was dissolved in 234.27 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). After reacting for 3 hours at 120 ° C., the peak loss of the IR spectrum of the reaction solution was measured 2275 cm ^-1, and was confirmed a peak residual 1860 cm ^-1.
Thereafter, 23.17 g of para-phenylenediamine (manufactured by Daishin Kasei Co., Ltd.) and 49.98 g of 3,3′4,4′-biphenyltetracarboxylic acid (manufactured by Mitsubishi Chemical Corporation) were added and reacted at 80 ° C. for 6 hours. Thus, 300 g of a 30 wt% NMP solution of the polyamide amic acid of the present invention was obtained.
The above polyamide amic acid solution is cast-coated on a releasable polyester film having a thickness of 100 μm so that the thickness after drying becomes 30 μm, and dried at 100 ° C. for 5 minutes and at 150 ° C. for 30 minutes. I was peeled off. The obtained polyamide-amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a film made of the polyamideimide of the present invention.
Table 1 shows the results of evaluation and measurement of the polyamideamic acid and polyamideimide of the present invention thus obtained.

Example 7
Using the 30 wt% NMP solution of polyamide amic acid synthesized in Example 1, blending was performed according to the following to obtain a photosensitive resin composition of the present invention.

Compounding amount (parts by weight)
Polyamide Amic Acid 30 wt% NMP Solution 333 of Example 1
KAYARAD PEG400DA 30
(Nippon Kayaku Co., Ltd.)
IRGACURE907 2
(Ciba Geigy)
KAYACURE DETX 2
(Nippon Kayaku Co., Ltd.)

After preparing said photosensitive resin composition, it apply | coated uniformly using the screen on the flexible printed wiring board by which pattern formation was carried out, and the glossy surface of 1 ounce rolled copper foil. Then, it dried at 80 degreeC for 60 minutes. The dried coating thickness was adjusted so that a photosensitive film of 20 to 25 μm was obtained on the conductor circuit and on the glossy surface of the copper foil.
Next, it exposed so that the light quantity of 500mj / cm < ² > might be irradiated to a photosensitive film | membrane with a 3kw ultrahigh pressure mercury lamp using the desired photomask. Development was performed by immersing the exposed photosensitive film in a developer adjusted to 30 ° C. with a 3.0 wt% aqueous sodium hydroxide solution for 120 seconds. The unexposed area was dissolved and a desired image was obtained. After drying at 100 ° C. for 5 minutes and 150 ° C. for 30 minutes, a test sample was prepared by heating at 300 ° C. for 60 minutes. Table 2 shows the evaluation results of the test samples.

Comparative Example 1
A stirrer, a reflux condenser, and a nitrogen inlet tube were installed in a 500 ml separable flask, and under a nitrogen atmosphere, ortho-tolidine diisocyanate (manufactured by Nippon Soda Co., Ltd.) 35.60 g, tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) 5.87 g And 33.35 g of trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 240.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). Reaction was performed at 120 ° C. for 6 hours to obtain 300 g of a 20 wt% NMP solution of polyamideimide.
From the release film, the above polyamideimide solution was cast and applied onto a release polyester film having a thickness of 100 μm so that the thickness after drying was 30 μm, and dried at 100 ° C. for 5 minutes and 150 ° C. for 30 minutes. I peeled it off. The obtained polyamide amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a comparative film made of polyamide imide.
Table 1 shows the results of evaluation and measurement of the comparative polyamideimide thus obtained.

Comparative Example 2
A stirrer, a reflux condenser, and a nitrogen inlet tube are installed in a 500 ml separable flask, and under a nitrogen atmosphere, 36.77 g of tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) and trimellitic anhydride (manufactured by Mitsubishi Gas Chemical Company) 41. 82 g was dissolved in 240.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan). Reaction was performed at 120 ° C. for 6 hours to obtain 300 g of a 20 wt% NMP solution of polyamideimide.
From the release film, the above polyamideimide solution was cast and applied onto a release polyester film having a thickness of 100 μm so that the thickness after drying was 30 μm, and dried at 100 ° C. for 5 minutes and 150 ° C. for 30 minutes. I peeled it off. The obtained polyamide amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a comparative film made of polyamide imide.
Table 1 shows the results of evaluation and measurement of the comparative polyamideimide thus obtained.

Comparative Example 3
A 500 ml separable flask was equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube. Under a nitrogen atmosphere, 41.67 g of 4,4'-diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) and trimellitic anhydride (Mitsubishi Gas Chemical Co., Ltd.) (Manufactured) 32.98 g was dissolved in 240.0 g of N-methyl-2-pyrrolidone (abbreviation NMP, manufactured by BASF Japan Ltd.). Reaction was performed at 120 ° C. for 6 hours to obtain 300 g of a 20 wt% NMP solution of polyamideimide.
From the release film, the above polyamideimide solution was cast and applied onto a release polyester film having a thickness of 100 μm so that the thickness after drying was 30 μm, and dried at 100 ° C. for 5 minutes and 150 ° C. for 30 minutes. I peeled it off. The obtained polyamide amic acid film was fixed to a metal frame and heated at 300 ° C. for 60 minutes to obtain a comparative film made of polyamide imide.
Table 1 shows the results of evaluation and measurement of the comparative polyamideimide thus obtained.

Comparative Example 4
A 20 wt% NMP solution of polyamideimide synthesized in Comparative Example 1 was used for blending according to the following to obtain a comparative resin composition.

Compounding amount (parts by weight)
20 wt% NMP solution of polyamideimide of Comparative Example 1 500
KAYARAD PEG400DA 30
(Nippon Kayaku Co., Ltd.)
IRGACURE907 2
(Ciba Geigy)
KAYACURE DETX 2
(Nippon Kayaku Co., Ltd.)

After adjusting said resin composition, it apply | coated uniformly using the screen on the flexible printed wiring board by which the pattern was formed, and the glossy surface of 1 ounce rolled copper foil. Then, it dried at 80 degreeC for 60 minutes. The dried coating thickness was adjusted so that a film of 20 to 25 μm was obtained on the conductor circuit and on the glossy surface of the copper foil.
Next, it exposed so that the light quantity of 500mj / cm < ² > might be irradiated to the said film | membrane with a 3kw ultrahigh pressure mercury lamp using the desired photomask. Development was performed by immersing the exposed film in a developer adjusted to 30 ° C. with a 3.0 wt% aqueous sodium hydroxide solution for 120 seconds. The unexposed area was not dissolved in the developer, and a desired image could not be obtained.

  As is apparent from the results in Table 1, the film obtained by heating the amide amic acid of the present invention has the same physical properties as a film obtained by heating a known amide imide. Further, as is apparent from Table 2, the photosensitive resin composition of the present invention has good alkali developability and various film properties after heat curing, and the amide amic acid of the present invention is used for resists. It can be seen that it functions as an aromatic polyamideimide resin precursor.

The polyamide amic acid of the present invention is useful as an aromatic polyamide-imide resin precursor that can be used as a resist composition. By using this polyamide amic acid, it can be used for a cover lay material of a flexible printed wiring board or a semiconductor passivation. A photosensitive resin composition suitable as a photosensitive resin composition for a film, a correlation insulating material, and a protective film material for a hard disk suspension substrate can be produced. The coating film obtained from the photosensitive resin composition is developable, and the film obtained by heat treatment after development has the same physical properties as polyamideimide in heat resistance, mechanical strength, electrical properties, chemical resistance, etc. It has the characteristic of expressing.
Further, the polyamide amic acid of the present invention is characterized in that when used as a curing agent for an epoxy resin, the cured product has excellent physical properties of a polyamideimide.

Claims (6)

Reacting a diisocyanate and trimellitic anhydride condensate (A) selected from tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and / or ortho-tolidine diisocyanate with diamine (B). Polyamide amic acid obtained by The polyamide amic acid according to claim 1, wherein the molar ratio of diisocyanate and trimellitic anhydride is 1.02: 2-1.5: 2.   The polyamide amic acid according to claim 1 or 2, wherein the solid acid value is 50 to 240 mg · KOH / g. The polyamide amic acid according to any one of claims 1 to 3, which has a weight average molecular weight of 5,000 to 150,000.   Polyamideimide derived from the polyamideamic acid according to any one of claims 1 to 4. The photosensitive resin composition containing the polyamide amic acid in any one of Claims 1-4, the compound which has a photoreactive group, and a photoinitiator.