JP2011052064A - Polyimide and method for preparing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyimide excellent in solubility and adhesion, and to provide a method for preparing the polyimide by performing direct imidization reaction of a phenylenediamine derivative and/or a salt thereof and an acid anhydride while suppressing oxidization of the phenylenediamine derivative and/or the salt thereof. <P>SOLUTION: The polyimide includes a hydrophilic group such as a phenol group, a thiol group and an amine group and is prepared by the direct imidization reaction of the phenylenediamine derivative and/or the salt thereof and the tetracarboxylic anhydride. The preparation method is also provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a polyimide obtained by using a phenylenediamine derivative and / or a salt thereof as a raw material monomer and excellent in solubility and adhesiveness, and a method for producing the same.

  The general method for producing polyimide is to mix a high-purity tetracarboxylic dianhydride and a diamine compound in equimolar amounts, and perform a low-temperature polycondensation reaction in a polar solvent to produce high molecular weight polyamic acid first. Then, a method is adopted in which a polyamic acid solution is cast and a dehydration ring closure reaction is performed by chemical treatment by heating or acetic anhydride addition. Polyimide is extremely high in thermal stability and is a polymer substance useful as an electrical insulating material, a heat-resistant coating film material, a high-performance printed circuit board material, and the like.

  In the polyimide production method, the polyamic acid produced as an intermediate is generally soluble in a solvent, but the polyamic acid solution is inferior in storage stability at room temperature and is extremely unstable to heat. Accordingly, when used as a product, it is preferably used in the form of polyimide.

  In particular, polyimides obtained by using monomers with hydrophilic groups such as phenol groups, thiol groups, and amine groups as starting materials have excellent solubility and adhesive properties, so surface protection films for semiconductor elements, interlayer insulation films, buffer coats, etc. In the field, it is expected as a material having excellent heat resistance, electrical characteristics, mechanical characteristics and the like (for example, see Non-Patent Document 1 below).

  Here, as described in Patent Document 1 below, phenylenediamine derivatives such as 4,6-diaminoresorcinol, 2,5-diamino-1,4-benzenedithiol, 1,2,4,5-tetraaminobenzene and / or It is known that the salt gives polybenzazole such as polybenzoxazole, polybenzthiazole, polybenzimidazole, etc. by polycondensation reaction with an aromatic dicarboxylic acid such as terephthalic acid.

  However, there are very few studies on a method for producing a polyimide by subjecting these phenylenediamine derivatives and / or salts thereof to a tetracarboxylic anhydride with a polycondensation reaction.

  The polyimide obtained using the above-mentioned phenylenediamine derivative and / or salt thereof as a starting material is extremely difficult to produce. One of the reasons is considered to be that the phenylenediamine derivative has a property of being easily oxidized. For example, 4,6-diaminoresorcinol is usually used in the form of a relatively stable inorganic acid salt to prevent oxidation. However, when it reacts with an acid anhydride and polymerization proceeds, There is a need to return to the 6-diaminoresorcinol form. However, 4,6-diaminoresorcinol is immediately oxidized when it is no longer in the form of an inorganic acid salt, and discolors from light pink to red and black. Therefore, it is difficult to synthesize a high molecular weight polymer. The coloration of the polymer became severe, and the physical properties of the resulting polymer, including the transparency, could be adversely affected.

Japanese Patent Laid-Open No. 11-60546

Japan Polyimide Study Group "Latest Polyimide-Basics and Applications-" Chapter 1

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyimide having excellent solubility and adhesiveness, while further suppressing oxidation of a phenylenediamine derivative and / or a salt thereof. Another object of the present invention is to provide a method for producing polyimide in which an acid anhydride and an acid anhydride are directly imidized.

That is, the polyimide according to the present invention is a phenylenediamine derivative represented by at least one of the following general formulas (1) and (2) and / or a salt thereof:
(In the general formula (1) or (2), Z represents O, S, or NH, which may be the same or different from each other) by a direct imidization reaction with a tetracarboxylic anhydride. A repeating unit obtained and represented by at least one of the following general formulas (3) and (4):
(In the general formula (3) or (4), Z represents O, S or NH, which may be the same or different from each other, and R ¹ is a residue of a tetracarboxylic anhydride.) And the light transmittance at 500 nm is 50% or more.

In addition, the method for producing a polyimide according to the present invention includes a phenylenediamine derivative represented by at least one of the following general formulas (1) and (2) and / or a salt thereof in the presence of a reducing agent:
(In the general formula (1) or (2), Z represents O, S or NH, which may be the same or different from each other) and a tetracarboxylic anhydride are directly imidized. Thus, a repeating unit represented by at least one of the following general formulas (3) and (4):
(In the general formula (3) or (4), Z represents O, S or NH, which may be the same or different from each other, and R ¹ is a residue of a tetracarboxylic anhydride.) It is characterized by manufacturing a polyimide containing.

  In the polyimide production method, in addition to the reducing agent, in the presence of a lactone polymerization catalyst, a phenylenediamine derivative represented by at least one of the general formulas (1) and (2) and / or It is preferable that the salt is directly imidized with tetracarboxylic anhydride.

  Moreover, in the said manufacturing method of a polyimide, it is preferable that the standard oxidation-reduction potential of the said reducing agent is -0.20 volt or more and 0.34 volt or less. The “standard oxidation-reduction potential” in the present invention is a value at 25 ° C. in water.

  In the polyimide production method, the lactone polymerization catalyst is preferably γ-valerolactone.

  Furthermore, the molded body according to the present invention is obtained by molding the polyimide described above.

  According to the present invention, it is possible to produce a polyimide having excellent solubility and adhesiveness by directly imidizing a phenylenediamine derivative and / or salt thereof with an acid anhydride while suppressing oxidation of the phenylenediamine derivative and / or salt thereof. it can. The polyimide according to the present invention has a particularly high light transmittance at 500 nm, and can be suitably used for applications that require transparency, such as an organic EL substrate.

  Although embodiments of the present invention will be described below, these are examples of the embodiments of the present invention, and are not limited to these contents.

In the present invention, the phenylenediamine derivative includes a phenylenediamine derivative represented by at least one of the following general formulas (1) and (2) and / or a salt thereof.
(In general formula (1) or (2), Z represents O, S or NH, which may be the same or different from each other.)

As a salt of a phenylenediamine derivative, hydrochloride of a phenylenediamine derivative is usually mentioned. When the phenylenediamine derivative represented by the general formula (1) or (2) is a hydrochloride, the following general formula (1A) or (2A):
(In general formula (1A) or (2A), Z is the same as described above, and n is equal to the number of NH ₂ groups contained in general formula (1A) or (2A)). preferable.

  In the present invention, the hydrochloride of the phenylenediamine derivative includes 4,6-diaminoresorcinol dihydrochloride, 2,5-diamino-1,4-benzenedithiol dihydrochloride, 1,2,4,5-tetraaminobenzene tetrahydrochloride. It is preferably one of hydrochlorides.

  In the present invention, the salt of the phenylenediamine derivative is not limited to the hydrochloride of the phenylenediamine derivative, but may be an inorganic acid salt such as sulfate or phosphate, or an organic acid salt such as terephthalate or acetate. May be.

  The tetracarboxylic acid anhydride used in the production of the polyimide is an aromatic or aliphatic acid anhydride and is not particularly limited with respect to the structure. Examples of preferred tetracarboxylic acid anhydrides include, for example, pyromellitic anhydride, biphenyl -3,4,3 ', 4'-tetracarboxylic dianhydride, benzophenone-3,4,3', 4'-tetracarboxylic dianhydride, oxydiphthalic dianhydride, diphenylsulfone-3,4 3 ′, 4′-tetracarboxylic dianhydride, 4,4 ′-(2,2-hexafluoroisopropylidene) diphthalic dianhydride, butane-1,2,3,4-tetracarboxylic dianhydride , Pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride , Cyclohexane-1,2,4,5-tetracarboxylic dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene- 3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohexane-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-methyl -3-Ethylcyclohex-1-ene-3- (1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1- (1,2), 3,4-tetracarboxylic acid Dianhydride, 1-propylcyclohexane-1- (2,3), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3 ) -Tetracarboxylic dianhydride, dicyclohexyl-3, , 3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propylcyclohexane-1- (2,3 ), 3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1- (2,3), 3- (2,3) -tetracarboxylic dianhydride, dicyclohexyl-3,4, 3 ′, 4′-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] octane-2, 3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride and the like. These tetracarboxylic dianhydrides may be used alone or in combination of two or more.

  In the present invention, when the polyimide is polymerized as long as the polymerization reactivity of polyimide and the required characteristics of polyimide are not impaired, aromatic diamines other than the phenylenediamine derivatives and / or salts thereof, or aliphatic diamines are used as raw material monomers. May be used as However, when the polymerization reactivity of polyimide and the required characteristics of polyimide are taken into consideration, the blending ratio of the phenylenediamine derivative and / or salt thereof and the diamine other than the phenylenediamine derivative and / or salt thereof is 50: It is preferable that it is 50-100: 0, and it is more preferable that it is 80: 20-100: 0.

  In the present invention, the partially usable aromatic diamine is not particularly limited, and examples thereof include 4,4′-bis (3-aminophenoxy) biphenyl and bis [4- (3-aminophenoxy) phenyl] ketone. Bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2 -Bis [4- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, m-aminobenzylamine P-aminobenzylamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4, '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfoxide, 3,4'-diaminodiphenyl sulfoxide, 4,4'-diaminodiphenyl sulfoxide, 3,3'-diaminodiphenyl sulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 3,4′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane.

  3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, bis [4- (4-aminophenoxy) phenyl] methane, 1,1-bis [4- (4-aminophenoxy) phenyl] ethane, 1, 2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] Propane, 1,3-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,1-bis [4- (4-amino) Phenoxy) phenyl] butane, 1,3-bis [4- (4-aminophenoxy) phenyl] butane, 1,4-bis [4- (4-aminophenoxy) phenyl] butane Emissions, 2,2-bis [4- (4-Aminofenoshi) phenyl] butane, 2,3-bis [4- (4-aminophenoxy) phenyl] butane.

  2- [4- (4-Aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3-methylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) -3- Methylphenyl] propane, 2- [4- (4-aminophenoxy) phenyl] -2- [4- (4-aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4 -Aminophenoxy) -3,5-dimethylphenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 1,4 -Bis (3-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) bif Nyl, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfoxide, bis [4- (4 -Aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, 1,3-bis [4- (4-aminophenoxy) Benzoyl] benzene, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 4,4′-bis [(3- Aminophenoxy) benzoyl] benzene, 1,1-bis [4- (3-aminophenoxy) phenyl] propane, 1,3-bis [ -(3-aminophenoxy) phenyl] propane, 3,4'-diaminodiphenyl sulfide, 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexa Fluoropropane, bis [4- (3-aminophenoxy) phenyl] methane, 1,1-bis [4- (3-aminophenoxy) phenyl] ethane, 1,2-bis [4- (3-aminophenoxy) phenyl ] Ethane, bis [4- (3-aminophenoxy) phenyl] sulfoxide, 4,4′-bis [3- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [3- (3-aminophenoxy) ) Benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4 ′ Bis [4- (4-amino-.alpha., alpha-dimethylbenzyl) phenoxy] diphenyl sulfone, bis [4- {4- (4-aminophenoxy) phenoxy} phenyl] sulfone.

  1,4-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) phenoxy-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-trifluoromethylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-fluorophenoxy) -α , Α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6-methylphenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-amino-6) -Cyanophenoxy) -α, α-dimethylbenzyl] benzene, 3,3′-diamino-4,4′-diphenoxybenzophenone, 4,4′-diamino-5,5′-diphenoxybenzopheno 3,4′-diamino-4,5′-diphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 4,4′-diamino-5-phenoxybenzophenone, 3,4′-diamino-4- Phenoxybenzophenone, 3,4'-diamino-5'-phenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 4,4'-diamino-5,5'-dibiphenoxybenzophenone, 3, 4'-diamino-4,5'-dibiphenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 4,4'-diamino-5-biphenoxybenzophenone, 3,4'-diamino-4-bi Phenoxybenzophenone, 3,4'-diamino-5'-biphenoxybenzophenone, 1,3-bis 3-amino-4-phenoxybenzoyl) benzene, 1,4-bis (3-amino-4-phenoxybenzoyl) benzene, 1,3-bis (4-amino-5-phenoxybenzoyl) benzene, 1,4-bis (4-amino-5-phenoxybenzoyl) benzene, 1,3-bis (3-amino-4-biphenoxybenzoyl) benzene, 1,4-bis (3-amino-4-biphenoxybenzoyl) benzene, 1, 3-bis (4-amino-5-biphenoxybenzoyl) benzene, 1,4-bis (4-amino-5-biphenoxybenzoyl) benzene, 2,6-bis [4- (4-amino-α, α -Dimethylbenzyl) phenoxy] benzonitrile and some or all of the hydrogen atoms on the aromatic ring in the aromatic diamine are halogen atoms, carbon number 1 3 alkyl group or alkoxyl group, cyano group, or aromatic group substituted with a halogenated alkyl group having 1 to 3 carbon atoms or alkoxyl group in which some or all of hydrogen atoms of alkyl group or alkoxyl group are substituted with halogen atoms Group diamine and the like. These diamines may be used alone or in combination of two or more.

  In the present invention, the partially usable aliphatic diamine is not particularly limited. For example, 4,4′-methylenebis (cyclohexylamine), isophoronediamine, trans-1,4-diaminocyclohexane, cis-1,4- Diaminocyclohexane, 1,4-cyclohexanebis (methylamine), 2,5-bis (aminomethyl) bicyclo [2,2,1] heptane, 2,6-bis (aminomethyl) bicyclo [2,2,1] Heptane, 3,8-bis (aminomethyl) tricyclo [5,2,1,0] decane, 1,3-diaminoadamantane, 2,2-bis (4-aminocyclohexyl) propane, 2,2-bis (4 -Aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, , 5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylene diamine, 1,8-octamethylene diamine, 1,9-like nonamethylenediamine, and the like. Two or more of these may be used in combination.

  The monomer mixing ratio (molar ratio) in producing the polyimide of the present invention is a notation method of (tetracarboxylic anhydride) / (diamine containing phenylenediamine derivative and / or salt thereof), preferably 0.800. 1.200 / 1.200 to 0.800, more preferably 0.900 to 1.100 / 1.100 to 0.900, still more preferably 0.950 to 1.150 / 1.150 to 0.950 is there.

  The polyimide of the present invention preferably has a light transmittance at 500 nm of 50% or more. When the light transmittance at 500 nm of polyimide is 50% or more, it can be suitably used for applications requiring transparency such as an organic EL substrate. When used for applications that require transparency, the light transmittance at 500 nm of polyimide is more preferably 60% or more, and particularly preferably 70% or more.

  The polyimide of the present invention preferably has an intrinsic viscosity of 0.3 to 4.0 dL / g, and preferably 0.5 to 2.5 dL / g.

  Moreover, terminal blockers, such as a dicarboxylic acid anhydride, a tricarboxylic acid anhydride, and an aniline derivative, can be used for the molecular terminal blockage of the present invention. Preferred for use in the present invention are phthalic anhydride, maleic anhydride, and ethynylaniline, and the use of maleic anhydride is more preferred. The usage-amount of terminal blocker is 0.001-1.0 molar ratio with respect to 1 mol of phenylenediamine derivatives and / or its salts.

  The reducing agent in the present invention is preferably a compound having a standard oxidation-reduction potential of −0.20 vol. Or more and 0.34 vol. Or less, more preferably 0.0 vol. Or more and 0.20 vol. Or less. If the standard oxidation-reduction potential of the reducing agent is less than −0.20 volt, side reactions of the reactants may be caused including phenylenediamine derivative hydrochloride. In addition, when the standard redox potential of the reducing agent exceeds 0.34 volt, the effect may not be exhibited because the standard redox potential of the phenylenediamine derivative hydrochloride is 0.34 volt.

Specific examples of the reducing agent that can be used in the present invention include metal salts such as TiCl ₃ , CuCl, and SnCl _2, and phosphorus or sulfur reducing oxides such as hypophosphorous acid and sodium thiosulfate. Among these, metal chlorides such as TiCl ₃ , CuCl, and SnCl ₂ are particularly preferable because they are effective even when used in small amounts. In particular, SnCl ₂ and its hydrate are most preferred because they are soluble in organic solvents and are colorless.

  In the present invention, the compounding amount of the reducing agent varies depending on the type, but it is at least 0.01% by weight (reducing agent weight / phenylenediamine derivative and / or salt weight). It is preferable to contain 0.1% by weight or more, and it is particularly preferable to contain 0.5% by weight or more. When the blending amount of the reducing agent is less than 0.01% by weight, the effect of stabilization by the reducing agent may not be sufficient, and when the blending amount of the reducing agent exceeds 30% by weight, the effect is sufficient, In addition to incurring an increase in cost, there are many unfavorable points such as polymer purification and a large amount of reducing agent mixed in the waste liquid.

  The organic solvent used when producing the polyimide of the present invention is not particularly limited as long as it dissolves both the raw material monomer, the intermediate product polyamic acid, and the product polyimide, but, for example, o- Cresol, m-cresol, p-cresol, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, Examples include sulfolane and halogenated phenols, and these solvents can be used alone or in combination. The amount of the polar organic solvent used may be an amount sufficient to dissolve the charged monomer, and is usually 1 to 50% by mass, preferably 5 to 30% by mass.

  As the lactone polymerization catalyst, γ-valerolactone, γ-butyllactone, γ-tetronic acid or the like is used. The amount of the lactone polymerization catalyst used is preferably 0.001 to 0.5% by weight based on the weight of the phenylenediamine derivative and / or salt thereof.

  In the production method of the present invention, a phenylenediamine derivative and / or a salt thereof and a tetracarboxylic acid anhydride are directly imidized. This reaction is carried out continuously for 10 minutes to 30 hours from room temperature to a temperature range of 60 to 250 ° C. with stirring and / or mixing in an organic solvent. You can move it up and down. In this case, the order of adding both reactants is not particularly limited, but it is preferable to add tetracarboxylic acid anhydrides to the solution of the phenylenediamine derivative and / or its salt.

  In the production method of the present invention, it is preferable to use a ring-closing catalyst. Specific examples of the ring-closing catalyst usable in the present invention include aromatic carboxylic acids such as benzoic acid, o-benzoic acid, m-benzoic acid and p-benzoic acid, aliphatic tertiary amines such as trimethylamine and triethylamine, Examples include heterocyclic tertiary amines such as isoquinoline, pyridine, and betapicoline. At least one amine selected from heterocyclic tertiary amines is preferably used. The content of the ring-closing catalyst is preferably (the content of the ring-closing catalyst (mole)) / (the content of the polyamic acid as the precursor (mole)) and a range of 0.01 to 10.00.

  In the production method of the present invention, a dehydrating agent may be used. Examples thereof include aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride. It is not limited. The content of the dehydrating agent is preferably in a range where the content of dehydrating agent (mole) / polyamic acid content (mole) is 0.01 to 10.00.

  In the production method of the present invention, a cosolvent may be used to azeotrope water. Examples thereof include toluene and xylene, but are not limited to these as long as water can be efficiently azeotroped.

  In the present invention, the polyimide obtained by the reaction may be reprecipitated from the reaction solution using an appropriate poor solvent. Examples of the poor solvent include acetone, methanol, ethanol, water, and the like. However, the poor solvent is not particularly limited as long as it can be efficiently re-precipitated. Moreover, although it does not specifically limit about the solvent which removes the residual reaction solvent after reprecipitation, It is preferable to use the solvent used at the time of reprecipitation.

  In this invention, it is good also as a polyimide composition which added the additive to the polyimide for the purpose of the performance improvement of a polyimide further. These additives vary depending on the purpose and are not particularly limited. Further, the addition method and the addition time are not particularly limited. Examples of the additive include known organic and inorganic fillers such as metal oxides such as silicon oxide, titanium oxide, and aluminum oxide, and phosphates such as calcium phosphate, calcium hydrogen phosphate, and calcium pyrophosphate.

  Next, an embodiment of the present invention will be described. The present invention is not limited to these examples. In addition, the evaluation item in an Example etc. measured as follows.

(1) Intrinsic viscosity (dL / g)
The intrinsic viscosity of the polyimide was measured by adjusting it to 25 ° C. after dissolving it in N, N-dimethylacetamide at a concentration of 0.04 g / 20 mL.

(2) Adhesion Create a 100 / cm ² grid on the coating film at room temperature according to the cross-cut test of JISK5400, affix the cellophane tape on top of it, and roll it down sufficiently. The adhesion was examined by the number of cells that were peeled off and remained on the substrate. The greater the number of residual cells remaining on the substrate after peeling the cellophane tape, the better the adhesion.
(3) Light transmittance Using a UV-visible light spectrophotometer (UV-2450) manufactured by SHIMAZU Japan, a polyimide film (thickness: about 10 μm) is irradiated with 500 nm light, and the light transmittance (%) at 500 nm is calculated. It was measured.

Example 1
A reaction vessel was constructed by attaching a condenser tube with a ball equipped with a trap with a silicon cock to a 100 mL separable three-necked flask equipped with a stirrer, and this reaction vessel contained 4,6-diaminoresorcinol hydrochloride (hereinafter referred to as DAR). 2,13 g), tin chloride 0.20 g, triethylamine 2.08 g, oxydiphthalic dianhydride (hereinafter referred to as ODPA) 3.10 g, γ-valerolactone 0.2 g, pyridine 0.16 g, N-methyl-2 -25 mL of pyrrolidone (hereinafter referred to as NMP) and 8 mL of toluene were added, and the mixture was stirred for 10 minutes with a stirrer at room temperature and in a nitrogen gas atmosphere.

  Next, the contents of the reaction vessel were heated to 180 ° C. and stirred for 5 hours. The reaction solution was clear and uniform. Then, it cooled to room temperature. The water generated during the reaction was excluded from the silicon cock.

Next, 20 mL of NMP is added to the obtained reaction liquid, diluted, and then poured into a large amount of methanol to separate the produced precipitate, and this is subjected to pulverization, filtration, washing and reduced-pressure drying in order. A pale yellow polymer was collected. This was measured infrared absorption spectrum of the polymer, observed characteristic absorptions distinct imide ring in the absorption band of 1,715Cm ^-1 and 1,785Cm ^-1, it is polyimide was confirmed. Furthermore, when the ¹ H-NMR spectrum of the polymer (the solvent at the time of measurement was DMSO-d6) was measured, a phenol-derived peak was confirmed in the vicinity of 10.1 ppm, and the peak derived from amide NH disappeared. The polymer was confirmed to be polyimide.

  The obtained polyimide was dissolved in an NMP solution (about 13 wt%), cast on a silicon wafer, and then heat-treated at 250 ° C. for 1 hour to produce a polymer film having a thickness of about 10 μm. Adhesion was evaluated by a cross-cut test. The evaluation results of the obtained polyimide are shown in Table 1.

Example 2
The reaction vessel used in Example 1 was charged with 2.20 g of pyromellitic anhydride and 2.45 g of 2,5-diamino-1,4-benzenedithiol dihydrochloride in equimolar amounts, 2.08 g of triethylamine, and γ-valero. A reaction solution was obtained by containing 0.2 g of lactone, 0.16 g of pyridine, 25 mL of NMP and 8 mL of toluene and passing through the same procedure as in Example 1. When this reaction solution was treated in the same manner as in Example 1, a polymer was collected, and the polymer was analyzed in the same manner as in Example 1, it was confirmed to be polyimide. The evaluation results of the obtained polyimide are shown in Table 1.

Examples 3-5
Example 1 except that the reducing agent shown in Table 1 was added instead of tin chloride in Example 1 (Example 3: TiCl ₃ addition amount 0.2 g, Example 4: CuCl addition amount 0.2 g, Example 5: H ₃ PO _The polymerization reaction was carried out under the same conditions as in Example 1 for ₃ addition amounts of 0.2 g). The formation of the target polyimide was confirmed by IR and NMR.

Comparative Example 1
The polymerization reaction was carried out in the same manner as in Example 1 except that the reducing agent tin chloride was not added. As soon as the reaction started, the polymerization system became colored and turbid and turned black after a while. After completion of the reaction, a black polymer was obtained. When this black polymer was dissolved in the NMP solvent, the solution became cloudy and a part of the polymer was insoluble.

Comparative Examples 2-3
A polymerization reaction was carried out in the same manner as in Example 1 except that the reducing agent shown in Table 1 was added instead of tin chloride in Example 1. The color of was also dark. When this polymer was dissolved in the NMP solvent, the solution became cloudy and a part of the polymer was insoluble. Further, in Comparative Example 3 using Zn, there was a risk of hydrogen generation, and the operation was very difficult.

  As described above, according to the present invention, based on a direct imidization reaction from an acid anhydride and a phenylenediamine derivative and / or a salt thereof, the molecular structure of the above general formula (3) or (4) is given. By this, the polyimide excellent in storage stability, solubility, and adhesiveness can be provided. The polyimide according to the present invention is extremely useful for the development of applications for surface protection films, interlayer insulation films, etc. of semiconductor elements such as ICs and LSIs, in particular, as electrical and electronic insulation materials in the production of semiconductor devices and the like.

Claims (6)

A phenylenediamine derivative represented by at least one of the following general formulas (1) and (2) and / or a salt thereof:




(In the general formula (1) or (2), Z represents O, S, or NH, which may be the same or different from each other) by a direct imidization reaction with a tetracarboxylic anhydride. A repeating unit obtained and represented by at least one of the following general formulas (3) and (4):



(In the general formula (3) or (4), Z represents O, S or NH, which may be the same or different from each other, and R ¹ is a residue of a tetracarboxylic anhydride.) And a light transmittance at 500 nm of 50% or more. In the presence of a reducing agent, a phenylenediamine derivative represented by at least one of the following general formulas (1) and (2) and / or a salt thereof:




(In the general formula (1) or (2), Z represents O, S or NH, which may be the same or different from each other) and a tetracarboxylic anhydride are directly imidized. By
A repeating unit represented by at least one of the following general formulas (3) and (4):



(In the general formula (3) or (4), Z represents O, S or NH, which may be the same or different from each other, and R ¹ is a residue of a tetracarboxylic anhydride.) The manufacturing method of the polyimide containing this.   In addition to the reducing agent, in the presence of a lactone polymerization catalyst, a phenylenediamine derivative represented by at least one of the general formulas (1) and (2) and / or a salt thereof, and a tetracarboxylic acid The method for producing a polyimide according to claim 2, wherein an anhydride is directly imidized.   4. The method for producing a polyimide according to claim 2, wherein a standard oxidation-reduction potential of the reducing agent is −0.20 vol. Or more and 0.34 vol. Or less.   The method for producing a polyimide according to claim 3 or 4, wherein the lactone polymerization catalyst is γ-valerolactone.   The molded object obtained by shape | molding the polyimide of Claim 1.