WO1993014148A1 - Polyimide resin compositions and processes for their production - Google Patents

Abstract

The following polyimide resin compositions (A) and (B) and processes for their production are disclosed. A: A polyimide resin composition which comprises a solution in an organic solvent of at least one polyimide having repeating units represented by general formula (I) (wherein Z represents -S-, (a), (b) or (c), wherein X represents -O-, -S- or (d), and Y represents a single bond or a divalent group selected from among -O-, -S-, -SO2-, (e) and -CO-, and R?1 and R2¿, which may be the same or different, each represents a hydrogen atom, a halogen atom or an optionally halogen-substituted lower alkyl group) and having an intrinsic viscosity of about 0.3 to 5.0 dl/g. B: A polyamide resin composition prepared by adding a silane coupling agent to the resin composition A.

Description

 Specification

 Polyimide resin composition and method for producing the same

 Technical field

 The present invention relates to a novel polyimide resin composition and a method for producing the same.

 Background art

 Aromatic polyimides have high heat resistance and good mechanical and electrical properties, but on the other hand, they do not generally melt and are insoluble in ordinary organic solvents, which makes them difficult to mold. have.

 Conventionally, in order to solve this problem, aromatic tetraimide dianhydride, which is a raw material of aromatic polyimide, and aromatic diamine are reacted in a polar organic solvent to obtain a polyamide acid. In general, a method of synthesizing a soluble intermediate such as a compound, giving a shape at this stage, and dehydrating and ring-closing under high temperature to obtain a polyimide is generally performed. However, in this method, the stability of the intermediate is poor, and the viscosity changes or becomes cloudy when left at room temperature. Since the dehydration reaction is performed after molding, defects such as voids and pinholes are likely to occur, and smooth and uniform molding is performed. The disadvantage is that it is difficult to get a body.

Therefore, there is a demand for the development of an organic solvent-soluble polyimide which can be easily formed into a film or the like and does not have the above-mentioned disadvantages. Various proposals have been made so far. For example, a method has been proposed in which a diester having lower reactivity with an aromatic diamine component than dianhydride is used as an aromatic tetracarboxylic acid component and the solvent is solubilized as a polyimide having a low polymerization degree. (Japanese Patent Laid-Open No. 61-83232). However, this polyimide has the drawback that its inherent heat resistance and mechanical properties, which are inherent properties of polyimide, are reduced due to its low molecular weight.o

 In addition, the use of a polynuclear m, m 'diamino compound in which a terminal amino group is bonded to the amino group as an aromatic diamine component disrupts the symmetry of the polymer structure and the regularity of the repeating unit, and the solvent A polyimide provided with solubility is known (Japanese Patent Publication No. 52-31019). However, this polyimide has drawbacks such as a decrease in heat resistance, that is, a thermal decomposition temperature and a glass transition temperature due to the non-uniformity of the polymer structure. In addition, the m, m 'diamino compound used has a disadvantage that it is extremely difficult to synthesize and has poor reactivity as compared with the P, p' diamino compound generally used as an aromatic diamine component. are doing.

Further, as a method for producing a soluble polyamide using a P, P 'diamino compound, a method using two or more kinds of aromatic tetracarboxylic acid components having different skeleton structures in combination is used. (Japanese Patent Application Laid-Open Nos. 61-28526 and 61-51033), however, it is difficult to produce the same material because the polymer structure is not uniform. There are disadvantages in that the quality becomes unstable and that the inherent toughness and electrical properties of polyimide cannot be sufficiently exhibited.

 As described above, all of the conventionally known methods for solubilizing polyimide in an organic solvent have a defect that the inherent excellent properties of aromatic polyimide are impaired due to imparting solvent solubility.

 Disclosure of the invention

 An object of the present invention is to provide a novel organic solvent solution polyimide resin composition and a method for producing the same.

 Another object of the present invention is to provide a novel polymer which is easy to mold because it is an organic solvent solution after sufficiently exhibiting the inherent properties of aromatic polyimide such as heat resistance, mechanical properties, and electrical properties. To provide a polyimide resin composition and a method for producing the same o

 Still another object of the present invention is to provide a novel organic solvent solution polyimide resin composition having excellent heat resistance, mechanical properties, electrical properties, etc., and also excellent adhesion to a substrate, It is to provide a manufacturing method.

These and other objects of the invention are set forth below. Will be revealed.

 The present invention provides the following polyimide resin composition and a method for producing the same.

A General formula

/ Ν' ( I )

/ Ν '(I)

[Where Z is

 C H

X X

CH ₃ CH ₃

 Is shown. Where X is one 0-, one S- or

R ¹

 One C-one, Y is a single bond or one 0-, one S-,

R ²

R ¹

-S 0 ₂ 1 or 1 C 1 or 1 C 0—

R ²

This shows the group of ffi. R ¹ and R ² may be substituted with a hydrogen atom, a halogen atom or a halogen atom It represents a lower alkyl group, which may be the same or different. ]

 Characterized in that at least one kind of polyimide having a repeating unit represented by the formula and having an intrinsic viscosity ni nh of about 0.3 to 5.0 dίg is dissolved in an organic solvent. Polyimide resin composition.

 B. A polyimide resin composition characterized by further adding a silane coupling agent to the composition.

C diphenylsulfone 1,3 ', 4,4'-tetracarboxylic dianhydride and general formula

Wherein Z is the same as above. ]

 Reacting with an aromatic diamine represented by the formula (1) in the presence of an organic solvent to produce a polyimide, or separating the produced polyimide and then re-dissolving it in an organic solvent. A method for producing a resin composition.

 D The method for producing a polyimide resin composition according to the above method, further comprising adding a silane coupling agent after completion of the polyimide generation reaction.

The inventor of the present invention has been keen to solve the above-mentioned drawbacks of the prior art. As a result of repeated research, we found the following new facts.

(1) Diphenylsulfone-1,3 ', 4,4'-tetracarboxylic acid dihydrate alone is used as the aromatic tetracarboxylic acid component, and the above is used as the aromatic diamine component. Polyimides obtained using specific p, p 'diamino compounds are soluble in organic solvents and have high intrinsic viscosity (ie, high molecular weight) and high uniformity of polymer structure. Excellent heat resistance, mechanical properties, electrical properties, etc.

 (2) Therefore, according to the above-mentioned solution of polyimide in an organic solvent, it is possible to easily form a molded body which can sufficiently exhibit the excellent characteristics inherent to polyimide.

 (3) In this case, an aromatic tetracarboxylic acid component other than the above, for example, benzophenone-1,3,3,4,4'-tetracarboxylic dianhydride メ pyromellitic dianhydride is used. However, it does not become soluble in organic solvents.

 (4) By adding a silane coupling agent to the above organic solvent solution of polyimide, excellent adhesion to the substrate can be imparted without deteriorating the heat resistance of the polyimide.

(5) Both the above tetracarboxylic dianhydride and the above P, p 'diamino compounds used as raw materials are synthesized. It is easy and cost-effective.

 The present invention has been completed based on these new findings.

 The polyimide resin composition of the above A can be produced by the production method of the above C. More specifically, it can be produced as follows.

 As the aromatic tetracarboxylic acid component, diphenylsulfone-1,3 ', 4,4'-tetracarboxylic dianhydride (hereinafter referred to as “DSTA”) is used alone, but it is used as a raw material. May contain a small amount of free carboxylic acid. In addition, as long as the intended effects of the present invention can be obtained, the use of other aromatic tetracarboxylic acid components is not prevented.

As the aromatic diamine component, a p, p'-diamino compound represented by the general formula (Π) is used. Preferred examples are 4,4'-diamino diphenyl sulfide and 2,2-bis [4- (p-amino phenoxy) phenyl] prono III. 2,2-bis [3- (p-aminophenol) phenyl] propane, 2,2-bis [4-1 (p-aminophenylthioether) phenyl] propane, 2,2- Bis [3- (p-aminophenylthioether) phenyl] prono. , 4, 4 '-bis (p-ami Nophenoxy) diphenylsulfone, 3,3'-bis (P-aminophenol) diphenylsulfone, 3,4'-bis (p-aminophenol) diphenylsulfone, 4,4'-bis (p —Aminophenylthioether) diphenylsulfone, 3,3′-bis (p-aminophenolthioether) diphenylsulfone, 3,4′-bis (p-aminophenol) Thioether) diphenylsulfone, 4,4'-bis (p-aminophenol) diphenylether, 3,3'-bis (p-aminophenol) diphenylether, 3,4'-bis (p-) (A-aminophenoxy) diphenyl ether, 4,4'-bis (p-aminophenol) diphenyl sulfide, 3, 3'-bis (p-aminophenol) diphenyl sulfide, 3, 4 'one screw (p Amino phenoxy) diphenyl sulfide, 4,4'-bis (p-amino phenyl thioether) diphenyl sulfide, 3,3'-bis (p-amino phenyl thioether) di Phenyl sulfide, 3,4'-bis (p-aminophenylthioether) diphenyl sulfide, 4,4'-bis (p-aminophenylthioether) diphenyl ether, 3,3 ' Screw

(p-aminophenylthioether) diphenylether, 3,4'-bis (p-aminophenylthioether) Diphenyl ether, 4,4'-bis (p-aminophenol) benzophenone, 3,3'-bis (p-aminophenol) benzophenone, 3,4'-bis (p-amino) Benzophenone, benzophenone, 4,4'-bis (p-aminophenolthioether) benzophenone, 3,3'-bis (p-aminophenolthioether) benzophenone, 3, 4'-bis (p-aminophenol) benzophenone, 4,4'-bis (p-aminophenol) diphenyl, 3,3'-bis (p-aminophenol) diphenyl , 4,4'-bis (p-aminophenylthioether) diphenyl, 3,3'-bis (p-aminophenylthioether) diphenyl, 1,4-bis (p-amino Phenyl thioether) benzene, 1, 3-bis (p-a Minophenylthioether) benzene, 4,4'-one (p-phenylenediisopropylidene) dianine, 4,4'-one (m-phenylenediisopropyl)

\ 2,2-Bi ^^ Mixi) Hue, Le] Hehe Saffle Lerov. Lono ,. ^ /

Ride: ^ Gianlin can be mentioned.

 As the aromatic diamine component, it is most preferable to use one of the above P, P'-diamino compounds alone from the viewpoint of homogeneity of the polymer structure, but if necessary, Terror

Two or more kinds can be used as a mixture. As long as the effects of the present invention can be obtained, other aromatic dia It does not prevent the combination of min components.

 The production reaction of polyimide is usually carried out by a two-step reaction of a synthesis reaction of polyamic acid, which is an intermediate, and a reaction of dehydrating and cyclizing this to form polyimide.

 That is, first, DSTA and an aromatic diamine of the general formula (H) are reacted in an organic solvent to synthesize polyamic acid.

 The molar ratio between DSTA and the aromatic diamin is preferably about 0.7 to 1.3 in order to obtain a high molecular weight polyimide, and particularly preferably 0.95 to 1.05. Range is preferred.

 In the production of polyamic acid, the reaction temperature is generally about 0 to 120, preferably 5 to 80. C, and the reaction time is usually about 0.5 to 50 hours, depending on the diamines, solvents and other conditions used.

Further, as the organic solvent used in this reaction, it is preferable to use a non-proton-based polar solvent or a phenol-based solvent that can dissolve the polyimide to be formed later. Such organic solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N, N— Non-protonic polar solvents such as dimethyl acetate, dimethyl sulfoxide, tetramethyl urea, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoramide; Examples include phenol solvents such as phenol, cresol, dimethylphenol, chlorophenol, and bromphenol.

 By using a non-proton polar solvent or a phenol solvent as the above reaction solvent, the reaction mixture does not gel even if some polyimide is formed in the synthesis of polyamic acid. Further, after the synthesis of the polyamic acid, the polyimide resin composition of the present invention can be directly subjected to an imidization reaction as it is, and can be directly used as the polyimide resin composition of the present invention after the imidization reaction. Very suitable.

In addition, in the polyamic acid synthesis reaction, other than the above-mentioned organic solvents, although having poor solubility, ketones, esters, lactones, ethers, and sesquisolves which are common organic solvents are used. , Halogenated hydrocarbons, hydrocarbons and the like can also be used. Specifically, for example, acetone, methylethylketone, methylisobutylketone, cyclohexanone, acetophenone, methyl acetate, ethyl acetate, butyl acetate, getyl oxalate, getyl malonate , Avetylolactone, getyl ether, ethylene glycol dimethyl ether, diethylene glycol cornole dimethyl ether, tetrahydrofuran, diglyme, methyl cellosolve, ethylene glycol monomethyl ether, dichloromethane Lumetane, 1,2-dichloronorethane, 1,4-dichlorobutane, trichloronorethane, chloronorbenzene, dichloronorbenzene, hexane, heptane, octane, benzene, toluene, xylene, etc. Can be used. However, in this case, the polyamic acid is recovered by a conventional method, purified if necessary, then dissolved again in a non-proton polar solvent or a phenol solvent, and the imidization reaction is performed. It is desirable.

 The organic solvent solution of the polyamic acid obtained in the above polyamic acid synthesis reaction may be used as it is or after recovering boriamic acid from the organic solvent solution by a conventional method, purifying as necessary, and then re-using the above-mentioned non-protic acid. It can be used in an imidization reaction after being dissolved in a ton-based polar solvent or a phenol-based solvent.

 The organic solvent in the above polyamic acid synthesis reaction and the subsequent imidization reaction may be used alone at any stage, or may be used as a mixture of two or more.

Usually, the imidization reaction can be suitably performed using a solution of a polyamic acid in a nonproton-based polar solvent or a phenol-based solvent. The reaction temperature is usually about 60 to 250 ° C, preferably 100 to 200 ° C. (: It is not possible to obtain an economical reaction rate below 60 ° C, and at 250 ° C or higher. In such a case, coloring of the reaction system and side reactions are disadvantageous.

 From the viewpoint of efficiently removing water by-produced during the imidization reaction to promote the reaction, a solvent azeotropic with water and Z or a dehydrating agent may be added. Such solvents include benzene, toluene, xylene, ethylbenzene, hexane, heptane, octane, nonane, decane, cyclohexane and the like, and dehydrating agents such as pentoxide, acetic anhydride, pyridine and acetic anhydride. Etc. are exemplified.

 The reaction time of the imidization reaction varies depending on various conditions such as the type of polyamic acid and the solvent, but is usually about 0.5 to 50 hours. Further, the concentration of the polyamic acid in the reaction solution is usually about 1 to 50% by weight, and particularly preferably 3 to 40% by weight. If it is less than 1% by weight, it is economically disadvantageous, and if it exceeds 50% by weight, the reaction solution is not preferred because it gels or the viscosity becomes too high and the reaction becomes uneven.

Thus, a polyimide is generated. The polyimide in the present invention has a high solubility in an organic solvent by using the specific aromatic tetracarboxylic acid component and the aromatic diamine component in a selective combination. In addition, it is possible to obtain a polyimide having a sufficiently large intrinsic viscosity (that is, a sufficiently large molecular weight) while maintaining high solubility in an organic solvent. Thus, the polymer in the present invention Do intrinsic viscosity? ? inh is 0.5 gZ1002 in solvent N-methyl-2-pyrrolidone, temperature 30 ± 1. C, which is usually between 0.3 and

It is about 5.0 d / g, preferably 0.4 to 2.0 d ^ / g. Due to such high intrinsic viscosity and high homogeneity of the polymer structure, sufficient moldability and excellent various characteristics inherent to aromatic polyimide are exhibited. In particular, it has a high thermal decomposition temperature and is extremely excellent in heat resistance.

 The polyimide resin composition of the present invention is obtained by dissolving the above polyimide in an organic solvent. As the organic solvent, it is particularly preferable to use at least one of the non-proton-based polar solvent and the phenol-based solvent mentioned in the polyimide formation reaction, from the viewpoints of solubility, stability of solution viscosity and the like.

 Therefore, when the imidization reaction is performed with a solution of a non-proton-based polar solvent or a phenol-based solvent, the composition of the present invention can be used as it is as a reaction product. In this case and when other solvents are mixed and used, if necessary, once the polyimide is once separated from the reaction product of the imidization reaction, preferably a non-proton-based polar solvent is used. Alternatively, the composition of the present invention can be re-dissolved in a funinol solvent or the like.

The concentration of the polyimide in the polyimide resin composition of the present invention is usually about 1 to 50% by weight, preferably 3 to 40% by weight. Good to do. If it is less than 1% by weight, it is economically disadvantageous, and if it exceeds 50% by weight, the composition gels or the viscosity becomes too high and the workability at the time of molding is unfavorably reduced.

 Next, the polyimide resin composition of the present invention can be obtained by further adding a silane coupling agent to the polyimide resin composition of the present invention.

 The above composition has excellent adhesion to a substrate without deteriorating heat resistance, mechanical properties, electrical properties, etc. of polyimide by adding a silane coupling agent. It is. The properties of polyimide are not impaired because the silane coupling agent is added after the imidization is completed, so that it is not incorporated into the polyimide molecular chain and is not affected by the generated water. it is conceivable that.

Examples of the silane coupling agent to be added include, for example, α-glycidoxypropyl trimethoxysilane, α- (2-aminoethyl) aminoprovir trimethoxysilane, and α- (2-amidoethyl). Noethyl) aminopropylmethyldimethoxysilane, α-methacryloxypropyl trimethoxysilane, α-methylcaptopropyl trimethoxysilane, methylmethoxysilane, methyltriethoxysilane, vinyl Rutriacetoxysilane, N — / 3 — CN 'vinyl benzylaminoethyl) monoamine propyl trimethoxysilane, “T Xametildisilazane, τ-anilinoprovir trimethoxysilane, vinyltrimethoxysilane, chloropropylmethyldimethoxysilane, α-mercaptopyrylmethyldimethoxysilane, methyltrichlorosilane, methyltrichlorosilane Methinoresichlorosirane, trimethinochlorosilane, aminaminopropylethoxysilane, vinyltriethoxysilane, vinyltrichlororane, vinyltri (yS-methoxyethoxy) silane, β — (3,4-epoxycyclohexyl) ethyl methoxysilane, Ν Examples thereof include phenyl 3-aminoprovir trimethoxysilane, etc. The amount of the additive is usually about 0.1 to 20% by weight, preferably about 1 to 20% by weight, based on polyimide. Suitably, L is 0% by weight.

The composition obtained by dissolving the polyimide of the present invention and the composition obtained by further adding a silane coupling agent are relatively low-viscosity solutions that are fluid at room temperature, and therefore, are difficult to handle and process. Extremely easy. In addition, it is highly stable in solution, and can be stored at room temperature for a long period of time without causing changes such as viscosity changes and precipitation of insolubles. These compositions of the present invention can be suitably used for, for example, heat-resistant varnishes, heat-resistant laminates, heat-resistant films, heat-resistant adhesives, and the like, electrical materials, electronic materials, and applied devices thereof. Specifically, it is used for a printed wiring board, a flexible wiring board, a tape carrier, a surface protective film or an interlayer insulating film of a semiconductor integrated circuit element, a covering material for an enameled electric wire, various laminated board gaskets, and the like.

 In particular, these compositions of the present invention are suitable for film use. For example, after casting or spin-coating on a smooth surface of a substrate such as a glass plate or a metal plate, the composition is relatively heated and the like. Organic solvents and the like can be removed at a low temperature, so that a transparent polyimide film can be easily obtained. This film has high mechanical strength and high flexibility. For example, a film with a thickness of 30 zm can sufficiently withstand repeated bending tests. Also, when the thermal decomposition temperature is 50,000 or more, good heat resistance is exhibited, and chemical resistance is also good. Furthermore, above the melting temperature, it shows thermoplasticity and can be thermocompression-bonded or compressed.

In addition, the composition of the present invention to which a silane coupling agent has been added can be used for various substrates, for example, metals such as glass, silicon, aluminum, copper, nickel, and iron, and oxides thereof, polyethylene, Polypropylene, Polyethylene terephthalate Good for application to plastics such as rates. In particular, the composition is extremely excellent in adhesiveness to the substrate, so that the polyimide film can be formed in a short time at a low temperature only by evaporating the solvent, and the substrate is heated to a high temperature. When it is difficult to do so, it is extremely advantageous for applications such as a semiconductor surface protective film, an insulating protective film for electronic component circuits, and an alignment film for a liquid crystal display element used as a plastic substrate.

 BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

 The solution viscosity, intrinsic viscosity, thermal decomposition temperature, softening point, tensile strength, and elastic modulus of polyimide in each of Examples and Comparative Examples were measured by the following methods.

 (1) Polyimide solution viscosity (ps)

 It was measured using an E-type viscometer at a polyimide concentration of 20% by weight and a temperature of 25.

 (2) Intrinsic viscosity of polyimide? Inh (d Zg)

0.5 g of polyimide was dissolved in N-methyl-2-piperidone of Ι Ο Οτηβ, and the temperature was 30 ± 0.1 using an Ostold viscometer. The falling time of the sample solution (seconds, t) and the falling time of the solvent (seconds, to) were measured at C and calculated by the following equation. 77 inh = H n (t / to) / 0.5

 (3) Thermal decomposition temperature of polyimide (° C)

 Using a differential thermal balance analyzer ("THERMAL ANALYZER DT-30", manufactured by Shimadzu Corporation), the temperature was raised at a speed of 10 minutes in the air, and the weight was reduced by 10% by weight from the initial weight. Then, the temperature at that time was determined.

 (4) Softening point of polyimide

 Using a differential thermal analyzer (“THERMAL ANALYZER DT-30”, manufactured by Shimadzu Corporation), the temperature is raised in the air at a speed of 10 minutes, and the softening point temperature is measured in the penetration mode. did.

(5) Tensile strength (kgZfflin ² ), elastic modulus (kgZinm ² ) Film with ₀ width 1 cin using a tensile tester (riNSTKON MODEL-1122, manufactured by Instron Japan Company Ltd); The test specimen was fixed at 1 cm on each of the upper and lower sides, the load was 5 kg, and the tensile speed was measured under the conditions of 1 速度 ιπιπΖ minute.

Example 1

In a reactor equipped with a stirrer, cooling pipe, thermometer and nitrogen gas inlet pipe, 43.2 g (0.1 mol) of 4,4'-bis (p-aminophenol) diphenylsulfone and N 30-Og of methyl 2-pyrrolidone (hereinafter referred to as "NMP") was charged, and the mixture was replaced with nitrogen and stirred at room temperature until dissolved. Next, DSTA 35.8 g (0.1 mol) Was gradually added and reacted at 25-30 ° C. for 1 hour to obtain a transparent viscous polyamic acid solution. This solution was heated to 160 and reacted for 5 hours to obtain a desired transparent viscous polyimide NMP solution. The viscosity of this solution was 35 poise (Table 1).

 The polyimide solution thus obtained was poured into methanol, the polymer obtained by reprecipitation was dried under reduced pressure, and the infrared absorption spectrum was measured.

1 6 7 0 absorption of cnr ¹ is not observed, 1 7 2 0 cnr ¹ and 1 7 7 O cffl "characteristic absorption based on I Mi de group ¹ was observed, was shown to be Porii Mi de The infrared absorption spectrum is shown in Fig. 1. The captured values in Fig. 1 are due to the polystyrene film.

 Table 2 shows the intrinsic viscosity, thermal decomposition temperature, softening point and other physical properties of the polyimide.

 In addition, this polyimide is composed of N, N-dimethylformamide (hereinafter referred to as "DMF"), N, N-dimethylacetamide, dimethylsulfoxide, tetramethylurine, 1, 3—Dimethyl-2-imidazolidinone, m—Cresol, xylenore, 0—Curofen phenol, and p—Bromophenol

A 10% by weight polyimide resin solution was obtained. Example 2

 Dissolve 41.0 g (0.1 mol) of 2,2-bis [4- (p-amino phenoxy) phenyl] propane in 300 g of DMF and add 35.8 g (0. (1 mol) was gradually added and reacted in the same manner as in Example 1 to obtain a polyamic acid solution. Then, the mixture was reacted at 150 for 5 hours to obtain a desired transparent viscous polyimide DMF solution. The viscosity of this solution was 40 boise (Table 1).

After the treatment in the same manner as in Example 1, the infrared absorption spectrum was measured. As a result, no absorption of about 167 Oenr ¹ by the acidic acid was observed, and the absorption was observed at about 172 Ocnr ¹ and 177 Ocnr ^1. Characteristic absorption based on the group was observed, indicating that it was a polyimide.

 Table 2 shows the intrinsic viscosity, thermal decomposition temperature, softening point and other physical properties of the polyimide. The polyimide also dissolves in NMP, dimethyl acetate, dimethyl sulfoxide, hexamethylphosphoramide, phenol, o-cresol, 2,6-xylenol, and P-chlorophenol. Then, a polyimide resin solution having a concentration of 10% by weight was obtained.

Example 3

4,4'-diamino diphenyl sulfide 21.6 g (0.1 mol) was dissolved in 250 g of m-cresole, and 5.8 g (0.1 mol) of DSTA was gradually added thereto, followed by reaction in the same manner as in Example 1. A polyamic acid solution was obtained. Then, the mixture was reacted at 17 CTC for 3 hours to obtain a desired transparent viscous polyimide solution. The viscosity of this solution was 34 Boise (Table 1).

After similarly treated as in Example 1, was measuring the infrared absorption scan base-vector, absorption of about ¹ 67 0 em _ 1 by § Mi-click acid was not observed, about ¹ 720 C1 "1 and 1770 cm " ¹ showed characteristic absorption based on imido groups, indicating that it was a polyimide.

 Table 2 shows the intrinsic viscosity, thermal decomposition temperature, softening point and other physical properties of the polyimide. In addition, this polyimide readily dissolves in NMP, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, tetramethylurea, phenol, and xylenol. A polyimide resin solution having a concentration of about 10% by weight was obtained. Examples 4 to 11

Various polyamides and DSTAs as shown in Table 1 were reacted in the same manner as in Example 1 to produce corresponding polyimides. After treating the polyimide obtained in each of the examples in the same manner as in Example 1, the infrared absorption spectrum was measured. Absorption of about ¹ 6 7 0 cnr 1 according § Mi click acid was not observed, characteristic absorption was observed based on Lee Mi de group about ¹ 7 2 0 cm "1 and ¹ 7 7 0 cm" 1, It was shown to be polyimide.

The solvent used and the viscosity of the polyimide solution after the reaction are shown in Table 1, and various properties of the obtained polyimide are shown in Table 2.

Example Dimamine solvent Solution viscosity

1 4, 4, —bis (p-aminophenol) diphenylsulfone NMP 35

2 2, 2-bis [4- (p-aminophenoxy) phenyl] propane DMF 40

3 4, 4 'diaminodiphenyl sulfide 01-cresol 34

4 1, 4-bis (p-aminophenyl thioether) benzene _ffl- cresol 32

5 4, 4'-bis (p-aminophenylthioether) diphenyl ether NMP 37

6 4, 4'-bis (p-aminopheninoxy) diphenyl sulfide NMP 36

7 4, 4, Monobis (p-aminophenylinoquine) benzophenone NMP 38

8 4, 4'-Bis (p-aminophenylthioether) diphenylsulfone _m- cresol 32

9 4, 4'-bis (p-aminophenyloxy) diphenyl ether DMF 41

10 4, A'-I (m-phenylenediisopropylidene) dianiline NMP 38

11 4,4'-1 (p-phenylenediisopropylidene) dianiline DMF 40

Table 2 Male example Intrinsic viscosity (ps) Thermal decomposition temperature CC) Soft, no, chemical, w point, ゝ C VO tensile ¾W (kg / mm ² ) v ^ ¹ ii.- ^! P ¹ \ i & / uiui no

 1 0.79 565 285 12 2 t

 2 0.883 535 250 11 5 R o

 3 0.65 500 300 8 2 9 q 17 n

 4 0.1 531 10 6 977

 5 0.75 525 290 9. 1 281 t

6 0.87 530 265 8.7 260

 7 0.81 565 260 9.5 257

 8 0.69 560 255 8.8 263

 9 0.81 542 262. 10. 2 280

 10 0.81 541 263 11.5 258

11 0.79 537 288 12.3 272

Example 1 2 to 3 6

 The corresponding polyamides were synthesized by reacting various diamines shown in Table 3 with DSTA in the same manner as in Example 1.

After treating the polyimide obtained in each of the examples in the same manner as in Example 1, the infrared absorption spectrum was measured. In each case, the absorption of about 670 cm " ¹ by the acidic acid was observed. It was not observed, about ¹ 7 2 0 cm "1 and ¹ 7 7 0 cm" 1 characteristic absorption based on I Mi de group, thus they were shown to be Porii mi de.

Table 3 shows the intrinsic viscosity (77 inh) of the polyimide obtained, the reaction solvent used, the viscosity of the polyimide solution after the reaction, and the thermal decomposition temperature.

Table 3

t

Table 3 (continued)

Example 1 Intrinsic viscosity Solvent Solution viscosity Thermal decomposition temperature

 (d5 g) (P s) CC)

 21 3, —Bis (p-aminophenol) 0.75 in-cresol 30 520

 1 ter) diphenyl sulfide

 22 3, y-bis (p-aminophenol thiol 0.73 01-cresol 28 522

 —Tel) diphenyl ether

 23 3, 3'-bis (p-aminophenylthioe 0.55 m-cresol 32 530

 One ter) benzophenone

 24 3, 3'-bis (p-aminophenokine) di 0.61 DMF 33 585 t phenyl

 25 3, 3'-bis (p-aminophenirthioe) 0.62 DMF 32 585

 One tell) diphenyl

 26 3, A'-bis (p-aminophenoxy) di 0.83 丽 P 29 513

 Phenyl sulfone

 27 3, 4 'Bis (p-aminophenylthioe 0.71 Sat P 30 509

 One ter) diphenyl sulfone

 28 3, Α'-bis (ρ-aminophenoxy) di 0.75 marauder P 31 515

 Phenyl sulfide

 29 3, 4'-bis (ρ-aminophosphoric 0.88 NMP 33 512

One ter) diphenyl sulfide

Table 3 (continued)

Example 37

 10 g of the polyimide obtained in Example 1 and 0.5 g of α-glycidoxyprovir trimethoxysilane were dissolved in 90 s of NMP, and cast on a glass plate while rotating the wheeler at 150 rpm. This was heated at 80 ° C. under reduced pressure, then at 150 ° and 200 ° for 1 hour each, and subjected to an adhesion test. The adhesion test is performed on the coating film

In accordance with 0202, 100 squares of 1 mm square were made, a cellophane tape was stuck and rapidly peeled off, and the tape was peeled off and evaluated by the number of peeled tape beer test.

 As a result, the cellotape peel test (the number peeled out of 100 pieces) was 0. The pyrolysis temperature was 558. When no silane coupling agent was present, the cellotape peel test was 60.

Example 38

 10 g of the polyimide obtained in Example 2 and 70- (2-aminoethyl) aminoprobitritrimethoxysilane

0.2 g was dissolved in 40 g of DMF to obtain a polyimide varnish. This was cast on a glass plate and heated in the same manner as in Example 37, and the adhesion test and the thermal decomposition temperature were measured. The results are shown in Table 4.

Example 39 A polyimide varnish was obtained by dissolving 5 g of the polyimide obtained in Example 3 and 0.4 g of amercaptopropyl trimethoxysilane in 50 g of NMP. The adhesion test and the thermal decomposition temperature were measured in the same manner as in Example 37, and the results are shown in Table 4. Example 40

 Three

 1

 5 g of the polyimide resin obtained in Example 4 and 0.3 g of Arc Mouth Probitritrimethoxysilane were dissolved in 50 g of N, N-dimethylacetamide to prepare a polyimide varnish. Obtained. The adhesion test and the thermal decomposition temperature were measured in the same manner as in Example 37, and the results are shown in Table 4. Examples 41 to 43 10 g of the polyimide obtained in Examples 5 to 7 and 0.2 g of 7-aminopropyltriethoxysilane were dissolved in 40 g of NMP, and the adhesion was obtained in the same manner as in Example 37. The test and pyrolysis temperature were measured, and the results are shown in Table 4. Examples 44 to 45 5 g of polyimide obtained in Examples 8 and 9 and ar (2-aminoethyl) aminoprovir trimethoxysilane

0.3 g was dissolved in 95 g of DMF, and the adhesion test and the thermal decomposition temperature were measured in the same manner as in Example 37. The result was fourth. Table 4

（ ） 内はシランカツプリ ング剤を共存させなかつ 口

(): The mouth does not contain the silane coupling agent.

 Examples 46-47

 5 g of the polyimide resin obtained in Examples 10 and 11 and 0.4 g of armcaptopropyl trimethoxysilane were dissolved in NMP100 g to obtain each polyimide resin varnish. Was. The adhesion test and the thermal decomposition temperature were measured in the same manner as in Example 37, and the results are shown in Table 5.

 Table 5

実施例 48〜65

Examples 48-65

Example 12-: Each polyimid obtained in 25, 32-35 Polyimide varnish was prepared by dissolving 5% by weight of 7-glycidoxyprobitrimethoxysilane in various non-protonic polar solvents. Table 6 shows the solvent used, the polyimide concentration, the adhesion test measured in the same manner as in Example 37, and the thermal decomposition temperature.

6 Table

 Polyimidide D Pyrolysis Solvent Solvent

 (MM) Test CO

1,3-Dimethyl 2--10 0 528 Imidazolidinone

 1,3-Dimethyl 2--10 0 519 Imidazolidinone

 NMP 20 0 603

DMF 10 0 593

N P 20 0 513

NMP 20 0 508

DMF 10 0 512

N, N—Jetilholm 10 0 521 Amide

 N, N—Jetiracet 10 0 503 Amid

Tetramethylurea 10 0 518

DMF 10 0 522

D F 10 0 528

DMF 10 0 583

DMF 10 0 579

NMP 20 0 528

NMP 10 0 512 Marauder P 10 0 509

NMP 10 0 513 Example 6 6 to 6 7

 10 g of polyimide obtained in Example 1 or 2 and 0.2 g of ferrinoprobitritrimethoxysilane were dissolved in 40 parts of a phenol-based solvent to obtain a polyimide varnish. Table 7 shows the solvent used, the adhesion test measured in the same manner as in Example 37, and the thermal decomposition temperature.

 Table 7

 (): No silane coupling agent coexists

* »-^ ¾ 口 '

 Comparative Example 1

43.2 g (0.1 mol) of 4,4'-bis (p-aminophenoxy) diphenyl sulfone was dissolved in 300 g of NMP, and benzophenone-1,3,3,4,4'- Tetracarboxylic dianhydride (hereinafter abbreviated as “BPTA”) 32.2 g (0.1 mol) was gradually added and reacted in the same manner as in Example 1 to obtain a polyamic acid solution. Was. Next, 150. (: Reaction for 5 hours will result in non-uniform gel I got it. An additional 300 g of NMP was added to this and stirred with heating, but a uniform solution was not obtained.

Comparative Example 2

 2,2—bis [4- (p-aminophenoxy) phenyl] propane (41.0 g, 0.1 mol) was dissolved in 300 g of DMF, and 32.2 g of BPTA (0.1 mol) was dissolved. ) Was gradually added and reacted in the same manner as in Example 2 to obtain a polyamic acid, and then reacted at 170 for 3 hours to obtain a heterogeneous gel. To this solution, 300 g of DMF was further added and heated with stirring, but a uniform solution was not obtained.

Comparative Example 3

 Except for using 32.4 g (0.1 mol) of 3,3 ', 4,4' diphenylsulfonetetracarboxylic acid dimethyl ester instead of 35.8 g (0.1 mol) of DSTA, The reaction was carried out under the same conditions as in Example 1.

The properties of the polyimide obtained are: intrinsic viscosity 0.15 d · βZg, thermal decomposition temperature 420, tensile strength 32 kg / in in ² , low intrinsic viscosity (low molecular weight ), Heat resistance and mechanical properties were inferior.

Comparative Example 4

2, 1-bis [4- (4-amino phenoxy) phenyl] propane 4 1 g (0.1 mol) to NMP 4◦0 g Dissolve and add 3,3 ', 4,4' monobenzophenone tetracarboxylic acid 32.2 g

 (0.1 mole) slowly, 25-30. C was reacted for 2 hours to obtain polyamic acid. The intrinsic viscosity of this polyamic acid was 1.2 dj ^ Zg.

 The adhesion test and the thermal decomposition temperature were measured in the same manner as in Example 37, using a phenol obtained by adding 1.lg of glycidoxyprovirt rimethoxysilane to 100 g of this polyamic acid solution. did. As a result, since the strength of the coating film was very low and not uniform, it was detached when the coating film was cut. The thermal decomposition temperature was as low as 483.

BRIEF DESCRIPTION OF THE FIGURES

 FIG. 1 is an infrared absorption spectrum of polyimide in Example 1.

Claims

The scope of the claims 1. —general formula (I) X

CH ₃ Indicates CH ₃ . Where is 0—, 1 S— or R—C—, Y is a single bond or 1 0—, 1 S—,  I R ^{2 1} -S 02 One, one C one or C 0 R 2 represents a divalent group. : R ¹ and R ² represent a hydrogen atom, a halogen atom or a lower alkyl group which may be substituted with a halogen atom, and may be the same or different. ] Characterized in that at least one kind of polyimide having a repeating unit represented by and having an intrinsic viscosity η inh of about 0.3 to 5.0 dZg is dissolved in an organic solvent. Polyimide resin composition. 2. The composition according to claim 1, wherein the organic solvent is at least one of a non-proton type polar organic solvent and a phenol type organic solvent. 3. The composition according to claim 1, wherein the concentration of the polyimide is about 1 to 50% by weight. 4. A polyimide resin composition, further comprising a silane coupling agent added to the composition according to claim 1.  5. The composition according to claim 4, wherein the organic solvent is at least one of a non-protonic polar organic solvent and a phenolic organic solvent.  6. The composition according to claim 4, wherein the concentration of the polyimide is about 1 to 50% by weight.  7. The composition according to claim 4, wherein the amount of the silane coupling agent added is about 0.1 to 20% by weight based on the amount of the polyimide. 8. Diphenylsulfone-1,3 ', 4,4'-tetracarboxylic dianhydride and general formula

[Where τ is the same as above. ]  Reacting an aromatic diamine represented by the formula (1) in the presence of an organic solvent to produce a polyimide, or separating the produced polyimide and then re-dissolving it in an organic solvent. A method for producing a resin composition.  9. The production method according to claim 8, wherein the organic solvent is at least one of a non-proton-based polar organic solvent and a phenol-based organic solvent.  10. The molar ratio of diphenylsulfone-1,3,3,4,4'-tetracarboxylic dianhydride to the aromatic diamine of the general formula (II) is about 0.7 to 1.3. The manufacturing method according to claim 8, wherein: 11. The method for producing a polyimide resin composition according to claim 8, wherein a silane coupling agent is further added after the completion of the polyimide generation reaction.  12. The organic solvent is at least one of a non-protonic polar organic solvent and a phenolic organic solvent. 11. The production method according to item 1. 13. Diphenylsulfone-1,3 ', 4,4' tetra 4.1 The production method according to claim 11, wherein the molar ratio of the carboxylic dianhydride to the aromatic diamine of the general formula (II) is about 0.7 to 1.3. 14. The production method according to claim 11, wherein the amount of the silane coupling agent added is about 0.1 to 20% by weight based on polyimide.