JPH10114824A - Production of polyimide, composition, and its product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyimide excellent in physical properties without conducting purification by subjecting a tetracarboxylic acid and a diamine to polycondensation and direct imidizing by using a γ-lactone and a basic org. compd. SOLUTION: A pref. imidizing agent is γ-valerolactone or γ-hexanolactone, and it is used in an amt. of 0.5wt.% of the mixture of a tetracarboxylic acid and a diamine. Together with the imidizing agent, a basic org. compd. (e.g. pyridine) in an equivalent ratio to the imidizing agent of 0.2-2 is used. A tetracarboxylic acid (e.g. 3,3',4,4'-biphenyltetracarboxylic acid) and a diamine e.g. bis[4-(4-aminophenoxy)phenyl] sulfone} are homogeneously mixed in a polar org. solvent at normal temp. and reacted at 80-200 deg.C to simultaneously conduct the polycondensation and imidizing, thus giving a polyimide by a one- stage method. The resultant product has a mol.wt. of 50,000-100,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process comprising heating a mixture of a tetracarboxylic acid and a diamine to cause imidization at the same time as polycondensation. It relates to a typical manufacturing method.

[0002]

2. Description of the Related Art Polyimide has high heat resistance, mechanical properties, chemical resistance, electrical insulation and the like, and is widely used in industrial fields such as electric, mechanical, aviation, and electronic.

As a general method for producing polyimides, particularly aromatic polyimides, (1) tetracarboxylic dianhydride and aromatic diamine are added in equimolar amounts, and N-methyl-2-pyrrolidone and N, N-dimethyl are added. After reacting in an organic polar solvent such as acetamide at room temperature to 50 ° C. to obtain a high molecular weight polyamic acid, a poor solvent such as an alcohol is added to precipitate the polyamic acid, and the resultant is filtered, washed, dried, and then obtained. Polyimide powder used for powder molding and the like is produced by heating the obtained polyamic acid at a high temperature of 250 ° C. or more in an oxygen-free atmosphere to cause a ring-closing dehydration reaction (imidization). In order to obtain a high-molecular-weight polyimide powder by this production method, it is necessary to go through a high-molecular-weight polyamic acid. The use of a raw material partially converted into a carboxylic acid by decomposition or the like has a drawback that a high molecular weight polyamic acid cannot be obtained. In addition, there is a problem in that the workability is troublesome and the cost is high, for example, after the polyamic acid fine powder is separated by filtration and dried in this manner, it is subjected to a high-temperature heat treatment in an oxygen-free atmosphere.

(2) While removing water by azeotropic distillation in a phenol or naphthol solvent, an imidization reaction of a high molecular weight polyamic acid or a one-step method is used to form a reaction between tetracarboxylic dianhydride and diamine. A method has been proposed in which a polycondensation reaction is carried out to precipitate and recover a polyimide powder, which is then dissolved again in the same solvent to produce a polyimide solution (Japanese Patent Publication No. 47-23191, Japanese Patent Application Laid-Open No. 60-19775).
No. 9, etc.) and phenol-based and naphthol-based solvents have an unpleasant odor and have strong irritation to the skin, so that they are not suitable for general use for coating agents and adhesives.

(3) It has been proposed to chemically imidize polyamic acid in an organic polar solvent in the presence of a fatty acid such as acetic anhydride and a basic compound such as pyridine to deposit polyimide. No. 37-97).
In these polyimide production methods, a large excess of acetic anhydride of 20% or more of the amount of the organic polar solvent used is required. , Precipitated as polyimide powder,
Acetic acid, pyridine and the like have been removed and recovered (JP-A-61-95029, JP-A-1-96220).
issue). For organic solvent-soluble polyimide, heat in an organic solvent in the presence of an organic acid such as p-toluenesulfonic acid, benzenesulfonic acid, crotonic acid, and remove water by-produced from the system by azeotropic distillation. It has been proposed to imidize polyamic acid and use the obtained polyimide solution as an electric wire coating agent or an adhesive (Japanese Patent Application Laid-Open No. HEI 1-1990).
-96220, JP-A-7-15750). Since an organic acid is present in the polyimide solution obtained in this manner, the molecular weight of the polyimide is reduced, and in particular, when used as an adhesive, a problem occurs in moisture resistance. It is necessary to remove the acid. For the first time after such purification, the obtained polyimide powder is redissolved in N-methyl-2-pyrrolidone or other organic polar solvents for use in molding,
It can be formed into a film or used as an electric wire coating agent or an adhesive.

(4) Polyamide acid in an organic polar solvent is cast or coated on a support, the organic solvent is removed by heating, and then the imidization is carried out by heating at a high temperature of 250 ° C. or more. This is a method for producing a polyimide film or a polyimide bonded product that has been adopted. Although it is possible to obtain a polyimide having a desired molecular weight by this production method, imidization requires high-temperature treatment in an oxygen-free atmosphere, which is disadvantageous in terms of work and cost. When casting a polyamic acid to form a film, first, on a support,
It is necessary to remove the organic polar solvent by heating until the polyamic acid film has a self-supporting property. At this stage, the molecular weight of the polyamic acid is reduced, the strength is remarkably reduced, and in some cases, the film is often broken. In order to prevent such troubles, it is necessary to use polyamic acid having a sufficient molecular weight.
It was necessary to use a tetracarboxylic dianhydride containing no carboxylic acid component produced by hydrolysis. Further, in a polyimide bonded product, a volume shrinkage strain is caused by a dehydration reaction at the time of an imidization reaction, so that a decrease in bonding strength becomes a problem.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing polyimides having excellent heat resistance and usable without substantial purification.

[0008]

As a result of intensive studies by the present inventors, the above object has been industrially advantageously achieved by the present invention described below. That is, this is a method for producing polyimides, which comprises imidizing simultaneously with polycondensation using a γ-lactone and a basic organic compound as an imidizing agent. The greatest feature of the present invention is that γ-
By using a lactone and a basic organic compound, a mixture of tetracarboxylic acids and a diamine is polycondensed and simultaneously imidized, thereby finding a method for producing polyimides having excellent physical properties without purification. It is in. According to the study of the present inventors, δ−
Lactones are also useful as imidating agents, but it has been found that γ-lactones are faster and more economically advantageous than ring-closing speeds, and have reached the present invention. Another feature of the present invention is that when reacted in the presence of a γ-lactone acting as an imidizing agent and a basic organic compound, tetracarboxylic acid which is a hydrolyzate of tetracarboxylic dianhydride as a starting material Another advantage is that polyimides having a sufficient molecular weight can be obtained even when the ester is used. Further, the present invention provides a method wherein the mixture comprises a low molecular weight polyimide oligomer and at least one of tetracarboxylic acids and / or
At least one kind of diamine having at least two carbon atoms is reacted to contain the obtained block copolymerized polyimide.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
The present invention solves various problems that occur when directly obtaining a mixture of a tetracarboxylic acid and a diamine to obtain a polyimide, and as a result of intensive studies to establish an efficient production method, lactones and lactones as imidating agents. In the presence of a basic organic compound, while removing water out of the system by azeotropic distillation,
The imidization reaction is carried out simultaneously with the condensation polymerization of the mixture. In the polyimide production method of the present invention, the reaction temperature used in the presence of a small amount of the imidizing agent is from 80 ° C. to the temperature at which the non-solvent used is refluxed, or the temperature below the boiling point of the organic polar solvent used. And preferably 1
It is in the range from 20 ° C. to 200 ° C., and the reaction time is from 30 minutes to 10 hours, preferably from 30 minutes to 5 hours. In this way, when used, they do not contain substances that may adversely affect various properties such as mechanical properties such as adhesion and strength, and electrical properties such as withstand voltage. Is obtained.

Hitherto, primary fatty acid anhydrides have been effective as imidizing agents, and acetic anhydride has been particularly preferred. However, the acetic anhydride used as described above has remarkable irritation and corrosiveness. Further, it is necessary to use a large amount of the organic solvent, that is, 20% or more of the amount of the polar organic solvent. The imidizing agent of the present invention has γ
A lactone or a precursor capable of producing γ-lactone under the reaction conditions, wherein the lactone is γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ
A lactone precursor which is at least one of octanolactone, γ-nonalactone and γ-decalactone, or which forms the lactone under the reaction conditions, is a γ-oxycarboxylic acid such as γ-oxyvaleric acid or a salt thereof; It is preferable to use at least one of these. The amount used may be 0.5% by weight or more of the mixture of the tetracarboxylic acid and the diamine used in the polymerization. Since these lactones do not prevent the dissolution of the polyimides of the present invention, they may be used in excess. The inventors have found that polyimides having an imidation ratio of 95% or more can be easily obtained in this manner, and have reached the present invention. Particularly desirable imidizing agents are γ-valerolactone and γ-hexanolactone.For example, γ-valerolactone contributes to the dehydration of polyamic acid in the presence of the following basic organic compound, and performs imidization and Changes to γ-oxyvaleric acid, but when the by-produced water is removed out of the system by azeotropic distillation, γ-oxyvaleric acid returns to γ-valerolactone again, so that the required amount of imidizing agent is reduced. In addition, there is an advantage that a purification step is not required because a free acid derived from an imidizing agent and impairing the stability of the polyimide is not present in the polyimide solution as in the conventional method. Further, it is desirable to use a basic organic compound such as pyridine, triethylamine, triethylenediamine, picoline, N-methylmorpholine or quinoline together with the imidizing agent in an amount of about 0.2 to 2 equivalents, preferably an equivalent amount, of the imidizing agent. . These may be used alone or as a mixture.

The tetracarboxylic acids used in the present invention are not particularly limited, but tetracarboxylic acids and esters thereof are used. It should be noted that tetracarboxylic acid may contain a monoanhydride or a dianhydride of by-product when the tetracarboxylic acid is dried by heating. Conventionally, to obtain a polyamic acid having a high molecular weight or a controlled molecular weight with good reproducibility by a two-stage method via a polyamic acid, it is necessary to use high-purity tetracarboxylic dianhydrides,
It was necessary to react with great care as described below. First, a high-purity dianhydride containing no carboxylic acid is added in the form of a powder in a polar organic solvent in which diamines are dissolved at low temperature under stirring, or tetracarboxylic acid is completely added to a solvent that is dehydrated and dried. Dissolve dianhydrides and add diamine while taking complete measures to prevent moisture absorption, or react by adding a solution of completely dehydrated and dried tetracarboxylic dianhydrides in diamine solution . Further, the tetracarboxylic dianhydride to be used must not contain a hydrolyzed carboxylic acid by recrystallization in acetic anhydride or sublimation purification under heating.

On the other hand, in the present method, a tetracarboxylic acid obtained by purifying from an aqueous solution or a tetracarboxylic acid partially containing tetracarboxylic dianhydride may be used. By accurately measuring the content of the group that can be a tetracarboxylic acid contained by titration or analysis such as gas chromatography, even if a tetracarboxylic acid partially containing tetracarboxylic dianhydride is used, One of the outstanding features of the present method is that polyimides having a target molecular weight can be obtained with good reproducibility regardless of the order and method of addition of diamine and tetracarboxylic acid.
One. As the ester, a lower alkyl ester obtained by reacting a tetracarboxylic acid with a C1 to C3 alcohol and an aryl ester obtained by reacting with a phenol or cresol are preferably used. Such tetracarboxylic acids include pyromellitic acid 3,3 ', 4,4'-benzophenonetetracarboxylic acid 3,3', 4,4'-biphenyltetracarboxylic acid 2,2-bis (3,4-carboxy) Phenyl) propane 4,4 ′-(hexafluoroisopropylidene) diphthalic acid 3,3 ′, 4,4′-diphenylethertetracarboxylic acid 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic acid 1,2,2 3,4-butenetetracarboxylic acid bicyclo [2,2,2] oct-7-ene-2,3,
Examples thereof include tetracarboxylic acids such as 5,6-tetracarboxylic acid, which may be used alone or as a mixture.

The diamine used in the present invention is not particularly limited, but 3,3'-diaminodiphenyl ether 4,4'-diaminodiphenyl ether 3,3'-diaminodiphenylmethane 4,4'-diaminodiphenylmethane 3,3'-diamino Diphenylpropane 4,4'-diaminodiphenylpropane 3,3'-diaminodiphenylsulfone 4,4'-diaminodiphenylsulfone 3,3'-diaminodiphenylsulfide 4,4'-diaminodiphenylsulfide 3,3'-diamino Benzophenone 4,4'-diaminobenzophenone 1-sulfo-2,4-diaminobenzene 2,4-diaminophenol 1-methoxy-2,4-diaminobenzene 3,3'-dimethyl-4,4'-diaminodiphenyl ether 3, 3'-Dimethyme -4,4'-diaminodiphenylmethane 4,4'-diamino-3,3'5,5'-tetramethylbiphenyl paraphenylenediamine metaphenylenediamine 2,4-diaminotoluene 2,4-diaminobenzoic acid 2,6- Diaminobenzoic acid 2,5-diaminobenzoic acid 4,4-bis (4-aminophenoxy) biphenyl 1,3-bis (3-aminophenoxy) benzene 1,3-bis (4-aminophenoxy) benzene 2,2- Bis [4- (4-aminophenoxy) phenyl] propane bis [4- (3-aminophenoxy) phenyl] sulfone bis [4- (4-aminophenoxy) phenyl] sulfone 2,2-bis [4- (4- Aminophenoxy) phenyl] hexafluoropropane 2,2-bis (4-aminophenyl) hexafluoro Propane 9,9-bis (4-aminophenyl) fluorene 2,6-diamino-4-trifluoromethylpyridine 1,3-bis (3-aminopropyl) -1,1,3,3
-Tetramethyldisiloxane 1,3-bis (3-aminophenoxymethyl) -1,
Diamines such as 1,3,3-tetramethyldisiloxane 1,3-bis (aminophenyl) -1,1,3,3-tetramethyldisiloxane α, ω-bis (3-aminopropyl) polydimethylsiloxane These may be used alone or as a mixture.

As a preferred organic polar solvent, N-
Methyl-2-pyrrolidone (NMP), N, N-dimethylformamide, N, N-dimethylacetamide (DMA
c), N, N-diethylacetamide, N, N, -dimethylmethoxyacetamide, imidazole, γ-butyrolactone, dimethylsulfoxide, dimethylsulfone, or the like is used alone or in combination. Depending on the use, phenols or naphthols may be used alone or in combination. In order to carry out the imidization reaction while removing by-product water out of the system by azeotropic distillation, benzene, nitrobenzene, toluene, xylene, cyclohexane, dioxane, tetralin or the like may be added to these organic polar solvents.

The polyimides produced by the method of the present invention have not only polyimides having an imide unit composed of a diamine and a tetracarboxylic acid, but having a two-component homopolymer structure composed of one kind of a diamine and a tetracarboxylic acid. Further, by adding other components, a multi-component polyimide suitable for a desired use can be obtained with a structure such as a random copolymer or a block copolymer.

The polyimide of the present invention is produced as follows. After uniformly mixing the diamine and the tetracarboxylic acid at room temperature in a polar organic solvent,
By conducting the reaction at a temperature of 120 ° C., preferably 120 to 180 ° C., polycondensation and imidization can proceed simultaneously, and a polyimide can be obtained by a one-step method. In the conventional one-step method, there is a problem that the molecular weight distribution of the obtained polyimide tends to be widened, the control of the molecular weight is difficult, and the viscosity tends to increase. Such problems are improved by the method of the present invention using lactones and a basic organic compound,
This has the advantage that the reaction time is shorter than that of the method via the polyamic acid. In the present invention, using a terminal stopper during the reaction for the purpose of controlling the molecular weight, the viscosity of the reaction during the reaction is strictly controlled by using a method of sealing the polymer molecular ends with dicarboxylic acid anhydride polyimide of the desired molecular weight Can be manufactured. As a method for adding a terminal stopper, a molecular weight of 1
When producing 10,000 or more polyimides, it is preferable to carry out the reaction by adding the raw material mixture and the terminal terminator all at once. When producing a polyimide having a molecular weight of 10,000 or less, it is desirable to lower the reaction temperature once during the reaction, add a terminal stopper, and then raise the reaction temperature to perform the imidization reaction. When obtaining a block copolymer, it is effective to add a tetracarboxylic acid and a calculated amount of a diamine to a low-molecular-weight polyimide oligomer at a time to adjust the molecular weight of the resulting block copolymer. Examples of the terminal stopper include phthalic anhydride,
At least one selected from dicarboxylic anhydrides such as benzophenone dicarboxylic anhydrides, maleic anhydride, nadic anhydride, and bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic anhydride; One is preferred.

In the case of producing a polyimide powder for molding,
A tetracarboxylic acid and a calculated amount of a diamine and a dicarboxylic acid are collectively added to an organic polar solvent such as dimethylacetamide, and water is removed azeotropically with γ-valerolactone as an imidizing agent and pyridine as a basic compound. For this purpose, toluene and the like are added, and after uniform mixing at room temperature, the temperature is increased and the reaction is performed at 120 ° C. to 200 ° C. while removing by-produced water out of the system by azeotropic distillation. Therefore, by filtering and drying the polyimide, a powdery polyimide resin having a molecular weight of about tens of thousands to 300,000 and an imidization ratio of 95% or more can be easily obtained.

In order to improve the dimensional stability, impact resistance, workability, etc., and to provide adhesion, etc. while satisfying the excellent heat resistance and electrical performance of the polyimide as much as possible, it is necessary to use one kind of tetracarboxylic acid. In addition to the two-component polyimide composed of one kind of diamine, a multi-component polyimide is also used.

Since the random copolymer has a tendency to converge on the low properties of each component rather than the excellent properties of each component, the block copolymer is more desirable than the random copolymer. This is preferable from the viewpoint of designing characteristics. The block copolymerized polyimide of the present invention can be produced as follows. In a polar organic solvent such as NMP in which a low molecular weight polyimide oligomer having a molecular weight of 5,000 or less, preferably 2,000 or less is dissolved, at least one kind of tetracarboxylic acids and / or at least one kind of diamine Is added, and in the presence of a lactone as an imidizing agent and a basic organic compound, an imidization reaction is carried out together with polycondensation while removing by-product water by azeotropic distillation, thereby producing NMP. Block copolymerized polyimides dissolved in such a polar solvent can be obtained.
When such a method is used, partial block copolymerization polyimides are obtained because partial random copolymerization is prevented by an exchange reaction during the reaction.

For polyimides for applications requiring adhesiveness, diaminosiloxane compounds, diaminofluoro compounds, diamino-containing sulfide compounds and the like are copolymerized as diamine components in order to impart adhesiveness and processability. It is preferable to use a terminator to block the polymer end, adjust the molecular weight to about 50,000 to 100,000, and partially crosslink by a heat treatment during or after bonding to increase the molecular weight.

For the purpose of imparting crosslinking property to the polyimide of the present invention, bicyclo [2,2,2] oct-7-ene-2,3,5,
Copolymerization of 6-tetracarboxylic dianhydride, use of maleic anhydride, nadic anhydride or 3-ethynylaniline as a terminal stopper, diamines and maleic anhydride or nadic anhydride May be blended with a bisimide obtained by reacting These polyimides are used after being dissolved in a polar solvent such as N-methylpyrrolidone and dimethylacetamide. If necessary, a solvent used in general adhesives such as mixed xylene may be added for the purpose of lowering the viscosity.

In order to impart electrodeposition property to the polyimide of the present invention, a basic compound such as triethylamine is added to a block copolymer polyimide composition solution containing 10 to 20 mol% of an aromatic diamine having a carboxyl group as a diamine component. After heating at about 40 ° C. for 1 hour to neutralize the carboxylic acid, water can be added to prepare an electrodeposition paint. The electrodeposition paint can be subjected to anion electrodeposition, and the resulting coating film has excellent adhesion and heat resistance.

As the aromatic diamine having a carboxyl group, a compound having two amino groups and one or two carboxyl groups on an aromatic ring such as benzene, naphthalene, diphenyl and diphenyl ether is used.
Examples thereof include 2,4-diaminobenzoic acid, 2,6-diaminobenzoic acid, and 3,5-diaminobenzoic acid, but are not particularly limited to these compounds.

Metal foils and sheets such as copper foils, stainless steel sheets and 42 nickel sheets, and material films represented by polyethylene terephthalate, polyethylene-2,6-naphthalate, polyphenylene sulfide, polyethersulfone films and sheets, etc. To improve chemical resistance, oxidation resistance, abrasion resistance, mechanical properties, etc.
By coating and disposing the polyimide of the present invention on one or both surfaces of the base film, a film laminate having improved properties can be obtained. The film laminate obtained in this way is
Since the properties of the base film are improved, it can be used beyond the conventional usage limits. Examples of such uses include a plate material for a screen printing plate for screen-printing a fine solder paste on a printed board, a flexible printed board, and the like.

The polyimide coating layer of the present invention provided on the surface layer of the film laminate can be used as an adhesive layer when laminating with the same or another base film material. Examples of the application include a heat-adhesive film, a cover film to be bonded to a flexible printed circuit board and a lead frame, and the like.

A particularly useful one among these uses is a film laminate obtained by applying the polyimide of the present invention to the surface of a commercially available polyimide film. When a polyimide film is used for a printed wiring board, it is necessary to provide fine through holes at predetermined positions of the polyimide film at a predetermined pitch by a method such as chemical etching. In such a case, photosensitive dry film is used as a resist material, but generally, dry film has poor adhesion to a polyimide film, and therefore, during chemical etching, etching is performed between the polyimide film and the dry film resist. There is a problem that the liquid penetrates and it is difficult to obtain a through hole having a predetermined shape. The film laminate obtained by applying the polyimide of the present invention to a commercially available polyimide film is well-adapted to dry film and exhibits good adhesiveness, so that problems during chemical etching can be solved.

Further, examples of uses of the polyimides of the present invention include insulating layers of printed wiring circuit boards and metal-based semiconductor packages, semiconductor encapsulants combining the polyimide of the present invention with fillers such as silica particles, and the like. There is a conductive adhesive and the like in which the polyimide of the present invention is blended with conductive carbon and metal fine particles such as silver, copper and nickel, and conductive fine particles such as plastic fine particles plated with a metal such as silver and nickel.

In order to impart adhesiveness, it is preferable to use block copolymer polyimides containing 3 to 50 mol% of a siloxane compound having a diamine at both ends as a diamine component.

A metal-based semiconductor package is suitable for high-density mounting because it can be mounted with good heat radiation by applying an electromagnetic wave shield. However, as an insulating layer required for a metal-based substrate, The polyimides of the present invention are preferable from the viewpoint of heat resistance and adhesive performance. The structure of the semiconductor package includes a mounted semiconductor chip,
It is composed of a conductor circuit, a plurality of external connection terminals, and a metal substrate whose necessary parts are covered with an insulation layer. The insulation layer made of polyimides is composed of one or more layers, and the conductor circuit is formed on each insulation layer. A structure that is formed and penetrates each insulating layer and is electrically connected between a plurality of conductor circuits is particularly preferable for high-density mounting.

As for the insulating layer of the metal-based printed circuit board, the polyimides of the present invention have good heat resistance and good adhesive properties. Can be obtained.

In particular, for a printed wiring circuit board for high-density mounting, a circuit board in which a fine wiring pattern is formed by electrolytic plating on a conductive substrate is coated on a polyimide insulating layer formed on a metal sheet. Thermal transfer from the substrate,
For a substrate in which a copper foil is bonded to an insulating layer formed on a metal sheet, a wiring pattern is formed on the copper foil by a photoetching method, or a copper thin film is formed on the insulating layer formed on the metal sheet by a sputtering method. A single-layer or multi-layer printed circuit board having a polyimide insulating layer can be formed by a method such as forming a wiring pattern thereon by photoplating.

The polyimide adhesives, coating agents, electrodeposition paints, heat-adhesive films and the like comprising the block copolymerized polyimide having a molecular weight of about 50,000 to about 100,000 according to the present invention are products of polyamic acid solutions which are currently widely used. Compared with the above, it is not gelled even when stored for a long period of time, has excellent storage stability, and does not require high-temperature heat treatment in an oxygen-free atmosphere, so that handling is very convenient. In particular, since it is possible to give a regular arrangement to the components involved in the adhesiveness, the degree of freedom in polymer design can be expanded.

[0033]

The present invention will be described below in detail with reference to examples. Note that the present invention is not limited to the following embodiments.

Example 1 A thermometer, a stirrer, a reflux condenser equipped with a water content receiver, and a nitrogen gas inlet 5
In a 00 ml four-neck separable flask, 195 g of N, N-dimethylacetamide and α, ω-bis (3-aminopropyl) polydimethylsiloxane (average molecular weight 802)
8.57 g, 21.07 g of bis [4- (4-aminophenoxy) phenyl] sulfone, 3,3 ′, recrystallized from water, dried at 100 ° C., 4,4 ′ containing 5% of water
-Biphenyltetracarboxylic acid 20.80 g, pyridine 1.03 g, toluene 50 g, γ-valerolactone 1.
Add 3 g. Stir at room temperature for 20 minutes, raise temperature to 160 ° C
After heating and stirring while distilling water under reflux for 1 hour,
The temperature is raised to 180 ° C., and the mixture is further heated and stirred for 2 hours. After air cooling, 0.71 g of phthalic anhydride was added, and the mixture was stirred at room temperature for 1 hour, and then heated and stirred under reflux at 180 ° C. for 1 hour.
The reaction was further continued for 2 hours while distilling off toluene to obtain a viscous polyimide solution.

On a copper foil having a thickness of 18 μm (Mitsui Metals 3E
C-HTE) and cast the above polyimide solution into 2
After drying at 40 ° C. for one hour, a flexible printed board having a polyimide layer thickness of 25 μm was obtained. 180 degree peel peel strength (measurement method JIS C 6471) is 1.6 kg / cm
The peel strength after hot water treatment at 85 ° C. for 30 minutes was 1.1 kg / cm.

Example 2 Using the same reactor as in Example 1, 180 g of N, N-dimethylacetamide was recrystallized from water, dried at 100 ° C., containing 5% of water.
3 ′, 4,4′-benzophenonetetracarboxylic acid 1
8.60 g, 1,3-bis (3-aminopropyl)-
1,1,3,3-tetramethyldisiloxane 0.51
g, γ-hexanolactone 1.48 g, pyridine 1.0
After adding 3 g and reacting in the same manner as in Example 1, the mixture is cooled. In the above solution, N, N-dimethylacetamide 4
0 g, 19.5 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1.03 g of pyridine, 50 g of toluene and 0.71 g of phthalic anhydride are added. The reaction was carried out in the same manner as in Example 1 to obtain a viscous polyimide solution.

18 μm thick copper foil (Mitsui Metals 3EC)
-HTE), cast the polyimide solution onto 240
After drying at 1 ° C. for 1 hour, a flexible printed board having a polyimide layer thickness of 25 μm was obtained. The 180 ° peel strength (measurement method JIS C 6471) is 1.5 kg / cm, and the peel strength after treatment at 85 ° C. with hot water for 30 minutes is 1.
It was 0 kg / cm.

Further, the polyimide surface of the above-mentioned flexible printed circuit board was superimposed on a 42 μm thick nickel sheet having a thickness of 200 μm, and a pressure of 20 kg / c was applied under reduced pressure of a vacuum pump.
Pressing was performed at 270 ° C. for 1 hour at a temperature of 270 ° C. to obtain a copper / 42 nickel bonding material (for metal-based printed circuit boards). The adhesion at the copper / polyimide interface and the 42 nickel / polyimide interface was sufficient, and did not peel even after treatment in hot water at 85 ° C. for 30 minutes.

Comparative Example 1 A polyimide solution was obtained under the same conditions as in Example 1 except that P-toluenesulfonic acid was used instead of the imidizing agent γ-hexanolactone used in Example 1. In the same manner as in Example 1, a polyimide solution was cast on a copper foil having a thickness of 18 μm (3EC-HTE made by Mitsui Kinzoku) to obtain a flexible printed board having a polyimide layer having a thickness of 25 μm. The 180 degree peel peel strength (measurement method JIS C 6471) is 0.7 kg / cm, and the peel peel strength after treatment for 30 minutes at 85 ° C. hot water is 0.25 kg / cm, which cannot be put to practical use. It was standard.

Comparative Example 2 A polyimide solution was obtained under the same conditions as in Example 2 except that an equimolar amount of crotonic acid was used instead of the imidizing agent γ-hexanolactone used in Example 2. 18μm thick copper foil (Mitsui Metals 3
A polyimide solution was cast on EC-HTE) to obtain a flexible printed board having a polyimide layer thickness of 25 μm. 180 degree peel peel strength (Measurement method JIS C
6471) is 0.8 kg / cm.
The peel strength after the treatment for 0 minutes was 0.3 kg / cm, which was a level that could not be put to practical use.

EXAMPLE 3 2.3 g of nickel- and gold-plated polystyrene particles having a particle diameter of 3 to 8 μm were dispersed in 20 g of the polyimide solution obtained in Example 1 for 30 minutes using a sand grind mill. 80 g of the above polyimide solution was added to the dispersion, which was subsequently dispersed by a sand grind mill for 30 minutes to obtain an anisotropic conductive paint. This anisotropic conductive paint is coated on a conductive terminal portion of a flexible circuit board having a pitch of 100 μm so that a film thickness of 20 μm can be obtained.
Dried for minutes. The conductive terminal portion of the obtained flexible circuit board is overlapped with an ITO circuit glass plate having the same pitch,
260 through the cushioning polyimide film
Pressure bonding was performed at 20 ° C. and a pressure of 20 kg / cm 2 for 20 seconds. The conduction resistance between the obtained thermocompression-bonded circuits is 0.5Ω or less, and the adhesive strength after a high-temperature and high-humidity test at 60 ° C. and 90% RH for 1000 hours also shows 0.5 kg / cm or more, showing good performance. Was.

Example 4 A polyimide film obtained in Example 2 was biaxially stretched with a thickness of 50 μm and a polyphenylene sulfide film (trade name: Torelina, manufactured by Toray Industries Ltd.) was used as a base film so that a film thickness of 20 μm could be obtained on the film surface. After coating, it was dried at 110 ° C. for 20 minutes using a vacuum dryer. The obtained film laminate and a metal layer of stainless steel SUS301 having a thickness of 30 μm are adhered to each other using a hot press machine, and the obtained metal laminate is fixed to a frame of a processing stage of a YAG laser beam machine. Is moved in accordance with a plurality of patterns to be drilled, and the second harmonic (wavelength: 532 nm) of the YAG laser is incident on the fourth harmonic generation unit (comprising a nonlinear optical crystal element) as laser light from the metal layer side. This is a product processed using the fourth harmonic (wavelength 266 nm) obtained as described above. An electrode was attached to the metal layer made of stainless steel, and electrolytic polishing was performed while applying a jet at 50 ° C. to an electrolytic aqueous solution consisting of phosphoric acid and sulfuric acid to smooth the unevenness of the inner wall of the through hole of the metal layer.
The outer periphery of the metal laminate with the substrate film is supported by an adhesive on a printing frame of an aluminum square pipe, and the metal layer, which is a main component of the printing plate, is disposed on the surface of the substrate film in the metal laminate. The structure having a plurality of opening through-holes can be used as a printing plate for screen printing. Since this plate uses a polyimide resin with high heat resistance as an adhesive for the base film, it has good adhesion to the printing substrate and does not show any foaming of the adhesive during laser processing.
No bleeding of the printing ink was observed on the printing medium even after 300 continuous printings.

[0043]

The present invention is as described above, and is not purified by directly imidizing a tetracarboxylic acid and a diamine using a γ-lactone and a basic organic compound as an imidizing agent. And a method for producing polyimides having excellent physical properties. further,
The obtained polyimides are not gelled even when stored for a long time, have excellent storage stability, and do not require high-temperature heat treatment in an oxygen-free atmosphere. Wide range of applications such as thermal adhesive film, adhesive layer of cover film to be bonded to flexible printed circuit board and lead frame, insulating layer of printed circuit board and semiconductor package, semiconductor encapsulant, conductive adhesive, electrodeposition paint, etc. Available to

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Claims (15)

[Claims] 1. A mixture comprising at least one tetracarboxylic acid (including the ester of the tetracarboxylic acid; the same applies hereinafter) and at least one diamine having two or more carbon atoms, a γ-lactone and In the presence of a basic organic compound, heat and react in an organic polar solvent,
A method for producing polyimides, comprising directly producing polyimides. 2. The mixture comprises a lower polyimide oligomer, at least one of tetracarboxylic acids and / or at least one of diamines having two or more carbon atoms, and the obtained polyimide is a block copolymerized polyimide. The method for producing polyimides according to claim 1, wherein 3. The γ-lactone according to claim 1, wherein the γ-lactone is at least one lactone having the following structure.
Production method of polyimides. Embedded image 4. The method according to claim 1, wherein the basic organic compound is at least one selected from pyridine, triethylamine, tetramethylenediamine, triethylenediamine, picoline, N-methylmorpholine and quinoline. A method for producing such polyimides. 5. The method for producing polyimides according to claim 1, wherein said mixture contains a diaminosiloxane compound as one component. 6. The method for producing a polyimide according to claim 1, wherein the mixture contains an aromatic diaminocarboxylic acid as one component. 7. An anionic electrodeposition coating composition comprising the polyimides, organic polar solvent, amines and water of claim 6 as main components. 8. A polyimide film comprising a composition containing the polyimides according to claim 1 as a main component. 9. A film laminate comprising the substrate film on which the polyimides according to claim 1 is disposed. 10. An adhesive composition comprising the polyimides according to claim 1 and an organic polar solvent as main components. 11. A printed circuit board comprising the polyimide of any one of claims 1 to 7 as an insulating layer. 12. A printed wiring circuit board comprising a conductor circuit, a plurality of external connection terminals, and a metal substrate having a necessary portion covered with an insulating layer, wherein the polyimide insulating layer according to claim 1 is used. A printed wiring circuit board comprising one or two or more layers, wherein a conductive circuit is formed on each insulating layer, and a plurality of electrical connections are made between the conductive circuits through each insulating layer. 13. A mounted semiconductor chip, a conductor circuit,
8. A semiconductor package comprising a plurality of external connection terminals and a metal substrate having a required portion covered with an insulating layer, wherein the polyimide insulating layer according to any one of claims 1 to 7 comprises one or more layers. A semiconductor package, wherein a conductor circuit is formed on an insulating layer, and a plurality of electrical connections are made between the conductor circuits through each insulating layer. 14. A semiconductor encapsulant comprising the polyimides according to claim 1 and a filler as essential components. 15. A conductive adhesive comprising the polyimide according to claim 1 and conductive fine particles.