JPH0678443B2 - Method for manufacturing laminated molded body - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a laminated molding from a prepreg sheet which is useful as a heat-resistant adhesive obtained by a novel production method, a heat-resistant composite material and the like.

[0002]

2. Description of the Related Art In the fields of electronics, aerospace equipment, transportation equipment, etc., various industrial materials are required to have high temperature characteristics in order to achieve high performance and light weight. Conventionally, epoxy-based, modified epoxy-based, phenolic-based resins, etc., which have been used as structural adhesives or prepregs for laminated molded bodies, have a remarkable drawback in heat resistance. Epoxy resins and the like have a problem in storage stability and have a drawback that they need to be stored at a low temperature. A polyimide resin is used as a material for improving such a defect. However, when a normal polyimide resin is completely cyclized to be in a polyimide state, its melt fluidity becomes very poor, which makes it difficult to use. On the other hand, although the melt fluidity improves in the state where the solvent or the polyamic acid remains, voids are generated in the molded product or the adhesive layer due to the water generated during the cyclization of the residual solvent or the amic acid group during processing, It is not preferable because it lowers the physical properties. As a polyimide resin having improved melt fluidity, tetracarboxylic dianhydride such as 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride and diamine such as 3,3′-diaminobenzophenone are used in an organic solvent. A polyimide resin obtained by heating and imidizing a polyamic acid obtained by the reaction was developed by the National Aeronautics and Space Administration (NASA). (For example, U.S. Pat.
No. 4,094,862. ) However, although this polyimide resin has good properties, a processing method by which its performance can be sufficiently obtained has not been provided.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made from the above point of view, and the object of the present invention is not to impair the good properties of the polyimide resin developed by NASA. It is an object of the present invention to provide a method for producing a heat-resistant laminated molded body using a material that can be used as a processing method.

[0004]

The present inventors finally arrived at the present invention as a result of intensive studies to achieve the above-mentioned object. That is, the present invention uses the formula (1)

[Chemical 3] [In the formula, R ₁ represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-bonded group in which aromatic nuclei are interconnected by a bridging member. Represents a divalent group selected from the group consisting of a condensed polycyclic aromatic group and a heterocyclic group,
R ₂ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic nuclei are interconnected by a bridging member. It represents a tetravalent group selected from the group consisting of aromatic groups and heterocyclic groups, and Y represents a group selected from the group consisting of hydrogen atoms, alkyl groups and aryl groups. ] After impregnating a fibrous reinforcing material with an organic solvent solution of a polyamic acid having a repeating unit represented by the following, the solvent contained is extracted with an extraction solvent, and then dried by heating to remove residual volatile components and polyamic acid. By heating to imidize the compound of formula (2)

[Chemical 4] [Wherein, R ₁ and R ₂ has the formula (1) is identical to R ₁ and R ₂ in] a prepreg obtained by a production method characterized by forming a polyimide having a repeating unit represented by the sheet Is laminated and heated to a temperature not lower than the glass transition point of the polyimide under pressure, which is a method for producing a laminated molded body.

In the present invention, polyamic acid is first synthesized. Polyamic acid can be synthesized by a known method. Generally, it is synthesized by reacting a tetracarboxylic dianhydride and a diamine compound in an organic solvent. Specifically, for example, by dissolving or suspending a diamine compound in an organic solvent and gradually adding tetracarboxylic dianhydride under a stream of dry nitrogen, or vice versa, to a tetracarboxylic dianhydride solution. It is synthesized by gradually adding a diamine compound.

The tetracarboxylic dianhydride used is preferably, for example, the following. Pyromellitic anhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3', 4'-benzophenone tetracarboxylic dianhydride, 2,2 ', 3,3' -Benzophenone tetracarboxylic dianhydride, 4,4 ',
5,5 ', 6,6'-hexafluorobenzophenone-
2,2 ', 3,3'-tetracarboxylic dianhydride, 3,
3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,5,6-trifluoro-3,
4-dicarboxyphenyl) methane dianhydride, 1,1-
Bis (3,4-dicarboxyphenyl) ethane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride Anhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, bis (2,5,5
6-trifluoro-3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, bis (2,5,6-trifluoro-3,4-dicarboxy) Phenyl) sulfone dianhydride, bis (3,4-dicarboxyphenyl) -phenylphosphonate dianhydride, bis (3,4-dicarboxyphenyl) -phenylphosphine oxide dianhydride, N,
N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride, bis (3,4-dicarboxyphenyl)
-Diethylsilane dianhydride, bis (3,4-dicarboxyphenyl) -tetramethyldisiloxane dianhydride,
3,3 ', 4,4'-Tetracarboxybenzoyloxybenzene dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,
7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride,
1,4,5,8-tetrafluoronaphthalene-2,3
6,7-Tetracarboxylic acid dianhydride, 1,8,9,10
-Phenanthrene tetracarboxylic dianhydride, 3,4
9,10-perylenetetracarboxylic dianhydride, 2,
3,4,5-thiophenetetracarboxylic dianhydride,
2,3,5,6-pyrazinetetracarboxylic dianhydride,
2,3,5,6-pyridinetetracarboxylic dianhydride,
Tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, 3,3 ', 4,4'-azobenzenetetracarboxylic dianhydride, 3,3', 4,4'-azoxybenzenetetracarboxylic Acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, ethylenetetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride and the like. A particularly preferable tetracarboxylic acid dianhydride is 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride (hereinafter abbreviated as BTDA). These tetracarboxylic dianhydrides may be used alone or in admixture of two or more.

The following diamine compounds are desirable. o-, m- and p-phenylenediamine,
2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene, 2,5-diaminoxylene, 1,3-
Diamino-4-chlorobenzene, 1,4-diamino-
2,5-dichlorobenzene, 1,4-diamino-2-bromobenzene, 1,3-diamino-4-isopropylbenzene, 2,2-dis (4-aminophenyl) propane, 3,3′- or 4, 4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-
Or 4,4′-diaminostilbene, 4,4′-diamino-2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octafluorodiphenylmethane, 3,3′- or 4,4 ′ −
Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diamino-2,2 ', 3
3 ', 5,5', 6,6'-octafluorodiphenyl ether, 3,4'-diaminodiphenylthioether, 3,3'- or 4,4'-diaminodiphenylthioether, 4,4'-diaminodiphenylsulfone,
3,3'-diminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4-aminobenzoic acid 4'-aminophenyl ester, 2,2'-, 3,3'- or 4,4'-diaminobenzophenone , 3,4'-diaminobenzophenone, 2,3'-diaminobenzophenone, 4,4'-diaminobenzyl, 4- (4-aminophenylcarbamoyl) aniline, bis (4-aminophenyl) -phosphine oxide, bis (4 -Aminophenyl) -methylphosphine oxide, bis (3-aminophenyl) -methylphosphine oxide, bis (4-aminophenyl) -cyclohexylphosphine oxide,
N, N-bis (4-aminophenyl) -N-phenylamine, N, N-bis (4-aminophenyl) -N-methylamine, 2,2 '-, 3,3'- or 4,4' -Diaminoazobenzene, 4,4'-diaminodiphenylurea, 1,8- or 1,5-diaminonaphthalene, 1,5
-Diaminoanthraquinone, diaminofluoranthene,
3,9-diaminochrysene, diaminopyrene, bis (4
-Aminophenyl) -diethylsilane, bis (4-aminophenyl) -dimethylsilane, bis (4-aminophenyl) -tetramethyldisiloxane, 2,6-diaminopyridine, 2,4-diaminopyrimidine, 3,6- Diaminoacridine, 2,4-diamino-S-triazine,
2,7-diamino-dibenzofuran, 2,7-diaminocarbazole, 3,7-diaminophenothiazine, 5,
6-diamino-1,3-dimethyluracil, 2,5-diamino-1,3,4-thiadiazole, dimethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nona Methylenediamine,
Decamethylenediamine, 2,2-dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine,
2,5-dimethylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 3-methoxyhexamethylenediamine,
5-methylnonamethylenediamine, 2,11-diaminododecane, 1,12-diaminooctadecane, 1,2-
Bis (3-aminopropoxy) -ethane and the like. Among them, a particularly preferred diamine compound is 3,3′-diaminobenzophenone (hereinafter abbreviated as 3,3′-DABP). These diamine compounds may be used alone or in 2
Use by mixing more than one species.

Further, N, N'-dialkyl or diaryl-substituted diamine compounds such as N, N'-diethylethylenediamine, N, N'-diethyl-1,3-diamino are used within a range that does not significantly affect the physical properties of the polyimide resin. Propane, N, N'-dimethyl-1,6-diaminohexane, N, N'-diphenyl-1,4-phenylenediamine and the like can be used in combination.

The organic solvent used is N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N-acetyl-2-pyrrolidone, sulfolane, dimethyl sulfoxide, diethylene glycol dimethyl ether and the like. These solvents are used alone or as a mixture. The resulting polyamic acid solution contains a normal resin content of 2 to 50%, or the viscosity of the solution is in the range of 10 to 50,000 centipoise as a viscosity measured by a Brookfield viscometer. It is preferable because it is easy and it is easy to impregnate the reinforcing material.

The intrinsic viscosity of the polyamic acid itself is
It is preferable that it is in the range of 0.2 to 2.0 dl / g from the viewpoint of mechanical strength, melt fluidity, heat resistance and the like of the obtained polyimide resin. The intrinsic viscosity is calculated by the following formula. η inh = (1 / C) · ln (η / η _O ) (In the above formula, ln = natural logarithm η = viscosity of a solution obtained by dissolving 0.5 g of polyamic acid in 100 ml of N, N-dimethylacetamide (35 ° C.) η _O = viscosity of N, N-dimethylacetamide (35 ° C.) C = polymer solution concentration expressed in g of polyamic acid per 100 ml of solvent.)

Typical examples of the fibrous reinforcing material used in the present invention are glass fiber, carbon fiber, aromatic polyamide fiber, aromatic polyamide non-woven fabric, boron fiber and the like, and these fibers may be used alone or in combination. Further, if necessary, other reinforcing materials such as silicon carbide fiber, mica, calcium silicate, silica and alumina may be used in combination with the above fiber. The simplest method of impregnation is to immerse the fibrous reinforcing material in a polyamic acid solution. Of course, it may be impregnated by another method. In the present invention, the solvent contained in the impregnated polyamic acid solution is first extracted with the extraction solvent.

The extraction solvent used here includes the following. Aliphatic hydrocarbons such as pentane, isopentane, hexane, cyclohexane, heptane, and otan,
Benzene, toluene, o-xylene, m-xylene, p
-Aromatic hydrocarbons such as xylene, mixed xylene, ethylbenzene, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2
-Aliphatic chlorides such as dichloroethane, 1,1,1-trichloroethane and tetrachloroethane, unsaturated chlorides such as cis-dichloroethylene, trans-dichloroethylene and trichloroethylene, chlorobenzene, o-dichlorobenzene, brombenzene, bromnaphthalene, iodobenzene and the like Aromatic halogen compounds, methyl iodide,
Aliphatic iodine compounds such as methane diiodide and ethyl iodide, methanol, 1,3-butanediol, ethanol (99.9%), methyl cellosolve, n-propanol, n
-Hydroxyl compounds such as butanol, isobutanol, n-amyl alcohol, n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, carboxylic acids such as acetic acid, formic acid, butyric acid, γ-butyrolactone,
Acetone, methyl ethyl ketone, diethyl ketone, dibutyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl butyl ketone and other ketones, methylal,
Ethers such as diethyl ether, furan, diisopropyl ether, methyl formate, ethyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, ethyl propionate, amyl formate, cellosolve acetate, butyl acetate, esters such as ethyl acetate, diethylamine, Amine such as dibutylamine, amide such as formic acid amide, acetic acid amide, dimethylformamide, dimethylacetamide, nitrile such as acetonitrile, propiononitrile, butyronitrile, nitromethane, nitroethane, 1-
Nitro compounds such as nitropropane, 2-nitropropane and nitrobenzene, carbon disulfide, ethyl mercaptan,
Sulfur compounds such as dimethyl sulfide and water.

These extraction solvents may be used alone or as a mixture. The extraction solvent used has a lower boiling point than the solvent contained in the polyamic acid solution. The simplest method for extraction is to immerse the fibrous reinforcing material impregnated with the polyamic acid solution in an extraction solvent. Of course, you may extract by another method. The extraction temperature is preferably -10 ° C to the boiling point of the extraction solvent at normal pressure. The prepreg sheet in which the solvent in the polyamic acid solution has been extracted as much as possible by the extraction operation is further dried by heating to remove the volatile components such as the unextracted solvent and the extraction solvent, and then subjected to the heat imidization. Volatile matter in the prepreg sheet causes blisters during the subsequent laminating operation or bonding operation, so it is preferable to remove it as much as possible, and the volatile matter content is 10% by weight or less of the entire prepreg sheet. desirable. Further, the resin content is preferably 20 to 80% by weight based on the whole prepreg sheet.

One of the features of the present invention is that when a prepreg sheet impregnated with a polyimide resin is produced, the solvent present in the polyamic acid solution is first extracted with a low boiling point solvent. As compared with the method of removing the solvent in the polyamic acid solution-impregnated fibrous reinforcing material only by heating and drying, the high boiling point solvent can be rapidly removed at a low temperature without rapidly increasing the temperature. Since it is not necessary to dry the prepreg sheet at a high temperature for a long time, there is almost no deterioration of the resin and it is an energy saving process. Further, the polyimide in the obtained prepreg sheet has excellent melt fluidity and is suitable as a material or an adhesive for a laminated molded body. The laminated molded product is obtained by laminating the prepreg sheets obtained as described above and heating and pressing. The heating temperature during lamination is equal to or higher than the glass transition point of the polyimide resin contained in the prepreg sheet, and preferably 240 to 360 ° C. The pressurizing pressure varies depending on the shape, but is preferably 1 to 500 kg / cm ² . The prepreg sheet of the present invention can be stored indoors at room temperature. In addition, the molding process is easy, and a molded product having a desired shape can be obtained by using an ordinary molding machine such as a hot press or an autoclave.

[0015]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples. Example-1 (a) Polymerization N, N-dimethylacetamide was added to a 500 ml four-necked flask.
300ml, 3,3'-DABP 31.85g (0.15mol) was added, and BTDA powder with stirring at 15 ° C under a dry nitrogen stream.
48.33 g (0.15 mol) was added slowly. The viscosity of the solution increases with the addition. After the addition was completed, stirring was continued for a further 4 hours to complete the reaction. The obtained polyamic acid was light brown and transparent and had an intrinsic viscosity of 0.74 dl / g (0.5 g / 100 ml N, N-dimethylacetamide solvent, 35 ° C.). (b) Impregnation and extraction The polyamic acid solution obtained in (a) was diluted with N, N-dimethylacetamide so that the resin content was not 8% by weight, and then a glass fiber cloth (WF-230 manufactured by Nitto Boseki). Was soaked.
The glass fiber cloth containing the polyamic acid solution taken out was dipped in an ethanol tank for 30 minutes to obtain N.V. Extraction of N-dimethylacedamide was performed. After air drying, the above operation was repeated once more to obtain a polyamic acid-impregnated prepreg sheet. (c) Drying and imidization The obtained prepreg sheet was heated at 60 ° C for 30 minutes and at 120 ° C for 30 minutes.
Min, 180 ° C. for 30 minutes, and 220 ° C. for 2 hours to dry for imidization and removal of volatile components to obtain a polyimide resin-impregnated prepreg sheet. The resin content of this prepreg sheet was 40%. (d) Molding The obtained prepreg sheets are laminated and then compressed by a compression molding machine.
It was molded at 50 ° C. and 100 kg / cm ² . The obtained molded product was brown and tough. The tensile strength of this molded product is 12.2 kg / m
m ² (23 ℃) (ASTM D-638), bending strength is 13.5kg / mm ²
(23 ℃) (ASTM D-790), Izod impact strength (with notch) is 4.9kg ・ cm / cm ² (23 ℃) (ASTM D-256)
Met.

Comparative Example-1 3,3'-DABP and BTDA under the same conditions as in Example-1.
Was reacted to obtain a polyamic acid solution having an intrinsic viscosity of 0.75 dl / g (0.5 g / 100 ml N, N-dimethylacetamide solvent, 35 ° C.). This solution was diluted with N, N-dimethylacetamide so that the resin content was 8% by weight, and then a glass fiber cloth was immersed. The glass fiber cloth was soaked and then air dried. Do this operation 3
This was repeated to obtain a polyamic acid-containing prepreg sheet. The resulting prepreg sheet was heated and dried at 100 ° C. for 1 hour, 150 ° C. for 1 hour, 180 ° C. for 1 hour, and 220 ° C. for 3 hours for imidization and removal of volatile components to obtain a polyimide resin-containing prepreg sheet. . (a) Molding The obtained prepreg sheets were laminated and molded in the same manner as in Example 1 (d). The tensile strength of this compact is 6.1 kg / mm ² (23
℃), the bending strength is 7.0kg / mm ² (23 ℃), and the Izod impact strength (with notch) is 2.4kg ・ cm / cm ² (23 ℃), which is inferior to Example-1 (d). It was

Examples 2 to 6 Various diamine compounds and tetracarboxylic acid dianhydride were polymerized in the same manner as in Example-1, and further impregnated into glass fiber, extracted, dried and imidized to produce a prepreg sheet. . Molding was performed using the obtained prepreg sheet, and the results shown in Table 1 were obtained.

[Table 1]

Example-7 (a) Polymerization A reactor similar to that used in Example-1 was charged with 48.33 g (0.15) of BTDA.
Mol) and N, N-dimethylacetamide (300 ml), and while stirring, add 3,3'-diaminodiphenyl ether (30.04 g, 0.15 mol) and allow the reaction to occur.
A polyamic acid solution having a concentration of 0.72 dl / g was obtained. N, N-dimethylacetamide was further added to this solution to adjust the resin concentration to 8% by weight. (b) Impregnation and Extraction The solution obtained in (a) was impregnated with a carbon fiber cloth (Torayca Trading # 6343). The polyamic acid solution-impregnated carbon fiber cloth taken out was dipped in a water tank for 30 minutes to obtain N.C. Extraction of N-dimethylacedamide was performed. After air drying, the above operation was repeated once more to obtain a polyamic acid-impregnated prepreg sheet. (c) Drying and imidization The obtained prepreg sheet was heated at 80 ° C for 1 hour and then at 150 ° C for 30 hours.
Min., 220 ° C. for 2 hours to dry for imidization and removal of volatile components to obtain a polyimide resin-impregnated prepreg sheet. (d) The prepreg sheets obtained in the molding (c) are laminated to form Example-1.
Molded under the same conditions as (d). The tensile strength of this molded body is
67kg / mm ² (23 ℃, fiber direction), bending strength 71kg / mm ² (23
℃, fiber direction), Izod impact strength (with notch) is 48
It was kg · cm / cm ² (23 ° C, fiber direction).

Examples 8 to 10 Polymerization was carried out in the same manner as in Example 7 (a) using various diamine compounds and tetracarboxylic acid dianhydride, and further similar to Examples 7 (b) and (c). Carbon fiber cloth (Torayca cloth # 63
43) was impregnated, extracted from water, dried and imidized to produce a prepreg sheet. Molding was performed using this prepreg sheet, and the results shown in Table 2 were obtained.

[Table 2]

[0020]

Since the present invention is constructed as described above,
According to the present invention, it is possible to provide a method for producing a laminated molding having excellent heat resistance using a novel prepreg sheet that exhibits particularly excellent strength even at high temperatures.

Claims (4)

[Claims] 1. Formula (1): [In the formula, R ₁ represents an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-bonded group in which aromatic nuclei are interconnected by a bridging member. Represents a divalent group selected from the group consisting of a condensed polycyclic aromatic group and a heterocyclic group,
R ₂ is an aliphatic group having 2 or more carbon atoms, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, or a non-condensed polycyclic group in which aromatic nuclei are interconnected by a bridging member. It represents a tetravalent group selected from the group consisting of aromatic groups and heterocyclic groups, and Y represents a group selected from the group consisting of hydrogen atoms, alkyl groups and aryl groups. ] After impregnating a fibrous reinforcing material with an organic solvent solution of a polyamic acid having a repeating unit represented by the following, the solvent contained is extracted with an extraction solvent, and then the solvent is removed by heating and drying to remove the polyamic acid. By heat imidization, the compound of formula (2) Wherein, R ₁ and R ₂ has the formula (1) is identical to R ₁ and R ₂ in] laminating the prepreg sheet obtained without a polyimide having a repeating unit represented by polyimide under pressure A method for producing a laminated molded article, which comprises heating the glass transition point to a temperature equal to or higher than the glass transition point. 2. The polyamic acid is obtained by reacting 3,3′-diaminobenzophenone and 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride in an organic solvent. A method for producing the laminated molded article described. 3. The method for producing a laminated molded article according to claim 1, wherein the extraction solvent is water. 4. The method for producing a laminated molded article according to claim 1, wherein the extraction solvent is an organic solvent having 1 or more carbon atoms and has a lower boiling point than the solvent contained in the polyamic acid solution.