JPS634577B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for manufacturing a laminate that can be plastically deformed and has excellent heat resistance. Conventional laminates are typically made of phenolic resin or epoxy resin and a fiber base material, but they have the disadvantage that the laminate will break if it is plastically deformed (for example, bent by 90 degrees). Ta. Under these circumstances, the present inventors
In order to obtain a laminate that can be plastically deformed even at room temperature and has good heat resistance, as a result of extensive research, we have found that a particularly aliphatic polyester is used as the polyester, and a specific aliphatic tetracarboxylic acid and an aliphatic polyvalent amine are further added to this. When the polyester amide-imide or polyester imide obtained by the reaction is heated at high temperature, it becomes an insoluble and infusible resin due to a complex reaction of free reactive acid groups or hydroxyl groups contained in the resin component. discovered that this resin exhibits extremely high flexibility and plasticity as well as good heat resistance properties, and when a plurality of prepregs obtained by impregnating a fiber base material with this resin were heated and pressed to form a laminate. We have obtained knowledge that can overcome the drawbacks of the laminates mentioned above. That is, the present invention uses a polyester consisting of an aliphatic or alicyclic dicarboxylic acid or a derivative thereof and an aliphatic polyhydric alcohol in which two or more hydroxyl groups are bonded to different carbon atoms to 1,2,3,4-butane. Flexibility mainly based on polyesteramide-imide or polyesterimide modified with tetracarboxylic acid (hereinafter referred to as BTC) or its derivative and an aliphatic polyvalent amine in which two or more amino groups are bonded to different carbon atoms. This invention relates to a method for manufacturing a laminate, which is characterized by using a heat-resistant resin with excellent heat resistance, impregnating a sheet-like heat-resistant fiber base material with the heat-resistant resin to form a prepreg, and laminating a plurality of the obtained prepregs and heating and pressurizing them. It is. Examples of the aliphatic or alicyclic dicarboxylic acids or derivatives thereof used as the acid component of the polyester in this invention include oxalic acid, succinic acid,
Aliphatic dicarboxylic acids such as malonic acid, adipic acid, 1,5-pentanedicarboxylic acid, 1,6-hexanedicarboxylic acid, azelaic acid, 1,9-nonadicarboxylic acid, sebacic acid, 1,10-decanedicarboxylic acid, One or more types of alicyclic dicarboxylic acids such as tetrahydroterephthalic acid, tetrahydrophthalic acid, tetrahydroisophthalic acid, and tetrahydrofuran dicarboxylic acid, or derivatives of these dicarboxylic acids such as lower alkyl esters and halides are used. Among these, the most preferred are linear aliphatic dicarboxylic acids having 1 to 10 carbon atoms or derivatives thereof. If necessary, aromatic dicarboxylic acids such as terephthalic acid or derivatives thereof may be used together with these dicarboxylic acids, but the proportion should be small enough to not impair flexibility after high-temperature heat treatment. It is. As the aliphatic polyhydric alcohol in which two or more hydroxyl groups are bonded to different carbon atoms and used as the alcohol component of the polyester in this invention, a wide variety of conventionally known aliphatic alcohols can be used, but it is particularly preferable that the number of carbon atoms is 2 to 10. It is preferable to use a straight chain aliphatic polyhydric alcohol. Specifically, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-
Examples include dihydric alcohols such as decanediol, diethylene glycol, and triethylene glycol, and trihydric alcohols such as glycerin, trimethylolpropane, and pentaerythritol, and one or more of these alcohols may be used. Generally, the ratio of these acid components and polyhydric alcohol components should be such that the total amount of hydroxyl groups (equivalent) is greater than the reactive acid groups (carboxyl groups, etc.) of the acid component. On the other hand, good results can be obtained when the alcohol component is increased 1.1 to 4.0 times, preferably 1.1 to 2.0 times (equivalent). In this invention, the above-mentioned acid component and alcohol component are generally subjected to a polycondensation reaction at 130 to 200°C for 0.5 to 4 hours to form a polyester having a high molecular weight sufficient to satisfy mechanical strength and flexibility. However, this polyester generally contains unreacted hydroxyl groups as well as unreacted reactive acid groups. The aliphatic polyvalent amine in which BTC or its derivative and two or more amino groups are bonded to different carbon atoms is used to modify the polyester, and it improves the heat resistance of the polyester and improves its flexibility and mechanical properties. In this case, if polybasic acids other than BTC, such as trimellitic acid or pyromellitic acid, or aromatic polyvalent amines are used, the above effects will be weaker. Not only that, but depending on the modification conditions and the molar ratio of polybasic acid and polyvalent amine, polyesterimide, which is difficult to dissolve in common organic solvents, may be produced, which may impede moldability. Derivatives of BTC include its monoanhydride, dianhydride, ester, and halide. Furthermore, as the aliphatic polyvalent amine in which two or more amino groups are bonded to different carbon atoms, linear aliphatic polyvalent amines having 2 to 8 carbon atoms are particularly preferably used, such as ethylenediamine. , propylene diamine, butanediamine, pentanediamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, triaminopropane, etc. are used one or more kinds. Furthermore, if particularly desired, an aromatic polyvalent amine such as phenylenediamine may be used in combination with such aliphatic polyvalent amine in an amount within a range that does not impede the effects of the present invention. The ratio of BTC or its derivative and aliphatic polyvalent amine to the polyester is usually 0.3 to 4.0 mol, preferably 0.5 mol of BTC or its derivative per 1 mol of dicarboxylic acid or its derivative, which is one of the polyester forming components. ~2.0 mol, while the aliphatic polyvalent amine is 0.4 to 1 mol of the above BTC or its derivative.
The usage ratio may be approximately 1.4 mol, preferably 0.6 to 1.2 mol. In the polyester modification reaction in this invention, BTC or its derivative and an aliphatic polyvalent amine are added to the system in which the polyester has been synthesized, a polycondensation reaction of both is carried out, and this condensation product is sequentially converted into a polyester. What you need to do is to react to this. Of course, if necessary, use outside the polyester synthetic system.
It is also possible to prepare a condensation product of BTC or its derivative with a polyvalent amine and react it with polyester. In addition, in some cases, a polyester forming component and a modifier component are simultaneously added to the reaction system to sequentially perform the polycondensation reaction of BTC or its derivative with a polyvalent amine, the polyester condensation reaction, and the polyester modification reaction in one step. It is also possible. In these methods, the condensation reaction between BTC or its derivatives and aliphatic polyvalent amine is generally
The reaction may be carried out by heating at a temperature of 60230°C, preferably 80 to 200°C, until the water produced by the reaction no longer distills out.
In addition, the reaction between this condensation product and polyester is generally carried out at a temperature of 100°C or higher, preferably 150 to 230°C, for a period of time until the reaction product water no longer distills out.
The reaction may be carried out by heating for about 0.5 to 4 hours. The polyester modified product obtained in this way is
When BTC or its derivatives are used in excess compared to the aliphatic polyvalent amine, it usually results in an imide-modified polyester, and the aliphatic polyvalent amine is
When used in an equal amount or in excess of BTC or its derivatives, it is usually amide-imide modified and becomes a polyester, which itself dissolves in organic solvents with free reactive acid groups or hydroxyl groups remaining in the polymer. It has the property of The heat-resistant resin used in this invention has such polyester amide-imide or polyester imide as its main component, and various optional components depending on the purpose of use, such as conventionally known epoxy to the extent that plasticity and flexibility are not impaired. Inert substances such as resins, resins such as polyester resins, organometallic compounds such as titanium and tin, pigments, dyes, and organic and inorganic fillers can be blended. Further, when a prepreg is obtained from this resin, an appropriate organic solvent may be added to improve the workability of coating, impregnation, etc. This organic solvent may be added during the polyester condensation reaction, polyester modification reaction, etc., and may be further added as a diluent thereafter. The organic solvent used here is preferably ethyl cellosolve, alcohols, ketones, etc. from the perspective of resource conservation, but other general-purpose solvents such as cresol and phenol, N/N-dimethylformamide, N/N-dimethylacetamide, Of course, polar solvents such as dimethyl sulfoxide can be used. Furthermore, the heat-resistant resin used in the present invention can be applied as a water-soluble type material, since the polyesteramide-imide or polyesterimide raw materials have the property of being soluble in water. In this case, it is usually preferable to react a nitrogenous base compound to the polyesteramide-imide or polyesterimide having a free reactive acid group or hydroxyl group in the molecule prepared by the above-mentioned method to form a water-soluble salt. Ammonia is preferred as the nitrogenous base compound, but various other primary amines, secondary amines, tertiary amines, heterocyclic compounds that act in the same way, and quaternary ammonium compounds can also be used. The heat-resistant resin used in the present invention, which is obtained in various forms such as a solvent-free type, an organic solvent type, and a water-solubilized type, can be coated or impregnated onto a sheet-like heat-resistant fiber base material as appropriate. By applying the following means, prepreg can be made, and this prepreg itself has self-bonding properties, that is, it has the ability to self-adhere to other articles as well as to other articles by moderate heating. By stacking multiple sheets and heating and pressurizing them at 200 to 250°C for 1 to 10 hours, free reactive acid groups or hydroxyl groups in polyesteramide-imide or polyesterimide molecules are removed. The laminate can be completely cured by reacting with the laminate, which is the object of the present invention. The thus obtained laminate has extremely high plastic deformability at room temperature and excellent heat resistance compared to conventional laminates using epoxy resins, phenolic resins, etc. In the present invention, examples of the sheet-like heat-resistant fiber base material include glass cloth, glass mat, heat-resistant nonwoven fabric, and nonwoven fabric obtained by mixing glass chops and heat-resistant fibers. In the present invention, the sheet-like heat-resistant fiber base material usually has a thickness of about 0.05 mm to 2 mm. In addition, in the present invention, the above prepreg is usually
By laminating about 10 to 10 sheets, it can be used practically as a laminate with a thickness of about 0.5 mm to 5 mm. The present invention will be specifically described below based on Examples. Example 1 (Production of heat-resistant resin) 36.5 g (0.25 mol) of adipic acid and 31.0 g (0.50 mol) of ethylene glycol were put into a 500 ml four-necked flask equipped with a stirrer, a side tube, and a thermometer.
The mixture was maintained at 180° C. for 2 hours with stirring to carry out a polyester condensation reaction. Distilled water from the side pipe
It was 7.2g. After cooling this reaction system to 70℃, BTC58.5
g (0.25 mol), followed by 29.1 g (0.25 mol)
A solution prepared by diluting 50.0 g of ion-exchanged water with 50.0 g of ion-exchanged water was gradually added dropwise to the BTC.
A polycondensation reaction was carried out between and hexamethylene diamine. The dropping time was 15 minutes, during which time the reaction system reached a maximum temperature of 105°C due to the reaction heat, and water was distilled out from the side pipe. Thereafter, the temperature of the reaction system was raised to 200°C, and water and unreacted components remaining in the system were distilled off. From the total amount of distilled water, it was found that the amount of reaction water in the polycondensation reaction of BTC and hexamethylene diamine was 18.0 g. Next, the mixture was maintained at the same temperature for 1.5 hours to carry out a polyester modification reaction. The amount of distilled water during this period was 68.0 g. The polyester modified product thus obtained had an acid value of 40, and was confirmed from nuclear magnetic resonance spectroscopy to be a polyester amide-imide containing an ester bond, an amide bond, an imide bond, and an imide bond. After cooling this polyesteramide-imide to 130℃, 128.1g of ethyl cellosolve was added.
was added to obtain the heat-resistant resin of the present invention. Example 2 (Production of heat-resistant resin) 57.5 g (0.25 mol) of 1,10-decanedicarboxylic acid was used instead of adipic acid, and 59 g (0.50 mol) of 1,6-hexanediol was used instead of ethylene glycol.
A modified polyester was obtained under exactly the same operation and reaction conditions as in Example 1, except that mol) was used. This polyester modified product had an acid value of 55, and was confirmed to be the same polyester amide-imide as in Example 1 from the nuclear magnetic resonance spectrum. After cooling this polyesteramide-imide to 130° C., 177.1 g of ethyl cellosolve was added to obtain a heat-resistant resin of the present invention. Example 3 (Production of heat-resistant resin) The amount of hexamethylene diamine used was 23.3g.
A modified polyester was obtained under exactly the same operation and reaction conditions as in Example 1, except that the amount was changed to (0.20 mol).
This modified product had an acid value of 70, and was confirmed by nuclear magnetic resonance spectroscopy to be a polyester imide containing ester bonds and imide bonds. After cooling this polyesterimide to 130° C., 122.3 g of ethyl cellosolve was added to obtain a heat-resistant resin of the present invention. Example A Epoxy resin (Epicoat 828 manufactured by Ciel) 100
parts by weight, 10 parts by weight of a curing agent (dicyandiamide) and 110 parts by weight of methyl ethyl ketone were mixed until homogeneous to prepare a resin solution. Example 1 A glass cloth (216AS308 manufactured by Asahi Schuebel Co., Ltd.) was impregnated with the heat-resistant resin obtained in Example 1.
The ethyl cellosolve was volatilized using a hot air dryer at ℃ to obtain a prepreg. Seven sheets of this prepreg were laminated and heated and pressed at 200° C. for 4 hours to form a laminate. Its properties are shown in Table 1 below. Example 2 The heat-resistant resin obtained in Example 2 was treated in the same manner as in Example 1 to obtain a laminate. The properties of the obtained laminate are shown in Table 1 below. Example 3 The heat-resistant resin obtained in Example 3 was treated in the same manner as in Example 1 to obtain a laminate. The properties of the obtained laminate are shown in Table 1 below. Comparative Example The glass cloth used in Example 1 was impregnated with the resin solution obtained in Example A, and methyl ethyl ketone was volatilized in a hot air dryer at 80°C to obtain a prepreg. Seven sheets of the obtained prepreg were laminated and heated at 150℃ for 2
A laminate was obtained by heating and pressing under certain conditions. The properties of the obtained laminate are shown in Table 1 below.

【table】

[Table] In Table 1 above, the bending angle is also expressed as the angle at which cracks begin to appear when the laminate is bent at 3.2R at room temperature. In addition, the solder heat resistance test was conducted in accordance with IPC-240B.

Claims (1)

[Claims] 1 A polyester consisting of an aliphatic or alicyclic dicarboxylic acid or a derivative thereof and an aliphatic polyhydric alcohol in which two or more hydroxyl groups are bonded to different carbon atoms is converted into 1,2,3,4-butanetetracarboxylic acid. or a polyester amide imide modified with a derivative thereof and an aliphatic polyvalent amine formed by bonding two or more amino groups to different carbon atoms, or a heat-resistant resin with excellent flexibility based on polyester imide. A method for manufacturing a laminate, comprising impregnating this into a sheet-like heat-resistant fiber base material to obtain a prepreg, laminating a plurality of the obtained prepregs, and heating and pressurizing them.