JPS6046132B2 - Composite material manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a composite material containing aromatic polyamide fibers and a thermosetting resin as main components.

In recent years, a composite material called FRP, which uses various reinforcing materials as a structural material, has become the successor of plastics.

Recently, attention has been newly focused on the production of composite materials that use lightweight aromatic polyamide fibers with extremely high strength and elasticity as reinforcing materials and various resins as matrices. by the way,
In the production of such composite materials of various matrices, the most important factor determining their performance is increasing the adhesion between the reinforcing material and the matrix, especially the interlaminar shear strength.

The aromatic polyamide fiber itself generally has a property of having low adhesion to a matrix, and therefore does not exhibit sufficient shear strength as a composite material. The present invention was completed as a result of various studies to solve these drawbacks, and its gist is that the general formula 1
The present invention provides a method for producing a composite material in which an aromatic polyamide fiber and a thermosetting resin are bonded together by heat curing using a lactam compound represented by Co(CH2)nNH (where n is an integer of 3 to 5) and an epoxy resin.

In the present invention, the aromatic polyamide fiber refers to a fiber in which 15 mol% or more of the bonding units of the polymer constituting the fiber is an amide bond, and for example, polyP-phenylene terephthalamide, polyP-aminobenzamide, etc. are used. .

The thermosetting resin is generally known as a thermosetting resin, and epoxy resins, phenol resins, unsaturated polyester resins, and the like are particularly preferably used.

In the present invention, the epoxy resin used for bonding fibers and resin includes, for example, bisphenol A diglycidyl ether,
Bisphenol A dimethyl glycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, phthalic acid diglycidyl ether, hexahydrophthalic acid diglycidyl ether, cyanuric acid triglycidyl ether, vinyl cyclohexene Diepoxide, dicyclopentadiene dioxide, etc., and any other substances used as so-called epoxy resins or epoxy novolak resins can be used.

In the present invention, the lactam compound has the above general formula ? −
? −? (However, n is an integer from 3 to 5 and CO(CH2)
There is NNH.

) Examples include 2-pyrrolidone, E-caprolactam, and α-piperidone.
Examples of forms in which such compounds are used in combination in the present invention include:
It may be used in the form of a simple blend of epoxy resin and lactam compound, or they may be prepared in advance from 80 to
It may be used as a reaction product which is reacted at a temperature of 150° C. for 1 to 5 hours.

Here, the bonding ratio is preferably 0.5 to 2, preferably 0.8 to 1.5 in terms of NH equivalent to 1 epoxy equivalent. As a method for producing a composite material, a mixture of such compounds or a reactant thereof may be used as an adhesive, for example. For example, (1) aromatic polyamide fibers or knitted fabrics or cords made of them are treated with an aqueous dispersion or an organic solvent solution of an adhesive, and the
A method may be used in which the adhesive is dried at about 350°C for 3 to 3 minutes and then impregnated with the thermosetting resin, or (2) after the adhesive is mixed with the thermosetting resin, the mixture is Although a method of impregnating the aromatic polyamide fiber with the resin may be used, the former method (1) is preferable because it is superior in terms of adhesiveness. In the present invention, the ratio of aromatic polyamide fibers and thermosetting resin (matrix component) varies depending on the use and purpose of the structure to be molded, but usually the range is relative to the structure. The amount of aromatic polyamide fiber is 10 to 9% by weight, and the amount of thermosetting resin is 90 to 1% by weight.

The amount of adhesive attached to the fibers is suitably 0.1 to 5%, preferably 0.3 to 3%, based on the weight of the fibers.

If the amount is less than 0.1%, the adhesion force is low and insufficient, and if the amount exceeds 5%, the adhesion force no longer increases and a disadvantageous force 5 is generated which makes the fibers stiff. Depending on the use and purpose of the structure, some additives such as fillers, pigments, weather-resistant and heat-resistant stabilizers may be added to the matrix component.

After being impregnated with resin and bonded, the resin is cured by heating and pressurizing in a conventional manner to obtain a thermosetting resin reinforced with aromatic polyamide fibers.

As the curing agent for the thermosetting resin, any conventionally known curing agent may be used, for example, boron trifluoride monoethylamine complex salt or the like may be used for the epoxy resin.

The composite structure manufactured by the method of the present invention can be applied to various uses and purposes.

For example, sports equipment, leisure equipment, various appliances, parts, etc. that require high strength and elastic modulus, as well as aerospace equipment, automobiles, and other products that require lightness and excellent properties of strength, elasticity, and heat resistance. It is effective when used in equipment, etc. The present invention will be explained in detail below with reference to Examples.

In the examples, % represents weight % unless otherwise specified.

Example 1 1500 d of high elasticity type poly P-phenylene terephthalamide filaments were mixed with an aqueous dispersion of Epikote 8812 (epoxy resin manufactured by Shell Chemical Co., Ltd.) and 2-pyrrolidone (Epicoat 812/2-pyrrolidone 1/5 (weight ratio),
Dispersant: Perex 0T-P (manufactured by Kao Atlas Co., Ltd.) was immersed and dried at 250°C for 1 minute.

The adhesion amount was 1%. The fibers treated in this way were coated with Epicoat (9828 (epoxy resin, manufactured by Shell Chemical Co., Ltd.) 1
(1) part, impregnated with a resin solution consisting of 5 parts of boron trifluoride monoethylamine complex salt, laminated an appropriate number of sheets, and with the fibers aligned in one direction, molded and cured at 150°C for 1 hour with a heat press (press pressure 10k91d) and further post-cured at 170°C for 2 hours. A test piece with a length of 20 wrm, 1 width of 6 gourds, and a thickness of 3 gourds was prepared from the obtained composite material (fiber content 60%) and subjected to short beam three-point bending method (distance between spans 13?, crosshead speed 17 rUn/min). ), the interlaminar shear strength (ILSS) was measured to be 6.9 kg'i.

The ILSS of the composite material prepared by treating only Epicote 9812 under the same conditions without using 2-pyrrolidone was 6.
1k91Tr! It was 1t. Also, the ILSS of the composite material prepared without adhesive treatment was 4.8k9 nod. Example 2 Epicote 8812 and 2-pyrrolidone were mixed in epoxy equivalent/
NH equivalent is 1/1.

The aromatic polyamide fiber used in Example 1 was immersed in the methyl ethyl ketone solution of the obtained reactant, and the aromatic polyamide fibers used in Example 1 were mixed at 250°C for 1 hour. Dry for a minute.

The adhesion amount was 1%. Example 1
Create a composite material (60% fiber content) in the same manner as
When ILSS was measured, it was 7.0 kgITfUi. Example 3 The aromatic polyamide fiber used in Example 1 was immersed in a methyl ethyl ketone solution containing Epicoat 8828 and ε-caprolactam in an equivalent ratio of epoxy equivalent/NR equivalent of 1/1.5, and then treated at 250°C. Dry for 1 minute.

The adhesion amount was 1%. Example 1
Create a composite material (60% fiber content) in the same manner as
When ILSS was measured, it was 6.7k9noi. The ILSS of a composite material prepared by treating Epicote (9828) under the same conditions was 5.9 kgIi.Example 4 The fibers treated with the mixture of Epicote 8812 and 2-pyrrolidone in Example 1 were treated with Sumilite 8 Resin PR. -5
Impregnated with 0691 (phenol resin manufactured by Sumitomo Chemical),
Laminate an appropriate number of sheets, align the fibers in one direction, and mold and cure using a heat press at 150°C for 1 hour (pressing pressure 10k).
gIw71t) and further post cured at 170'C for 2 hours.

A composite material obtained in the same manner as in Example 1 (fiber content: 6
When the ILSS of 0%) was measured, it was 6.5k91d. The one made without adhesive treatment is 4.5k9
It was hot. Example 5 In Example 1, 1 (1) part of an unsaturated polyester resin (Polymer 330 & Takeda Pharmaceutical Co., Ltd.) was used instead of the epoxy resin for the matrix, and the product name was Nyper BO (benzoyl peroxide made into a paste with DOP, Japan). Molding and curing was carried out at 130°C for 1 hour in the same manner as in Example 1 except that a resin liquid consisting of 2 parts (made of oil and fat) was used.
A pressing pressure of 10 k91 cT1) was applied, followed by post-curing at 130° C. for 1 hour to obtain a composite material.

Claims (1)

[Claims] 1. A mixture or pre-reacted reaction of a lactam compound and an epoxy resin represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (where n is an integer from 3 to 5) A method for producing a composite material containing aromatic polyamide fibers and a thermosetting resin as main components, characterized in that the aromatic polyamide fiber and the thermosetting resin are bonded together by heat curing using a product. 2 Aromatic polyamide fiber is treated with an aqueous dispersion or an organic solvent solution of a mixture of a lactam compound and an epoxy resin or a reaction product reacted in advance, dried, and then impregnated with a thermosetting resin. A method for producing a composite material according to item 1.