JPS6011741B2 - Composite material whose main components are aromatic polyamide fiber and thermosetting resin and its manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to improvements in a composite material whose main components are aromatic polyamide fibers and a thermosetting resin, and a method for producing the same.

In recent years, composite materials that use various reinforcing materials as structural materials have been attracting attention, and in particular, composite materials that use lightweight, strong, and highly elastic aromatic polyamide fibers as reinforcement materials and various resins as matrices are being manufactured. is being attempted. 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.
Aromatic polyamide fiber itself generally has low adhesion to a matrix and does not exhibit sufficient shear strength as a composite material.

The present invention has been completed as a result of various studies to eliminate such drawbacks of the prior art, and its gist is to solve the following problems: is an integer.

Aromatic polyamide fiber and thermosetting resin, characterized in that a lactam compound represented by () or a water-dispersible related ring polymer thereof is present at the interface between the aromatic polyamide fiber and the thermosetting resin. A composite material whose main components are: and a method for producing the same. In the present invention, the aromatic polyamide fiber is one in which 15 mol% or more of the bonding units are amide bonds, and examples thereof include poly p-phenylene terephthalamide, poly p-aminobenzamide, and the like.

Further, as the thermosetting resin, commonly known epoxy resins, phenol resins, unsaturated polyester resins, etc. are used.

In the present invention, lactam compounds used for bonding fibers and resins include, for example, 2-pyrrolidosoQ-piveridone, go-caprolactam, N-acetyl-2-pyrrolidone, N-acetyl Q-piveridone, N-acetyl go-cabrolactam, etc. The term "containable ring polymer" refers to a product prepared by subjecting the lactam compound to ring ring polymerization using an alkali metal or its hydroxide and an acylating agent such as acetic anhydride or penzoyl chloride as a catalyst, or a water-dispersed polymer. "Possible" refers to a ring-opening polymer that is extracted with water and methanol and has an insoluble content of 3% or less.

In order to make a lactam compound and a ring-opening polymer thereof exist at the interface between the aromatic polyamide fiber and the thermosetting resin according to the present invention, [1] The aromatic polyamide fiber or the knitted fabric or cord made of the aromatic polyamide fiber is coated with a lactam compound. Alternatively, a method may be used in which lactam compounds and their related ring polymers are treated with an aqueous dispersion or an organic solvent solution, dried and then impregnated with a thermosetting resin. Although a method may be used in which the mixture is mixed with a resin and then impregnated with aromatic polyamide fibers, the former [11] is preferable because it has better adhesive properties.

In the above method, the amount of the lactam compound and its related ring polymer attached is preferably 0.1 to 5%, preferably 0.3 to 3%, based on the weight of the fiber, and the heat drying conditions are 100 to 3%.
Dry heat for about 30 minutes is preferable.

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

As the curing agent for the thermosetting resin, any conventionally known curing agent may be used. For example, boron trifluoride monoethylamine complex salt may be used for epoxy resin, and penzoyl peroxide may be used for unsaturated polyester resin. In the present invention, the ratio of aromatic polyamide fiber and thermosetting resin (matrix component) is determined depending on the purpose of the structure to be molded.
Although it varies depending on the purpose, the range is usually 10 to 9% by weight of aromatic polyamide fiber and 90 to 1% by weight of thermosetting resin based on the structure.

In addition to the above composition, the lactam compound is attached to the interface between the aromatic polyamide fiber and the thermosetting resin, and the amount of the lactam compound attached is 0-1 to 5% based on the weight of the fiber, as described above. Preferably it is 0.3 to 3%.

Furthermore, depending on the use and purpose of the structure, some additives such as fillers, pigments, and stabilizers for weather resistance or heat resistance may be added to the matrix component.

The amount of this additive is usually 20% or less based on the weight of the structure. The composite structure manufactured by the method of the present invention can be applied to various uses and purposes.

Examples include sports equipment, leisure equipment, and various appliance parts that require high strength and elasticity, as well as aerospace equipment, automobiles, and other equipment that are lightweight and require excellent strength, elasticity, and heat resistance. The present invention will be described in detail with reference to Examples below.

% represents weight % unless otherwise specified. Example 1 150 high-modulus poly p-phenylene terephthalamide filaments were soaked in an aqueous dispersion containing the lactam compound shown in Table 1 and 10% sodium hydroxide for the lactam compound. Dry for a minute.

The adhesion amount was 1%. The thus treated fibers were impregnated with a resin solution consisting of 5 parts of a boron trifluoride monoethylamine complex salt of 10 parts of EPICOAT ■828 (epoxy resin manufactured by Shell Chemical Co., Ltd.), and an appropriate number of layers were layered to align the fibers in one direction. In this state, the molded product was molded and cured by hot pressing at 150 qo for 1 hour (pressing pressure 10 k9/base), and then post-cured for 2 hours at 170 CO. The resulting composite material (fiber content 60%
), a test piece with a length of 2 ribs, a medium 6 willow, and a thickness of 3 was created using the short beam three-point bending method (distance between spans 13
The interlaminar shear strength (Inter Shear Stre
ngth, hereinafter abbreviated as Yama SS.

) are shown in Table 1. The pile SS of the composite material prepared without using a lactam compound was 4.8k9/mm2. As shown in Table 1, it can be seen that according to the present invention, excellent adhesion between fiber and resin can be obtained.

Example 2 The fibers treated with 2-pyrrolidone in Example 1 were impregnated with Sumilite resin PR-50691 (phenol resin manufactured by Sumitomo Chemical), laminated in an appropriate number, and hot pressed with the fibers aligned in one direction. Molding and curing at 150oo for 1 hour (press pressure 10k9/ground), and then 170oooo
I did post cure for 2 hours.

A composite material obtained in the same manner as in Example 1 (fiber content: 6
0%) was measured and found to be 6.3k9/mm2. 4.5 for those made without using 2-pyrrolidone
It was k9/mm2.

Example 3 In Example 2, unsaturated polyester resin (trade name Polymer 3308 manufactured by Takeda Pharmaceutical Co., Ltd.) 1 was used instead of the phenolic resin.
0 Ikaribe, product name Nyper-B○ (do not use penzoyl peroxide)
The process was carried out in the same manner as in Example 2, except that a resin solution consisting of 2 parts of P (made into a paste, manufactured by NOF Corporation) was used, and the composite material (fiber 1 with 60% content is 4.0 kg of S.
/mm2.

Composite material mountain SS made without using 2-pyrrolidone
was 3.0k9/mm2.

Example 4 A monomer was prepared by heating 2-pyrrolidone at 95q0 bipedal Hg to remove moisture and passing dry N2 gas for 2 hours.

Next, 2 mol% of potassium hydroxide was added to give 2 g, 9 g.
After reacting for 1 hour while removing water at 5°C, 60oo
It was cooled to On the other hand, 1 female (0.11 mol) of 2-pyrrolidone and 37 g (0.35 mol) of acetic anhydride were heated under reflux for 14 hours.
After reacting at 0°C for 4 hours, excess acetic anhydride was removed, vacuum distillation was performed, and a fraction at 92-93°C/2 skin Hg was taken out to obtain N-acetyl-pyrrolidone. 1 mol % of the obtained N-acetyl-2-pyrrolidone was added to the above reaction solution, and the reaction was allowed to proceed for 1 hour while passing dry nitrogen gas. The produced polymer was taken out and water was added to terminate the reaction. The infrared spectrum of this polymer is 3.0
Absorption of -NH groups at 3 points and amide groups at 6.14 peaks and 6.55 peaks was observed, and when this polymer was extracted with water and methanol, the residual content was less than 3%, indicating that it was water-dispersible. It was something. The aromatic polyamide fibers used in Example 1 were impregnated into the aqueous dispersion of this polymer, and a composite material (fiber content 60%) was produced using the same machine as in Example 1.
LSS was 7.3k9/mm2.

Further, in the case of using a phenol resin as in Example 2, the peak SS was 6.6 x 9/mm2. As is clear from the above examples, the aromatic polyamide fiber-reinforced resin produced by the method of the present invention has excellent adhesion between fibers and resin, and the excellent properties of aromatic polyamide fiber are fully reflected.

Claims (1)

[Claims] 1. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is H, CH_3, COCH_3; n is 3 to 5
is an integer. ) or a water-dispersible ring-opening polymer thereof, present at the interface between the aromatic polyamide fiber and the thermosetting resin. A composite material whose main component is resin. 2 General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R is H, CH_3, COCH_3, n is 3 to 5
is an integer. ) An aromatic polyamide fiber characterized in that the fiber is treated with an aqueous dispersion or an organic solvent solution of a lactam compound or a ring-opening polymer thereof, dried, and then impregnated with a thermosetting resin. A method for producing a composite material whose main components are a thermosetting resin and a thermosetting resin.