JPH024838A - Fiber-reinforced resin composite material - Google Patents

Abstract

PURPOSE:To obtain the subject material having heat-resistance, sufficiently durable to drilling owing to excellent interfacial adhesivity and useful as a material for printed circuit board, etc., by treating a raised aromatic polyamide fiber with an amino polyamide and adding the fiber to a heat-resistant resin. CONSTITUTION:The objective composite material is produced by treating a raised aromatic polyamide fiber [preferably poly(p-phenylene terephthalamide)] with an amino polyamide produced by the polycondensation of an unsaturated fatty acid dimer and a polyamide and adding the treated polyamide fiber to a heat-resistant resin (preferably polyamide or epoxy resin).

Description

[Detailed description of the invention] (Industrial application field) The present invention uses aromatic polyamide w4m and polyimide.

This invention relates to a heat-resistant WA fiber-reinforced resin composite material that is composited with a heat-resistant resin such as epoxy.

(Prior Art) In general, fiber-filled composite materials include fiber-impregnated mats, prepreg laminates made of fiber fabric and resin, materials made by the filament winding method, and injection molded materials in which short fibers are dispersed. All of these were made with the expectation of improving tensile strength, impact strength, Young's modulus, etc., improving dimensional stability, improving heat resistance, etc., and have also produced practical effects. However, its properties are influenced by the properties of the resin, the structure, shape, and organization of the filler, but the influence of the filler *M and the boundary blood of the matrix resin is particularly large.
It is customary to treat sa and taxi with a coupling agent. Important fibers used in fiber-filled composite materials include glass fibers and carbon fibers, which are provided after being subjected to the above-mentioned treatments.

Aromatic polyamide fibers, such as poly(1)-phenylene terephthalamide) fibers, have a density of 1.45 f/cm', are significantly lighter than glass fibers, and have superior specific strength and specific modulus, making them suitable for aircraft applications. It is attracting attention as a structural material for bones. Also, as a printed wiring board, it has superior electrical properties and heat resistance compared to paper/phenol and glass LA fiber/epoxy resin laminates, and also has a negative coefficient of thermal expansion.By combining it with an appropriate matrix resin, ceramic and silicon It is expected that the same dimensional stability can be achieved. In other words, glass/epoxy resin laminates have been widely used as LBI mounting substrates in industrial equipment. The lack of stability has made it difficult to manufacture high-precision circuits. A laminate made from a combination of aromatic polyamide and polyimide (thermal resin such as polyamino bismaleimide), which has excellent mechanical properties and electrical properties at high temperatures and has good dimensional stability, is not only heat resistant but also has excellent dimensional stability.
/” has a coefficient of thermal expansion on the order of c, 2.8X that of silicon.
10'/'C, which is close to 6X10/'C of a ceramic package, making it possible to obtain a highly reliable circuit board.

However, aromatic polyamide is highly crystalline and has difficulty adhering to the matrix resin that can be applied to the surface.

After surface treatment with coupling agent, epoxy resin, etc., it is made into a composite, but sufficient effects cannot be obtained, and when used as a printing board, the perforation processability (trisongability) is insufficient and high-density perforation is required. was intolerable.

To solve this problem, JP-A-61-204229 proposes a fiber-reinforced resin composite material in which aromatic polyamide #i fibers treated with aminopolyamide are contained in a heat-resistant resin. Treatment with polyamide alone has the problem that there remains some difficulty in adhesion between the aromatic polyamide and the matrix resin.

(Problems to be Solved by the Invention) The purpose of the present invention is to improve these defects and to provide a material with excellent heat resistance and interfacial adhesion that fully utilizes the characteristics of aromatic polyamide and heat-resistant resins such as polyimide or epoxy.・Do IJ IJ
The present invention provides a composite material with song and dimensional stability.

(Means for solving the problem) The above object is to incorporate aromatic polyamide fibers that have been brushed and treated with aminopolyamide, which is a polycondensate of an unsaturated fatty acid dimer and a polyamine, into a heat-resistant resin. This is achieved by using an am-reinforced resin base material.

The aromatic polyamide fiber used in the present invention is poly(p-
Poly(phenylene terephthalamide), poly(m-phenylene terephthalamide), etc. can be used, but usually poly(
p-phenylene terephthalamide) is often used.

Also, 1a fiber is a woven fabric.

Although any shape such as knitted fabric or thread may be used, woven fabric or aligned thread are advantageous due to the characteristics of the composite material. Furthermore, although aromatic polyamide fibers are highly crystalline, they have a relatively high moisture absorption rate, so it is necessary to dry them sufficiently before processing and impregnating them with resin.

For raising the aromatic polyamide &am, a needle cloth raising machine, a thistle raising machine, an emery raising machine, etc. can be used, and an emery raising machine is usually used. Further, the degree of napping is appropriately selected depending on the purpose, appearance 9 strength, etc.

t'R of the aminopolyamide resin used in the present invention
The structure can be summarized as the general formula % Formula % An example of this is linoleic acid dimer, in which vegetable oil fatty acids are often used.

These aminopolyamides have already been used as a type of epoxy resin curing agent, and the present invention uses them as a surface treatment agent for aromatic polyamide fibers. Aminopolyamide resin can be used in solid, liquid, etc.
There are various types depending on the combination of amines and degree of polymerization, but
Water in the present invention.

Alternatively, since it is used dissolved in methanol or other solvents, solubility, stability of the solution, and uniformity of the treated surface layer when treating aromatic polyamide (A fiber) are required.Aminopolyamide resin Among the unsaturated fatty acids used for this purpose, fatty acids containing two unsaturated groups, mainly linoleic acid, are particularly effective, but those having a carbon number ranging from 4 to 22 are generally used, and polyamines include diamines, triamines, When pentamine etc. are used and actually produced industrially,
Even if it is not only a single component but also a mixture,
Those within the above ranges for l, m, and n are commonly used in the process of the present invention. However, those with high molecular weight and amine value (1
50 or less: The amine value is potassium hydroxide (
(mg)) Aminopolyamides are insoluble in water and difficult to dissolve in methanol, resulting in decreased solubility and limitations in treatment methods.

Aromatic polyamide Ija pongee is sufficiently dried and soaked or coated in an aminopolyamide resin solution of usually 1 to 20% by weight to prevent it from being affected by hygroscopic water. ]! % and then dry. Ideally, the aminopolyamide resin is desirably thin so as to form an MI layer of approximately the molecular layer, but if it is too thick, the adhesive force will actually decrease, which may adversely affect the properties of the composite material. Water, alcohol, and aromatic solvents can be used as the solvent for the aminopolyamide resin, but organic solvents are preferred from the viewpoint of permeability into the aromatic polyamide.

The #J thermal resin used as the matrix is not limited to a special number as long as it can form a composite material that takes advantage of the characteristics of aromatic polyamide lI/4 fibers, but swallow-curing resins are preferred, and polyimide and epoxy resins are particularly preferred. suitable.

Polyimide resins are used for addition polymerization type thermosetting, solvent soluble, and ease of molding process. A prepolymer (polyamino bismaleimide) obtained by reacting at least one bismaleimide with at least one diamine selected from aromatic or aliphatic diamines is usually used.

Epoxy resins include diglycidyl ether obtained by reacting bisphenol 8 or halogenated bisphenol A with epihalohydrin, polyether type polyglycidyl ether obtained by reacting 1i11i alcohol obtained from bisphenol A and alkylene oxide with epihalohydrin, and novolak type phenol. - Polyglycidyl ether of formaldehyde resin is used, and as the epoxy curing agent, a heat-resistant aromatic polyamine type is generally used. Further, the amount of resin is 80 to 70% by weight in the entire composite material.

The aromatic polyamide fibers that have been brushed and then treated with an aminopolyamide resin are then impregnated with a solution of the above-mentioned polyimide or epoxy resin, saturated to form a prepreg, and then tanned in a predetermined number of sheets and processed. A composite material is obtained by pressure heating.

The weight of resin in the entire laminate is usually 80 to 70% by weight. If the amount of resin is too small, the electrical and mechanical properties will be poor or cause deformation, and even if the amount is too much, it will be difficult to form uniformly. Regarding the drying of prepreg, the type of heat-resistant resin,
It is necessary to maintain appropriate conditions such as resin solution concentration.

As the solvent for preparing the resin solution, any resin solvent that is inert to the aromatic polyamide can be used.

Lamination press is usually at a temperature of 150 to 200℃ and a pressure of 10 to 1
A laminate is obtained by applying pressure in the range of 50 kg/cm2 for 1 to 5 hours.

(Function) Since the present invention forms naps on the delicate aromatic polyamide surface through the napping treatment, the aminopolyamide easily adheres to the aromatic polyamide pongee during the next aminopolyamide treatment. It works to contribute to improving the adhesiveness between the aromatic polyamide and the matrix resin.

(Example) Example 1 Plain woven fabric (basis weight 62 f/m,
Thickness Q, l l mm, dense vertical x horizontal 84 pieces/2.
5cm x 84 pieces / 2.5 cm, Kevlar thread: 19
5D/184F) was raised using an emery raising machine with 240 meshes.

This was dried in a hot air dryer at 150° C. for 2 hours to bring it to an almost completely dry state. A 2% by weight solution of an aminopolyamide resin treatment agent having an amine value of 780 was prepared using ethanol as a solvent. A Kevlar cloth was dipped in each of the solutions, squeezed with a mangle and dried at 110°C for 5 minutes to obtain a coating with a coating amount of 1.1% by weight.

Next, an N-methylpyrrolidone solution (50% by weight) of polyimide resin (Kelimide 601, manufactured by Nippon Polyimide Co., Ltd.) was prepared as a heat-resistant resin, and the treated Kevlar cloth was impregnated with this and dried at 160'C for 7 minutes to form a prepreg. Obtained. Carefully take 12 sheets of each prepreg, place 18μ thick 81 foil on both outermost surfaces, and heat to 180°C! 1 50 kg/
The laminate according to the embodiment of the present invention was prepared by pressing for 1 hour using a cm2 (7) press machine, taking it out after cooling, and post-curing for 148 hours at 200°C. G.

As a comparison, a laminate of a comparative example was similarly prepared using Kevlar cloth that was not subjected to the napping treatment and the aminopolyamide treatment.

The beer strength of these laminates is determined by JIS (3-648
1 method, and the measurement results are shown in Table 1.

Table 1 As is clear from Table 1, the beer strength of the single fiber reinforced resin composite material of the present invention is significantly improved compared to the comparative example of the conventional product.

(Effects of the invention) The fiber-reinforced resin composite material of the present invention has heat resistance and excellent bonding properties, so it can withstand perforation processing (drilling) sufficiently, and can be used as a lightweight advanced composite material, including printed wiring board materials. It can also be effectively used as a structural material for aircraft, automobiles, etc.

Claims (1)

[Claims] (1) A fiber-reinforced resin composite material comprising a heat-resistant resin containing aromatic polyamide fibers that have been brushed and treated with aminopolyamide, which is a polycondensate of an unsaturated fatty acid dimer and a polyamine.