JPS61204229A - Fiber reinforced resin composite material - Google Patents

Abstract

PURPOSE:The titled composite material useful as printed circuit substrate materials, lightweight advanced composite material, etc., having heat resistance, interfacial adhesiveness, drilling properties, and dimensional stability, obtained by blending a heat-resistant resin with aromatic polyamide fibers treated with a specific aminopolyamide. CONSTITUTION:An aminopolyamide which is a polycondensate [preferably compound shown by the formula (R is hydrocarbon of unsaturated fatty acid dimer; l and m are 1-8; n is 1-5)] of an unsaturated fatty acid dimer (e.g., linoleic acid dimer, etc.) and a polyamide is usually dissolved in water, methanol, etc., to give a treatment and aromatic polyamide fibers are treated with the treatment. The treated aromatic polyamide fibers are added to a heat-resistant resin (e.g., polyimide, epoxy resin, etc.), to give the aimed composite material.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to aromatic polyamide fibers and polyimide.

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

(Prior art) Reinforced composite materials made by filling resin with fibers include fiber-impregnated mats, prepreg laminates made of woven fabric and resin, and those made using the filament winding method.

There are various types of molded products in which short fibers are dispersed. All of these have strong properties such as tensile strength, Young's modulus, and impact strength.

It is expected that it will improve rigidity, improve dimensional stability, improve heat resistance, etc., and although the effects have actually been achieved,
It is the structural shape of the resin and filler.

It is influenced by the structure, etc., and in particular, the properties of the interface between the fiber (filler) and resin (matrix). For this reason, fiber-reinforced composite materials whose surfaces have been treated with a coupling agent are provided with surface treatment.

Aromatic polyamide fibers, such as poly(P-phenylene terephthalamide) fibers, have a density of 1.45 f/-, which is significantly lighter than the most commonly used glass fibers and carbon fibers, and are superior to composites in terms of specific strength and specific stiffness. Due to its characteristics as a material, it has attracted attention as a structural material for aircraft, etc., and in the electronics industry, paper/phenol,
It is expected to be a reinforcing fiber with excellent electrical properties and heat resistance for glass/epoxy materials.In particular, due to its unique characteristic of having a negative coefficient of thermal expansion or in combination with a suitable matrix resin, it has the same level of dimensional stability as LSI chips. It is expected to be used as a material for Glass/epoxy, composite, and laminate boards have been widely used in industrial equipment as LSI tower substrates, but as LSIs become more dense, high-temperature properties, especially dimensional stability, are essential for manufacturing high-precision circuits. We are in trouble. A laminate made by combining an aromatic polyamide and a heat-resistant resin, such as polyimide, takes advantage of the electrical properties, mechanical properties, and heat resistance of the fibers, resin, and partner, but the thermal expansion coefficient is 1O-6/℃. It is possible to directly mount an LSI on a laminate and form a highly reliable circuit at the same level as silicon's 2.8XIQ-s6 and ceramics'6X10-a/'e.However, Perhaps due to its high crystallinity, aromatic polyamides have difficulty adhesion to resins, and although surface treatments have been carried out in the past, it has not been possible to obtain fully satisfactory products.For this reason, they are not used for printing substrates, etc. In such cases, the voids appear as a drawback in that sufficient high-density processing cannot be performed by drilling due to insufficient adhesive strength.

(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 heat-resistant resins such as aromatic polyamide, polyimide, or epoxy. The present invention provides a composite abrasive material having good drilling properties and dimensional stability.

(Means for solving the problem) The present invention is a fiber-reinforced composite comprising aromatic polyamide fibers treated with aminopolyamide, which is a polycondensate of an unsaturated fatty acid dimer and a polyamine, in a heat-resistant resin. It is the material.

The structure of the above-mentioned aminopolyamide resin used in the present invention is, for example, as shown in the general formula % R as an example of linoleic acid dimer, and 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.
Water in the present invention.

Alternatively, since it is used after being dissolved in methanol or other solvents, solubility, stability of the solution, and uniformity of the treated surface layer when treating aromatic polyamide fibers are required. The unsaturated fatty acids used in aminopolyamide resins are particularly effective, such as fatty acids containing two unsaturated groups, mainly linoleic acid, but those having a carbon number of 4 to 22 are generally used, and polyamines are also used as diamines. , triamine, pentamine, etc. are used, and as seen in actual industrial production, only a single component is used (even if mixed, 11 m
+H within the above range are commonly used in the process of the present invention. However, those with high molecular weight or low amine value (15
0 or less: The amine value is potassium hydroxide (w
The aminopolyamide shown in 9) is insoluble in water and difficult to dissolve even in methanol, resulting in decreased solubility and limitations in treatment methods.

The aromatic polyamide fiber used in the present invention is Po17 (
Both poly(P-phenylene terephthalamide) and poly(m-phenylene terephthalamide) can be used, but poly(P-phenylene terephthalamide) is usually used. Further, the fibers can be in any form such as woven fabrics, knitted fabrics, threads, etc., but woven fabrics and aligned threads are advantageous due to the characteristics of the composite material. Further, although aromatic polyamide fibers are highly crystalline, their moisture absorption rate is relatively high, so it is necessary to dry them sufficiently before treatment and impregnating with resin.

After thoroughly drying the aromatic polyamide fibers, immersing or coating them in an aminopolyamide resin solution of usually 1 to 20% by weight to avoid the influence of hygroscopic moisture, and reducing the amount by 0.0% by weight based on the weight of the fibers.
After applying 1 to 5% by weight, drying is performed. Ideally, the aminopolyamide resin should be thin so as to form a thin layer of about 1 molecule, but if it is too thick, the adhesive force will actually decrease, and the properties of the composite material may be adversely affected. As the solvent for the aminopolyamide resin, water, alcohol, and aromatic solvents can generally be used, but organic solvents are advantageous from the viewpoint of permeability into the aromatic polyamide.

The heat-resistant resin used as the matrix is not particularly limited as long as it can form a composite material that takes advantage of the characteristics of aromatic polyamide fibers, but thermosetting resins are preferred;
Particularly suitable are polyimide and epoxy resin.

Polyimide resins are used for addition polymerization type thermosetting, solvent soluble, and ease of molding process.NN represented by the general formula (R: aliphatic, alicyclic, or aromatic divalent organic group) ' 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 A or halogenated bisphenol A with epihalohydrin, polyether type polyglycidyl ether obtained by reacting epihalohydrin with a polyhydric alcohol obtained from bisphenol A and alkylene oxide, and novolac type. Polyglycidyl ether of phenol/formaldehyde resin is used, and as the epoxy curing agent, a heat-resistant aromatic polyamine type is generally used. Also, the amount of resin is in all composite materials.

The weight ratio is 30 to 70%.

The aromatic polyamide fibers treated with the aminopolyamide resin are then impregnated with the aforementioned polyimide or epoxy resin solution and dried to form a prepreg, and then a predetermined number of fibers are laminated and heated under pressure to obtain a composite material.

The weight of the 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 the prepreg, it is necessary to maintain appropriate conditions depending on the type of heat-resistant resin, resin solution concentration, etc.

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 lθ to 1.
A laminate is formed by applying pressure in the range of 50 Kf/cd for 1 to 5 hours.

Example! Plain woven fabric (basis weight 62 f/rl) of poly(P-)unine terephthalamide) fiber (DuPont, Kevlar 49)
, thickness 0.1-2 density 34 vertical x horizontal / 2.5 tan x 3
4/2.5 tyn Kevlar thread: 195D/184
F) was dried in a hot air dryer at 150° C. for 2 hours until it was almost completely dry. Eight types of aminopolyamide resin treatment agents having an amine value of 100 to 1,000 were added to the mixture using methanol as a solvent to prepare a 1 weight solution. A Kevlar cloth was immersed in each solution, squeezed with a mangle, and dried at 100° C. for 5 minutes to measure the amount of treatment agent attached.

Next, an N-methylpyrrolidone solution (50% by weight) of a polyimide resin (Kelimide 601, manufactured by Nippon Polyimide) 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 obtain a prepreg. Ta. Two sheets of each prepreg were stacked for 11 days at 180°C and 50°C.
Pressing was performed for 1 hour using a Kf/m press machine, and after cooling, the product was taken out and subjected to post curing at 200° C. for 48 hours to obtain a two-layer laminate. For comparison, a two-layer @ body was also produced using Kevlar cloth that was not treated with the aminopolyamide resin.

Table 1 shows the results of measuring peel strength, resin content, etc. using a T-type peel test method using a tensile tester for these laminates.
The table shows that when treated with eight types of aminopolyamide treatment agents, the peel strength was improved in all cases, indicating that the adhesive strength was improved.

Example 2 Using an aminopolyamide resin with an amine value of 780, using two types of solvents, water and methanol, -0.5, 1.0, and 2, respectively.
．． A 0.5% by weight treatment agent solution was prepared, and a dried Kevlar cloth of the same type as in Example 1 was treated with this solution in advance.

Prepreg, 1 body fabrication was carried out in the same manner as in Example 1,
Peeling strength was measured and the effects of treatment solvent type and concentration were examined.

Table 2 (Effects of the Invention) The fiber-reinforced resin composite material of the present invention has heat resistance and excellent interfacial adhesion, so it can withstand perforation processing (drilling) sufficiently, and is used as a lightweight, advanced material, including printed wiring board materials. As a composite material, it can also be effectively used as a structural material for aircraft, automobiles, etc.

Claims (2)

[Claims] (1) A fiber-reinforced resin composite material in which a heat-resistant resin contains aromatic polyamide fibers treated with aminopolyamide, which is a polycondensate of an unsaturated fatty acid dimer and a polyamine. (2) The material according to claim 1, wherein the polycondensate is represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R: hydrocarbon group of unsaturated fatty acid dimer l, m: an integer from 1 to 8 n: an integer from 1 to 5)