JPS6114166B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composite material whose main components are aromatic polyamide fibers and a thermosetting resin.

In recent years, FRP, a composite material that uses various reinforcing materials as a structural material, has become the darling of plastics. Recently, the production of composite materials using aromatic polyamide fibers, which are extremely lightweight and highly elastic, as reinforcing materials and various resins as matrices, has received new attention.

By the way, in the production of such composite materials of various matrices, the biggest factor determining their performance is increasing the adhesion between the reinforcing material and the matrix, especially the interlaminar shear strength. However, 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 a polyurethane compound is present at the interface between an aromatic polyamide fiber and a thermosetting resin. A composite material whose main components are aromatic polyamide fiber and thermosetting resin.

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-aminobenzenzamide, and the like.

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

In the present invention, the polyurethane compound used for bonding fibers and resin has hydroxyl groups in the molecule,
It refers to a reaction product of a polyisocyanate and a substance containing two or more active hydrogen groups such as a carboxyl group, an amino group, or an active methylene group, such as a compound commonly called a polyol such as polyester or polyether.

Here, polyester refers to acids such as oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, and isophthalic acid, or their acid anhydrides. one or more of these and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol,
butylene glycol, trimethylolpropane,
It is obtained by esterification reaction with polyol compounds such as trimethylolethane, hexanetriol, glycerin, and sorbitol.

Polyethers include ethylene oxide, propylene oxide, trimethylene oxide, butylene oxide, α-methyltrimethylene oxide, 3,3'-dimethyltrimethylene oxide, tetrahydrofuran, dioxane,
It is obtained by ring-opening polymerization or copolymerization of cyclic ethers such as dioxamine.

Furthermore, polyisocyanate includes tolylene diisocyanate, 3,3'-bitrylene 4,4'-diisocyanate, diphenylmethane 4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane 4,4'-diisocyanate, 2, 4-tolylene diisocyanate dimer, 1,5-naphthylene diisocyanate, metaphenylene diisocyanate, triphenylmethane 4,4″ triisocyanate, hexamethylene diisocyanate, hexanetriol or trimerolpropane and 2,
Refers to triphenyl urethane, etc., which is a reaction product with 4-tolylene diisocyanate.

In order to make the polyurethane compound exist at the interface between the aromatic polyamide fiber and the thermosetting resin according to the present invention, (1) aromatic polyamide fibers or knitted fabrics and cords made of the aromatic polyamide fibers are mixed with an aqueous dispersion of a polyurethane compound, an organic Treated with solvent solution, usually 100~
You may also use a method of drying at about 350°C for 30 seconds to 30 minutes and then impregnating it into the thermosetting resin. (2) After mixing the polyurethane compound with the thermosetting resin,
Although a method of impregnating the mixture with aromatic polyamide fibers may be used, the former method (1) is preferred because it is excellent in terms of adhesiveness.

In the present invention, the fibers may be treated with a mixture of polyester or polyether and polyisocyanate, and the two may be reacted on the fibers to form a polyurethane compound.

In addition, when using a polyurethane compound, depending on the type of the terminal group of the polyurethane compound, that is, for a polyurethane compound whose terminal group is a -NCO group, an amine compound such as methylene bis 2-chloroaniline etc. may be used. It is preferable to use an isocyanate compound in combination with the polyurethane compound because it provides excellent adhesion.

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 10-90% by weight polyamide fiber, 90% thermosetting resin
~10% by weight.

In addition to the above composition, the polyurethane compound is attached to the interface between the aromatic polyamide fiber and the thermosetting resin, and the amount of the attached polyurethane compound is 0.1 to 5%, preferably 0.3 to 3%, based on the weight of the fiber. It is.

Further, depending on the use and purpose of the structure, some additives such as fillers, pigments, stabilizers for weather resistance or heat resistance, etc. may be added to the matrix component. Suitably, the amount of this additive is usually 20% or less based on the weight of the structure.

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, conventionally known ones may be used, such as boron trifluoride monoethylamine complex salt for epoxy resins, benzoyl peroxide, etc. for unsaturated polyester resins.

The composite structure manufactured by the method of the present invention can be applied to various uses and purposes. For example, sports equipment that requires high strength and elasticity,
It is effective for use in leisure equipment, various instruments, parts, etc., as well as aerospace products, automobiles, and other equipment that require lightness and excellent properties of strength, elasticity, and heat resistance.

The present invention will be explained in detail below with reference to Examples.

Example 1 A highly elastic type poly p-phenylene terephthalamide filament 1500d was mixed with a methyl ethyl ketone solution of Desmocol 400 (trade name, polyurethane with hydroxyl groups at both ends, manufactured by Bayer), Desmocol 400 and Takenate D-102 (trade name). A reaction product of diisocyanate and trimethylolpropane (manufactured by Takeda Pharmaceutical Co., Ltd.) with OH equivalent/NCO equivalent
Each sample was immersed in a methyl ethyl ketone solution mixed at an equivalent ratio of 1/1.3, and dried at 250°C for 1 minute.
The adhesion amount was 1%. The treated fibers are manufactured under the trade name Polymer 308 (unsaturated polyether resin,
(manufactured by Takeda Pharmaceutical Co., Ltd.) 100 copies, product name Niper BO (benzoyl peroxide made into a paste with DOP,
They were impregnated with a resin liquid consisting of 2 parts (NOF) and laminated in an appropriate number of layers, and with the fibers aligned in one direction, they were molded and cured for 1 hour at 130℃ using a heat press (press pressure 10
Kg/cm ² ) and further post-cured at 130°C for 1 hour.

The length of the resulting composite material (60% fiber content)
A test piece of 20 mm, width 6 mm, and thickness 3 mm was made, and the short beam three-point bending method (distance between spans 13
When the interlaminar shear strength (ILSS) was measured using Desmocol 400 alone (1mm/min, crosshead speed 1mm/min), it was 5.1 Kl/mm ² and 5.5 for the Desmocol 400 and Takenate D-102 combination.
It was Kg/ ^mm2 . The ILSS of the composite material prepared without using a polyurethane compound was 3.0 Kg/mm ² .

Example 2 The fibers treated with a combination of Desmocol 400 and Takenate D-102 in Example 1 were treated with 100 parts of Epikote 828 (epoxy resin, manufactured by Ciel Chemical),
Impregnated with a resin solution consisting of 5 parts of boron trifluoride monoethylamine complex salt, an appropriate number of sheets are laminated, and with the fibers aligned in one direction, molding and curing are performed at 150℃ for 1 hour using a hot press (press pressure 10Kg/cm ² ) and further
Post-cure was performed at 170°C for 2 hours.

ILSS of the obtained composite material (60% fiber content)
When measured in the same manner as in Example 1, it was 6.6 Kg/mm ² . The ILSS of the composite material prepared without using a polyurethane compound was 4.8 Kg/ ^mm2 .

Example 3 The aromatic polyamide fiber used in Example 1 was
A methyl ethyl ketone solution of 1007 (isocyanate group at both ends, prepolymer for polyurethane elastomer, manufactured by Takeda Pharmaceutical Co., Ltd.), L-1007 and the trade name Kyuamine M (4,4'-methylenebis-(2-chloroaniline), manufactured by Ihara Nogyaku) were added. Each sample was immersed in a methyl ethyl ketone solution containing a ratio of NH ₂ equivalent/NCO equivalent of 0.9, and dried at 250° C. for 1 minute. The adhesion amount was 1%. A composite material (fiber content: 60%) consisting of the thus treated fibers and unsaturated polyester resin was prepared in the same manner as in Example 1, and the ILSS was measured, and it was found that the ILSS of only L-1007 was 4.5 kg/
mm ² , 5.3 for the combination of L-1007 and Kyuamine M
It was Kg/ ^mm2 .

Example 4 The fibers treated with a combination of L-1007 and Kyuamine M in Example 3 were treated with the product name Sumilight Resin.
Impregnated with PR-5091 (phenolic resin, manufactured by Sumitomo Chemical), an appropriate number of sheets were laminated, and with the fibers aligned in one direction, the fibers were molded and cured at 150℃ for 1 hour (press pressure 10Kg/cm ² ). , and further post-cured at 170°C for 2 hours. The LISS of the obtained composite material (60% fiber content) was 6.1 Kg/mm ² . ILSS of composite materials created without using polyurethane compounds
was 4.5Kg/ ^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)

[Scope of Claims] 1 A polyurethane compound is present at the interface between the aromatic polyamide fiber and the thermosetting resin, and the aromatic polyamide fiber and the thermosetting resin are cured by heating. composite material. 2. A composite material comprising an aromatic polyamide fiber and a thermosetting resin as main components according to claim 1, in which a polyurethane compound whose terminal group is an isocyanate and an amine compound are present in combination. 3. A composite material mainly composed of aromatic polyamide fiber and thermosetting resin according to claim 1, in which a polyurethane compound whose terminal group is hydroxyl and an isocyanate compound are present in combination.