JPS625447B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is a novel strand prepreg consisting of a strand, a specific resin, a hydrocarbon material, etc.
More specifically, the present invention relates to the strand prepreg that is non-sticky, highly flexible, has good workability and excellent moldability, and is capable of imparting excellent composite properties to molded products. In recent years, fiber-reinforced plastics have been used in many fields due to their characteristics such as light weight, high strength, and high rigidity. When manufacturing fiber-reinforced plastic molded products, prepreg sheets or woven prepregs are generally used, which are laminated at a predetermined angle and molded under heat and pressure. By the way, some prepregs have fibers in the form of strands (sometimes called rovings) depending on their use. Such strand prepregs are used, for example, as braided prepregs in the manufacture of tennis rackets. Strand prepreg is also used when manufacturing tubular molded products such as automobile propeller shafts, fishing rods, and golf shafts using the filament winding method, and when manufacturing molded products with various cross-sectional shapes using the pultrusion method. . Strand prepreg is a strand in the form of fibers that is pre-impregnated with resin, so it can be used as is in these molding methods, eliminating the need for on-site resin impregnation and speeding up the process. It has the advantage that the resin content of the molded product can be adjusted accurately. Strand prepreg has one fiber diameter of 5
A fiber bundle consisting of 1,000 to 30,000 filaments with a diameter of ~200μ is impregnated with resin, and because it is used by winding it directly on a bobbin without using a release paper, it is not self-adhesive and Requires flexibility. However, it is difficult to satisfy this requirement with a material impregnated only with a normal thermosetting resin such as an epoxy resin. Therefore, a method of blending a thermoplastic resin with a thermosetting resin (Japanese Unexamined Patent Publication No. 15870/1987) and a method of blending a high molecular weight epoxy resin with a molecular weight of 5000 or more (Japanese Patent Application Laid-open No. 78022/1989) have been proposed. has been done.
However, even with these methods, if left at room temperature for a long time or stored for a long time, the strand prepregs will stick to each other and lose their flexibility. On the other hand, there is a method of attaching talc to the surface of the strand prepreg in order to prevent self-adhesion, and although this method can prevent adhesion to a certain extent, on the other hand, such strand prepreg has a method of attaching talc to the surface of the strand prepreg. Problems arise in appearance and workability, and molded products made from strand prepreg with talc attached to the surface have the disadvantage of deteriorating composite properties. In view of the above-mentioned circumstances, the inventor of the present invention has made extensive studies to develop a strand prepreg that does not have the drawbacks of the conventional method, and as a result, the inventor has applied petroleum jelly to the surface of a strand prepreg impregnated with a thermosetting resin and a thermoplastic resin. It has been discovered that an excellent anti-adhesive effect can be obtained by adhering the like, and the present invention has been achieved. That is, an object of the present invention is to provide a strand prepreg that is free from self-adhesion and has high flexibility, and is made by combining a strand and a thermosetting resin.
(A), a phenoxy resin with a molecular weight of 10,000 or more (B) or/and a thermoplastic resin (B'), a higher alcohol, a higher fatty acid, its glycerin ester, or a hydrocarbon-based substance (C) or/and a silicone oil (C). ′). Hydrocarbon substances such as vaseline, liquid paraffin, etc. and silicone oil have poor compatibility with thermosetting resins and poor bonding properties with reinforcing fibers, so they are generally not considered for use as matrix components. Until now, a strand prepreg having the same composition as in the present invention has not been known. The strand prepreg of the present invention does not cause self-adhesion like conventional products even when stored for a long period of time, so it can exhibit a significantly improved anti-adhesion effect. Moreover, this material maintains flexibility and has good moldability, and also has no problems in appearance and is excellent in workability. In addition, surprisingly, the composite properties of the molded product made from the strand prepreg of the present invention are superior to those in which the above-mentioned higher alcohols, higher fatty acids and their glycerin esters, hydrocarbon substances, and silicone oil are not added. It shows a high value. This is completely unexpected from the conventional knowledge that petrolatum and silicone oil have poor compatibility with thermosetting resins and poor bonding properties with reinforcing fibers, as described above. The fibers of the strands in the present invention may be those commonly used for resin reinforcement, and preferred examples include carbon fibers, glass fibers, Kevlar fibers, boron fibers, and silicone carbide fibers.
Here, a strand is one fiber with a diameter of 5~
Refers to a fiber bundle consisting of 1,000 to 30,000 filaments with a diameter of 200μ. The thermosetting resin (A) in the present invention may be one normally used for producing prepregs, such as epoxy resins, unsaturated polyester resins, phenol resins, and polyimide resins, of which epoxy resins are most suitable. Among the epoxy resins, bisphenol A type epoxy resins, novolak type epoxy resins, glycidylamine type epoxy resins and the like are preferred. One or more of these can be used. Specific examples of these epoxy resins include EPN1138, ECN1235, 1280 (manufactured by Ciba Geigy), Epicote 152, 154 (manufactured by Ciel Chemical), DER438, 485 (manufactured by Dow Chemical),
Epicote 828, 827, 834, 1001, 1002, 1004,
1009 (manufactured by Ciel Chemical Co., Ltd.), Araldite
MY720 (manufactured by Ciba Geigy), Epotote YH434
(Toto Kasei) etc. As phenoxy resin (B) with a molecular weight of 10,000 or more,
Specifically, Epicote OL53B40 (manufactured by Ciel Chemical Co.), DER684-EK-40 (manufactured by Dow Chemical Company),
Phenotote YP50EK40 (manufactured by Toto Kasei Co., Ltd.) is suitable. Those with a molecular weight of 10,000 or more, particularly 80,000 or more are preferable, and those with a molecular weight of less than 10,000 cannot provide the required anti-adhesive effect to the prepreg. Examples of the thermoplastic resin (B') include polysulfone,
Polycarbonate, polyvinyl acetate, polystyrene, polyacrylate, polymethacrylate, cellulose acetate, etc. can be used. Examples of the hydrocarbon substance (C) in the present invention include aliphatic or alicyclic hydrocarbons, with n-paraffin, isoparaffin, olefin hydrocarbon, and naphthenic hydrocarbon being particularly preferred.
Specifically, there are petrolatum, liquid paraffin, paraffin wax, etc. The higher alcohol and higher fatty acid preferably have 10 to 22 carbon atoms. As the silicone oil (C'), commercially available products can be used, such as TSR165 (manufactured by Toshiba Silicon Co., Ltd.), KF96 (manufactured by Shin-Etsu Chemical Co., Ltd.), as well as silicone grease called "silicolube" G40, G30 (manufactured by Shin-Etsu Chemical Co., Ltd.). ), called silicone varnish
ES1001, ES1001N, ES1002T, KR213,
There are KR214, KR216 (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. The relationship of the amounts of the above components in the present invention can be determined as appropriate to suit the purpose. The resin content in the prepreg of the present invention is generally 25 to 70
%, preferably 30-60% by weight. In the case of carbon fiber prepreg, particularly preferable conditions are 35
~45%, 25-40% for glass fiber prepreg,
In the case of Kevlar prepreg, it is 50-70%. or,
The mutual ratio of components A to C is B/A of 5 to 40%, especially 10
-30%, preferably 5-30% for C/A+B, especially 10-20%. (Here, B and C include B' and (C'), respectively). A curing agent and a curing accelerator are also added to cure the resin. Examples of curing agents include dicyandiamide and curing accelerators such as 3-(3,4
-dichlorophenyl)-1,1-dimethylurea is preferred. In addition, other components may be added in appropriate amounts within the scope of the purpose of the present invention. In the present invention, it is most effective to apply the hydrocarbon-based substance or silicone oil to the surface of the strand prepreg, but they may also be blended with the thermosetting resin. The strand prepreg of the present invention can be manufactured by a known method. For example, the strand is impregnated by passing it through a solution in which necessary components such as resin are dissolved, and then dried, and the obtained strand prepreg is wound on a bobbin. As described above, the strand prepreg of the present invention is effective in preventing adhesion and has flexibility, so it is easy to take off from the bobbin, does not break, and has excellent drape properties and does not become cloudy. Also, after molding
High ILSS values can also be obtained. Examples of the present invention will be shown below. Example 1 Epoxy resin EPN1138 (Ciba, manufactured by Geigy), which is semi-solid at room temperature, 100 parts by weight, average molecular weight approximately 8
35% of the resin solid content of phenoxy resin Epicoat OL53B40 (manufactured by Ciel Chemical Co., Ltd.) was dissolved in acetone to give a resin concentration of 35%. To this, 3 parts by weight of dicyandiamide and a methyl cellosolve solution of 3-(3,4 dichlorophenyl-1,1-dimethylurea) were added to make a homogeneous solution. To this resin solution was added a carbon fiber (diameter 7μ, filament number 12,000 manufactured by Toho Veslon Co., Ltd.). After impregnating the resin through Besphite HTA-7-12000), heat it in a hot air drying oven at 100℃ for 5 minutes.
The solvent was removed for a minute to form a strand prepreg. The resin content of the resulting strand prepreg was 48%, and the residual solvent was 0.8%. The anti-adhesion property of the strand prepreg coated with 10% vaseline was determined by the tack evaluation method described later and was found to be sufficiently satisfactory. Furthermore, this strand prepreg was pulled in one direction and pressed at 100℃ to form a sheet prepreg, then laminated and molded at 120℃, 7Kg/cm ² for 90 minutes.The physical properties of the unidirectional molded product are as follows. It was hot. On the other hand, the strand prepregs without Vaseline applied adhered to each other within 3 days at room temperature. Further, the physical properties of a molded product made in the same manner were as follows.

[Table] Example 2 Silicone resin instead of vaseline in Example 1
Strand prepreg was made using TSK165 (manufactured by Toshiba Silicon Corporation). When this strand prepreg was evaluated using the tackiness evaluation method described below, its non-tackiness was found to be satisfactory. Further, the physical properties of the composite made in the same manner as in Example 1 were as follows. Bending strength 165Kg/mm ² Modulus of elasticity 11.9ton/mm ² ILSS 10.8Kg/mm ² V 57% Similar results as above were obtained when petrolatum and silicone resin TSK165 were used in place of petrolatum in Example 1. Comparative example: When talc was attached instead of silicone oil, its non-stick properties were almost satisfactory even after being left at room temperature for a week, but the appearance was poor and talc was deposited during manufacturing or the winding process of strand prepreg. Workability was poor due to scattering, and physical properties (ILSS) also deteriorated as shown below. Bending strength 166Kg/mm ² Modulus of elasticity 11.8Ton/mm ² ILSS 8.9Kg/mm ² V 56% Adhesive evaluation method After winding the strand prepreg into a paper tube with a diameter of 2cm and a length of 15cm using a winder and leaving it at 23℃ for one week. Strand prepreg tension 500~700g, speed
Judgment is made by whether the strand prepregs do not adhere to each other and can be pulled out smoothly from the paper tube when rewinding at 30 m/min. Example 3 Epoxy resin EPN1138 (Ciba Geigy) 100
35 parts by weight of phenoxy resin Epicoat OL53B40 (Ciel Chemical) with an average molecular weight of about 80,000 (Ciel Chemical) and 30 parts by weight of linear alcohol Dyanol (manufactured by Mitsubishi Kasei, carbon number 12 and 14) were dissolved in methyl ethyl ketone, and the resin was dissolved in methyl ethyl ketone. The concentration was set to 35%. In addition to this, 3 parts by weight of dicyandiamide and 3-
A methyl cellosolve solution containing 5 parts by weight of (3,4-dichlorophenyl)-1,1-dimethylurea was added to form a homogeneous solution. This resin solution is impregnated with resin through carbon fibers (Veshuite HTA-7-12000 manufactured by Toho Veslon, with a diameter of 7 μm and 12,000 filaments), and then passed through a hot air drying oven at 100°C for 5 minutes to remove the solvent and form a strand prepreg. Tsukutsuta. The resin content of the resulting strand prepreg is
45%, and the residual solvent was 0.6%. Moreover, even when this strand prepreg was left at room temperature for 10 days, its anti-adhesive properties were sufficiently satisfactory. Further, the physical properties of the composite molded in the same manner as in Example 1 were as follows. Bending strength 153Kg/mm ² Modulus of elasticity 11.0T/mm ² ILSS 9.4Kg/mm ² V 54% Example 4 Unsaturated polyester resin prepolymer, Polymer 6228 (manufactured by Takeda Pharmaceutical Company) 100 parts by weight, crosslinking monomer, dia 35 parts by weight of real phthalate, 3 parts by weight of curing catalyst tert-butyl peroxybenzoate, phenoxy resin Epicoat
A strand prepreg was prepared in exactly the same manner using 35 parts by weight of OL53B40 (manufactured by Ciel Chemical Co., Ltd.) as a resin solid content and 13 parts by weight of silicone varnish ES1001 (manufactured by Shin-Etsu Chemical Co., Ltd.). The resulting strand prepreg had excellent non-adhesive properties, and the composite properties of the molded product obtained from this prepreg under molding conditions of 130° C., 10 Kg/cm ² and 45 minutes were also good as shown below. Bending strength 157Kg/mm ² Modulus of elasticity 11.9T/mm ² ILSS 9.1Kg/mm ² Vf 57% Example 5 In place of the phenoxy resin in Example 1, 28 parts by weight of polysulfone P-1700 (manufactured by Union Carbide) was used as a solvent. A strand prepreg was prepared in exactly the same manner as in Example 1, except that dichloroethane was used as the strand prepreg. The resulting strand prepreg had excellent non-adhesion properties, and the composite properties of a molded product obtained from this prepreg under the same molding conditions as in Example 4 were also good as shown below. Bending strength 154Kg/mm ² Modulus of elasticity 11.8T/mm ² Vf 56% Example 6 Bismaleimide resin (B) T resin (manufactured by Mitsubishi Gas Chemical Co., Ltd.) 100 parts by weight, dicumyl peroxide 0.1
A strand prepreg was prepared in exactly the same manner using 0.02 parts by weight of zinc octylate, 28 parts by weight of phenoxy resin Epicoat OL53B40 as a solid content, and 15 parts by weight of silicone varnish ES1001. The resulting strand prepreg had excellent flexibility and non-stick properties. This strand prepreg is aligned in one direction.
Press at 100℃ to form a sheet prepreg.
This was laminated and cured at 180° C. and 5 kg/cm ² for 2 hours. The composite physical properties of this molded plate were good as shown below. Bending strength 163Kg/mm ² Modulus of elasticity 12.0T/mm ² ILSS 11.0Kg/mm ² Vf 59%

Claims (1)

[Claims] 1. A strand, a thermosetting resin (A), and a molecular weight of 1.
Strand prepreg made of phenoxy resin (B) or/and thermoplastic resin (B') and higher alcohol, higher fatty acid, their glycerin esters or hydrocarbon substances (C) or/and silicone oil (C') . 2. The strand prepreg according to claim 1, wherein the strand is any one of carbon fiber, glass fiber, Kevlar fiber, boron fiber, and silicone carbide fiber. 3. The strand prepreg according to claim 1, wherein the thermosetting resin is one or more of epoxy resin, unsaturated polyester resin, phenolic resin, and polyimide resin. 4. The strand prepreg according to claim 1, wherein the hydrocarbon material is petrolatum or liquid paraffin. 5 Higher alcohols have the general formula CnH ₂ n ₊₁ OH (n:
10-22) and _CnH2nOH (n: 10-22). 6 Higher fatty acids have the general formula CnH ₂ n ₊₁ COOH (n: 10
~22) and _CnH2nCOOH (n: 10-22).