JP2603521B2 - Method of manufacturing fiber body for resin reinforcement and method of manufacturing fiber reinforced resin body - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for manufacturing a fiber body for resin reinforcement such as roving, which is suitably used for manufacturing a fiber reinforced resin body (ERP), and a filament winding method (FW). Law) by FR
P, in particular, to a method for manufacturing a leaf spring.

[Prior art] Glass fiber bundles such as rovings and strands are manufactured by applying a sizing agent to glass fibers drawn from a bushing, bundling a predetermined number of the bundles, and winding them into a cake or a cylinder. Widely used as a reinforcing fiber body.

The sizing agent is determined according to the type of liquid thermosetting resin used in the production of FRP, but when using epoxy resin as the liquid thermosetting resin, an epoxy resin-based one must be used as a film forming agent. There are many.

Often, an amine compound such as aminosilane is added to a sizing agent containing an ethoxy resin.

FRP is manufactured by various methods. For example, in order to manufacture a product requiring high strength such as a leaf spring, the FW method or the drawing method is often used.

[Problems to be Solved by the Invention] When a glass fiber bundle using a sizing agent containing an epoxy resin is heated and dried, the performance of the sizing agent tends to be reduced by heating.

This tendency is particularly remarkable when the sizing agent contains an amine compound such as aminosilane. Amine compound acts as a curing agent for epoxy resin, ring opening of epoxy resin,
Probably to promote polymerization.

This tendency is remarkably increased when a large amount of glass fiber bundle of 10 kg or more is wound into a cylindrical shape and dried.

In the case of FRP that does not require large strength, the above performance decrease does not significantly affect FRP performance,
When a leaf spring is manufactured by a FW method using a high-strength FRP, particularly an epoxy resin as a liquid thermosetting resin, it is recognized as a decrease in strength after a boiling test and a remarkable decrease in fatigue strength.

[Means for Solving the Problems] In order to achieve the above object, in the present invention, a glass fiber is impregnated with a sizing agent containing an epoxy resin and an amine compound, and bundled to form a glass fiber bundle. The glass fiber bundle is wound into a predetermined shape, preferably a cylindrical shape, and then dried under reduced pressure to produce a fiber body for resin reinforcement, and when producing the fiber reinforcement resin body by a filament winding method, the fiber body is wound into a rotating mold. As a fiber body to be attached, a glass fiber is impregnated with a sizing agent containing an epoxy resin and an amine compound, bundled into a glass fiber bundle, and the glass fiber bundle is wound into a predetermined shape, preferably a cylindrical shape, and then subjected to reduced pressure. Then, a fiber-reinforced resin body is manufactured by using a resin-containing fiber body impregnated with a liquid thermosetting resin.

 Next, the present invention will be described more specifically.

In the present invention, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, phenol novolak type or the like is used as the epoxy resin to be contained in the sizing agent, and γ-aminopropyl triethoxy silane, N-β aminoethyl is used as the amine. γ-aminopropyl trimethoxy silane or N-β N vinylbenzylaminoethyl γ-aminopropyl triethoxy silane is suitable.

The amounts of the epoxy resin and the amine compound to be contained in the sizing agent are respectively 0.1 to 10 wt%, 0.05 to 2 wt%, preferably
It is appropriate that the content is 0.5 to 5% by weight and 0.1 to 1% by weight.

In addition to the epoxy resin and the amine compound, the sizing agent may contain a lubricant such as higher fatty acid ester and polyethylene glycol, and a film forming agent such as polyester resin and polyurethane resin.

The added amounts of the epoxy resin and the amine compound are 0.05 to 2% by weight, 0.005 to 0.2% by weight, and
It is appropriate that the content is 0.5 to 1 wt% and 0.01 to 0.1 wt%.

The number of glass fibers bundled is usually about 100 to 8,000, preferably about 200 to 4,000.

The glass fiber bundle can be wound on a rotating mandrel while traversing it using a traverse wire, and it can be a so-called cake, but a bundle of about 1,000 to 4,000 glass fibers is cylindrically placed on a rotating mandrel. It can also be wound up and made into a straight-wound roving, and the effect of the present invention is remarkable in the case of a straight-wound roving, especially when it is a straight-wound roving in which a large amount of glass fiber of about 10 kg to 25 kg is wound. .

The wound glass fiber bundle (referred to as a wound fiber bundle) is dried by heating under reduced pressure.

The degree of decompression is 500 torr or less, preferably 400 to 10 torr
Is appropriate.

It is desirable to change the degree of pressure reduction periodically, and it is particularly appropriate to change the degree of pressure reduction from 10 to 50 torr to 700 to 760 torr, which can shorten the time required for drying.

The heating temperature is suitably from 30 to 90 ° C, preferably from 40 to 80 ° C.

When drying at normal pressure, in the initial stage of drying when the wound fiber body contains a large amount of water, the moisture evaporating from the surface of the wound fiber body and the water moving from the inside to the surface are equal, and both are equal. The constant-rate drying is maintained at a predetermined rate, and the surface temperature of the wound fiber body is maintained at the boiling temperature of water.However, as the evaporation of water progresses, the amount of water transferred from the inside to the surface gradually increases. Decreasing loss drying is performed.

When the rate-decreasing drying is performed, the surface temperature of the wound fiber body gradually increases and reaches the temperature of the drying atmosphere.

In order to sufficiently dry the wound fiber body, it is necessary to perform the reduced-rate drying for a considerably long time. However, when the wound fiber is large, the reduced-rate drying time increases, and the performance of the sizing agent deteriorates. Becomes significant.

On the other hand, in the reduced-pressure drying of the present invention, the time of the reduced-rate drying is extremely short and the temperature of the atmosphere is kept low,
It is considered that the performance of the FRP is improved without a decrease in the performance of the sizing agent.

Note that the method of manufacturing a leaf spring by the FW method using the above-described glass fiber bundle does not differ from a known technique, and thus a detailed description is omitted.

[Operation] By drying the wound fiber body under reduced pressure, the lapse rate drying time is shortened, and by lowering the drying temperature, the performance of the sizing agent due to the reaction between the epoxy resin and the amine is prevented. Of the strength of the leaf spring manufactured by the method after the boiling test and the strength due to fatigue are prevented.

[Examples] A sizing agent having the following composition was added to 23 µ glass fiber as a solid component at 0.5 wt%, and 4,000 were bundled to form strands.

Composition of sizing agent Emulsified epoxy resin (epoxy equivalent 190) 4.5wt% γ-aminopropyltriethoxysilane 0.5wt% higher fatty acid ester 0.6wt% acetic acid 0.2wt% This strand is wound into a 20kg cylindrical shape, and from 30torr to 76
The moisture was reduced to 0.03% or less by performing constant-rate drying at 115 ° C. for 23 hours while periodically changing the degree of pressure reduction between 0 torr.

This strand was impregnated with a resin composition having the following composition, and a one-way reinforced sheet of 70 wt% GC was manufactured by the FW method.

Shear strength of this sheet was 7.56kg / mm ^2, also boiled 10
The strength retention after 0 hr was 92%.

Resin composition Epicoat 828 (trade name; manufactured by Yuka Shell) 100 parts by weight Amine-based curing agent 10 parts by weight [Comparative Example] Using the same sizing agent as in the example, at 130 ° C. for 24 hours under normal pressure at normal pressure
A similar experiment was performed using dried strands. The results were as follows.

Shear strength 7.10 kg / mm ² Strength retention rate 87% [Effect of the invention] Prevents performance degradation of the sizing agent, increases the strength of FRP such as leaf springs obtained by the FW method, and reduces the strength reduction due to FRP fatigue. To prevent.

Claims (20)

(57) [Claims] 1. A glass fiber is impregnated with a sizing agent containing an epoxy resin and an amine compound into a glass fiber bundle. The glass fiber bundle is wound into a predetermined shape, preferably a cylindrical shape, and then reduced under reduced pressure. A method for producing a resin body for resin reinforcement, characterized by drying the resin body. 2. The method according to claim 1, wherein the degree of pressure reduction is changed periodically. 3. The method according to claim 2, wherein the degree of reduced pressure is changed from 10 to 50 torr to 700 to 760 torr. 4. The epoxy resin of claim 1, 2, or 3, wherein said epoxy resin is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or phenol novolak.
A method for producing a fibrous body for resin reinforcement according to the above. 5. The method according to claim 1, wherein the amount of the epoxy resin is 0.05 to 2% by weight based on the glass fiber. 6. The amine compound is γ-aminopropyltriethoxysilane, N-βaminoethyl γ-aminopropyltrimethoxysilane or N-βN vinylbenzylaminoethyl γ-aminopropyltriethoxysilane. The method for producing a resin-reinforcing fibrous body according to claim 1, 2, 3, 4, or 5. 7. The method according to claim 1, wherein the amount of the amine compound is 0.005 to 0.2% by weight based on the glass fiber.
7. The method for producing a resin reinforcing fiber according to 4, 5, or 6. 8. The method according to claim 1, wherein drying is performed at a reduced pressure of 500 torr or less. 9. The winding amount of the glass fiber bundle is 5 to 25 kg, preferably 10 to 25 kg.
9. The method for producing a fibrous body for resin reinforcement according to 6, 7, or 8. 10. A glass fiber impregnated with a sizing agent containing an epoxy resin and an amine compound as a fibrous body wound around a rotating mold when a fiber reinforced resin body is produced by a filament winding method, and the glass fiber is bundled. A fiber bundle is formed. The glass fiber bundle is wound into a predetermined shape, preferably a cylindrical shape, dried under reduced pressure, and then a resin-containing fiber body impregnated with a liquid thermosetting resin is used. A method for producing a fiber-reinforced resin body. 11. The method for producing a fiber-reinforced resin body according to claim 10, wherein the degree of pressure reduction is changed periodically. 12. The method for producing a fiber-reinforced resin body according to claim 11, wherein the degree of reduced pressure is changed from 10 to 50 torr to 700 to 760 torr. 13. The method for producing a fiber reinforced resin body according to claim 10, wherein the fiber reinforced resin body is a leaf spring. 14. The epoxy resin is of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether or phenol novolak type.
14. A method for producing a fiber-reinforced resin body according to item 13. 15. The method according to claim 10, wherein the amount of the epoxy resin is 0.05 to 2% by weight based on the glass fiber.
15. The method for producing a fiber-reinforced resin body according to 2, 13, or 14. 16. The amine compound is γ-aminopropyltriethoxysilane, N-βaminoethyl γ-aminopropyltrimethoxysilane or N-βN vinylbenzylaminoethyl γ-aminopropyltriethoxysilane. Claims 10, 11, 12, 13, 14, or 15 characterized by the following:
A method for producing the fiber-reinforced resin body according to the above. 17. The method according to claim 10, wherein the addition amount of the amine compound is 0.005 to 0.2% by weight based on the glass fiber.
17. The method for producing a fiber-reinforced resin body according to 12, 13, 14, 15, or 16. 18. The method for producing a fiber reinforced resin body according to claim 10, wherein the drying is performed at a reduced pressure of 500 torr or less. 19. The method for producing a fiber-reinforced resin body according to claim 10, wherein the liquid thermosetting resin is an epoxy resin. 20. The winding amount of the glass fiber bundle is 5 to 25 kg, preferably 10 to 25 kg.
20. The method for producing a fiber-reinforced resin body according to 2, 13, 14, 15, 16, 17, 18 or 19.