JPH06106631A - Manufacture of fiber reinforced resin molded body - Google Patents

Abstract

PURPOSE:To obtain a continuous molded body consisting of a surface containing function imparting agent and a core material having less function imparting agent than the surface by supplying functional resin on an inner face of a cylindrical mold through a functional resin supplying hole, impregnating a fiber base material which forms the surface with the resin, and curing thermosetting resin in the cylindrical mold. CONSTITUTION:In a hollow of a cylindrical mold 7 with openings at its both sides having therein a supply hole 12 for supplying a functional resin 5, a curing resin- containing fiber base material 6 obtained by impregnating a fiber base material having a core material 2 with curing resin and a fiber base material 4 forming a surface 1 are pulled from one end of the cylindrical mold 7. The fiber base material 6 is arranged in a cylindrical shape along the inner face of the cylindrical mold 7. Next, the fiber base material 6 is arranged in a manner penetrating the inside of the fiber base material 4 in the cylindrical mold 7, and the fiber base material 6 and the fiber base material 4 are pulled out from other end. The functional resin 5 is supplied on the inner face of the cylindrical mold 7 through the supply hole 12 so as to impregnate the fiber base material 6 with the resin, and the thermosetting resin 5 is cured in the cylindrical mold 7.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a long fiber-reinforced resin molding comprising a surface layer containing a functionalizing agent and a core material having a lower content of the functionalizing agent than the surface layer.

[0002]

2. Description of the Related Art A resin-impregnated fiber base material is continuously supplied while being molded and cured by supplying the resin-impregnated fiber base material to a tubular mold having a desired shape in order to manufacture a long fiber-reinforced resin molded product having excellent strength in the longitudinal direction. The pultrusion molding method is used. Further, in order to impart a function such as weather resistance, flame retardancy, antifungal property to the fiber-reinforced resin molded product, or to color the resin molded product, the resin compound contains an ultraviolet absorber, an antioxidant, a flame retardant, an inorganic substance. Functionality-imparting agents such as fillers, fungicides and pigments are mixed.

By the way, since the function of the function-imparting agent is exerted only in the surface layer of the fiber-reinforced resin molded body, it is not possible to use the function-imparting agent in the fiber-reinforced resin molded body at the same content as that of the surface layer. The functionality-imparting agent is wasted. Therefore, there has been a demand for a method for producing a fiber-reinforced resin molded product including a surface layer containing a function-imparting agent and a core material having a content ratio of the function-imparting agent lower than that of the surface layer.

In the method for producing such a fiber-reinforced resin molded article, a functional resin comprising a functionalizing agent and a thermosetting resin is supplied to a functional resin impregnation tank, and a functional composition comprising a thermosetting resin is provided. A functional resin-impregnated fiber base material obtained by supplying a curable resin having a lower content of a function-imparting agent than a resin to a curable resin impregnation tank and impregnating the fiber base material with the functional resin in the functional resin impregnation tank. The functional resin-impregnated fiber base material is introduced by pulling the curable resin-impregnated fiber base material in which the fibrous base material is impregnated with the curable resin in the curable resin impregnation tank from one end side into the tubular hollow part with both ends open. The curable resin-impregnated fiber base material is placed along the inner surface of the tubular mold so as to be arranged in a tubular shape, and the curable resin-impregnated fiber base material is arranged so as to penetrate inside the tubular functional resin-impregnated fiber base material in the cylindrical mold. ,
A method for producing a fiber-reinforced resin molded body is used in which a thermosetting resin is cured in a tubular mold while pulling out the functional resin-impregnated fiber base material and the curable resin-impregnated fiber base material from the other end side.

However, this method for producing a fiber-reinforced resin molded article is such that when the functional resin-impregnated fiber base material and the curable resin-impregnated fiber base material are drawn into the hollow portion of the tubular mold from one end side, The functional resin and curable resin impregnated in the resin are squeezed out, the squeezed resin is mixed, and even if the squeezed out resin is collected, it cannot be used as the functional resin and the functionalizing agent is wasted. However, the functional resin of the functional resin-impregnated fiber base material is replaced by the mixed resin, and a portion having a low content of the function-imparting agent is generated on the surface layer.

In Japanese Patent Publication No. 60-5454, a core material is continuously inserted into a tubular mold, and a fibrous base material is passed through a gap between the core material and the cylindrical mold and pulled out together with the core material. There has been proposed a method for producing a long fiber-reinforced resin molded body in which a thermosetting resin is filled in the void between the core material and the tubular mold in the tubular mold. This manufacturing method does not generate a portion having a low content of the functionality-imparting agent on the surface layer and does not waste the functionality-imparting agent, but forms the core material before feeding the core material to the tubular mold. There is a drawback that requires another mold for

Further, Japanese Patent Application Laid-Open No. 2-182437 discloses that
A cylindrical mold with resin supply holes for supplying resin to the inner surface of the mold is installed in the mold, and a large number of glass rovings impregnated with phenol resin and a large number of resin-unimpregnated glass rovings are provided. There is a pultrusion molding method in which the phenol resin is pressed into the tubular mold through the resin supply hole while the glass roving penetrating the tubular mold is pulled out from the other end by penetrating the hollow part of the tubular mold from the one end side. Have been described. However, this production method is a method for producing a molded product having a uniform resin distribution composed of a phenol resin and glass roving having a good surface state, and therefore, in the case of producing a fiber-reinforced resin molded product using a functionalizing agent. It does not solve the problem of waste of the functionalizing agent.

[0008]

In view of the above-mentioned drawbacks, the present invention provides a long fiber-reinforced resin comprising a surface layer containing a function-imparting agent and a core material having a content ratio of the function-imparting agent lower than that of the surface layer. Provided is a method for producing a fiber-reinforced resin molded product, which does not require another molding die, without wasting the functionalizing agent, forming a portion having a low content of the functionalizing agent in the surface layer. The purpose is to

[0009]

The present invention will be described below with reference to the drawings. FIG. 1 is an explanatory view showing an example of the manufacturing method of the present invention.

In FIG. 1, 1 is a surface layer containing a function-imparting agent of a fiber-reinforced resin molding, and 2 is a core material having a lower content of the function-imparting agent than the surface layer 1 of the fiber-reinforced resin molding. Yes, 3 is a fiber reinforced resin molded body composed of the surface layer 1 and the core material 2.

Reference numeral 4 denotes a fiber base material constituting the surface layer 1, and 5
Is a functional resin composed of a functionalizing agent that constitutes the surface layer 1 and a thermosetting resin. The functional resin 5 is impregnated into the fiber base material 4 that constitutes the surface layer and cured to obtain the surface layer 1. To be Reference numeral 11 denotes an original fabric roll of the fiber base material 4 constituting the surface layer, and the fiber base material 4 constituting the surface layer is supplied from the original fabric roll 11.

6 is a curable resin-impregnated fiber base material, and 22
Is a fibrous base material that constitutes the core material, 23 is a curable resin composed of a thermosetting resin, and the curable resin 23 has a lower content of the function-imparting agent than the functional resin 5, and is a curable resin. Two
The curable resin-impregnated fiber base material 6 is obtained by impregnating the fiber base material 22 constituting the core material with 3, and the core material 2 is obtained by curing the curable resin-impregnated fiber base material 6. Reference numeral 21 is an original fabric roll of a fiber base material 22 constituting a core material, and 24 is a curable resin impregnation tank for impregnating the fiber base material 22 constituting the core material with a curable resin 23, which constitutes a core material. The fibrous base material 22 is supplied from the original fabric roll 21 and is impregnated with the curable resin 23 supplied to the curable resin impregnation tank 24 to form the curable resin-impregnated fiber base material 6.

Reference numeral 7 is a cylindrical mold having functional resin supply holes for supplying the functional resin to the inner surface of the mold, the cylindrical mold having openings at both ends, and 12 supplying the functional resin 5 to the inner surface of the mold. The functional resin 5 is impregnated with the functional resin 5 into the fiber base material 4 which is the functional resin supply hole and constitutes the surface layer in the cylindrical mold 7.
And the curable resin 23 are heated and cured to produce a fiber-reinforced resin molded body 3 including the surface layer 1 and the core material 2. Reference numeral 8 is a take-up machine for taking up the fiber-reinforced resin molded body 3, 9 is a guide for aligning and guiding the fiber base material 4, the fiber base material 22 and the curable resin-impregnated fiber base material 6, and curing the fiber base material 4 The resin-impregnated fiber base material 6 is guided by the guide 9 to one end of the opening of the hollow portion of the tubular mold 7, and is pulled out by the take-out machine 8.

Examples of the thermosetting resin used in the present invention include thermosetting resins such as unsaturated polyester resin, epoxy resin, vinyl ester resin and phenol resin.

The functionality imparting agent used in the present invention includes 2,4-dihydroxybenzophenone and 2-
Ultraviolet absorbers such as (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,6-di-t-butyl-4-ethylphenol, 2,2′-methylene-bis- (4-methyl-6). -T-butylphenol) and other antioxidants, halogen compounds, flame retardants such as phosphoric acid esters, inorganic fillers such as aluminum hydroxide and magnesium hydroxide, and antifungal agents such as 10,10′-oxybisphenoxyarsine, Examples include pigments and the like.

The fibers of the fiber base material 22 constituting the core material and the fiber base material 4 constituting the surface layer used in the present invention include glass fiber, aramid fiber, vinylon fiber, carbon fiber and the like. May be combined. Fiber base material 22 constituting the core material and fiber base material 4 constituting the surface layer
Examples of the form include roving, chopped strand mat, continuous mat, and roving cloth, which may be used in combination.

In the present invention, the curable resin-impregnated fibrous base material 6 and the fibrous base material 4 constituting the surface layer are drawn into the hollow portion of the tubular mold 7 from one end side to form the fibrous base material 4 as the surface layer. Is arranged along the inner surface of the tubular mold 7 so as to penetrate the tubular mold 7, and the curable resin-impregnated fiber base material 6 is placed inside the fiber base material 4 constituting the tubular surface layer in the tubular mold 7. The curable resin-impregnated fibrous base material 6 and the fibrous base material 4 constituting the surface layer are pulled out from the other end side while the functional resin 5 is passed through the functional resin supply hole 12 and the inner surface of the cylindrical mold 7 is arranged. And the fiber base material 4 constituting the surface layer is impregnated. The position of the functional resin supply hole 12 for supplying the functional resin 5 into the tubular mold 7 is such that the thermosetting resin of the functional resin 5 is sufficiently cured in the tubular mold 7. It is better to be away from the other end side of.

Next, in the tubular mold 7, the fibrous base material 4 and the curable resin-impregnated fibrous base material 6 constituting the tubular surface layer impregnated with the functional resin 5 are heated, and thermosetting contained therein. The functional resin is cured to obtain a fiber-reinforced resin molded body 3 including a surface layer 1 containing a function-imparting agent and a core material 2 having a content ratio of the function-imparting agent lower than that of the surface layer. The fiber-reinforced resin molded body 3 thus obtained is continuously drawn from the tubular mold 7 to the take-up machine 8 and is subjected to post-processing such as cutting into a predetermined length by a cutting machine or the like.

[0019]

In the method for producing a fiber-reinforced resin molding of the present invention, when the resin-impregnated fiber base material is drawn into the tubular mold, the resin is made of a thermosetting resin at one end of the tubular mold. Since it is composed only of a curable resin having a lower content of the function-imparting agent than the resin, the squeezed resin can be recovered as a curable resin, and even if the curable resin once adheres to the fiber base material constituting the surface layer. Since the functional resin is supplied from the inner surface side of the cylindrical mold in the cylindrical mold, it is possible to obtain the surface layer composed of the functional resin and the fiber base material without producing a portion having a low content of the functionalizing agent. it can. Further, the functional resin exists only in the surface layer of the fiber-reinforced resin molded body, the core material has a lower content of the function-imparting agent than the surface layer, and the resin squeezed out and collected is the resin constituting the core material. Therefore, the function-imparting agent is not consumed unnecessarily, and therefore the function-imparting agent is not wasted. Further, since the fiber-reinforced resin molded body is manufactured with only one molding die, another molding die is not required.

[0020]

Embodiments of the present invention will be specifically described below with reference to FIG. Example 1 A fiber-reinforced resin molded body was manufactured by installing the manufacturing process shown in FIG. The resin squeezed out from the one end side of the tubular mold was collected and added to the curable resin impregnation tank 24.

The hollow portion of the cylindrical mold 7 has a height of 30 mm and a width of 20.
It is a rectangle of 0 mm and has a length of 1000 mm and is open at both ends. In addition, the functional resin supply hole 1 is provided 100 mm from the drawing-in side opening of the inner surface of the hollow portion of the tubular mold 7.
The tip of 2 is open. The temperature of the cylindrical mold 7 was set with a temperature gradient from 100 ° C. on the drawing side to 150 ° C. on the drawing side.

Unsaturated polyester resin (manufactured by Nippon Yupica Co., trade name Yupica 3512) 100 parts by weight, t-butyl peroxybenzoate (manufactured by Kayaku Akzo Co., trade name Kayabutyl B) 1 part by weight, bis (4-t- Butylcyclohexyl) peroxydicarbonate (manufactured by Kayaku AKZO Co., Ltd., trade name Perkadox 16) 0.5 part by weight, orthophosphoric acid type internal release agent (manufactured by DUPONT, USA, trade name ZELEC)
UN) 0.7 part by weight and aluminum hydroxide 10 parts by weight were mixed to obtain a curable resin 23, and the obtained curable resin 23 was supplied to a curable resin impregnation tank 24.

The fiber base material 22 constituting the core material is made of glass fiber roving (Asahi Fiber Co., No. 4450), and the fiber base material 4 constituting the surface layer is made of glass fiber continuous mat (Asahi Fiber Co., Ltd., No. 450) and glass fiber roving (No. 4450, manufactured by Asahi Fiber Co., Ltd.), and the number of roving rovings of the fiber base material 22 constituting the core material and the fiber base material 4 constituting the surface layer is 80, respectively. The number of continuous mats was 40, and the weight per meter of the continuous mat was adjusted to 178 g.

The raw material roll 1 is made up of the fiber base material 4 constituting the surface layer.
From 1 to the guide 9, the roving is converged and the continuous mat is bent according to the inner surface shape of the tubular mold 7, and the hollow portion of the tubular mold 7 is penetrated along the inner surface of the tubular mold 7 to form a tubular shape. The fiber base material 22 constituting the core material is arranged and guided from the original fabric roll 21 through the guide 9 to the curable resin 23 supplied to the curable resin impregnation tank 24,
Curable resin-impregnated fiber base material 6 impregnated with curable resin 23
Then, the roving is converged through the guide 9 in accordance with the shape of the inside of the fiber base material 4 forming the cylindrical surface layer in the cylindrical mold 7 to form the cylindrical surface layer in the cylindrical mold 7. The inside of the fiber base material 4 was penetrated.

The curable resin-impregnated fibrous base material 6 and the fibrous base material 4 constituting the surface layer are pulled out from the other end of the cylindrical mold 7, passed through a take-off machine 8 and pulled out at 50 cm / min to obtain an unsaturated polyester resin. 100 parts by weight, 1 part by weight of t-butylperoxybenzoate, 0.5 part by weight of bis (4-t-butylcyclohexyl) peroxydicarbonate, 0.7 part by weight of orthophosphoric acid internal release agent, and hydroxylation The functional resin 5 consisting of 200 parts by weight of aluminum was supplied to the inner surface of the cylindrical mold 7 through the functional resin supply hole 12 at 3.0 kgf / cm ² . As a result, a long fiber-reinforced resin molded body 3 comprising a surface layer 1 containing aluminum hydroxide and a core material 2 having a lower aluminum hydroxide content than the surface layer 1,
It was possible to manufacture without producing a portion having a low content of aluminum hydroxide on the surface. At this time, 2 l of the functional resin 5 was consumed while the fiber-reinforced resin molding 3 was manufactured for 1 m.

Comparative Example 1 The same procedure was carried out except that the resin used for the core material of Example 1 was replaced with the curable resin and the same functional resin as used in Example 1 was used. As a result, a fiber-reinforced resin molded product having a uniform resin distribution composed of the functional resin and the fiber base material could be manufactured. At this time, while the fiber-reinforced resin molding was manufactured for 1 m, the functional resin was
1 consumed.

COMPARATIVE EXAMPLE 2 The functional resin was impregnated with the fibrous base material constituting the surface layer of Example 1, and then the fibrous base material was supplied together with the curable resin-impregnated fibrous base material to the cylindrical mold to supply the functional resin. The same operation was performed except that the holes were not supplied. As a result, a long fiber-reinforced resin molded product having a portion having a low aluminum hydroxide content on the surface thereof was produced. In addition, 1 fiber-reinforced resin molding
3l of the functional resin was consumed during the production.

[0028]

According to the method for producing a fiber-reinforced resin molding of the present invention, the functional resin comprises a functionalizing agent and a thermosetting resin, and the curable resin contains the functionalizing agent rather than the functional resin. Fibers that make up the core material in the hollow part of the tubular mold that is made of a thermosetting resin with a low rate and that has a functional resin supply hole that supplies the functional resin to the inner surface of the mold and is open at both ends. A curable resin-impregnated fiber base material in which a base material is impregnated with a curable resin and a fiber base material forming a surface layer are drawn in from one end side of the tubular mold,
A fiber base material forming the surface layer is arranged in a tubular shape so as to penetrate along the inner surface of the tubular mold, and the curable resin-impregnated fiber base material constitutes the tubular surface layer in the tubular mold. The functional resin is supplied to the inner surface of the cylindrical mold through the functional resin supply hole while the curable resin-impregnated fiber base material and the fiber base material that constitutes the surface layer are pulled out from the other end side. Then, the fiber base material constituting the surface layer is impregnated, and the thermosetting resin is cured in the tubular mold. Therefore, without wasting the functionality-imparting agent, without generating a portion having a low content rate of the functionality-imparting agent in the surface layer, without requiring another mold, the surface layer containing the functionality-imparting agent and the surface layer. It is possible to manufacture a long fiber-reinforced resin molded product composed of a core material having a lower content of the function-imparting agent.

[Brief description of drawings]

FIG. 1 is an explanatory view showing an example of a manufacturing method of the present invention.

[Explanation of symbols]

 1 Surface Layer 2 Core Material 3 Fiber Reinforced Resin Molded Body 4 Fiber Base Material Constituting Surface Layer 5 Functional Resin 6 Curable Resin Impregnated Fiber Base Material 7 Cylindrical Mold 8 Pulling Machine 9 Guide

Claims (1)

[Claims] 1. A surface layer and a core material, wherein the surface layer comprises a functional resin and a fiber base material forming the surface layer, and the core material comprises a curable resin and a fiber base material forming the core material. A long fiber-reinforced resin molded product in which the functional resin is composed of a functionalizing agent and a thermosetting resin, and the curable resin is composed of a thermosetting resin having a lower content of the functionalizing agent than the functional resin. In manufacturing, the resin supply holes for supplying the functional resin to the inner surface of the mold are installed in the mold. In the hollow part of the cylindrical mold with both ends opened, a curable resin is added to the fiber base material that constitutes the core material. The impregnated curable resin-impregnated fiber base material and the fiber base material forming the surface layer are drawn in from one end side of the tubular mold, and the fiber base material forming the surface layer is passed along the inner surface of the cylindrical mold. Fibers that are arranged in a tubular shape and that form a curable resin-impregnated fiber base material that forms the tubular surface layer in the tubular mold. The inner surface of the tubular mold is arranged so as to penetrate inside the fiber base material, and while pulling out the curable resin-impregnated fiber base material and the fiber base material forming the surface layer from the other end side, the functional resin is passed through the functional resin supply hole. The method for producing a fiber-reinforced resin molded product, characterized in that the fibrous base material constituting the surface layer is impregnated and the thermosetting resin is cured in a tubular mold.