JP2009119613A - Fiber-reinforced plastic molding and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem that a conventional method makes heat curing necessary at a temperature of at least the melting point of an added wax, requires a long time for the complete curing of an unsaturated polyester gel coat resin, or causes a paraffin component added into the unsaturated polyester gel coat resin to ooze out on the surface to demonstrate a mold release effect, so that a desired adhesive properties can not be obtained. <P>SOLUTION: A fiber-reinforced plastic molding using a phenol resin as a matrix resin has a gel coat layer made of an unsaturated polyester resin on the outer surface side of the fiber-reinforced plastic molding and a surface layer in which a vinyl ester resin layer including a glass mat is arranged on the side of a body. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention provides a fiber reinforced plastic (hereinafter sometimes referred to as “FRP”) molded article having an unsaturated polyester gel coat layer and using a phenol resin as a matrix resin, and has an adhesive property between the gel coat layer and the FRP layer. The present invention relates to an excellent FRP and a method for producing the same.

  In FRP molded products using phenolic resin as a matrix resin, unsaturated polyester gel coat resin is not often used on the surface of FRP using phenolic resin due to adhesion problems. there were.

  Even when a normal unsaturated polyester gel coat resin is sufficiently cured using a peroxide, the surface thereof is always in contact with oxygen in the air, so that it is in an uncured state due to a polymerization inhibiting action. On the other hand, the phenol resin is an ionic reaction, unlike the unsaturated polyester resin, and the condensed water and phenol itself by the reaction serve as a polymerization inhibitor for the unsaturated polyester resin. Therefore, the phenol resin is formed on the unsaturated polyester gel coat resin. When FRP is laminated, adhesion is poor and peeling occurs at the interface, and the gel coat layer does not adhere or peels off with a small impact or deformation. In addition, there is a disadvantage that a space is generated by the condensed water of the phenol resin, which leads to swelling and cracking of the gel coat surface later.

As a means for solving the above-mentioned problems, a wax having a melting point of 40 to 86 ° C. made of petroleum wax or mineral wax, usually called paraffin, is added to the unsaturated polyester gel coat resin to make it air curable, and the surface is made Production of FRP using phenolic resin as a matrix resin by curing and then heat-curing at a temperature equal to or higher than the melting point after lamination molding using a resol-type phenolic resin and a substrate made of organic or inorganic fibers. A method is disclosed (for example, see Patent Document 1).
Japanese Patent Laid-Open No. 1-36417

  However, according to such a method, heat curing is required above the melting point of the added wax, and it takes time to completely cure the unsaturated polyester gel coat resin. Moreover, the paraffin component added to unsaturated polyester gel coat resin floated on the surface, and there existed problems, such as exhibiting a mold release effect and not obtaining desired adhesiveness.

  In the present invention, as a result of intensive studies to improve the adhesion between the gel coat layer and FRP using a phenol resin as a matrix resin, a known curing agent is blended in the gel coat resin, applied to a mold, and cured, and then glass After matting and vinyl ester resin are placed and impregnated and cured, a fiber reinforced phenolic resin layer is laminated thereon, and the gel coat layer and FRP layer using phenol as a matrix resin are adhered to each other by room temperature or heat curing. The present inventors have found that the properties can be greatly improved and have reached the present invention.

The present invention for solving the above-described problems employs the following configuration. That is,
(1) A fiber reinforced plastic molded article using a phenol resin as a matrix resin, a vinyl ester resin comprising a gel coat layer of an unsaturated polyester resin on the outer surface side of the fiber reinforced plastic molded article and a glass mat on the main body side A fiber reinforced plastic molded article having a surface layer on which the above layer is disposed.

  (2) The fiber reinforced plastic molded article according to (1), wherein the fiber volume content of the glass mat in the vinyl ester resin layer is 5 to 40%.

  (3) The fiber-reinforced plastic molded article according to (1) or (2), wherein a thickness of the vinyl ester resin layer is equal to or greater than a thickness of the gel coat layer of the unsaturated polyester resin.

  (4) An unsaturated polyester gel coat layer is formed on a mold and cured, and then a glass mat and a vinyl ester resin layer are placed on the unsaturated polyester gel coat layer and impregnated and cured, and then the vinyl ester resin is cured. A method for producing a fiber-reinforced plastic molded article, comprising: arranging a reinforcing fiber base on the layer, impregnating the reinforcing fiber base with a matrix resin made of a phenol resin, and curing the matrix resin.

(5) The method for producing a fiber-reinforced plastic molded article according to (4), wherein the vinyl ester resin layer is disposed so that the fiber deposition content of the glass fiber in the vinyl ester resin layer is 5 to 40%. (6) The method for producing a fiber-reinforced plastic molded article according to (4) or (5), wherein the vinyl ester resin layer is thicker than the gel coat layer of the unsaturated polyester resin.

  A fiber reinforced plastic (hereinafter, referred to as “fiber reinforced phenol resin”) molded body using a phenol resin as a matrix resin obtained by the production method of the present invention is an outer surface side of the fiber reinforced phenol resin molded body. It has a structure with a gel coat layer of unsaturated polyester resin and a surface layer in which a vinyl ester resin layer containing a glass mat is placed on the main body side, and it has excellent aesthetics, there is no concern about peeling of the gel coat layer, and there is no gel coat There are many advantages, such as the need to finish coloring by post-coating, such as the fiber-reinforced phenol molded body molded in, building materials, roofing materials, fences, louvers, noise barriers, vehicle parts, vehicle interior materials, aircraft For parts, aircraft interior materials, ducts, interior decoration materials, ceiling materials, wall materials, pipes, ship parts, ship interior materials, bathtubs, tanks, silos, etc. It is.

  The fiber-reinforced plastic molded body according to the present invention is a fiber-reinforced plastic molded body (fiber-reinforced phenolic resin molded body) using a phenol resin as a matrix resin, and is unsaturated on the outer surface side of the fiber-reinforced plastic molded body. It has a gel coat layer of polyester resin and a surface layer in which a vinyl ester resin layer including a glass mat is disposed on the main body side. In this configuration, that is, the vinyl ester resin layer including the glass mat is configured such that the vinyl ester resin layer including the glass mat is disposed between the fiber reinforced phenol resin layer and the unsaturated polyester resin gel coat layer. Thus, it is possible to obtain a molded body that has an excellent appearance and is difficult to peel off the gel coat layer.

  Such a fiber reinforced phenolic resin molded article is formed by forming and curing the unsaturated polyester gel coat layer on a mold, and then placing and impregnating the glass mat and vinyl ester resin layer, and then curing the vinyl ester resin. It is obtained by disposing a reinforcing fiber base material on the layer, impregnating the reinforcing fiber base material with a matrix resin made of a phenol resin, and curing the matrix resin.

  As the phenol resin to be used, either a resol type phenol resin or a novolac type phenol resin may be used, or a mixture thereof may be used.

  In addition, as the reinforcing fiber base used, organic fibers such as aramid fiber, polyethylene fiber, polyparaphenylene benzoxador (PBO) fiber, glass fiber, carbon fiber, silicon carbide fiber, alumina fiber, Tyranno fiber, basalt ( Basalt), inorganic fibers such as ceramic fibers, metal fibers such as stainless fibers and steel fibers, and other reinforcing fibers using boron fibers, natural fibers, modified natural fibers and the like as fibers are preferably used. Among them, carbon fiber is lighter among these reinforcing fibers, and has particularly excellent properties in specific strength and specific modulus, and is also excellent in heat resistance and chemical resistance, so it is lightweight. It is suitable for a member that is desired. Furthermore, among carbon fibers, PAN-based carbon fibers from which high-strength carbon fibers can be easily obtained are particularly preferable. As the form of the reinforcing fiber base, it is preferable to form a mat, cloth, nonwoven fabric, or the like.

  In the present invention, by providing a glass mat in the vinyl ester resin layer, the anchor effect is obtained and the vinyl ester resin layer is stabilized. From this viewpoint, the glass mat in the vinyl ester resin layer The fiber volume content is preferably 5 to 40%, more preferably 15 to 36%. Further, in addition to the stabilization of the vinyl ester resin layer and the good appearance (surface appearance) of the obtained molded product, considering that the gel coat layer has a structure that is difficult to peel off from the FRP layer, the vinyl ester The thickness of the resin layer is preferably equal to or greater than the thickness of the gel coat layer of the unsaturated polyester resin.

  The fiber reinforced phenolic resin molding obtained in this way is excellent in aesthetics, there is no concern about peeling of the gel coat layer, and it is colored by post-coating like a fiber reinforced phenol molding molded without a gel coat. It has many advantages such as no need to do so. Taking advantage of such advantages, the fiber reinforced phenolic resin molding according to the present invention is a building material, roofing material, fence, louver, sound barrier, vehicle part, vehicle interior material, aircraft part, aircraft interior material, duct, indoor It is suitably used for applications such as decorative materials, ceiling materials, wall materials, pipes, ship parts, ship interior materials, bathtubs, tanks, silos and the like.

  Next, an Example and a comparative example are shown and this invention is demonstrated concretely. Note that the present invention is not limited to the embodiments described below.

(Examples 1-4)
As shown in Table 1, 100 parts of an iso-type unsaturated polyester gel coat (Mikuni Dye Co., Ltd., NF Beige # 11363) is added with 1 part of a known unsaturated polyester resin curing agent, methyl ethyl ketone peroxide (Nippon Yushi Co., Ltd., Permec N). After blending and applying to a mold with a release agent applied at a thickness of 0.5 mm by spraying and curing at room temperature for about 2 hours, a glass mat (Central Glass Co., Ltd.) was then placed on the unsaturated polyester gel coat layer. Company ECM-501P-230) and vinyl ester resin (Showa High Polymer Co., Ltd., Lipoxy R-802) 100 parts blended with known vinyl ester resin curing agent, methyl ethyl ketone peroxide (Nippon Yushi Co., Ltd., Parmec N) 1 part After impregnation and curing at room temperature for about 2 hours, phenol resin (Gunei Chemical Industry Co., Ltd. Top XPL-6828B) is blended with 10 parts of curing agent (Gunei Chemical Industry Co., Ltd. XHL-4112C) and laminated by hand lay-up molding using carbon fiber cloth (Toray Co., Ltd. CK6440EL) 2 plies. Then, it was cured at room temperature to obtain a fiber reinforced phenolic resin molded product.

  The fiber reinforced phenolic resin molded product was removed from the mold, and the excess portion was cut with a hand grinder with a cutting grindstone for FRP (New Resistant Co., Ltd., Sandfoil C80). A fiber reinforced phenolic resin molded article having a surface coated with the gel coat layer without peeling of the gel coat layer and the phenol FRP layer at the time of demolding and cutting was obtained.

(Comparative Example 1)
A fiber reinforced phenolic resin molded body was molded by the same method as in Examples 1 to 4, omitting the glass mat placement step used in Examples 1 to 4. A part of the gel coat layer on the cut surface was slightly peeled off from the fiber-reinforced phenol resin molded article due to the heat and stress of the cutting cutter during demolding and during cutting.

(Comparative Examples 2 to 4)
The fiber reinforced phenolic resin molding was shape | molded by the method similar to Examples 1-4, omitting the application | coating process of the glass mat and vinyl ester resin used in Examples 1-4. The gel coat layer on the cut surface peeled off from the fiber-reinforced phenolic resin molded article due to the heat and stress of the cutting cutter during demolding and during cutting, and was lifted by 2 to 3 mm.

  In the above examples and comparative examples, Table 1, Table 1 shows the gel coat brand, glass mat brand, carbon fiber brand, vinyl ester brand, blending amount, curing conditions, etc. It is shown in 2.

<Adhesion strength test>
The adhesion strength test of the fiber reinforced phenol resin moldings obtained in Examples 1 to 4 and Comparative Examples 1 to 4 was performed. The results are shown in Tables 1 and 2. The test was conducted as follows.

  As shown in FIG. 1, the fiber-reinforced phenolic resin molded bodies obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were cut into about 150 mm squares, and the positions where they were adhered to the dolly (adhesion piece) and FRP were polished. Wash and apply epoxy adhesive (100 parts of Nagase ChemteX Corporation AV-138 mixed with 40 parts of HV-998), hold it by hand, and let it harden at room temperature for 12 hours. It was created. After curing, the gel coat layer and the FRP layer near the dolly (adhesion piece) were cut with a dedicated tool, and the adhesion strength was measured with an adhesion tester (coating film adhesion tester F106). The results are shown in Tables 1 and 2.

However, the gel coat, curing agent, primer, phenol resin, and fiber reinforcing material used were as follows. Gel coat: Iso unsaturated polyester gel coat (Mikuni Dye Co., Ltd., N beige F # 11363) Vinyl ester resin (Showa Polymer Co., Ltd., Lipoxy R-802) Curing agent: Methyl ethyl ketone peroxide (Nippon Yushi Co., Ltd.) Permec N) Glass fiber reinforcement: Chopped strand glass mat (Central Glass Co., Ltd., ECM-501-230) Phenol resin: Phenol resin (Gunei Chemical Industry Co., Ltd., Resitop XPL-6828B) Phenol resin curing agent: Phenol Resin hardener (Gunei Chemical Industry Co., Ltd. XHL-4112C)
Carbon fiber cloth: Carbon fiber cloth (Toray Industries, Inc., Torayca cloth CK6440EL) For convenience of work, the coating amounts of polyester gel coat and vinyl ester resin are unified. In Example 1, the glass mat was torn off and sprayed to correspond to a basis weight of 70 g / m ² .

  However, the gel coat, curing agent, primer, phenol resin, and fiber reinforcement used were as follows. Gel coat: Iso unsaturated polyester gel coat (Mikuni Dye Co., Ltd., N beige F # 11363) Vinyl ester resin (Showa Polymer Co., Ltd., Lipoxy R-802) Curing agent: Methyl ethyl ketone peroxide (Nippon Yushi Co., Ltd.) Permec N) Glass fiber reinforcement: Chopped strand glass mat (Central Glass Co., Ltd., ECM-501-230) Phenol resin: Phenol resin (Gunei Chemical Industry Co., Ltd., Resitop XPL-6828B) Phenol resin curing agent: Phenol Resin curing agent (Gunei Chemical Industry Co., Ltd. XHL-4112C) Carbon fiber cloth: Carbon fiber cloth (Toray Industries, Inc., Trading Card CK6440EL).

It is the schematic of the adhesion strength test apparatus of the molded article obtained by the Example and the comparative example, and an adhesion position.

Claims (6)

A fiber reinforced plastic molded article using a phenol resin as a matrix resin, comprising a gel coat layer of unsaturated polyester resin on the outer surface side of the fiber reinforced plastic molded article, and a vinyl ester resin layer containing a glass mat on the main body side. A fiber-reinforced plastic molded body having an arranged surface layer. The fiber reinforced plastic molded product according to claim 1, wherein the fiber volume content of the glass mat in the vinyl ester resin layer is 5 to 40%. The fiber-reinforced plastic molded body according to claim 1 or 2, wherein a thickness of the vinyl ester resin layer is equal to or greater than a thickness of the gel coat layer of the unsaturated polyester resin. An unsaturated polyester gel coat layer is formed and cured on a mold, and then a glass mat and a vinyl ester resin layer are placed and impregnated on the unsaturated polyester gel coat layer, and after curing, the vinyl ester resin layer is coated on the mold. A method for producing a fiber-reinforced plastic molded article, comprising: arranging a reinforcing fiber base material, impregnating the reinforcing fiber base material with a matrix resin made of a phenol resin, and curing the matrix resin. The manufacturing method of the fiber reinforced plastic molding of Claim 4 which arrange | positions the layer of vinyl ester resin so that the fiber deposition content rate of the glass fiber in the layer of the said vinyl ester resin may be 5 to 40%. The method for producing a fiber-reinforced plastic molded body according to claim 4 or 5, wherein the vinyl ester resin layer is thicker than the gel coat layer of the unsaturated polyester resin.

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