JP2013216823A - Method for producing molding material, molding material, and fiber-reinforced resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a molding material which can make high strength and uniformity molded fiber-reinforced resin molding and can control generation of a burr part, and to provide a molding material and a fiber-reinforced resin molding.SOLUTION: There is provided a method for producing a molding material 6 comprising an unsaturated polyester resin and a reinforcing fiber. After a compound 20 comprising at least a thickener and the unsaturated polyester resin is coated to the surface of a long reinforcing fiber, and the compound 20 on the surface of the long reinforcing fiber is thickened, and the long reinforcing fiber coated by the compound 20 is cut in a prescribed length.

Description

  The present invention relates to a molding material manufacturing method, a molding material, and a fiber-reinforced resin molded body.

  Fiber reinforced resin moldings are materials in which reinforced fibers such as glass fibers are hardened with resin. As composite materials with excellent mechanical strength, chemical resistance, heat resistance, and electrical properties, they are used in bathtubs, vanities, and kitchens. Used for counters.

  Various methods are known as a method for molding a fiber reinforced resin molded body. Among them, a heat and pressure molding method using a molding material such as a sheet molding compound (hereinafter abbreviated as SMC) is widely used. Yes.

  In a general SMC manufacturing method, SMC is manufactured by impregnating a reinforcing fiber piece such as a glass fiber piece with a compound containing an unsaturated polyester resin, an inorganic filler, and other additives.

  As a specific SMC manufacturing method, as shown in FIG. 2, the compound 22 is applied on the film 70, and the glass roving 10 is passed between the cutter roll 50 and the rubber roll 51 from above to obtain a predetermined SMC. A certain amount of reinforcing fiber pieces 11 cut into lengths are dispersed to form a reinforcing fiber piece layer 12.

  Then, the film 71 coated with the compound 23 is placed thereon and pressed with a roll 8 or a mesh belt, whereby the reinforcing fiber piece layer 12 is impregnated with the compounds 22 and 23 to obtain the SMC 9.

  On the other hand, in order to increase the strength of a fiber-reinforced resin molded body molded using SMC9, one having an increased content of reinforcing fiber pieces 11 has been proposed (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 10-71625

  However, if the content of the reinforcing fiber pieces 11 is increased, the reinforcing fiber piece layer 12 becomes thick and the central portion in the thickness direction tends to be poorly impregnated with the compounds 22 and 23. Therefore, the content of the reinforcing fiber pieces 11 is reduced to a predetermined amount ( In general, it was difficult to increase the amount exceeding 25% by mass relative to the entire SMC.

  Moreover, in the manufacturing method of said SMC9, the part (henceforth a mimetic part) which compound 22 and 23 oozed to the end exceeding the spreading width of the reinforcing fiber piece 11 generate | occur | produces.

  Since the reinforcing fiber pieces 11 are not included in the mimetic part, cracks or the like due to the mimetic part may occur during the molding of the fiber reinforced resin molded body.

  For this reason, cutting of the mimetic portion in advance is performed before molding, which causes problems such as loss of the compounds 22 and 23 and an increase in work processes.

  The present invention has been made in view of the circumstances as described above, and is capable of producing a molding material capable of making the strength of a molded fiber-reinforced resin molded body high in strength and uniform and suppressing occurrence of a mimetic portion. It is an object to provide a method, a molding material, and a fiber-reinforced resin molding.

  The present invention is characterized by the following in order to solve the above problems.

  That is, the method for producing a molding material of the present invention is a method for producing a molding material comprising an unsaturated polyester resin and a reinforcing fiber, and at least a compound comprising a thickener and an unsaturated polyester resin is applied to the surface of the long reinforcing fiber. After the coating, the compound on the surface of the long reinforcing fiber is thickened, and then the long reinforcing fiber coated with the compound is cut into a predetermined length.

  Moreover, in this manufacturing method of a molding material, it is preferable to cool a compound before coat | covering a compound on the surface of a long reinforcing fiber.

  Further, the molding material of the present invention is a molding material produced by the above-described molding material production method, and is a compound comprising a thickener and an unsaturated polyester resin on the surface of a reinforcing fiber cut to a predetermined length. Is characterized by being coated.

  The fiber-reinforced resin molded article of the present invention is characterized by being molded using the molding material.

  According to the method for producing a molding material of the present invention, since the resin content with respect to the reinforcing fiber becomes uniform in any part of the molding material, the strength of the molded fiber-reinforced resin molded body can be made uniform. Moreover, since the reinforcement fiber content rate of a fiber reinforced resin molding can be raised, intensity | strength can be improved and generation | occurrence | production of a mim part can be suppressed further.

It is the schematic which shows the manufacturing apparatus of the molding material of this invention. It is the schematic which shows the manufacturing apparatus of the conventional SMC.

  Hereinafter, the manufacturing method of the molding material of this invention is demonstrated in detail.

  The compound used in the present invention contains at least a thickener with respect to the unsaturated polyester resin, and as other components, for example, a curing agent, a polymerization inhibitor, a polymerizable monomer, a low shrinkage Agent, inorganic filler and the like. And this compound is coat | covered on the surface of a long reinforcing fiber, it cut | disconnects and it is set as a molding material.

  The unsaturated polyester resin used in the present invention is an unsaturated or saturated polycarboxylic acid such as aliphatic unsaturated polycarboxylic acid, aliphatic saturated polycarboxylic acid, aromatic polycarboxylic acid, diol, triol, tetraol, etc. This is a thermosetting resin obtained by a condensation reaction with an organic polyol, in which an unsaturated monomer such as a vinyl monomer may be dissolved.

  Examples of the aliphatic unsaturated polycarboxylic acid include (anhydrous) maleic acid and fumaric acid. Examples of the aliphatic saturated polycarboxylic acid include sebacic acid, (anhydrous) succinic acid, adipic acid and the like. Can be mentioned. Examples of the aromatic polycarboxylic acid include (anhydrous) phthalic acid, isophthalic acid, terephthalic acid and the like.

  These may be used alone or in combination of two or more.

  Examples of organic polyols include aliphatic polyols and aromatic polyols. Aliphatic polyols include ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, triethylene glycol, neopentyl glycol, Examples include hexamethylene glycol, trimethylene glycol, and glycerin.

  Examples of the aromatic polyol include bisphenol A, hydrogenated bisphenol A, and bisphenol S. These may be used alone or in combination of two or more.

  As the thickener used in the present invention, for example, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, potassium oxide, potassium hydroxide, tolylene diisocyanate, diphenylmethane diisocyanate and the like can be used.

  These may be used alone or in combination of two or more.

  It is preferable to make the compounding quantity of a thickener into the range of 0.6-2.0 mass parts with respect to the total amount of the component of a compound. By setting the blending amount of the thickener within this range, it is possible to satisfactorily coat the long reinforcing fibers, and the proper thickening proceeds, so that a molding material having excellent handling properties can be obtained.

  The curing agent used in the present invention is a curing agent used in the unsaturated polyester resin composition, and is used when molding under a high temperature condition of 100 ° C. or higher using a molding machine such as a decorative board, a mold or the like. A high temperature curing type curing agent can be used.

  These high-temperature curing agents include methyl ethyl ketone peroxide, t-butyl peroxy 2-ethyl hexanate, benzoyl peroxide, di-t-butyl peroxy 3,3,5 trimethylcyclohexane, t-butyl peroxybenzoate. , Dicumyl peroxide, t-butyl hydroperoxide and the like.

  As the polymerization inhibitor used in the present invention, at least either a quinone polymerization inhibitor or a phenol polymerization inhibitor can be used.

  Examples of the quinone polymerization inhibitor include p-benzoquinone, t-butyl p-benzoquinone, naphthoquinone, phenanthraquinone, tolquinone, 2,5-diphenyl p-benzoquinone, 2,5-diacetoxy p-benzoquinone, 2,5- Examples include diaroxy p-benzoquinone.

  In addition, phenolic polymerization inhibitors include hydroquinone, pt-butylcatechol, 2,5-dit-butylhydroquinone, mono-t-butylhydroquinone, 2,5-dit-aluminumhydroquinone, 2,6-di Examples thereof include t-butyl 1-4-methylphenol.

  The polymerizable monomer used in the present invention is not particularly limited as long as it is usually used in an unsaturated polyester resin composition. For example, styrene, vinyl toluene, vinyl acetate, diallyl phthalate, triallyl cyanurate. And acrylic acid esters (methyl acrylate, ethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate), and the like.

  The low shrinkage agent is blended for the purpose of reducing the cure shrinkage of the unsaturated polyester resin, and a thermoplastic resin is usually used.

  Examples of these low shrinkage agents include polystyrene, polymethyl methacrylate, cellulose acetate butyrate, polycaprolactan, polyethylene, polyvinyl chloride, polyester, polyvinyl acetate, polystyrene vinyl acetate copolymer, and the like. A copolymer etc. can be mentioned.

  These may be used alone or in combination of two or more.

  As the inorganic filler used in the present invention, for example, inorganic substances such as calcium carbonate, aluminum hydroxide, silica, and alumina can be used. These may be used alone or in combination of two or more.

  As for the compounding quantity of an inorganic filler, 100-300 mass parts is preferable when the mixture of an unsaturated polyester resin, a polymerizable monomer, and a low shrinkage agent is 100 mass parts.

  When the blending amount of the inorganic filler is within this range, the flow dispersion of the reinforcing fibers in the molding material at the time of molding becomes uniform, so that the variation in strength of the fiber reinforced resin molded product is reduced.

  Moreover, since the viscosity of the compound becomes appropriate, the coating of the compound on the long reinforcing fiber becomes good, and the strength of the fiber reinforced resin molded product is expressed.

  In addition, since the inorganic filler is more likely to be aggregated or oil-absorbed as it is finer and the filling may be difficult, the surface of the inorganic filler is preferably surface-treated with a fatty acid, a coupling agent, or the like. .

  The fatty acid is represented by the general formula CnHmCOOH, n is 3 to 23, m is 7 to 47, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, Saturated fatty acids such as stearic acid, arachidic acid, behenic acid, lignoceric acid, α-linolenic acid, stearidonic acid, eicosapentaenoic acid, docosapentaenoic acid, linoleic acid, γ-linolenic acid, dihomo-γ-linolenic acid, arachidon Any of unsaturated fatty acids such as acid, oleic acid, elaidic acid, erucic acid, and nervonic acid can be used.

Moreover, as a coupling agent, the silane coupling agent etc. which are shown by general formula R-Si (OR ') ₃ can be used.

  In the above general formula, R is a functional group and represents an aminopropyl group, a glycidoxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercato group, a vinyl group, or the like, and R ′ represents a methyl group or an ethyl group.

  In addition to the above-described components, other components can be blended in the compound using the unsaturated polyester resin used in the present invention as necessary. Examples of such other components include colorants such as carbon black and mold release agents such as carnauba wax.

  In the method for producing a molding material of the present invention, the long reinforcing fiber covering the above compound can be used without particular limitation as long as it is a reinforcing fiber that is generally used in a fiber reinforced resin molded body of an unsaturated polyester resin. Usually, glass fiber is preferably used.

  Moreover, as an alternative to glass fiber, for example, carbon fiber, metal fiber, vinylon fiber, aramid fiber, polyester fiber, or the like can be used. These long reinforcing fibers may be a roving shape or a strand-like continuous body constituting the roving.

  It is preferable that the compounding quantity of the reinforced fiber with respect to the fiber reinforced resin molded object which is a final molded product exists in the range of 10-70 mass%. When the blending amount of the reinforcing fibers is within this range, the reinforcing action by the reinforcing fibers can be sufficiently exhibited, and a good appearance can be obtained.

  Below, one Embodiment of the manufacturing method of the molding material used by this invention is described in detail using figures. FIG. 1 is a schematic view of an apparatus for producing a molding material of the present invention.

  First, the glass roving 10 which is a long reinforcing fiber is introduced into a compound tank 21 containing the compound 20. At this time, it is desirable to cool the compound 20 in the compound tank 21 in order to extend the impregnation life due to thickening.

  The cooling temperature of the compound 20 can be appropriately set in consideration of the compounding components of the compound 20 and the like, but is usually 15 ° C. or less, preferably 0 to 10 ° C. If the temperature is too low, the viscosity increases, so it is preferable to ensure 0 ° C. or higher.

  Next, the compound 20 on the surface of the glass roving 10 is squeezed out by the squeezing roll 3 to obtain an appropriate coating amount. The coating amount can be set to a desired coating amount by adjusting the tightening force of the squeezing roll 3.

  The compound 20 coated on the surface of the glass roving 10 immediately after coating has adhesiveness and is difficult to cut as it is, so that the compound 20 is heated by passing through the aging box 4 and subjected to thickening treatment.

  The set temperature of the aging box 4 is not particularly limited as long as it is a temperature at which cutting can be performed, but is usually 30 to 80 ° C., preferably about 40 ° C. when the curing conditions of the compound 20 are taken into consideration.

  The glass roving 10 coated with the compound 20 that has passed through the aging box 4 and can be cut is passed between the cutter roll 50 and the rubber roll 51 and cut into a predetermined length. 6 is manufactured.

  The cutting length can be appropriately set according to the design, use, etc. of the fiber reinforced resin molded article to be molded, but a length of about 0.2 to 2 inches, preferably about 1 inch is considered.

  The molding material 6 of the present invention produced by the above method may be used as a molding material in a cut state, or may be a bulk or sheet-like molding material.

  The fiber-reinforced resin molded body using the molding material 6 of the present invention can be molded by a normal molding method. Specifically, the fiber-reinforced resin molded body can be molded by heating and pressing the molding material of the present invention with the upper mold and the lower mold.

  Although the molding conditions are not particularly limited, for example, molding conditions of a molding pressure of 3 to 10 MPa, a mold temperature of 125 to 150 ° C., and a molding time of 3 to 7 minutes are considered.

  Thus, since the fiber reinforced resin molded object shape | molded using the molding material of this invention can raise the content rate of a reinforced fiber, it can improve an intensity | strength.

  Moreover, since the compound content with respect to the reinforcing fiber is uniform in any part of the molding material, the strength of the fiber-reinforced resin molded body is uniform, and the quality can be improved.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples at all.

<Example>
The following were used as the compound material and the long reinforcing fibers for producing the fiber reinforced resin moldings of the examples.

(Unsaturated polyester resin)
M-580 manufactured by Showa Denko K.K.
(Thickener)
Magnesium oxide, Kyowa Chemical Co., Ltd. Kyowa Mug # 40

(Curing agent)
t-Butyl peroxybenzoate, Perbutyl Z, manufactured by NOF Corporation
(Polymerizable monomer)
Styrene, styrene monomer based on CAS (100-42-5) manufactured by Mitsubishi Chemical Corporation

(Low shrinkage agent)
Polystyrene, GPPS manufactured by PS Japan
(Polymerization inhibitor)
Quinone series: p-benzoquinone, manufactured by Wako Pure Chemical Industries, Ltd.

(Inorganic filler)
Calcium carbonate, manufactured by Shiraishi Kogyo Co., Ltd.
Zinc stearate, manufactured by Kawamura Chemical Co., Ltd.

(Long reinforcing fiber)
Glass roving, manufactured by Nittobo Co., Ltd. RS480PB-549

  First, 80 parts by weight of unsaturated polyester resin, 1 part by weight of magnesium oxide, 1 part by weight of t-butyl peroxybenzoate, 20 parts by weight of styrene, 5 parts by weight of polystyrene, 0.05 part by weight of p-benzoquinone, 150 parts by weight of calcium carbonate Then, 5 parts by mass of zinc stearate was mixed to obtain a compound.

  Next, as shown in FIG. 1, the compound 20 was put into the compound tank 21 and cooled to about 5 ° C. in order to extend the impregnation life due to thickening.

  Next, after the glass roving 10 was introduced into the compound tank 21 and impregnated with the compound 20, coating was performed by squeezing the excess compound 20 with the squeezing roll 3. The adjustment of the coating amount was performed by adjusting the tightening force between the squeezing rolls 3.

  After coating, the aging chamber 4 set at 40 ° C. is passed to increase the viscosity, and then passed between the cutter roll 50 and the rubber roll 51 and continuously cut to a length of 1 inch to form a molding material. 6 was obtained.

  Using the molding material 6 obtained above, a fiber-reinforced resin molded body having a size of 200 mm square and a thickness of 3 mm was produced by a flat plate press at 140 ° C.

<Comparative example>
The SMC 9 was produced by using the same compounds 22 and 23 as those used for the reinforcing fiber piece 11 made of glass fiber using the conventional manufacturing apparatus shown in FIG.

  After peeling off the films 70 and 71 on the surface of this SMC9, a predetermined number of sheets were stacked and a 200 mm square, 3 mm thick fiber reinforced resin molded product was produced by a flat plate press at 140 ° C.

<Measurement and evaluation>
The following measurements and evaluations were performed on each of the fiber reinforced resin molded articles of Examples and Comparative Examples obtained as described above.

[Glass fiber content]
About the molding material used in the Example and SMC used in the comparative example, the content of the glass fiber relative to the molding material and SMC was determined.

[Impregnation uniformity]
The impregnation uniformity of the compound with respect to the reinforcing fiber in the molding material used in the example and the SMC used in the comparative example was visually evaluated according to the following criteria.
○: No unimpregnated part ×: Unimpregnated part

[Bending strength]
The bending strength of the fiber reinforced resin molded articles of Examples and Comparative Examples was measured according to JIS K 7171.

[Percentage of Mimi part]
The mim part of the fiber reinforced resin moldings of Examples and Comparative Examples was cut, and the ratio of the mim part to the entire fiber reinforced resin molding was determined from the weight of the cut mim parts.

  Table 1 shows the measurement results and evaluation results of the glass fiber content, the impregnation uniformity, the bending strength, and the ratio of the Mimi portion.

  From Table 1, the molding material and the fiber reinforced resin molded body of the examples were excellent in all items as compared with the SMC and the fiber reinforced resin molded body of the comparative example.

  In particular, the glass fiber content of the molding material of the example is 60% by mass, which is much higher than 35% by mass of the SMC of the comparative example, and the bending strength of the fiber-reinforced resin molded body of the example is that of the comparative example. A value nearly 5 times the bending strength of the fiber-reinforced resin molded product was shown.

  Moreover, although 2 mass% of Mimi parts were recognized by the fiber reinforced resin molded object of the comparative example, the Mimi part was not recognized by the fiber reinforced resin molded object of an Example.

10 Glass roving 20 Compound 6 Molding material

Claims (4)

  A method for producing a molding material comprising an unsaturated polyester resin and a reinforcing fiber, wherein at least a compound comprising a thickener and an unsaturated polyester resin is coated on the surface of the long reinforcing fiber, and then the compound on the surface of the long reinforcing fiber. A method for producing a molding material, characterized in that a long reinforcing fiber covered with a compound is cut into a predetermined length.   The method for producing a molding material according to claim 1, wherein the compound is cooled before the compound is coated on the surface of the long reinforcing fiber.   A molding material produced by the method for producing a molding material according to claim 1 or 2, wherein the surface of the reinforcing fiber cut into a predetermined length is coated with a compound comprising a thickener and an unsaturated polyester resin. A molding material characterized by A fiber-reinforced resin molded article, which is molded using the molding material according to claim 3.

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