JP5950050B2 - Molding material for heat compression molding, molded product using the same, and method for producing the same - Google Patents

Description

  The present invention can increase the viscosity by urethane formation reaction of hydroxyl groups and isocyanate groups in the resin composition, has excellent film releasability, excellent heat compression moldability in a mold having a shear edge, and high strength molding The present invention relates to a carbon fiber reinforced plastic molding material from which a body is obtained, a sheet molding compound, a bulk molding compound, a molded product thereof, and a manufacturing method thereof.

  In general, molding materials using unsaturated polyester resins as matrix resins, sheet-like molding materials called sheet molding compounds, and bulk molding materials called bulk molding compounds are widely used in housing components, automobile parts, electrical parts, etc. Yes. The sheet molding compound consists of two resin compound layers in which a liquid resin compound consisting of a matrix resin, inorganic filler, curing agent, thickener, and other additives is applied to a carrier film with a certain thickness by a doctor knife method. A fiber-reinforced material made of glass fiber, carbon fiber, or the like is sandwiched between them, and the fiber-reinforced material is impregnated with a resin compound, and then the resin is thickened (B-stage). It is obtained as a material. This sheet-shaped resin compound is required to be in a liquid state when applied to a carrier film with a certain thickness and thickened after impregnating the fiber reinforcement. These sheet-shaped molding materials are sometimes referred to as prepregs. Bulk molding compounds, on the other hand, are mixed into a matrix resin, inorganic fillers, curing agents, thickeners, and relatively short fiber reinforcements called chopped strands by mixing them with a kneader kneader etc. A material is obtained.

  The molding method is press-heat compression molding, in which a molding material is molded at a pressure of 1 to 20 MPa in a 110 to 180 ° C. mold having a shear edge, and these molding conditions are set for a predetermined time. A molded product is manufactured by holding. Although the predetermined holding time depends on the curing characteristics of the material, the predetermined holding time is 1 to 2 minutes per 1 mm of the molded product thickness. For example, if the molded product thickness is 3 mm, the predetermined holding time is generally 3 to 6 minutes.

  However, the unsaturated polyester resin has the disadvantages of high molding shrinkage, fatigue resistance, and poor thermal properties at high temperatures. Also, when carbon fibers are used as fiber reinforcement, the interfacial adhesion between unsaturated polyester resin and carbon fiber is insufficient, so the study of molding materials using epoxy resins having these characteristics as matrix resins is underway. ing.

The molding method of these epoxy molding materials is mainly an autoclave molding method. That is, the molding material is shaped by heating and pressing. However, this molding method generally requires a long time of 30 minutes to 2 hours at a temperature of 110 to 180 ° C., and is free to form by pressurization compared to the press heating compression molding method. A small degree is mentioned as a drawback. Therefore, assuming that the epoxy molding material is molded in a relatively short time by the press heating compression molding method, a molded product having a thickness of 2.2 mm is obtained by the press heating compression molding method at a temperature of 140 ° C., a pressure of 8 MPa, and a molding time of 5 minutes. Proposed technology (see, for example, Patent Document 1).
It consists of a bisphenol A type epoxy resin and an amine compound, but its curing characteristics are still inferior to the sheet molding compound using the above unsaturated polyester resin as a matrix resin, and it is B-staged. Since there is no description, it is presumed that the molding material has insufficient curing characteristics and handleability.

  A resin composition containing an alicyclic epoxy resin and an onium salt-based thermal cation polymerization initiator has been proposed (for example, Patent Documents 2 and 3) as an improvement in the problem of curability of the epoxy resin. In addition, as a molding material for press heating compression molding, a molding material partially including an alicyclic epoxy resin has been proposed (see, for example, Patent Document 4), and an epoxy prepreg excellent in curability at a low temperature of 100 ° C. or lower. Is described.

  However, a molded product of an epoxy molding material obtained by molding a molding material at a pressure of 1 to 20 MPa in a mold having a shear edge at a pressure of 1 to 20 MPa and curing for 1 to 2 minutes per 1 mm of the molded product thickness. I didn't.

  In order to solve the above-described problems, a carbon fiber reinforcing material is impregnated with a resin composition containing an onium salt-based thermal cationic polymerization initiator in combination with an alicyclic epoxy resin and an epoxy resin such as bisphenol A type. A molding material for molding has been proposed (for example, Patent Document 5).

  However, the molded product obtained from the molding material for heat compression molding obtained above has a problem that there is a part where the mechanical strength is partially inferior, and a molded product with no bias in mechanical strength is molded. There has been a demand for a molding material for heat compression molding.

JP 2004-338270 A Japanese Unexamined Patent Publication No. 3-017101 JP-A-3-059001 JP 2000-297141 A JP 2007-270136 A

  The problem to be solved by the present invention is a molding material for heat compression molding capable of molding a plastic molded product reinforced with carbon fiber having no bias in mechanical strength in a short time, a molded product using the same, and a production thereof Is to provide a method.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have identified a resin composition containing a poly (meth) acrylate compound having a hydroxyl group, a polyisocyanate compound and a polymerization initiator as a specific carbon fiber reinforcing material. The present inventors have found that the molding material for heat compression molding obtained by impregnating the above can be molded into a molded product having no bias in mechanical strength, thereby completing the present invention.

That is, the present invention provides a resin composition (A) containing a poly (meth) acrylate compound (a1) having a hydroxyl group, a polyisocyanate compound (a2), and a polymerization initiator (a3) as a carbon fiber reinforcing material ( B) a molding material for heat compression molding obtained by impregnation, wherein the carbon fiber reinforcing material (B) is carbon paper surface-treated with a water-soluble resin (b1) having a hydroxyl group, and the carbon fiber The unit weight of the reinforcing material (B) is 380 to 500 g / m ² , and the content of the water-soluble resin (b1) in the carbon fiber reinforcing material (B) is in the range of 1 to 15% by mass. The present invention relates to a molding material for heat compression molding.

  In addition, the present invention provides a molded product obtained by molding the above-mentioned molding material for heat compression molding, and heat compression molding the molding material for heat compression molding at 110 to 180 ° C. in a mold. The present invention relates to a method for manufacturing a molded product.

  The molding material for heat compression molding of the present invention can be suitably used for housing members, automobile parts, electrical parts, civil engineering materials and the like because a molded product with no bias in mechanical strength can be obtained.

The molding composition for heat compression molding of the present invention comprises a resin composition (A) containing a poly (meth) acrylate compound (a1) having a hydroxyl group, a polyisocyanate compound (a2), and a polymerization initiator (a3). A carbon paper reinforcing material obtained by impregnating a carbon fiber reinforcing material (B), wherein the carbon fiber reinforcing material (B) is a carbon paper surface-treated with a water-soluble resin (b1) having a hydroxyl group. Yes, the unit weight of the carbon fiber reinforcement (B) is 380 to 500 g / m ² , and the content of the water-soluble resin (b1) in the carbon fiber reinforcement (B) is 1 to 15% by mass. It is within the range.

  First, the resin composition (A) will be described. The resin composition (A) contains a poly (meth) acrylate compound (a1) having a hydroxyl group, a polyisocyanate compound (a2), and a polymerization initiator (a3).

  The poly (meth) acrylate compound (a1) having a hydroxyl group has two or more (meth) acryloyl groups and one or more hydroxyl groups in one molecule. Examples of the poly (meth) acrylate compound (a1) having a hydroxyl group include a vinyl ester resin obtained by acrylating an epoxy part of an epoxy resin, pentaerythritol triacrylate (PETA), dipentaerythritol pentaacrylate (modified DPHA). Etc. Among these, a vinyl ester resin obtained by a reaction between an epoxy resin and an unsaturated monobasic acid is preferable because viscosity increase due to a urethane-forming reaction with an isocyanate compound can be easily controlled. These poly (meth) acrylate compounds (a1) having a hydroxyl group can be used alone or in combination of two or more.

  Examples of the epoxy resin include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin, novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin, and bromination of these resins. Polyhydric alcohols such as epoxy glycidyl ether such as epoxy resin, dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A, diglycidyl ether of hydrogenated bisphenol A, etc. Glycidyl ether, 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 1-epoxyethyl Alicyclic epoxy resins such as 3,4-epoxycyclohexane, glycidyl esters such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl-p-oxybenzoic acid, dimer acid glycidyl ester, tetraglycidyl diaminodiphenylmethane, tetra Heterocyclic epoxies such as glycidylamine such as glycidyl-m-xylenediamine, triglycidyl-p-aminophenol, N, N-diglycidylaniline, 1,3-diglycidyl-5,5-dimethylhydantoin, and triglycidyl isocyanurate Resin etc. are mentioned. Moreover, these epoxy resins can be used alone or in combination of two or more.

  Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethyl malate, monomethyl fumarate, monocyclohexyl fumarate, and sorbic acid. These unsaturated monobasic acids can be used alone or in combination of two or more.

  Further, the obtained vinyl ester resin may be modified with an acid anhydride such as maleic anhydride or succinic anhydride, an isocyanate compound such as toluene diisocyanate, isopropenyl-dimethyl-benzyl isocyanate, or the like.

  Examples of the polyisocyanate compound (a2) include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), polymeric MDI, and hydrogenated MDI. Etc. Moreover, these polyisocyanate compounds (a2) can be used alone or in combination of two or more.

  The polymerization initiator (a3) is not particularly limited, but is preferably an organic peroxide, such as a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a ketone peroxide compound, an alkyl perester compound, and a carbonate. Examples thereof include compounds, and can be appropriately selected according to molding conditions. These polymerization initiators can be used alone or in combination of two or more.

Further, the resin composition (A) is a radically polymerizable two-component compound other than the poly (meth) acrylate compound (a1) having a hydroxyl group, the polyisocyanate compound (a2), and the polymerization initiator (a3). You may use together the monomer, oligomer, polymer, etc. which have a heavy bond. For example, vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, divinylbenzene, t-butylstyrene, vinyltoluene, vinyl acetate, diarylphthalate, triarylcyanurate, (meth) acrylic acid, (meth) acrylic Examples include acid esters, (anhydrous) phthalic acid, and polymers thereof, unsaturated polyester resins, and urethane acrylate resins.

  Since the workability, moldability, and strength of the molded product of the molding material of the present invention are further improved, the hydroxyl group (OH) in the poly (meth) acrylate resin (a1) having the hydroxyl group in the resin composition (A). And the molar ratio (NCO / OH) of isocyanate groups (NCO) in the polyisocyanate compound (a2) is preferably in the range of 0.1-1. If it is smaller than the above range, the thickening reaction is insufficient and the resulting molding material is too soft, resulting in poor workability. If it exceeds the above range, the polyisocyanate compound (a2) becomes excessive, causing coloration and strength reduction due to side reactions. there is a possibility. For the said reason, More preferably, it is the range of 0.2-0.8.

The content of the polymerization initiator (a3) in the resin composition (A) is not particularly limited as long as the object of the present invention is achieved, but the curing characteristics of the molding material of the present invention. And storage stability are both excellent, the range of 0.3 to 3% by mass is preferred.

Next, the carbon fiber reinforcing material (B) will be described. The carbon fiber reinforcing material (B) is a carbon paper surface-treated with a water-soluble resin (b1) having a hydroxyl group. In the aqueous solution in which the water-soluble resin (b1) is dissolved to have an appropriate viscosity, It is obtained by dispersing fibers, making paper, and drying.
Examples of the water-soluble resin (b1) include natural polymers such as starch, saccharides, agar, dextrin, and gelatin, and synthetic polymers such as hydroxyethyl cellulose and polyvinyl alcohol (PVA).

The water-soluble resin (b1) has a hydroxyl group in the molecular structure, generates a polyisocyanate compound and a urethane bond, and improves the interfacial adhesion with the matrix resin, but is present on the carbon fiber surface. The content of the water-soluble resin (b1) in the carbon fiber reinforcing material (B) is 1 to 15% by mass because there is a possibility that the strength of the resulting molded article is reduced even if the amount is too small or too small. This is important because better interfacial adhesion can be obtained.

The carbon paper is uniformly surface-treated with the water-soluble resin (b1), and from the viewpoint of cost, carbon short fibers having a fiber length of 6 to 60 mm are dispersed in an aqueous solution of the water-soluble resin (b1). It is preferable to use a paper-made one. If the short carbon fiber is shorter than the above range, the strength of the molded body obtained from the molding material of the present invention will be insufficient. If longer than the above range, the short carbon fiber will not flow easily during compression molding. There is a possibility that a resin-rich portion is generated in a complex-shaped molded body having a structure or the like. Further, from the viewpoint of uniformity at the time of papermaking, the carbon short fibers may be non-uniform when the length exceeds 60 mm. Furthermore, it is important that the unit weight of the paper-reinforced carbon fiber reinforcement (B) is in the range of 380 to 500 g / m ² from the viewpoint of impregnation with the resin composition (A).

  The molding material for heat compression molding of the present invention is obtained by impregnating the resin composition (A) into the carbon fiber reinforcing material (B). However, since the strength of the resulting molded body is further improved, the resin composition The carbon fiber reinforcing material (B) is preferably in the range of 10 to 60% by mass relative to the product (A).

  A polymerization inhibitor can be added to the resin composition (A) of the present invention. The polymerization inhibitor is not particularly limited. For example, hydroquinone, trimethylhydroquinone, pt-butylcatechol, t-butylhydroquinone, toluhydroquinone, p-benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate And copper chloride. These polymerization inhibitors may be used alone or in combination of two or more. In addition, the addition amount of the said polymerization inhibitor is although it does not specifically limit, Preferably 10-1000 ppm can be added in a resin composition.

  A curing accelerator can be contained in the molding material for heat compression molding of the present invention. Examples thereof include metal soaps such as cobalt naphthenate, cobalt octenoate, vanadyl octenoate, copper naphthenate, and barium naphthenate, and metal chelate compounds such as vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetyl acetonate. As amine compounds, N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-ethyl-m-toluidine, triethanol Examples include amine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline and the like.

  In the molding material for heat compression molding of the present invention, other fillers, internal mold release agents and the like can be contained. Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, asbestos, barlite, baryta, silica, silica sand, dolomite limestone, gypsum, aluminum fine powder, hollow balloon, alumina , Glass powder, aluminum hydroxide, cryolite, zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like. 10-500 mass parts is preferable with respect to 100 mass parts of resin compositions, and, as for the addition amount of these fillers, 30-300 mass parts is more preferable.

  Examples of the internal mold release agent include zinc stearate, calcium stearate, paraffin wax, polyethylene wax, carnauba wax and the like. Paraffin wax, polyethylene wax, and carnauba wax are preferable.

  Furthermore, in the molding material for heat compression molding of the present invention, a thermoplastic resin may be added as a low shrinkage agent. Examples of the low shrinkage agent include polystyrene, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, styrene-butadiene copolymer, poly (meth) acrylic acid ester, and the like. When these are heat compression molded at 110 to 180 ° C., they can suppress the molding shrinkage of the molded product obtained because they cause thermal expansion or foaming.

  Further, in the molding material for heat compression molding of the present invention, as other components, an ultraviolet absorber, a pigment, a thickener, a thickener, an anti-aging agent, a plasticizer, a flame retardant, an antibacterial agent, a stabilizer, A reinforcing material, a photocuring agent, etc. can be contained.

  The molding material for heat compression molding of the present invention can be thickened by a urethane formation reaction between a hydroxyl group and an isocyanate group in the resin composition, and can be made into a B-stage. Depending on the type of the isocyanate compound (a2), aging is preferably performed for 12 to 48 hours within a range of room temperature to 50 ° C. Thereby, the molding material can be made tack-free. When the aging temperature exceeds 50 ° C., the curing reaction proceeds too much, so that a B-staged molding material cannot be obtained. The viscosity of the molding material after thickening is preferably 10,000 poise or more at 25 ° C., more preferably from 20,000 poise to 100,000 poise.

  The molding material for heat compression molding of the present invention is preferably a sheet molding compound or a bulk molding compound because it can be easily molded and has excellent reproducibility even in a complicated shape.

  As a method for producing the sheet molding compound, each component of the resin compound is mixed by mixing a liquid component and a powder component using a mixer such as a normal roll, an intermixer, a planetary mixer, a kneader, and an extruder. Mix and disperse. The order of mixing the components is not particularly limited, but the polyisocyanate compound (a2) is added to the hydroxyl group-containing poly (meth) acrylate compound (a1) at room temperature and then dispersed using the stirring device. Is preferred. If necessary, an inorganic filler or the like is subsequently added and mixed and dispersed. Next, as a method of forming a sheet, a lacquer method in which a matrix resin solution containing a solvent is applied to a fiber reinforcing material and then desolvated after impregnation with the resin solution, which is conventionally used in epoxy molding materials, without using a solvent. Examples thereof include a hot melt method in which a matrix resin is heated and dissolved in advance, and a resin film is prepared in advance and then impregnated by being bonded to a fiber reinforcing material, a dip method in which a fiber reinforcing material is immersed in a resin solution, and a doctor knife method. In the case of the present invention, among these, the doctor knife method generally employed in the sheet molding compound is preferable.

  As a method for producing the bulk molding compound, each component of the resin compound is mixed by mixing a liquid component and a powder component using a mixer such as a normal roll, an intermixer, a planetary mixer, a kneader, and an extruder. Mix and disperse. The order of mixing the components is not particularly limited, but the polyisocyanate compound (a2) is added to the hydroxyl group-containing poly (meth) acrylate compound (a1) at room temperature and then dispersed using the stirring device. Is preferred. If necessary, an inorganic filler or the like is subsequently added and mixed and dispersed. Thereafter, a fiber reinforcing material is added and mixed and dispersed.

  In the molding of the molding material of the present invention, a predetermined amount of the molding material is weighed, put into a mold heated in advance to 110 to 180 ° C., clamped with a compression molding machine, and the molding material is molded. A manufacturing method is used in which a molding material is cured by maintaining a molding pressure of 1 to 20 MPa, and then a molded product is taken out to obtain a molded product. In this case, in a mold having a shear edge, a manufacturing method for heat compression molding while maintaining a molding pressure of 1 to 10 MPa at a mold temperature of 120 to 160 ° C. for a prescribed time of 1 to 2 minutes per 1 mm of a molded product thickness. Is preferred.

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

(Preparation Example 1: Preparation of resin composition (A-1))
Mixture of vinyl ester resin and styrene (DIC Corporation "Dicklight UE-3505", vinyl ester resin / styrene = 58/42 (mass%)) 100 parts by mass, Polymeric MDI (Mitsui Chemicals "Cosmonate" LL ") 8.5 parts by mass and 1 part of a polymerization initiator (Kayakaku AIC-75 manufactured by Kayaku Akzo Co., Ltd., organic peroxide) were mixed to obtain a resin composition (A-1). The molar ratio (NCO / OH) in the resin composition was 0.30.

(Preparation Example 2: Preparation of resin composition (A-2))
A resin composition (A-2) was obtained in the same manner as in Preparation Example 1, except that the amount of polymeric MDI used in Preparation Example 1 was changed from 8.5 parts by mass to 13 parts by mass. The molar ratio (NCO / OH) in the resin composition was 0.46.

(Preparation Example 3: Preparation of resin composition (A-3))
A resin composition (A-3) was obtained in the same manner as in Preparation Example 1 except that the amount of polymeric MDI used in Preparation Example 1 was changed from 8.5 parts by mass to 19.8 parts by mass. The molar ratio (NCO / OH) in the resin composition was 0.70.

(Preparation Example 4: Preparation of resin composition (A-4))
Resin was prepared in the same manner as in Preparation Example 1 except that 8.5 parts by mass of polymeric MDI used in Preparation Example 1 was changed to 16.1 parts by mass of HDI-based polyisocyanate (“Bernock DN-902S” manufactured by DIC Corporation). A composition (A-4) was obtained. The molar ratio (NCO / OH) in the resin composition was 0.46.

(Preparation Example 5: Preparation of resin composition (A-5))
In the same manner as in Preparation Example 1, except that 8.5 parts by mass of polymeric MDI used in Preparation Example 1 was changed to 8.5 parts of XDI (“Takenate 500” manufactured by Mitsui Chemicals, Inc.), a resin composition (A- 5) was obtained. The molar ratio (NCO / OH) in the resin composition was 0.46.

(Preparation Example 6: Preparation of resin composition (A-6))
Resin was prepared in the same manner as in Preparation Example 1 except that 8.5 parts by mass of polymeric MDI used in Preparation Example 1 was changed to 11.7 parts of hydrogenated MDI (“Dismodule W” manufactured by Sumika Bayer Urethane Co., Ltd.). A composition (A-6) was obtained. The molar ratio (NCO / OH) in the resin composition was 0.46.

  Table 1 shows the compositions of the resin compositions (A-1) to (A-6) obtained above.

(Example 1: Production and evaluation of molding material (1) for heat compression)
Carbon obtained by applying the resin composition (A-1) obtained above to two 30 μm polypropylene films so that the average coating amount is 385 g / m ² and surface-treating with polyvinyl alcohol (PVA). Paper ("CF paper" manufactured by Nippon Polymer Sangyo Co., Ltd., unit weight 380 g / m ² , hereinafter abbreviated as carbon fiber reinforcement (B-1)) is sandwiched between the resin-coated films to form a sandwich structure, and the PVA surface The carbon fiber content including the treatment agent was impregnated so as to be 33% by mass, and left in an oven at 45 ° C. for 24 hours to obtain a molding material (1) (sheet molding compound) for heat compression. The unit weight of the obtained molding material was 1.15 kg / m ² . The carbon fiber reinforcing material (B-1) was obtained by dispersing carbon fibers cut into 1 inch (25.4 mm) in an aqueous PVA solution, and making paper and drying. The content of PVA in the carbon fiber reinforcing material (B-1) was 5% by mass.

  Subsequently, the following molded articles were evaluated using the obtained molding material for heat compression (1).

[Production of molded product for evaluation]
The heat compression molding material (1) obtained above is cut into 280 mm x 280 mm to form 360 g by stacking four sheets, and then heat compression molding using a plate-shaped mold of 300 mm x 300 mm x 3 mm. 1) was obtained. As the heat compression molding conditions, the mold temperature was (lower) 130 ° C./(upper) 145 ° C., and after placing the four-layered molding material on the lower mold, the mold was held at a mold closing pressure of 5 MPa for 6 minutes, After the mold was opened, it was taken out and allowed to cool at room temperature.

[Bending test method for molded products]
Ten test pieces (width 25 mm × length 80 mm × thickness 3 mm) cut out from the molded product obtained above are compliant with JIS K7171, a three-point bending test (distance between gauge points 40 mm, test speed 1 mm / min) ) And the flexural strength and flexural modulus were measured. Further, each standard deviation was obtained, and the variation was evaluated according to the following criteria.
◎: Standard deviation is less than 5% of average value ○: Standard deviation is 5% or more and less than 10% of average value △: Standard deviation is 10% or more and less than 30% of average value ×: Standard deviation is 30% or more of average value

[Tensile test method for molded products]
About five test pieces (width 10 mm × length 180 mm × thickness 3 mm) cut out from the molded product obtained above, a tensile test (distance between gauge points 115 mm, test speed 1 mm / min) was performed in accordance with JIS K7161. The tensile strength and the tensile modulus were measured. Further, each standard deviation was obtained, and the variation was evaluated according to the following criteria.
◎: Standard deviation is less than 5% of average value ○: Standard deviation is 5% or more and less than 10% of average value △: Standard deviation is 10% or more and less than 30% of average value ×: Standard deviation is 30% or more of average value

(Examples 2 to 6: Production and evaluation of molding materials for heat compression (2) to (6))
In the same manner as in Example 1 except that the resin compositions (A-2) to (A-6) were used instead of the resin composition (A-1) used in Example 1, a molding material for heat compression was used. (2) to (6) were obtained.

  Further, a molded product was produced in the same manner as in Example 1 except that the heating compression molding materials (2) to (6) were used instead of the heating compression molding material (1), and bending strength, bending The elastic modulus, tensile strength, and tensile elastic modulus were measured. In addition, each standard deviation was obtained and the variation was evaluated.

  Table 2 shows the evaluation results of the heating compression molding materials (1) to (6) obtained above.

(Comparative Example 1: Production and evaluation of heat compression molding material (R-1))
The resin composition (A-1) obtained above was applied to two 30 μm polypropylene films so that the average coating amount was 385 g / m ^2, and carbon fiber roving (Toray Industries, Inc. Torayca “T700SC” -12000-50C "(hereinafter abbreviated as carbon fiber reinforcing material (RB-1)) is cut as 1 inch (25.4 mm) and becomes as uniform as possible on the resin of one resin coated film. And sandwiched by another resin-coated film so as to impregnate so that the carbon fiber content is 33% by mass, and left in a 45 ° C. oven for 24 hours to form a heating compression molding material (R- 1) (Sheet molding compound) was obtained.

  Moreover, it replaced with the heating compression molding material (1), and produced the molded article similarly to Example 1 except having used the heating compression molding material (R-1), bending strength, bending elastic modulus. The tensile strength and tensile modulus were measured. In addition, each standard deviation was obtained and the variation was evaluated.

(Comparative Examples 2-3: Production and Evaluation of Molding Materials for Heat Compression (R-2) to (R-3))
Molding for heat compression in the same manner as in Comparative Example 1 except that the resin compositions (A-2) to (A-3) were used instead of the resin composition (A-1) used in Comparative Example 1. Materials (R-2) to (R-3) were obtained.

  Further, a molded product was produced and bent in the same manner as in Example 1 except that the heat compression molding materials (R-2) to (R-3) were used instead of the heat compression molding material (1). Strength, flexural modulus, tensile strength, and tensile modulus were measured. In addition, each standard deviation was obtained and the variation was evaluated.

  Table 3 shows the evaluation results of the heating compression molding materials (R-1) to (R-3) obtained above.

  It was confirmed that the molded articles obtained from the molding materials for heating and compression of Examples 1 to 6 had high bending strength, bending elastic modulus, tensile strength, and tensile elastic modulus. Moreover, it was confirmed that those standard deviations were small and there was little dispersion.

  On the other hand, Comparative Examples 1 to 3 are examples in which carbon paper surface-treated with a water-soluble resin having a hydroxyl group was not used as the carbon fiber reinforcement, but the standard deviation of tensile strength and tensile modulus was large. It was confirmed that the variation was remarkable.

Claims (5)

A carbon fiber reinforcement (B) is impregnated with a resin composition (A) containing a poly (meth) acrylate compound (a1) having a hydroxyl group, a polyisocyanate compound (a2), and a polymerization initiator (a3). a molding material for heat compression molding the resulting Te, wherein the carbon fiber reinforcement (B) is a carbon paper that is surface treated with a water-soluble resin (b1) having a hydroxyl group, wherein the carbon fiber reinforcement (B) The unit weight is 380 to 500 g / m ² and the content of the water-soluble resin (b1) in the carbon fiber reinforcing material (B) is in the range of 1 to 15% by mass. Molding material for compression molding.   The molding material for heat compression molding according to claim 1, wherein the carbon paper is made by dispersing carbon short fibers having a fiber length of 6 to 60 mm in an aqueous solution of the water-soluble resin (b1) having a hydroxyl group. Production method.   The molar ratio (NCO / OH) of the hydroxyl group (OH) in the poly (meth) acrylate compound (a1) having the hydroxyl group to the isocyanate group (NCO) in the polyisocyanate compound (a2) is 0.1 to 0.1. The molding material for heat compression molding according to claim 1, which is within the range of 1.   The molded article of the molding material for heat compression molding of any one of Claim 1 or 3. Method for producing a molded article, characterized in that the claim 1 or molding material for hot compression molding as described in any one of 3 to heat compression molding at 110 to 180 ° C. in a mold.