JPH0674300B2 - Molding material for FRP - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is a molding for FRP suitable for a heating and pressure molding method, in which a molded article having improved surface hardness, excellent scratch resistance and heat resistance can be obtained. It is about materials.

(Prior art and problems) FRP molding material is unsaturated polyester resin, fiber reinforcement,
Sheet molding compound (SMC) in the form of a sheet by blending organic peroxide, thickener, organic and inorganic fillers, pigments, low-contracting agent, etc., if necessary, bulk molding compound in the form of bulk (BMC) Etc. These FRP molding materials are generally used by applying pressure using a heated mold, and are widely used because of their excellent moldability and strength.

Generally, molding materials for FRP such as SMC and BMC have low hardness and have a drawback that they are easily scratched with a pencil scratch test of 4H or less. Further, it has a drawback that the heat resistant temperature is low and blisters and cracks occur at about 200 ° C.

A combination of an unsaturated polyester resin and an acrylic compound is disclosed in JP-A-51-103994 and JP-A-60-47039. For example, JP-A-51-103994 discloses FRP molding. Unsaturated polyesters with a low degree of unsaturation are suitable because they are not intended as materials, and
As the acrylic compound, a compound having two unsaturated double bonds in one molecule can be mentioned, and a compound in which a compound having one unsaturated double bond in one molecule is used together is suitable.

Further, the composition is intended to eliminate the styrene odor by using the total amount of the acrylic compound without using the styrene monomer, and also uses the low viscosity acrylic compound for workability. is there. When such a composition is used as an FRP molding material, styrene monomer is not used, so that the curability is poor, and the hardness is poor, and the scratch resistance is
There is a problem that it cannot be a FRP molding material with excellent heat resistance.

Further, JP-A-60-47039 discloses that since it is used as a composition for coating expanded polystyrene molded articles, the polymerizable monomer used cannot dissolve or erode the expanded polystyrene molded articles, that is, When 15 to 60 parts by weight of styrene monomer is used as in the present invention, it is not preferable because it corrodes the surface of the expanded polystyrene molded product.
It is said that only 10 parts by weight or less can be used. From this point of view, the acrylic compound used is a trifunctional or lower functional acrylic compound such as trimethylpropane triacrylate. Therefore, a high hardness FRP molding material such as that of the present invention cannot be obtained.

(Means for Solving Problems) As a result of intensive studies on the FRP molding material having excellent scratch resistance and heat resistance, the present inventors have found a molding material for FRP in which the above-mentioned drawbacks are improved and found the present invention. I arrived.

(A) (A) 10-45 parts by weight of unsaturated polyester having an unsaturated group equivalent of 100-300, (B) 15-60 parts by weight of styrene monomer, (C) 15-75 parts by weight of dipentaerythritol hexa (meth) acrylate. And (c) a glass fiber reinforcing material, and (c) an organic peroxide, such as an SMC / BMC molding material for FRP.

The unsaturated polyester (A) used in the present invention is produced by a known method, and specifically, it has no activity of phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and the like. Dicarboxylic acids that do not have a saturated bond and fumaric acid, maleic acid, dicarboxylic acids that have an active unsaturated bond such as itaconic acid as an acid component, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentane Diol, 1,3
-Polyhydric alcohols such as butanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol A, etc. Is obtained as an alcohol component.

The vinyl ester of the present invention is produced by a known method, and an epoxy acrylate obtained by using an epoxy resin and acrylic acid or methacrylic acid as components, or a saturated dicarboxylic acid and an unsaturated dicarboxylic acid or either dicarboxylic acid. Unsaturated polyester obtained from acid and polyhydric alcohol as components, saturated polyester and α,
An unsaturated polyester acrylate and a saturated polyester acrylate obtained by using an epoxy compound having a β-unsaturated carboxylic acid ester group as a component. Examples of the saturated dicarboxylic acid having no active unsaturated group include orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and the like. Examples of the unsaturated dicarboxylic acid having an active unsaturated group include fumaric acid, maleic acid, itaconic acid and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, butylene glycol, 1,5-pentadiol, 1,3-butanediol, 1,6
-Hexanediol, 2,2-dimethyl-1,3-propanediol, diethylene glycol, triethylene glycol, propylene oxide adduct of bisphenol A,
Examples include ethylene oxide adducts of bisphenol A and glycerin.

Representative examples of the epoxy resin include bisphenol A diglycidyl ether and its high molecular weight homologues, and novolac type polyglycidyl ethers.

A typical example of the epoxy compound containing an α, β-unsaturated carboxylic acid ester group is glycidyl methacrylate.

The unsaturated polyester or vinyl ester preferably has a high degree of unsaturation and has an unsaturated group equivalent of 100 to 300 and is used in an amount of 10 to 45 parts by weight. If the unsaturated group equivalent is less than 100, it cannot be synthesized, and if it is more than 350, the one with high hardness cannot be obtained. On the other hand, if the amount used is less than 10 parts by weight, it is not preferable in terms of curability and moldability, and a high hardness exceeding 45 parts by weight cannot be obtained.

The styrene monomer (B) used in the present invention is kneadability and impregnability with the fiber reinforcing material and the filler at the time of manufacturing the FRP molding material, that is, the productivity of the FRP molding material, and the curability, that is, high. It is important in that it can be hardened, and is used in an amount of 15 to 60 parts by weight, preferably 20 to 60 parts by weight. If the amount used is less than 15 parts by weight, the curability will be inferior, and if it is more than 60 parts by weight, high hardness will not be obtained and the heat resistance will be inferior, which is not preferable as an FRP molding material. When the styrene monomer is replaced with another monomer, there are problems in the above-mentioned kneading property, impregnating property and curability.

In the present invention, dipentaerythritol hexa (meth) acrylate is used as the polyfunctional (meth) acrylic compound. Also, these may be used in combination.

Further, the polyfunctional (meth) acrylic compound in the present invention is 15 to 75
Parts by weight, preferably 20 to 70 parts by weight are used. Used 15
If it is less than 75 parts by weight, high hardness cannot be obtained, and if it is more than 75 parts by weight, curability and productivity of the FRP molding material are poor, which is not preferable.

The glass fiber reinforcing material (a) used in the present invention may be used in combination with other fiber reinforcing materials, for example, known materials such as carbon fiber, aramid fiber, vinylon fiber, polyethylene terephthalate fiber are used, and the form is chop. Shape, string shape,
A woven fabric or the like is used. Of course, these may be used in combination. The addition amount is preferably 3 to 300 parts by weight,
It is particularly preferably 5 to 280 parts by weight.

The organic peroxide used in the present invention is, for example, a known one such as a hydroperoxide type, a diacyl peroxide type, a peroxyketal type, an alkyl perester type, or a percarbonate type, which is appropriately selected depending on the molding temperature. To be selected. The addition amount is 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the resin composition. Of course, these may be used in combination.

The FRP molding material of the present invention includes various types of thickeners, organic and inorganic pigments, internal release agents, stabilizers, defoamers, organic and inorganic fillers, low-shrinking agents, curing accelerators, etc., as necessary. Additives can be added.

The form of the FRP molding material of the present invention is a sheet-like SMC or the like, a bulk-like BMC or the like, and a thickener may or may not be used when an organic and inorganic filler is blended. . When organic and inorganic fillers are not blended, it is better to use thickeners.

As the organic and inorganic fillers used at this time, generally known ones such as calcium carbonate, talc, clay and aluminum hydroxide are used. Of course, these may be used in combination. Examples of the thickener include alkaline earth metals (magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide), metal complex salts (aluminum alcoholate), isocyanate compounds such as 4,4 ′.
-Dicyclohexylmethane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, xylylene diisocyanate, 2,4-tolylene diisocyanate, 2,6
-A known one such as tolylene diisocyanate can be used.

The FRP molding material of the present invention is preferably a mold having an unspecified mold shape heated to 100 to 160 ° C., and the FRP molding material of the present invention placed in the mold is preferably 40 to 200 kg / cm ^2. It is possible to obtain a FRP molded product by performing mold filling with the pressure of, and removing the molded product after curing in the mold.

(Effects) The FRP molding material of the present invention can be used by molding and curing under the same conditions, equipment and process as generally known (commercially available) FRP molding materials such as SMC and BMC, and can be generally known. The surface hardness is 7-8H, which is higher than that of the material (surface hardness 3-4H in the pencil scratch test), and the scratch resistance load of steel wool # 0000 is about 12.5 times that of the conventional 50g 600-650g. The present invention provides a FRP molding material which is significantly improved in scratch resistance by daily-use instruments. Further, the heat resistance of the present invention which causes blistering and cracks at 200 ° C. is greatly improved to 300 ° C. or more in the present invention. Therefore, the molding material of the present invention can be molded into a molded product by compression molding by heating, pressing, etc., as a molding material for FRP which requires scratch resistance and heat resistance which could not be used conventionally, and thus is suitable for mass production. Can be used.

For example, automobile parts (foot panel, distributor, radiator grille, headlamp reflector, instrument panel), electric and electronic parts (microwave container, microwave oven, printed board, insulating board, thermal head,
Connectors, housings, circuit breakers, insulating spacers, brackets), industrial parts, machine parts (gears, heat-resistant panels), household household items (ash trays, chairs,
It can be used for things that require various scratch resistance and heat resistance such as lighters).

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to this example. In addition, "%" and "part" in the present are based on weight.

Example 1 According to a usual reaction method, propylene glycol and maleic anhydride were reacted at a molar ratio of 1.1: 1.0 to give an acid value of 2
7 unsaturated polyester (I) was obtained.

Such unsaturated polyester (I) has an unsaturated group equivalent of about 156
Met. Next, 40 parts of styrene monomer, 30 parts of dipentaerythritol hexaacrylate and 0.01 part of hydroquinone were added to 30 parts of unsaturated polyester (I) to obtain a composition No. 1.

Next, with respect to 100 parts of the composition No. 1, 10 parts of a 50% styrene solution of polystyrene (weight average molecular weight of about 200,000) and calcium carbonate (# 200) manufactured by Nitto Koka Kogyo Co., Ltd.
Part, 5 parts of zinc stearate as an internal mold release agent, 1 part of t-butyl perbenzoate as a curing agent are kneaded in a kneader, and then 60 parts of 6 mm long glass chopped strands are added to form a bulk molding material for FRP (BMC ) Got.

This molding material is used at a temperature of 150 ° C for 3 minutes and a pressure of 100 kg / c.
FRP molded product A with a thickness of 5 mm after being heated and pressed under m ² conditions
Got

The surface hardness of the molded plate and the result of the heating test are shown in Table 1.

The test was conducted as follows. The same applies to the following examples.

1) Pencil scratch test It was carried out in accordance with JIS-K-5400-1979 paint general test method 6.14.

2) Heating test The molded plate was put in a dryer at each set temperature for 1 hour, then taken out, cooled, and visually observed for blisters and cracks.

3) Steel wool property test Steel wool # 1000 is fixed to the shaft of the abrasion wheel of the Taber type abrasion tester, and after contacting the sample, the sample is rotated 100 times. At this time, it is represented by the steel wool load at the point where the sample is damaged.

Comparative Example-1 According to a conventional reaction method, propylene glycol and maleic anhydride were reacted at a molar ratio of 1.1: 1.0 to give an acid value of 2
7 unsaturated polyester (I) was obtained.

Such unsaturated polyester (I) has an unsaturated group equivalent of about 156
Met. Then, to 60 parts of unsaturated polyester (I),
An unsaturated polyester resin was obtained by adding 40 parts of styrene monomer and 0.01 part of hydroquinone. Next, with respect to 100 parts of the unsaturated polyester resin, 10 parts of a 50% styrene solution of polystyrene, 300 parts of calcium carbonate as a filler, 5 parts of zinc stearate as an internal release agent, and 1 part of t-butyl perbenzoate as a curing agent. Kneading in a kneader,
Then, 60 parts of 6 mm-long glass chopped strands were added to obtain a bulk FRP molding material (BMC).

The molding material was molded under the same molding conditions as in Example 1 to obtain a molding plate B having a thickness of 5 mm. The surface hardness of the molded plate and the result of the heating test are shown in Table 1.

Example 2 According to a conventional method, 2,2 dimethyl-1,3-propanediol and isophthalic acid were reacted at a molar ratio of 2.0: 1.0 to give an acid value of 2, propylene glycol and fumaric acid. An unsaturated polyester (II) having an acid value of 25 was obtained in a molar ratio of 1.15: 2.0 of acid. Such unsaturated polyester (I
The unsaturated group equivalent of I) was 287.

30 parts of unsaturated polyester (II), 40 parts of styrene monomer, 30 parts of dipentaerythritol hexaacrylate
Parts and 0.01 parts of hydroquinone were added to obtain a composition No. 2.

Next, with respect to 100 parts of the composition No. 2, 5 parts of polystyrene
25 parts 0% styrene solution, 6 parts zinc stearate as an internal release agent, 190 parts calcium carbonate as a filler, 6 parts blue pigment, t-butyl perbenzoate as a hardening agent 1.
2 parts and 1.2 parts of magnesium oxide were mixed to obtain a pasty compound. Next, apply this compound to a thickness of 30μ
Spread on a polyethylene sheet, and 110 parts of 25 mm long glass chopped strands are uniformly dispersed, covered with a polyethylene sheet again, pressure-impregnated, defoamed and left at 40 ° C for 24 hours to obtain a sheet-shaped molding material. It was

This molding material is used at a temperature of 140 ° C, a time of 4 minutes, and a pressure of 50 kg / cm.
Heated and pressure-molded under the conditions of ² to obtain a molded plate C having a thickness of 5 mm.

Table 2 shows the surface hardness of the molded plate and the result of the heating test.

Comparative Example-2 According to a conventional method, 2,2 dimethyl-1,3 propanediol and isophthalic acid were reacted at a molar ratio of 2.0: 1.0, and when the acid value reached 2, propylene glycol,
An unsaturated polyester (II) having an acid value of 25 was obtained in a molar ratio of phthalic acid of 1.15: 2.0. The unsaturated group equivalent weight of the unsaturated polyester (II) was 287.

Then, 60 parts of unsaturated polyester (II), 40 parts of styrene monomer and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin.

Next, with respect to 100 parts of the unsaturated polyester resin, 25 parts of 50% styrene solution of polystyrene, 6 parts of zinc stearate as an internal release agent, 190 parts of calcium carbonate as a filler,
6 parts of blue pigment, 1.2 parts of t-butyl perbenzoate as a curing agent, and 1.2 parts of magnesium oxide were mixed to obtain a paste-like compound. Thickness of such compound
Spread on a 30μ polyethylene sheet, 110 parts of glass chopped strands with a length of 25mm are evenly dispersed, then covered with a polyethylene sheet again, pressurized, impregnated, degassed and at 40 ° C.
After standing for 24 hours, a sheet-shaped molding material was obtained.

The molding material was molded under the same molding conditions as in Example-2 to obtain a molding plate D having a thickness of 5 mm. The surface hardness of the molded plate and the result of the heating test are shown in Table 2.

Example 3 According to a conventional reaction method, 2,2 dimethyl-1,3-propanediol and isophthalic acid were reacted at a molar ratio of 2.0: 1.0 to give an acid value of 2, propylene glycol and maleic acid. Acid at a molar ratio of 1.3 / 2.0, acid value 10,
An unsaturated polyester (III) having a hydroxyl value of 25 was obtained.

The unsaturated group equivalent weight of the unsaturated polyester (III) is 287.
Met. Next, to 30 parts of unsaturated polyester (III),
Composition No. 3 was obtained by adding 45 parts of styrene monomer, 35 parts of dipentaerythritol hexaacrylate and 0.01 part of hydroquinone.

Next, with respect to 100 parts of the composition No. 3, 2 parts of zinc stearate as an internal release agent, 1 part of t-butyl perbenzoate as a curing agent, and a diphenylmethane diisocyanate compound (trade name: ISONATE 143-L Kasei Upjohn)
Was added and mixed with stirring to obtain a compound. Then spread this compound on a polyethylene sheet with a thickness of 30μ and put glass chopped strands with a length of 25 mm
Part was evenly dispersed, covered again with a polyethylene sheet, pressure-impregnated and degassed, and left at room temperature for 24 hours to obtain a sheet-shaped molding material.

This molding material is heated at 140 ° C for 4 minutes and at a pressure of 100kg / cm ²
By heating and pressure molding under the conditions of, a molded plate E having a thickness of 5 mm was obtained.

The surface hardness of the molded plate and the result of the heating test are shown in Table 3.

Comparative Example-3 According to a usual reaction method, 2,2 dimethyl-1,3-propanediol and isophthalic acid were reacted at a molar ratio of 2.0: 1.0, and when the acid value became 2, propylene glycol and maleic acid were obtained. Acid at a molar ratio of 1.3 / 2.0, acid value 10,
An unsaturated polyester (III) having a hydroxyl value of 25 was obtained. The unsaturated group equivalent weight of this unsaturated polyester was 287.

Then, 60 parts of unsaturated polyester (III), 40 parts of styrene monomer and 0.01 part of hydroquinone were added to obtain an unsaturated polyester resin.

Next, with respect to 100 parts of the unsaturated polyester resin, 2 parts of zinc stearate as an internal release agent and t-type as a curing agent.
1 part of butyl perbenzoate and 5 parts of diphenylmethane diisocyanate compound (trade name: ISONATE 143-L, manufactured by Kasei Upjohn) were added and mixed with stirring to obtain a compound. Spread this compound on a polyethylene sheet with a thickness of 30μ, 113 parts of glass chopped strands 25 mm in length are uniformly dispersed, again covered with a polyethylene sheet, pressurized, impregnated, defoamed and left at room temperature for 24 hours. A sheet-shaped molding material was obtained.

The molding material was heated and pressure-molded under the same molding conditions as in Example-3 to obtain a molding plate F having a thickness of 5 mm.

The surface hardness of the molded plate and the result of the heating test are shown in Table 3.

Comparative Example-4 Dipentaerythritol Hexaacrylate of Example 2
30 parts of trimethylolpropane triacrylate 30
An FRP molded plate G having a thickness of 5 mm was obtained by the same method except that the parts were changed.

Comparative Example-5 Dipentaerythritol Hexaacrylate of Example 2
An FRP molded plate H having a thickness of 5 mm was obtained by the same method except that 30 parts were changed to 30 parts DPCA-30 (product of Nippon Kayaku Co., structural formula).

Structural formula- [However, α in the formula is Β in the formula is (M = 1, a = 3, b = 3)] Comparative Example-6 According to a conventional reaction method, propylene glycol, phthalic anhydride, and maleic anhydride were reacted at a molar ratio of 2.2: 1.0: 1.0, An unsaturated polyester (a) having an acid value of 26 was obtained. The unsaturated polyester (a) had an unsaturated group equivalent weight of about 362.

Hereinafter, a FRP molded plate I having a thickness of 5 mm was obtained in the same manner as in Example 1.

The results of the surface hardness, the heating test and the steel wool property test of the molded plates of Comparative Example-4, Comparative Example-5 and Comparative Example-6 are shown in Table 4 together with the results of Example 1 and Example 2.

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Claims (1)

[Claims] 1. (A) (A) 10-45 parts by weight of unsaturated polyester having an unsaturated group equivalent of 100-300, (B) 15-60 parts by weight of styrene monomer, (C) dipentaerythritol hexa (meth) acrylate. A resin composition consisting of 15 to 75 parts by weight, (a) a glass fiber reinforcing material, and (c) a molding material for FRP such as SMC / BMC composed of an organic peroxide.