JPH0531896B2 - - Google Patents

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a molding material for reinforced plastics that provides a molded product with a pearlescent luster pattern by injection molding, compression molding, etc. based on an unsaturated polyester resin. It is related to the manufacturing method.

(Prior art and its problems) Based on unsaturated polyester resin,
By pressurizing and heating molding using molding materials consisting of fillers, curing agents, internal mold release agents, reinforcing materials, pigments, etc.
Techniques for obtaining marble-like or patterned molded products include, for example, JP-A-54-71181;
Publication No. 55-32646, Japanese Patent Application Publication No. 55-37307, etc.
Alternatively, Japanese Patent Publication No. 60-29745 is known. These have problems such as decreased workability in the production of molding materials and decreased workability during molding.Although mica was used as a filler in these molding materials, it was not used as a pigment. However, it was not possible to obtain a high-quality pearl-like glossy pattern.

On the other hand, there is a trend in recent years for molded products to have a high-class feel.

(Means for Solving the Problems) As a result of various studies on molding materials that can produce molded products with a high-class feel and excellent appearance, the present inventors found that mica with a particle size of 1 to 200 μm coated with titanium oxide (b) is used, and the mica (b) is used as a molding material.
Instead of adding and mixing the mica (b) and the unsaturated polyester resin (a), first mix and stir the mica (b) and the unsaturated polyester resin (a) to wet and uniformly disperse them, and then add and mix the filler (c) and reinforcing material (d). As a result, they discovered a molding material that can produce an excellent molded product with a high-quality feel, and completed the present invention.

That is, the present invention mixes and stirs an unsaturated polyester resin (a) and titanium oxide and/or mica (b) coated with titanium oxide and iron oxide and having a particle size of 1 to 200 μm,
The present invention provides a method for producing a molding material for reinforced plastics, which comprises adding and mixing a filler (c), a reinforcing material (d), and an additive (e) after wet and uniformly dispersing the material.

(Structure) The additives used in the present invention include a thickener, a coloring agent, a curing catalyst, an internal mold release agent, a shrinkage reducing agent, etc., and these are added and mixed as necessary.

The unsaturated polyester resin used in the present invention includes α,β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its acid anhydride,
30 to 80 parts by weight of an unsaturated polyester produced by polycondensation of glycols, and in some cases using an aliphatic or alicyclic saturated dibasic acid as an acid component, is added to α,β-unsaturated polyester. Examples include those obtained by dissolving in 70 to 20 parts by weight of a saturated monomer, but also include unsaturated polyesters with vinyl-modified ends, vinyl esters with vinyl-modified ends of epoxy skeleton, etc. shall be.

Examples of α,β-unsaturated dibasic acids or their acid anhydrides include maleic acid, maleic anhydride, fumaric acid, itaconic acid, ditraconic acid, chlormaleic acid, and their esters, and aromatic saturated dibasic acids Or its acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,
These include halogenated phthalic anhydride and their esters, and examples of aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid,
Examples include hexahydrophthalic anhydride and esters thereof, each of which is used alone or in combination. Glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, Tetraethylene glycol, 1,5-pentanediol, 1,
Examples include 6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di(-4-hydroxypropoxydiphenyl-)propane, which are used alone or in combination, but others Oxides such as ethylene oxide and propylene oxide can also be used. Moreover, polycondensates such as polyethylene terephthalate can also be used as part of the glycols and the oxidizing component. As α,β-unsaturated monomers,
Vinyl compounds and diallyl phthalate such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as allyl compounds such as diallyl fumarate, diallyl succinate, and triallyl cyanurate, and may be used alone or in combination.
Styrene is commonly used.

The thickener is the hydroxyl group that unsaturated polyester has,
It has the property of chemically bonding with carboxyl groups, ester bonds, etc. to form linear or partially cross-linked bonds to increase the molecular weight and thicken the unsaturated polyester resin, such as diisocyanates such as toluene diisocyanate. , metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, divalent metal oxides such as magnesium oxide, calcium oxide, and beryllium oxide, and divalent metal hydroxides such as calcium hydroxide. . The amount of thickener used is usually based on 100 parts by weight of unsaturated polyester resin.
The proportion is from 0.2 to 10 parts by weight, preferably from 0.5 to 4 parts by weight. And if necessary, a small amount of a less polar substance such as water can be used as a thickening agent.

As the coloring agent, any conventionally known organic or inorganic dyes and pigments can be used, but among them, those having excellent heat resistance and transparency and not significantly interfering with the curing of the unsaturated polyester resin are preferred. The amount of the colorant to be used is not particularly limited, but is usually 0.01 to 20 parts by weight per 100 parts by weight of the unsaturated polyester resin.

The reinforcing material used in the present invention generally includes glass fiber, but also vinylon,
Examples include organic fibers such as polyester and phenol, asbestos, and carbon fiber. The fiber length of the reinforcing material is usually 0.1 to 50 mm, but the above-mentioned chopped mat and woven fibers can also be used. The amount added is usually 0 to 60% by weight in the molding material.
The fiber length is within the range of 6 to 6.
25 mm, and the amount added is preferably in the range of 5 to 30% by weight.

As fillers, calcium carbonate powder, clay,
Alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, cellulose thread, silica sand,
Known materials such as river sand, kansui stone, marble chips, and crushed stone may be used, and among them, glass powder, aluminum hydroxide, barium sulfate, and the like are preferred because they provide transparency after curing.

The filler can be used in an amount of usually 10 to 400 parts by weight per 100 parts by weight of the unsaturated polyester resin, and preferably 50 to 300 parts by weight, since this provides an unsaturated polyester resin composition with an appropriate viscosity.

Curing catalysts that act on unsaturated polyester resins include azo compounds such as azoisobutyronitrile, tertiary butyl perbenzoate, tertiary peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, etc. These organic peroxides can be used in an amount of usually 0.3 to 3 parts by weight per 100 parts by weight of the unsaturated polyester resin.

Examples of the internal mold release agent include conventionally known ones such as higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters, and unsaturated polyester resins.
It can be used usually in a proportion of 0.5 to 5 parts by weight per 100 parts by weight.

Specific examples of thermoplastic resins used as low shrinkage agents include lower alkyl esters of acrylic acid or methacrylic acid such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate, styrene, vinyl chloride, vinyl acetate, Homopolymers or copolymers of monomers such as ethylene, at least one of the above vinyl monomers, and lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrylonitrile, methacrylonitrile In addition to copolymers of at least one monomer consisting of , acrylic acid, methacrylic acid, and cetylstearyl methacrylate, examples include cellulose acetate butyrate, cellulose acetate propionate, polyethylene, polypropylene, and saturated polyester. .

Mica coated with titanium oxide and/or titanium oxide and iron oxide and having a particle size of 1 to 200 μm is available in silver types, iridescent types, colored types, etc., and can be given pearlescent luster and patterns. For example, some silver types have different silver-white luster depending on the ratio of titanium oxide to be coated and the particle size of mica. The iris color type changes color depending on the thickness of the titanium oxide coating. Furthermore, colored types include those in which the surface of mica is coated with titanium oxide and further coated with iron oxide or chromium.

Anatase type or rutile type titanium oxide is used for the coating. The color changes slightly depending on the coverage of titanium oxide and the particle size of mica.
The coverage rate of titanium oxide is 1 to 60%, preferably 34%.
-55%, mica particle size is 1-200 μm, preferably 10-60 μm, and in the case of colored type, iron oxide content is preferably 1-50%.

The amount of mica used is 100% of the unsaturated polyester resin.
Generally, 1 to 50 parts by weight, preferably 5 to 20 parts by weight, is used. It is also possible to use a combination of mica of different forms.

The molding material used in the present invention is supplied in the form of a sheet molding compound (abbreviated as SMC) or a bulk molding compound (abbreviated as BMC).

For producing the molding material of the present invention as SMC, any conventionally known production method can be used except for the mixing order of the mica. For example, the mica is mixed in advance with an unsaturated polyester resin, stirred and dispersed uniformly, and then fillers and additives are mixed and the molding material composition of the present invention is coated on a polyethylene film. This method involves scattering a reinforcing material such as glass chips, covering it with another polyethylene film to form a sandwiched cheese, pressurizing, impregnating, defoaming, and winding it up into a roll.

In addition, as a method for producing BMC, as is conventionally known, unsaturated polyester resin (a) and the mica (b) are put into a kneader, mixed and stirred to uniformly disperse, and then filler (c) is added. ), additives (e), and reinforcing materials (d) such as glass chops are added and kneaded into a bulk form.

In addition, the method of thickening the SMC, BMC, etc. is to wrap it with vinylon film and double wrap it, or further wrap it with aluminum foil etc. and leave it at room temperature for 3 to 5 days or at 40 to 50℃. This method involves aging for about 10 to 48 hours.

The molding conditions for SMC and BMC are selected appropriately, but preferably the pressure is 5 to 200 Kg/ ^cm2 , the temperature is 100 to 160°C,
The time is preferably selected to be 20 to 120 seconds per 1 mm of molded product thickness.

In addition, the molding method is not limited to compression molding, but can also be performed by injection molding, transfer molding, or the like.

(Effects of the Invention) According to the manufacturing method of the present invention, it is possible to provide a molding material that can industrially and efficiently produce an excellent molded product with a pearlescent glossy pattern and a luxurious feel. As a molded product, a molded product with excellent surface smoothness and high strength without cracks or pinholes can be obtained.
Examples include various molded products such as luxury bathtubs, washstands, artificial marble preparations, kitchen counters, countertops, and ornaments.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples. Note that all parts and percentages in the examples are based on weight.

Example 1 Unsaturated polyester resin (Polylite PS-260
85 parts of Iriodin (manufactured by Dainippon Ink and Chemicals Co., Ltd.)
After adding 10 parts of iris type mica 200 (iris type mica manufactured by Merck Japan Co., Ltd.) and stirring for 5 minutes with a high-speed dispersion stirrer at 1200 rpm, the low shrinkage agent Polylite PB-956 (manufactured by Merck Japan Co., Ltd.) 15
100 parts of aluminum hydroxide, 5 parts of zinc stearate, 1 part of t-butyl perbenzoate, 0.1 part of green toner, and 10 parts of styrene monomer were stirred and mixed using a high-speed dispersion stirrer. Furthermore, 1 part of magnesium oxide as a thickener was mixed, stirred and dispersed to obtain a paste composition. After uniformly spreading the paste composition into a polyethylene sheet, 10% by weight of glass chopped strands with a length of 25 mm were added.
After uniformly dispersing, the mixture was again covered with a polyethylene sheet, impregnated and defoamed with a roll, and aged at 40 to 50°C for 24 hours to obtain a sheet-shaped molding material. The molding material was molded into a bathtub under molding conditions of a pressure of 50 kg/cm ² , a temperature of 140° C., and a time of 5 minutes. The molded bathtub is transparent and has a pearl-like luster and pattern.
It was aesthetically pleasing.

Example 2 Unsaturated polyester resin Polylite PS-260
80 parts and 15 parts of Iriodin 163 (silver type mica manufactured by Merck Japan Co., Ltd.) were mixed and stirred in a kneader for 5 minutes, followed by 20 parts of low shrinkage agent Polylite PB-956, 150 parts of aluminum hydroxide, 5 parts of zinc stearate,
1 part of t-butyl perbenzoate and 0.1 part of green toner are added and stirred in a kneader. Further, 1.5 parts of magnesium oxide was added as a thickener and stirred and mixed. After dispersing and mixing 5% glass chopped strands having a length of 6 mm in the obtained paste, the paste was taken out and aged at 40 to 50°C for 24 hours to obtain a bulk molding material. Pressure the molding material to 60
The countertop was molded under the following molding conditions: Kg/cm ² , temperature, 150° C., time: 8 minutes. The molded countertop is transparent and has a pearl-like luster.
It had a pattern and was aesthetically pleasing.

Comparative Example 1 A molding material using ordinary natural mica instead of the mica of Example 2 was molded under the same conditions, and although it had a transparent feel, no pearlescent luster or the like was obtained.

Comparative Example 2 A molding material prepared by omitting the mica of Example 2 was molded under the same conditions, and although it had a transparent feel, no pearlescent gloss pattern was obtained.

Comparative example 3 Unsaturated polyester resin Polylite PS-260
85 parts, 15 parts of low shrinkage agent Polylite PB-956, 100 parts of aluminum hydroxide, 5 parts of zinc stearate,
1 part of t-butyl perbenzoate, 0.1 part of green toner, 10 parts of styrene monomer, and 15 parts of Iriodin 163 (manufactured by Merck Japan Co., Ltd.) at 1200 rpm.
After stirring for 5 minutes using a high-speed disperser, 1 part of magnesium oxide as a thickener was further mixed and stirred to obtain a paste composition. After uniformly spreading the paste composition on a polyethylene sheet, 10% by weight of glass chopped strands with a length of 25 mm were uniformly dispersed, and then covered with a polyethylene sheet again and impregnated with a roll and defoamed. After that, it was aged at 40 to 50°C for 24 hours to obtain a sheet-shaped molding material. Pressure the molding material
A bathtub was molded under the following molding conditions: 50 kg/cm ² , temperature 140° C., and time 5 minutes. Although the molded bathtub had a sense of transparency, the pearl-like luster pattern was uneven and uneven, detracting from its aesthetic appearance.

Claims (1)

[Claims] 1 Particle size 1 to 200μ coated with unsaturated polyester resin (a) and titanium oxide or titanium oxide and iron oxide
A method for producing a molding material for reinforced plastics, which comprises mixing and stirring mica with mica (b) to wet and uniformly disperse it, and then mixing filler (c), reinforcing material (d), and additive (e). .