JPH04348155A - Sheet molding compound - Google Patents

Abstract

PURPOSE:To obtain a sheet molding compound suitable for bathtub, waterproofing pan, etc., having uniform pattern and good appearance. CONSTITUTION:In producing a sheet molding compound by blending a resin (e.g. unsaturated polyester resin or epoxyacrylate) with a low shrinkage agent, a curing catalyst, a filler, etc., impregnating the blend into a fiber reinforced material into a sheetlike shape and thickening, in the blending process, the blend is mixed with 0.1-4wt.% colored fibrous substance having 1-8 aspect ratio and further 0.01-0.499wt.% square, spherical or scaly lubricant having 400-5 mesh size.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a patterned sheet molding compound (hereinafter abbreviated as SMC), and more specifically, a patterned SMC having an arbitrarily uniform pattern and aesthetic appearance.
Regarding.

0002

[Prior Art] Conventionally, when manufacturing FRP molded products with patterns from molding materials such as SMC and bulk molding compounds, there have been methods in which resin compounds of different colors are partially scattered, or marble-like molded products are produced. As a method for obtaining the material, a method is known in which a flaky material such as aluminum foil, polyester film, or mica is mixed (Japanese Patent Publication No. 2-44324).

0003

[Problems to be Solved by the Invention] However, the method of partially scattering resin compounds of different colors results in a flowing pattern and is not satisfactory in terms of reproducibility.

[0004] On the other hand, the method of adding a flaky material was not completely satisfactory because the pattern was monotonous and a complex high-grade pattern could not be obtained.

[0005]

[Means for Solving the Problems] The present inventors have completed the present invention as a result of intensive research to solve the above problems. That is, the present invention provides a patterned SMC characterized by mixing 0.1 to 4% by weight of a colored fibrous material with an aspect ratio of 1 to 8, and furthermore, an angular shaped SMC having a mesh size of 400 to 5. The object of the present invention is to provide a patterned SMC in which one or more pattern agents selected from the shapes of spherical, flaky, etc. are dispersed, preferably in an amount of 0.01 to 0.499% by weight.

[0006]

[Structure] The SMC of the present invention can be manufactured using known techniques, and is generally manufactured by the following method.

That is, a low shrinkage agent, a curing catalyst,
It is manufactured by adding and kneading a filler, an internal mold release agent, a thickener, and a coloring agent if necessary, and impregnating the resin mixture into a fibrous reinforcing material in the form of a sheet to increase the viscosity. The resin is preferably an unsaturated polyester resin.

The patterned SMC of the present invention is produced by adding and mixing a colored fibrous material or, if necessary, a pattern agent such as a square, spherical or flaky shape in the kneading process.

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

[0010] As the α,β-unsaturated dibasic acid or its acid anhydride, maleic acid, maleic anhydride, fumaric acid,
Examples include itaconic acid, citraconic acid, chlormaleic acid, and esters thereof. Examples of aromatic saturated dibasic acids or their acid anhydrides include phthalic acid, phthalic anhydride, ifsothalic acid, terephthalic acid, nitrophthalic acid, and tetrahydrophthalic anhydride. acids, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and their esters.As aliphatic or alicyclic saturated dibasic acids,
Examples include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination.

Examples of glycols include ethylene gtacol, 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, 1,6-hexanediol, bisphenol A
, hydrogenated bisphenol A, ethylene glycol carbonate, 2,2-di-(4-hydroxypropoxydiphenyl)-propane, etc., which are used alone or in combination, but in addition, oxides such as ethylene oxide, propylene oxide, etc. can be used as well. Polycondensates such as polyethylene terephthalate can also be used as part of the glycol and acid components.

Examples of α,β-unsaturated monomers include styrene, vinyltoluene, α-methylstyrene, chlorostyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate, ethyl acrylate, and methyl methane. Examples include vinyl monomers or vinyl oligomers that can be crosslinked with unsaturated polyesters such as vinyl compounds such as acrylate, acrylonitrile, and methacrylonitrile, and allyl compounds such as diallyl phthalate, diallyl fumarate, diallyl succinate, and triallyl cyanurate. It can be used alone or in combination, but styrene is generally used.

Examples of the thermoplastic resin used as a low shrinkage agent include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate,
Lower alkyl esters of acrylic acid or methacrylic acid such as ethyl acrylate, homopolymers or copolymers of monomers such as styrene, vinyl chloride, vinyl acetate, and ethylene, and at least one of the above vinyl monomers; lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxylalkyl acrylate or methacrylate, acrylonitrile,
Examples include copolymers of at least one monomer consisting of methacrylonitrile, acrylic acid, methacrylic acid, and cetylstearyl methacrylate, as well as cellulose acetate butyrate, cellulose acetate propionate, polyethylene, polypropylene, and saturated polyesters. be able to.

The curing catalyst is one that acts on unsaturated polyester, such as an azo compound such as azoisobutyronitrile, tertiary butyl perbenzoate,
Examples include organic peroxides such as tertiary peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, etc.
Usually 0.0% per 100 parts by weight of unsaturated polyester resin.
It can be used in a range of 3 to 3 parts by weight.

Examples of fillers include calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass beads, mica, aluminum hydroxide, silica sand, river sand, kansui stone, marble chips, Known materials such as crushed stone can be used, and among them, glass powder, aluminum hydroxide, barium sulfate, etc. are preferable because they provide transparency after curing.

[0016] The filler is unsaturated polyester resin 100
It can be used in an amount of usually 10 to 400 parts by weight, and 50 to 300 parts by weight is particularly preferred since it provides an unsaturated polyester resin composition with an appropriate viscosity.

[0017] As the internal mold release agent, conventionally known ones such as higher fatty acids such as stearic acid and zinc stearate, higher fatty acid esters, and alkyl phosphate esters can be mentioned. It can be used usually in a proportion of 0.5 to 5 parts by weight.

The thickener increases the molecular weight by chemically bonding with the hydroxyl group, carboxyl group, ester bond, etc. possessed by the unsaturated polyester to form linear or partially cross-linked bonds, thereby increasing the molecular weight of the unsaturated polyester resin. Substances that have viscous properties, such as diisocyanates such as toluene diisocyanate, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, and 2 such as magnesium oxide, calcium oxide, and beryllium oxide.
Examples include oxides of valent metals and hydroxides of divalent metals such as calcium hydroxide. The amount of thickener used is usually 0.2 parts by weight per 100 parts by weight of unsaturated polyester resin.
The proportion is between 10 and 10 parts by weight, preferably between 0.5 and 4 parts by weight. And if necessary, a small amount of a highly polar substance such as water can be used as a thickening agent.

As the coloring agent, any 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 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.

[0020] The reinforcing material used in the present invention generally includes glass fiber, but also includes organic fibers such as vinylon, 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 reinforcing material is preferably added in an amount of 10 to 60% by weight in the SMC. Among them, the fiber length is 6 to 25 mm, and the amount added is 2
More preferably, it is contained in an amount of 0 to 50% by weight.

The colored fibrous material used in the present invention has an aspect ratio of 1 to 8 and preferably a fiber diameter of 4 to 50 microns. As such fibers, synthetic fibers such as vinylon, polyester, phenol, aramid, etc., and cellulose fibers can be used. The amount added is 0.1
~4% by weight. If it is less than 0.1%, the pattern cannot be seen sufficiently, and if it is more than 4%, the pattern will appear on the entire surface, which is not preferable.

[0022] As a pattern material with a size of 400 mesh to 5 mesh, the shape does not matter, such as square, spherical, flaky, etc., but the length in each three-dimensional direction is 4 microns to 2000 microns. Preferably. In the case of a spherical material, the diameter is preferably from 40 microns to 2000 microns. Examples of such pattern materials include crushed natural minerals, colored materials used as fillers, and colored thermoplastic resins and thermosetting resins such as acrylic resin and polyester resin. It will be done.

The colored fibrous material and pattern agent are SM
Use materials that are not bleached or discolored by the raw materials blended in C, and that do not change shape, bleach, or discolor due to heating and pressure during SMC molding.

[0024] The amount of the colored fibrous material or the fibrous material and the angular, spherical, flaky, etc. pattern agent added varies depending on the intended molded product, but is 0.01 to 0.4.
A molded article with a uniform pattern can be obtained at 99% by weight. When using a pattern agent with a small bulk specific gravity, the desired molded product can be obtained preferably at 0.1% to 0.4% by weight.

By changing the base color of SMC, the color tone of the pattern material, the amount added, and the type of filler, a wide variety of molded products can be obtained, and an infinite number of combinations can be made. Next, the present invention will be further explained with reference to Examples. "Parts" in the examples represent "parts by weight" unless otherwise specified.

[0026]

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

Application Example 1 When a wall panel was molded using the SMC obtained in Example 1, black particles were uniformly dispersed in the white molded product, and a molded product with an excellent appearance with a sandstone-like pattern was obtained. Ta.

Comparative Application Example 1 When a wall panel was molded using the SMC obtained in Comparative Example 1, the entire surface became black and a satisfactory product could not be obtained.

Application Examples 2 and 3 When a waterproof pan was molded using the SMC obtained in Examples 2 and 3, a molded product with excellent aesthetic appearance was obtained, with a stone-like pattern uniformly dispersed in a pale green color. Obtained.

Comparative Application Example 2 When a waterproof pan was molded using the SMC obtained in Comparative Example 2, a molded product with the desired pattern could not be obtained.

Application Examples 4 and 5 When a floor tile was molded using the SMC obtained in Examples 4 and 5, a molded product with a uniform stone grain pattern and excellent appearance was obtained.

Application Examples 7 and 8 When a multifunctional panel was molded using the SMC obtained in Examples 7 and 8, a molded product with a uniform pattern and excellent appearance was obtained.

[0036]

[Effects of the Invention] The patterned SMC of the present invention allows a molded product with a uniform pattern and excellent appearance to be obtained using an ordinary mold. For example, a wide range of fields such as bathtubs, waterproof pans, wall panels, multifunctional panels, washing machine pans, bathroom vanities, countertops, kitchen counters, containers, chairs, flooring, furniture, building materials, decorations, automobiles, and electrical parts. Available at

Claims (3)

[Claims] 1. A patterned sheet molding compound characterized in that 0.1 to 4% by weight of a colored fibrous material having an aspect ratio of 1 to 8 is mixed therein. 2. A patterned sheet molding compound according to claim 1, further comprising dispersing one or more pattern agents selected from angular, spherical, and flaky shapes having a mesh size of 400 to 5. 3. The patterned sheet molding compound according to claim 2, wherein the pattern agent is dispersed in an amount of 0.01 to 0.499% by weight.