JP7261021B2 - Method for producing marble-like molded product and molding material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a marble-like molded article and a molding material.

2. Description of the Related Art In recent years, in order to improve design properties, it has been studied to impart a marble-like pattern to a resin molded product.

For example, after applying a thermosetting resin composition having a color tone different from that of SMC to the surface of a plurality of sheet molding compounds (hereinafter referred to as SMC), the plurality of SMCs are stacked and placed in a mold and heated and pressurized. A method for manufacturing an SMC molded product has been proposed (see, for example, Patent Document 1).

In such a method for producing an SMC molded product, when a plurality of stacked SMCs are heated and pressurized, the resin compound of the SMC flows and the thermosetting resin composition flows to form the SMC molded product. A marble-like pattern is formed.

JP 2015-229277 A

However, the method for producing an SMC molded product described in Patent Document 1 does not actually achieve a natural marble tone close to that of natural marble.

The present invention provides a method for producing a marble-like molded product and a molding material that can achieve a natural marble-like appearance similar to that of natural marble, although it is a simple method.

The present invention [1] comprises the steps of preparing a first resin material in the form of small pieces, and preparing a second resin material in the form of liquid or small pieces that is different in color and/or tone from the first resin material. mixing the first resin material and the second resin material to prepare a resin mixture; and molding the resin mixture. .

In the present invention [2], the step of preparing the first resin material comprises: preparing a first resin molding compound made of the first resin material; and cutting out the first resin material.

The present invention [3] includes the method for producing a marble-like molded article according to [1] or [2] above, wherein the second resin material is liquid.

The present invention [4] further comprises the step of preparing a third resin material having a color and/or color tone different from that of the first resin material and having the shape of small pieces, wherein the step of preparing the resin mixture includes: The method for manufacturing a marble-like molded product according to [3] above, wherein the resin material, the second resin material, and the third resin material are mixed.

The present invention [5] includes the method for producing a marble-like molded product according to [4] above, wherein the first resin material and the third resin material have different sizes.

The present invention [6] includes the method for producing a marble-like molded article according to the above [1] or [2], wherein the second resin material is in the form of small pieces.

The present invention [7] includes the method for producing a marble-like molded article according to [6] above, wherein the first resin material and the second resin material have different sizes.

The present invention [8] is a molding comprising a first resin material having a small piece shape and a second resin material having a liquid or small piece shape and having a color and/or tone different from that of the first resin material. Including materials.

In the method for producing a marble-like molded article of the present invention, a first resin material having a small piece shape and a second resin material having a liquid or small piece shape and having a different color and/or tone from the first resin material are used. After mixing, the resin mixture is molded.

Therefore, when molding the resin mixture, the first resin material in the form of small pieces and the second resin material in the form of liquid or small pieces are mixed with each other so as to form a natural marble tone. As a result, although it is a simple method, it is possible to realize a natural marble tone close to that of natural marble in the molded product.

The molding material of the present invention comprises a first resin material in the form of small pieces, and a second resin material in the form of liquid or small pieces that differs in color and/or tone from the first resin material. It is suitably used in the method for producing a marble-like molded article described above, and can smoothly produce a molded article having a natural marble-like appearance close to that of natural marble.

FIG. 1 shows a photograph in plan view of the flat molded product of Example 1. FIG. FIG. 2 shows a photograph in plan view of the flat plate molded product of Comparative Example 1. FIG.

The method for producing a marble-like molded article of the present invention includes the step of preparing a first resin material having a small piece shape, and a second resin material having a liquid or small piece shape different in color and/or tone from the first resin material. The method includes preparing a resin material, mixing a first resin material and a second resin material to prepare a resin mixture, and molding the resin mixture. In addition, the color tone means the tone of color intensity and shade, and the tone of color depending on the presence or absence of a pattern material (for example, flake material, lame material, pearl material, etc.).

<First embodiment>
A first embodiment of the method for producing a marble-like molded article of the present invention will be described below. In the first embodiment, the second resin material has a liquid state.

1-1. Step of Preparing First Resin Material In the first embodiment, first, a first resin material having a small piece shape is prepared (first preparing step).

To prepare the first resin material having the shape of small pieces, for example, after preparing a first resin molding compound made of the first resin material, the first resin material having the shape of small pieces is cut out from the first resin molding compound. . That is, the step of preparing the first resin material includes a step of preparing a first resin molding compound made of the first resin material (molding compound preparation step), and a step of preparing small pieces of the first resin material from the first resin molding compound. and a step of cutting out (cutting step).

The first resin molding compound includes, for example, a thermosetting resin composition and reinforcing fibers impregnated with the thermosetting resin composition.

The thermosetting resin composition includes, for example, a first thermosetting resin and a first coloring agent.

The first thermosetting resin contains a resin base and an ethylenically unsaturated monomer, and has a smaller ethylenically unsaturated monomer content than the later-described second thermosetting resin.

Specifically, the content of the ethylenically unsaturated monomer in the first thermosetting resin is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 90% by mass or less, preferably 60% by mass or more. % by mass or less.

Specific examples of the first thermosetting resin include a first unsaturated polyester resin, a first vinyl ester resin, and a first acrylic syrup. A 1st thermosetting resin can be used individually or in combination of 2 or more types.

That is, the first thermosetting resin contains, for example, at least one selected from the group consisting of the first unsaturated polyester resin, the first vinyl ester resin and the first acrylic syrup.

The first unsaturated polyester resin comprises an unsaturated polyester as a resin base and an ethylenically unsaturated monomer.

An unsaturated polyester is a polymerization product (polymer) of a polybasic acid and a polyhydric alcohol.

The polybasic acid contains at least a polybasic acid having an ethylenically unsaturated double bond (hereinafter referred to as an ethylenically unsaturated bond-containing polybasic acid), and preferably does not have an ethylenically unsaturated double bond. Polybasic acid (hereinafter referred to as polybasic acid without ethylenically unsaturated bonds) is further included.

Examples of ethylenically unsaturated bond-containing polybasic acids include unsaturated aliphatic dicarboxylic acids (e.g., maleic acid, fumaric acid, itaconic acid, etc.), acid anhydrides derived from unsaturated aliphatic dicarboxylic acids (e.g., anhydrous maleic acid, etc.). Ethylenically unsaturated bond-containing polybasic acids can be used alone or in combination of two or more.

Among the ethylenically unsaturated bond-containing polybasic acids, acid anhydrides of unsaturated aliphatic dicarboxylic acids are preferred, and maleic anhydride is more preferred.

Examples of ethylenically unsaturated bond-free polybasic acids include saturated aliphatic dicarboxylic acids (e.g., oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, etc.), aromatic dicarboxylic acids (e.g., orthophthalic acid, isophthalic acid, acids, terephthalic acid, etc.), saturated alicyclic dicarboxylic acids (eg, hexahydrophthalic acid, etc.), acid anhydrides derived from these dicarboxylic acids, and the like. Ethylenically unsaturated bond-free polybasic acids can be used alone or in combination of two or more.

Among the ethylenically unsaturated bond-free polybasic acids, aromatic dicarboxylic acids are preferred, and isophthalic acid is more preferred.

Examples of polyhydric alcohols include alkanediols (e.g., ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, etc.), polyoxyalkylene glycols (e.g., diethylene glycol, etc.). polyethylene glycol, polypropylene glycol such as dipropylene glycol, etc.), alicyclic diols (eg, cyclohexanediol, hydrogenated bisphenol A, etc.), aromatic diols (eg, bisphenols such as bisphenol A). A polyhydric alcohol can be used individually or in combination of 2 or more types.

Among polyhydric alcohols, alkanediols are preferred, propylene glycol and neopentyl glycol are preferred, and combined use of propylene glycol and neopentyl glycol is more preferred.

Such unsaturated polyesters are prepared by condensation polymerization of the above-described polybasic acid and the above-described polyhydric alcohol under known reaction conditions.

The unsaturated polyester also preferably has an acid number.

As a method for preparing an unsaturated polyester having an acid value, for example, a method of condensation polymerization of an excess polybasic acid with respect to a polyhydric alcohol, and a condensation polymerization reaction of a polybasic acid and a polyhydric alcohol to obtain a desired acid value. For example, a method of stopping at the stage where

An ethylenically unsaturated monomer is a polymerizable monomer (vinyl monomer) having an ethylenically unsaturated double bond. In the unsaturated polyester resin, the ethylenically unsaturated monomer is a reactive diluent capable of dissolving the unsaturated polyester and polymerizable (crosslinkable) with the unsaturated polyester.

Examples of ethylenically unsaturated monomers include styrenic monomers and (meth)acrylates. (Meth)acrylic is synonymous with methacrylic and/or acryl (the same shall apply hereinafter). Ethylenically unsaturated monomers can be used singly or in combination of two or more.

Among the ethylenically unsaturated monomers contained in the first unsaturated polyester resin, styrenic monomers are preferred.

Styrenic monomers include, for example, styrene, α-methylstyrene, α-ethylstyrene, vinyltoluene, t-butylstyrene, chlorostyrene and the like, preferably styrene. Styrenic monomers can be used singly or in combination of two or more.

The content of the ethylenically unsaturated monomer in the first unsaturated polyester resin is, for example, 10 parts by mass or more per 100 parts by mass of the sum of the unsaturated polyester and the ethylenically unsaturated monomer, preferably 30 parts by mass or more, for example, 90 parts by mass or less, preferably 60 parts by mass or less.

The first vinyl ester resin comprises a vinyl ester as the resin base and the ethylenically unsaturated monomers described above.

A vinyl ester is an addition reaction product of an epoxy resin and an unsaturated monobasic acid.

Examples of epoxy resins include bisphenol type epoxy resins (e.g., bisphenol A type epoxy resins, bisphenol F type epoxy resins, brominated bisphenol A type epoxy resins, etc.), novolac type epoxy resins (e.g., phenol novolac type epoxy resins, cresol novolac type epoxy resins, brominated novolac type epoxy resins, etc.), aliphatic type epoxy resins, alicyclic epoxy resins, hydrogenated bisphenol type epoxy resins, amine type epoxy resins, and the like. Epoxy resins can be used singly or in combination of two or more.

An unsaturated monobasic acid has an ethylenically unsaturated double bond. Examples of unsaturated monobasic acids include unsaturated monofatty acids (e.g., (meth)acrylic acid, crotonic acid, sorbic acid, etc.), aromatic unsaturated monocarboxylic acids (e.g., cinnamic acid, etc.), ester bond-containing unsaturated Saturated monocarboxylic acids (for example, reaction products of acid anhydrides and unsaturated alcohols, etc.) and the like can be mentioned. Unsaturated monobasic acids can be used alone or in combination of two or more.

Such a vinyl ester is prepared by subjecting the above-described epoxy resin and the above-described unsaturated monobasic acid to a ring-opening addition reaction under known reaction conditions.

Vinyl esters include not only unmodified vinyl esters (unmodified vinyl esters) but also acid-modified vinyl esters derived from unmodified vinyl esters.

An acid-modified vinyl ester is an acid-modified vinyl ester, and a carboxyl group is introduced into the side chain of the vinyl ester. The acid-modified vinyl ester is, for example, the reaction product of the unmodified vinyl ester described above and an acid anhydride.

Examples of acid anhydrides include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and trimellitic anhydride. Acid anhydrides can be used singly or in combination of two or more.

The acid-modified vinyl ester is prepared, for example, by reacting the hydroxyl group contained in the above-described unmodified vinyl ester with the acid anhydride group of the acid anhydride under known reaction conditions. A hydroxyl group and an acid anhydride group react to form an ester bond and a carboxyl group.

In the first vinyl ester resin, the ethylenically unsaturated monomer is a reactive diluent capable of dissolving the above vinyl ester and polymerizable (crosslinkable) with the above vinyl ester.

Among the ethylenically unsaturated monomers contained in the first vinyl ester resin, the above-described styrene-based monomers are preferred, and styrene is more preferred.

The content of the ethylenically unsaturated monomer in the first vinyl ester resin is, for example, 10 parts by mass or more, preferably 30 parts by mass, per 100 parts by mass of the total of the vinyl ester resin and the ethylenically unsaturated monomer. Part by mass or more, for example, 90 parts by mass or less, preferably 60 parts by mass or less.

The first acrylic syrup contains poly(meth)acrylate and/or acid-modified poly(meth)acrylate as a resin base and the ethylenically unsaturated monomers described above.

Poly(meth)acrylate is a polymerization product (polymer) of (meth)acrylate.

(Meth)acrylates include, for example, mono(meth)acrylates having one (meth)acryloyl group, polyfunctional (meth)acrylates having two or more (meth)acryloyl groups, and the like.

Examples of mono (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) ) isobutyl acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, alkyl (meth)acrylate (12 or 13 carbon atoms), tridecyl (meth)acrylate, stearyl (meth)acrylate, ( Cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, allyl (meth)acrylate, 2-(meth)acrylate Hydroxyethyl, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminoethylmethyl chloride (meth)acrylate salt, dimethylaminoethylbenzyl chloride (meth)acrylate, diethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate and the like. Such mono(meth)acrylates may also be copolymerized with styrene.

Examples of polyfunctional (meth)acrylates include alkane glycol di(meth)acrylates (e.g., ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate), polyoxyalkyl range (meth)acrylates (eg, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, etc.);

Such (meth)acrylates can be used alone or in combination of two or more.

Poly(meth)acrylates are prepared, for example, by polymerizing the above-described (meth)acrylates under known reaction conditions.

Acid-modified poly (meth) acrylate has a side chain component represented by -OCO-X-COOH (wherein X represents an aromatic group, an alicyclic group or an aliphatic group) in the side chain, and / or , is a (meth)acrylic acid ester copolymer resin containing a component derived from (meth)acrylic acid.

Acid-modified poly(meth)acrylates are, for example, hydroxy group-containing vinyl monomers (e.g., hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, etc.) and the addition reaction product obtained by the addition reaction with the above acid anhydride is copolymerized with the above (meth)acrylate, or the above hydroxyl group-containing vinyl monomer and the above (meth)acrylate is prepared by addition reaction of the above acid anhydride to the copolymer of

In the first acrylic syrup, the ethylenically unsaturated monomer is capable of dissolving the vinyl ester described above, but cannot be polymerized with the poly(meth)acrylate and/or acid-modified poly(meth)acrylate described above.

Among the ethylenically unsaturated monomers contained in the first acrylic syrup, the above-described (meth)acrylates are preferred, and methyl (meth)acrylate is more preferred.

The content ratio of the ethylenically unsaturated monomer in the first acrylic syrup is, for example, with respect to 100 parts by mass of the total of the poly(meth)acrylate, the acid-modified poly(meth)acrylate and the ethylenically unsaturated monomer. 10 parts by mass or more, preferably 30 parts by mass or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less.

The first coloring agent is a pigment that imparts a desired color to the molded article, which will be described later, and is appropriately selected according to the color and pattern required for the molded article.

Examples of the first coloring agent include known pigments, and specific examples include white pigments (e.g., titanium white, zinc sulfide, white toners containing them), black pigments (e.g., carbon black, iron oxide, blue pigments (e.g., cobalt blue, phthalocyanine blue, blue toners having them, etc.), pearl pigments (e.g., titanium dioxide-coated muscovite, basic lead carbonate, etc.), special pigments (e.g., fluorescent pigments, phosphorescent pigments, etc.). The first coloring agent can be used alone or in combination of two or more, and the above pigments may be selected and used depending on the molded product.

By appropriately selecting the first coloring agent, the thermosetting resin composition (first resin material described later) can be adjusted to a desired color.

The content of the first coloring agent is, for example, 1 part by mass or more, for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 10 parts by mass, with respect to 100 parts by mass of the first thermosetting resin. It is below the department.

By adjusting the content of the first coloring agent, the thermosetting resin composition (first resin material described later) can be adjusted to a desired color tone.

In addition, the thermosetting resin composition may contain other additives such as fillers, thickeners, low shrinkage agents, curing agents, polymerization inhibitors, and release agents.

Examples of fillers include inorganic fillers. Examples of inorganic fillers include oxides (e.g., alumina, titania, etc.), hydroxides (e.g., aluminum hydroxide, etc.), carbonates (e.g., calcium carbonate, etc.), sulfates (e.g., barium sulfate, etc.), Silica (e.g., crystalline silica, fused silica, fumed silica, fumed silica (Aerosil), etc.), glass powder, hollow fillers (e.g., glass hollow spheres, silica hollow spheres, alumina hollow spheres, etc.), silicates (e.g., , silica sand, diatomaceous earth, mica, clay, kaolin, talc, etc.), fluorides (e.g., fluorite, etc.), phosphates (e.g., calcium phosphate, etc.), clay minerals (e.g., smectite, etc.), milled fibers (e.g., glass long fibers pulverized to a length of 30 to 300 μm), preferably hydroxides, carbonates and glass powders, more preferably aluminum hydroxide and glass powders. The fillers can be used singly or in combination of two or more.

The content of the filler is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 100 parts by mass or more, for example 500 parts by mass or less, with respect to 100 parts by mass of the first thermosetting resin. , preferably 400 parts by mass or less.

Examples of thickeners include alkaline earth metal oxides (e.g., magnesium oxide), alkaline earth metal hydroxides (e.g., magnesium hydroxide, calcium hydroxide, etc.), polyisocyanates (e.g., tolylene diisocyanate ( TDI), aromatic polyisocyanates such as 4,4′-diphenylmethane diisocyanate (MDI), for example hydrogenated xylylene diisocyanate (H _XDI ), isophorone diisocyanate (IPDI), hydrogenated 4,4′-diphenylmethane diisocyanate (H ₁₂ MDI), alicyclic polyisocyanates such as norbornanemethane diisocyanate (NBDI), araliphatic polyisocyanates such as xylylene diisocyanate (XDI), aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), and these and the like), preferably alkaline earth metal oxides, and more preferably magnesium oxide. A thickener can be used individually or in combination of 2 or more types.

The content ratio of the thickener is not particularly limited, but is, for example, 0.1 parts by mass or more, for example, 4 parts by mass or less, preferably 2 parts by mass or less with respect to 100 parts by mass of the first thermosetting resin. be.

Examples of low shrinkage agents include polyvinyl acetate, poly(meth)acrylate resin, cellulose ester resin (e.g., cellulose acetate butyrate), polystyrene, crosslinked polystyrene, polyethylene, polyvinyl acetate-polystyrene block copolymer, SBS (rubber ), SEPS (rubber), and saturated polyester resins, preferably polystyrene, crosslinked polystyrene, polyethylene, and polyvinyl acetate-polystyrene block copolymers. The low shrinkage agents can be used alone or in combination of two or more.

The content of the low shrinkage agent is not particularly limited, but is preferably 1 part by mass or more, preferably 5 parts by mass or more, for example 40 parts by mass or less, relative to 100 parts by mass of the first thermosetting resin. is 25 parts by mass or less.

Curing agents (polymerization initiators) include, for example, peroxides. Peroxides such as benzoyl peroxide, t-butylperoxyisopropylmonocarbonate, t-amylperoxyisopropylmonocarbonate, t-hexylperoxyisopropylmonocarbonate, 1,1-bis(t-butylperoxy)cyclohexane , t-butylperoxy-2-ethylhexanoate, amylperoxy-2-ethylhexanoate, 2-ethylhexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-hexylperoxy Benzoate, t-hexylperoxyacetate, etc., preferably benzoyl peroxide, t-butylperoxyisopropylmonocarbonate, t-amylperoxyisopropylmonocarbonate. Peroxides can be used singly or in combination of two or more.

The content of the curing agent is not particularly limited, but is, for example, 0.5 parts by mass or more, preferably 0.8 parts by mass or more, and for example, 10 parts by mass or less with respect to 100 parts by mass of the first thermosetting resin. , preferably 3 parts by mass or less.

Examples of polymerization inhibitors include hydroquinone compounds (e.g., hydroquinone, methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, etc.), benzoquinone compounds (e.g., parabenzoquinone , 2,5-di-t-butylbenzoquinone, etc.), naphthoquinone compounds (e.g., naphthoquinone, etc.), catechol compounds (e.g., pt-butylcatechol, etc.), aromatic amine compounds (e.g., phenothiazine, etc.), N- Examples include oxyl compounds, preferably benzoquinone compounds and N-oxyl compounds, and more preferably parabenzoquinone. A polymerization inhibitor can be used individually or in combination of 2 or more types.

The content of the polymerization inhibitor is not particularly limited, but is, for example, 0.005 parts by mass or more, preferably 0.01 parts by mass or more, for example, 0.5 parts by mass with respect to 100 parts by mass of the first thermosetting resin. Part by mass or less, preferably 0.20 part by mass or less.

Release agents (internal release agents) include, for example, fatty acids (e.g., stearic acid, lauric acid, etc.), fatty acid metal salts (e.g., zinc stearate, calcium stearate, etc.), paraffin, liquid waxes, fluoropolymers, silicone-based Examples thereof include polymers, preferably fatty acids and fatty acid metal salts, and more preferably stearic acid and zinc stearate. The releasing agent can be used alone or in combination of two or more.

The content of the release agent is not particularly limited, but is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 10 parts by mass or less with respect to 100 parts by mass of the first thermosetting resin.

Furthermore, the thermosetting resin composition may contain other additives such as wetting and dispersing agents, anti-separation agents, flame retardants, conductive agents, and UV absorbers in appropriate proportions, if necessary.

Examples of reinforcing fibers include inorganic fibers (e.g., glass fibers, carbon fibers, metal fibers, ceramic fibers, etc.), organic fibers (e.g., polyvinyl alcohol fibers, polyester fibers, polyamide fibers, fluororesin fibers, phenolic fibers, etc.). fiber, etc.), natural fibers (e.g., hemp, kenaf, etc.), preferably inorganic fibers, more preferably carbon fibers and glass fibers, and particularly preferably glass fibers. . The reinforcing fibers can be used singly or in combination of two or more.

Examples of the shape of the reinforcing fiber include cloth such as roving cloth, mat such as chopped strand mat, preformable mat, continuous strand mat and surfacing mat, strand, chopped strand, roving, non-woven fabric, etc. Paper-like and the like, preferably roving-like.

The dimensions and compounding ratio of such reinforcing fibers are appropriately changed according to the aspect of the first resin molding compound.

Embodiments of the first resin molding compound include, for example, a sheet molding compound (hereinafter referred to as SMC), a thick molding compound (hereinafter referred to as TMC), a bulk molding compound (hereinafter referred to as BMC), and the like. .

SMC has, for example, a sheet shape. SMC has, for example, a rectangular shape when viewed from the thickness direction. The thickness of SMC is, for example, 0.5 mm or more and 6.0 mm or less. The dimension of the SMC in the direction orthogonal to the thickness direction is, for example, 50 cm or more and 200 cm or less. The mass of SMC is appropriately determined so as to match the mass and thickness of the molded product.

Also, a plurality of SMCs can be laminated in the thickness direction to form the first resin molding compound. In this case, the mass of the first resin molding compound is appropriately determined so as to match the mass and thickness of the molded product.

Such an SMC is produced, for example, by mixing the first thermosetting resin, the first coloring agent, and, if necessary, an additive other than a thickening agent, and adding the thickening agent to the mixture. It is prepared by adding a sticky agent and then adding the above reinforcing fibers by a known SMC impregnator.

In addition, when the first resin molding compound is SMC, the length of the reinforcing fiber is, for example, 10 mm or more, preferably 12 mm or more, for example, 60 mm or less, preferably 30 mm or less, and the blending ratio of the reinforcing fiber is For 100 parts by mass of the first thermosetting resin, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 200 parts by mass or less, preferably 150 parts by mass or less.

TMC has, for example, a block shape or a sheet shape. When the TMC has a sheet shape, the TMC has, for example, a rectangular shape when viewed from the thickness direction. The thickness of TMC is, for example, 2.0 mm or more and 30.0 mm or less. The dimension of the TMC in the direction orthogonal to the thickness direction is, for example, 50 cm or more and 200 cm or less. The mass of TMC is appropriately determined so as to match the mass and thickness of the molded product.

For TMC, for example, after mixing the first thermosetting resin, the first coloring agent, and, if necessary, additives other than the thickening agent, the thickening agent is added to the mixture. and then by a known TMC impregnator to add the reinforcing fibers described above.

In addition, when the first resin molding compound is TMC, the length of the reinforcing fiber is, for example, 3 mm or more, preferably 5 mm or more, for example, 60 mm or less, preferably 30 mm or less, and the blending ratio of the reinforcing fiber is For 100 parts by mass of the first thermosetting resin, for example, 10 parts by mass or more, preferably 20 parts by mass or more, for example, 200 parts by mass or less, preferably 150 parts by mass or less.

The BMC has, for example, a cylindrical or rectangular parallelepiped block shape. The block unit of BMC is, for example, 0.1 kg or more and 30 kg or less.

For BMC, for example, after mixing the first thermosetting resin, the first coloring agent, and, if necessary, additives other than the thickening agent, the thickening agent is added to the mixture. It is prepared by adding, then adding reinforcing fibers and mixing with a known BMC kneader.

In addition, when the first resin molding compound is BMC, the length of the reinforcing fiber is, for example, 1 mm or more, preferably 2 mm or more, for example, 30 mm or less, preferably 25 mm or less, and the blending ratio of the reinforcing fiber is , for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 100 parts by mass or less, preferably 60 parts by mass or less, relative to 100 parts by mass of the first thermosetting resin.

Among such first resin molding compounds, BMC is preferred.

As described above, the first resin molding compound is prepared. In addition, the manufacturing method of the molding compound described above does not limit the present invention.

Next, the first resin material having a small piece shape is cut out from the first resin molding compound by a known cutting method. For example, an extruder and a cutting machine are combined, and the first resin molding compound extruded in a predetermined shape (for example, cylindrical, prismatic, etc.) is cut into a predetermined length using the cutting machine. Therefore, the first resin material having a small piece shape contains the first thermosetting resin composition described above and the reinforcing fibers described above.

As described above, the first resin material having the shape of small pieces is prepared. It should be noted that the method of cutting the molding compound described above does not limit the present invention.

The shape of each first resin material is a small piece shape, and more specifically, a cubic shape (dice shape), a rectangular parallelepiped shape, a columnar shape, a prismatic shape, a spherical shape, a random shape, etc., can be mentioned. A cubic shape (dice shape), a rectangular parallelepiped shape, and a columnar shape are mentioned.

The maximum dimension of each first resin material is, for example, 1 mm or more, preferably 2 mm or more, and for example, 150 mm or less, preferably 50 mm or less, and more preferably 10 mm or less.

If the maximum dimension of each first resin material is equal to or greater than the above lower limit, the first resin material can be easily and smoothly cut out from the first resin molding compound. If the maximum dimension of each first resin material is equal to or greater than the above lower limit, a more complicated marble-like pattern can be imparted to the molded product, which will be described later.

The shape and dimensions of the cut first resin material are appropriately selected according to the pattern required for the molded product.

1-2. Step of Preparing Second Resin Material Next, a second resin material having a liquid state is prepared (second preparing step).

The second resin material differs in color and/or tone from the first resin material, and is in a fluid state at room temperature (23° C.).

The second resin material includes, for example, a second thermosetting resin and a second coloring agent.

The second thermosetting resin is the same as the first thermosetting resin except for the content of the ethylenically unsaturated monomer. The content of the ethylenically unsaturated monomer in the second thermosetting resin is greater than the content of the ethylenically unsaturated monomer in the first thermosetting resin, for example, 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, particularly preferably 65% by mass or more, for example, 95% by mass or less, preferably 80% by mass or less.

As the second thermosetting resin, the same thermosetting resin as the above-described first thermosetting resin can be mentioned except for the content of the ethylenically unsaturated monomer. Specifically, the second unsaturated polyester A resin, a second vinyl ester resin, a second acrylic syrup, and the like are included. A 2nd thermosetting resin can be used individually or in combination of 2 or more types.

That is, the second thermosetting resin contains, for example, at least one selected from the group consisting of the second unsaturated polyester resin, the second vinyl ester resin and the second acrylic syrup.

The second unsaturated polyester resin is the same as the first unsaturated polyester resin described above, except for the content of the ethylenically unsaturated monomer.

The content of the ethylenically unsaturated monomer in the second unsaturated polyester resin is, for example, 10 parts by mass or more per 100 parts by mass of the sum of the unsaturated polyester and the ethylenically unsaturated monomer, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, particularly preferably 65 parts by mass or more, for example, 95 parts by mass or less, preferably 80 parts by mass or less.

The second vinyl ester resin is the same as the first vinyl ester resin described above, except for the content of the ethylenically unsaturated monomer.

The content ratio of the ethylenically unsaturated monomer in the second vinyl ester resin is higher than the content ratio of the ethylenically unsaturated monomer in the first vinyl ester resin, and the vinyl ester resin and the ethylenically unsaturated monomer For example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, particularly preferably 65 parts by mass or more , for example, 95 parts by mass or less, preferably 80 parts by mass or less.

The second acrylic syrup is the same as the first acrylic syrup described above, except for the content of the ethylenically unsaturated monomer.

The content of the ethylenically unsaturated monomer in the second acrylic syrup is higher than the content of the ethylenically unsaturated monomer in the first acrylic syrup, and the poly(meth)acrylate and the acid-modified poly(meth)acrylate For example, 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and particularly preferably 40 parts by mass or more, with respect to 100 parts by mass in total with the ethylenically unsaturated monomer, For example, it is 95 parts by mass or less, preferably 85 parts by mass or less, and more preferably 80 parts by mass or less.

As a combination of the first thermosetting resin and the second thermosetting resin, a combination of the first unsaturated polyester resin and the second unsaturated polyester resin, a combination of the first vinyl ester resin and the second vinyl ester resin, and and a combination of a first acrylic syrup and a second acrylic syrup.

Examples of the second coloring agent include pigments similar to the above-described first coloring agent, and specific examples include the above-described white pigment, the above-described black pigment, the above-described blue pigment, the above-described pearl pigment, fluorescent paint, Phosphorescent paint etc. are mentioned. A 2nd coloring agent can be used individually or in combination of 2 or more types. The second coloring agent has, for example, a different color than the first coloring agent.

By appropriately selecting the second coloring agent, the second resin material can be adjusted to a desired color so that the color differs from that of the first resin material.

As a combination of the first coloring agent and the second coloring agent, a combination of a black pigment (first coloring agent) and a white pigment (second coloring agent) is preferably used.

The content of the second coloring agent is, for example, 0.5 parts by mass or more, preferably 3 parts by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass or less, with respect to 100 parts by mass of the second thermosetting resin. Part by mass or less.

By adjusting the content ratio of the second coloring agent, the second resin material can be adjusted to a desired color tone so that the color tone differs from that of the first resin material. In addition, the coloring agent and the content ratio of the coloring agent described above do not limit the present invention.

In addition, the second resin material can contain other additives such as the above-described filler, the above-described curing agent, the above-described polymerization inhibitor, the above-described releasing agent, and the above-described thickening agent.

The filler contained in the second resin material preferably includes the above-described hydroxides and carbonates, and more preferably includes aluminum hydroxide. The fillers can be used singly or in combination of two or more.

The content of the filler is, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 50 parts by mass or more, for example 300 parts by mass or less, with respect to 100 parts by mass of the second thermosetting resin. , preferably 200 parts by mass or less, more preferably 150 parts by mass or less, and particularly preferably less than 100 parts by mass.

The curing agent contained in the second resin material preferably includes the above peroxides, more preferably benzoyl peroxide, t-butylperoxyisopropylmonocarbonate, and t-amylperoxyisopropylmonocarbonate. . Curing agents can be used alone or in combination of two or more.

Although the content of the curing agent is not particularly limited, it is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 10 parts by mass or less with respect to 100 parts by mass of the second thermosetting resin. , preferably 3 parts by mass or less.

Polymerization inhibitors contained in the second resin material include, for example, hydroquinone compounds (e.g., hydroquinone, methylhydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, trimethylhydroquinone, methoxyhydroquinone, etc.), Benzoquinone compounds (e.g., parabenzoquinone, 2,5-di-t-butylbenzoquinone, etc.), naphthoquinone compounds (e.g., naphthoquinone, etc.), catechol compounds (e.g., pt-butylcatechol, etc.), aromatic amine compounds (e.g., , phenothiazine, etc.) and N-oxyl compounds, preferably benzoquinone compounds and N-oxyl compounds, more preferably parabenzoquinone. A polymerization inhibitor can be used individually or in combination of 2 or more types.

A polymerization inhibitor may not be added, but when a polymerization inhibitor is added, the content ratio of the polymerization inhibitor is not particularly limited, but for 100 parts by mass of the second thermosetting resin, for example, 0.0001 parts by mass or more, preferably 0.005 parts by mass or more, for example, 0.3 parts by mass or less, preferably 0.20 parts by mass or less, more preferably 0.030 parts by mass or less, and particularly preferably 0.030 parts by mass or less. 010 parts by mass or less.

The release agent contained in the second resin material preferably includes fatty acid and fatty acid metal salt, and more preferably includes stearic acid and zinc stearate. The releasing agent can be used alone or in combination of two or more.

The content of the release agent is not particularly limited, but is, for example, 0.3 parts by mass or more, preferably 0.5 parts by mass or more, for example 10 parts by mass, with respect to 100 parts by mass of the second thermosetting resin. It is below.

The thickener contained in the second resin material is preferably an alkaline earth metal oxide, more preferably magnesium oxide. A thickener can be used individually or in combination of 2 or more types.

The content ratio of the thickener is not particularly limited, but is, for example, 0.1 parts by mass or more, for example, 4 parts by mass or less, preferably 2 parts by mass or less with respect to 100 parts by mass of the second thermosetting resin. be.

Furthermore, the second resin material may contain other additives such as a low-shrinkage agent, a wetting and dispersing agent, an anti-separation agent, a flame retardant, a conductive agent, and an ultraviolet absorber in appropriate proportions, if necessary. good too.

In addition, the second resin material preferably does not contain the reinforcing fibers described above. Therefore, the viscosity of the second resin material can be stably adjusted within the following range.

The viscosity (at 25° C.) of the second resin material is, for example, 1 mPa·s or more, preferably 2 mPa·s or more, and for example, 30000 mPa·s or less, preferably 10000 mPa·s or less. The viscosity (at 25° C.) of the second resin material can be measured by, for example, a Brookfield viscometer (the same applies hereinafter).

Such a second resin material is prepared, for example, by mixing the above-described second thermosetting resin, the above-described second coloring agent, and, if necessary, other additives.

As described above, the second resin material having a liquid state is prepared.

1-3. Step of preparing the third resin material In the first embodiment, preferably, a step of preparing a third resin material having a small piece shape and having a color and/or tone different from that of the first resin material (third preparing step) further includes

The third resin material having the shape of small pieces is the same as the first resin material except that it differs from the first resin material in color and/or tone.

To prepare the third resin material having the shape of small pieces, for example, first, the third resin molding compound is prepared in the same manner as the molding compound preparation step.

The third resin molding compound may have a different formulation from the first resin molding compound, or may be the same as the first resin molding compound except for color and/or tone. In other words, the third resin molding compound may be the same as the first resin molding compound, except that the first coloring agent is changed to the third coloring agent.

Examples of the third coloring agent include pigments similar to the first coloring agent described above, and specific examples include the white pigment described above, the black pigment described above, the blue pigment described above, the pearl pigment described above, and the like. . The third coloring agent can be used alone or in combination of two or more.

The third colorant preferably has a different color than the first colorant. Also, the third coloring agent may have the same color as the second coloring agent, or may have a different color from the second coloring agent.

Further, as a combination of the first coloring agent, the second coloring agent, and the third coloring agent, for example, a black pigment (first coloring agent), a white pigment (second coloring agent), and a white pigment (third coloring agent) A combination of

The range of the content ratio of the third coloring agent is the same as the range of the content ratio of the first coloring agent described above.

Next, a third resin material having a small piece shape is cut out from the third resin molding compound by a known cutting method.

A third resin material having a small piece shape is thus prepared.

The shape of each third resin material is a small piece shape, and more specifically, a cubic shape (dice shape), a rectangular parallelepiped shape, a columnar shape, a prismatic shape, a spherical shape, a random shape, and the like. A cubic shape (dice shape), a rectangular parallelepiped shape, and a columnar shape are mentioned.

The size of the third resin material is preferably different from the size of the first resin material, more preferably larger than the size of the first resin material.

The maximum dimension of each third resin material is, for example, 1 time or more, preferably 5 times or more, for example, 500 times or less, preferably 100 times or less, with respect to the maximum dimension of each first resin material. More preferably, it is 50 times or less. Specifically, the maximum dimension of each third resin material is, for example, 1 mm or more, preferably 5 mm or more, and for example, 500 mm or less, preferably 100 mm or less, and more preferably 50 mm or less.

The mass of one cut third resin material is, for example, 0.01 g or more, preferably 2 g or more, for example, 30 kg or less, preferably 3 kg or less, and more preferably 300 g or less. In addition, the above-described mass does not restrict the present invention.

1-4. Step of Preparing Resin Mixture Next, the first resin material, the second resin material, and preferably the third resin material are mixed to prepare a resin mixture (preparation step).

As a method of mixing the first resin material and the second resin material, for example, a method of spraying the second resin material having a liquid state onto the first resin material having a small piece shape, or a method of spraying the first resin material having a small piece shape. , a method of immersing in a second resin material having a liquid state, a method of applying the second resin material to the surface of a first resin material having a small piece shape, and the like.

When the third resin material is mixed, the first resin material having the small piece shape and the third resin material having the small piece shape are dry-mixed in advance, and then the resin material having the small piece shape (the first The resin material and the third resin material) and the liquid second resin material can be mixed by the mixing method described above.

Among such mixing methods, a method of spraying a second resin material having a liquid state on a resin material having a small piece shape is preferably used.

The mixing ratio of the second resin material is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 50 parts by mass or less, preferably 20 parts by mass with respect to 100 parts by mass of the first resin material. Part by mass or less.

The mixing ratio of the third resin material is, for example, 1 part by mass or more, preferably 10 parts by mass or more, for example 5000 parts by mass or less, preferably 1000 parts by mass or less with respect to 100 parts by mass of the first resin material. be.

As described above, the resin mixture is prepared by mixing the first resin material, the second resin material, and preferably the third resin material.

1-5. Molding Step Next, the resin mixture is molded (molding step).

Examples of the method for molding the resin mixture include press molding and injection molding, preferably press molding.

Specifically, after placing the resin mixture in the first mold, the second mold is moved toward the first mold to sandwich the resin mixture between the first mold and the second mold, and The resin mixture is cured and molded under molding conditions (molding pressure, temperature and time).

The molding pressure is, for example, 1 MPa or more, preferably 5 MPa or more, for example 30 MPa or less, preferably 15 MPa or less.

The molding temperature of the first mold is, for example, 80° C. or higher, preferably 125° C. or higher, and for example, 200° C. or lower, preferably 135° C. or lower. The molding temperature of the second mold is, for example, 80° C. or higher, preferably 140° C. or higher, and for example, 200° C. or lower, preferably 150° C. or lower.

The molding time is, for example, 1 minute or longer, preferably 3 minutes or longer, and for example, 30 minutes or shorter, preferably 10 minutes or shorter.

In such a molding process, the resin materials having small pieces (the first resin material and the third resin material) are crushed, and the liquid second resin is filled in the gaps between the resin materials having the small pieces. Material flows smoothly. Thereby, the respective resin materials (the first resin material, the second resin material and the third resin material) are mixed with each other so as to form a marble tone. After that, each resin material is cured, so that a natural marble-like pattern close to natural marble is formed.

As described above, a molded article having a natural marbled appearance and a desired shape is prepared.

When BMC is used as a molding material, compared to a molded product using SMC or TMC, the strength is inferior at the same thickness. There is a method of reinforcing by spraying glass fiber and resin.

The molded article includes the cured product of the thermosetting resin composition described above and the reinforcing fibers described above.

Such molded articles are suitably used for various industrial products, and are particularly suitably used for products requiring excellent designability (highly designed products). Examples of highly designed products include plumbing products (bathtubs, washbasin counters, kitchen counters, kitchen sinks, bathroom unit washing areas, floors, ceilings, walls, bathtubs with washing areas, etc.), construction materials (e.g. wall materials, floor materials, etc.) ), automobile materials (for example, interior parts, etc.), and the like.

1-6. Effect In the above-described method for producing a marble-like molded article, after mixing the first resin material in the form of small pieces and the second resin material in the form of a liquid which is different in color and/or tone from the first resin material, , molding their resin mixture.

Therefore, when molding the resin mixture, the first resin material having a small piece shape and the second resin material having a liquid shape are mixed with each other so as to form a marble tone. As a result, although it is a simple method, it is possible to realize a natural marble tone close to that of natural marble in the molded product.

A first resin material is prepared by cutting from a first resin molding compound. Therefore, it is possible to smoothly prepare the first resin material having a predetermined shape and size.

The second resin material has a liquid state. Therefore, when molding the resin mixture, it smoothly flows into the gaps between the small pieces of the resin material. As a result, it is possible to more reliably realize a natural marble tone close to that of natural marble in the molded product.

In addition to the first resin material and the second resin material, the resin mixture is prepared by mixing a third resin material that is different in color and/or tone from the first resin material and has a small piece shape. Therefore, a more complicated marbled pattern can be imparted to the molded product.

The first resin material and the third resin material have different sizes. Therefore, it is possible to impart a more complicated marble-like pattern to the molded product.

<Second embodiment>
Next, a second embodiment of the invention will be described. In the second embodiment, the second resin material has a piece shape. In addition, the detailed description of the steps similar to those of the above-described first embodiment will be omitted.

The second resin material having the shape of small pieces is the same as the first resin material except that it differs from the first resin material in color and/or tone.

In order to prepare the second resin material having the shape of small pieces, for example, first, the second resin molding compound is prepared in the same manner as the molding compound preparation step.

The second resin molding compound is similar to the first resin molding compound, except for color and/or tone. In other words, the second resin molding compound is the same as the first resin molding compound except that the first coloring agent is changed to the second coloring agent described above.

Next, a second resin material having a small piece shape is cut out from the second resin molding compound by a known cutting method.

Thereby, the second resin material having the shape of small pieces is prepared.

The shape of each second resin material is a small piece shape, and more specifically, a cubic shape (dice shape), a rectangular parallelepiped shape, a columnar shape, a prismatic shape, a spherical shape, a random shape, etc. can be mentioned. A cubic shape (dice shape), a rectangular parallelepiped shape, and a columnar shape are mentioned.

The size of the second resin material may be the same as or different from the size of the first resin material.

The maximum dimension of each second resin material is, for example, 1 time or more, preferably 5 times or more, for example, 500 times or less, preferably 100 times or less, with respect to the maximum dimension of each first resin material. More preferably, it is 50 times or less. Specifically, the maximum dimension of each second resin material is, for example, 1 mm or more, preferably 5 mm or more, and for example, 500 mm or less, preferably 100 mm or less, and more preferably 50 mm or less.

The mass of one cut second resin material is, for example, 0.01 g or more, preferably 2 g or more, for example, 30 kg or less, preferably 3 kg or less, and more preferably 300 g or less. In addition, the above-described mass does not restrict the present invention.

If the sizes of the first resin material and the second resin material are different from each other, it is possible to reliably impart a marble-like pattern close to that of natural marble to the molded product.

In the second embodiment, a resin mixture is prepared by dry-mixing the second resin material having the shape of small pieces and the above-described first resin material (preparation step).

The mixing ratio of the second resin material is, for example, 1 part by mass or more, preferably 10 parts by mass or more, for example 5000 parts by mass or less, preferably 1000 parts by mass or less with respect to 100 parts by mass of the first resin material. be.

Next, the resin mixture is cured and molded under the molding conditions described above (molding step).

As a result, the small pieces of the first resin material and the small pieces of the second resin material are crushed and mixed with each other to form a marble pattern. After that, each resin material (the first resin material and the second resin material) is cured, so that a natural marble-like pattern close to natural marble is formed.

As described above, a molded article having a natural marbled appearance and a desired shape is prepared.

Therefore, also in the second embodiment, it is possible to achieve the same effects as in the first embodiment.

<Molding material>
Next, one embodiment of the molding material of the present invention will be described. In the description of the molding material, detailed descriptions of members similar to those of the first embodiment and/or the second embodiment of the method for manufacturing a marble-like molded product will be omitted.

The molding material is a molding material used in the above-described method for producing a marble-like molded product, and includes the above-described first resin material and the above-described second resin material.

The molding material may be a resin mixture obtained by mixing the above-described first resin material and the above-described second resin material by the above-described mixing method. It may be a separately provided kit.

Further, the molding material preferably includes the above-described third resin material in addition to the above-described first resin material and the above-described second resin material.

In this case, the molding material may be a resin mixture obtained by mixing the above-described first resin material to the above-described third resin material by the above-described mixing method, and the above-described first resin material and the above-described second resin material. , and the third resin material described above separately.

Furthermore, the molding material may be a kit separately comprising a mixture of the first resin material and the third resin material, and the second resin material. A kit may separately include the mixture of the second resin material and the third resin material described above, and the mixture of the second resin material and the third resin material described above and the first resin material described above may be used. may be a kit separately provided.

These molding materials include at least a first resin material having the shape of small pieces and a second resin material having a color and/or tone different from that of the first resin material and having the shape of liquid or small pieces. It further comprises a third resin material having a flake shape.

Therefore, it can be suitably used in the above-described method for producing a marble-like molded article, and can smoothly produce a molded article having a natural marble-like appearance close to that of natural marble.

<Modification>
In the first embodiment described above, the resin mixture is prepared by mixing the first resin material in the form of small pieces, the second resin material in the form of liquid, and the third resin material in the form of small pieces. The mixture is not limited to this.

The resin mixture may be prepared by mixing only the small piece-like first resin material and the liquid second resin material, and in addition to the small piece-like first resin material and the liquid second resin material, , may be prepared by further mixing a liquid resin material. Furthermore, the resin mixture may be prepared by further mixing other resin materials in the form of small pieces or liquid in addition to the first to third resin materials.

In the first embodiment and the second embodiment described above, the resin material having a small piece shape (the first resin material and the third resin material in the first embodiment, the first resin material and the second resin material in the second embodiment) ) is prepared by cutting out from the resin molding compound, but the preparation process of the resin material having a small piece shape is not limited to this.

For example, the above-described thermosetting resin composition and the above-described reinforcing fibers may be supplied to a known kneader, and the resin material having the shape of small pieces may be discharged directly from the kneader.

Although only the resin mixture is molded in the above-described first and second embodiments, the molding process is not limited to this. For example, the resin mixture may be placed on the SMC, and the resin mixture and the SMC may be collectively press-molded.

These modifications can also provide the same effects as the first and second embodiments described above.

Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical properties, parameters, etc. can. In the description below, "parts" and "%" are based on mass unless otherwise specified.

Example 1
<Preparation of first resin material>
A flask equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser and a stirrer was used as a reactor. Into this reactor, 2.0 mol of isophthalic acid, 5.5 mol of propylene glycol, and 5.0 mol of neopentyl glycol were charged and polycondensed at a temperature of 200 to 210° C. while stirring in a nitrogen gas atmosphere. When the acid value reaches 10 mgKOH/g, the mixture is cooled to 150°C, charged with 8.0 mol of maleic anhydride, and reacted again at 210 to 220°C until the acid value reaches 27.0 mgKOH/g, and unsaturated. A polyester was prepared.

Next, 40 parts by mass of unsaturated polyester and 40 parts by mass of styrene were mixed to prepare a first unsaturated polyester resin.

Next, 80 parts by mass of the first unsaturated polyester resin, 15 parts by mass of crosslinked polystyrene (low shrinkage agent), 1.0 parts by mass of t-butyl peroxyisopropyl monocarbonate (curing agent), and parabenzoquinone (polymerization inhibition agent) 0.05 parts by mass, aluminum hydroxide (filler) 250 parts by mass, zinc stearate (release agent) 5 parts by mass, and black toner (first coloring agent, polyester toner having carbon black) 5 Parts by mass were mixed to prepare a thermosetting resin composition.

Next, 1.0 parts by mass of magnesium oxide (thickener) was added to the thermosetting resin composition, and then 40 parts by mass of chopped glass obtained by continuously cutting glass fiber rovings into 3 mm pieces was added. By mixing with a BMC kneader, 5 kg of block unit BMC (molding material) was prepared.

Next, from the BMC, a plurality of pieces of the first resin material were cut out. The first resin material had a cubic shape (dice shape) with a side of 5 mm.

<Preparation of second resin material>
A second unsaturated polyester resin was prepared by mixing 40 parts by mass of the unsaturated polyester prepared in the same manner as above and 120 parts by mass of styrene.

Then, 160 parts by mass of the second unsaturated polyester resin, 1.0 parts by mass of t-butyl peroxyisopropyl monocarbonate (curing agent), 0.008 parts by mass of hydroquinone (polymerization inhibitor), aluminum hydroxide (filling Material) 100 parts by mass, zinc stearate (releasing agent) 5 parts by mass, and white toner (second colorant, polyester toner having titanium white) 5 parts by mass are mixed to form a liquid second toner. A resin material was prepared.

<Preparation of the third resin material>
A third resin material having small pieces was prepared in the same manner as the first resin material described above, except that the black toner (first coloring agent) was changed to a white toner (third coloring agent).

The third resin material had a cubic shape (dice shape) with one side of 25 mm.

<Preparation of resin mixture>
Next, 100 parts by mass of the first resin material having the shape of small pieces and 700 parts by mass of the third resin material having the shape of small pieces are dry-mixed, and the mixed first resin material and the third resin material are added in a liquid state. was sprayed with 15 parts by mass of the second resin material having As a result, the second resin material was applied to the surfaces of the first resin material and the third resin material. A resin mixture was prepared as described above.

<Preparation of molded article>
Next, after placing the resin mixture on the first flat plate mold (lower mold, 300 mm square), the second flat plate mold (upper mold, 300 mm square) is moved toward the first flat mold, and the first The resin mixture is sandwiched between the flat plate mold and the second flat plate mold, and the resin mixture is cured and molded under the following conditions: molding temperature: upper mold/lower mold = 145°C/130°C; molding pressure: surface pressure: 10MPa; molding time: 6 minutes. bottom.

As described above, a 300 mm square flat plate molded article was prepared.

The flat plate molded article had a natural marble-like pattern close to that of natural marble. FIG. 1 shows a photograph of the flat plate molded product in a plan view.

Comparative example 1
<Preparation of first resin material>
A first resin material was prepared in the same manner as described above. The first resin material had a cubic shape (dice shape) with one side of 25 mm.

<Preparation of second resin material>
A second resin material having small pieces was prepared in the same manner as the first resin material described above, except that the black toner (first coloring agent) was changed to a white toner (second coloring agent).

The second resin material had a cubic shape (dice shape) with a side of 25 mm.

<Preparation of resin mixture>
Next, 400 parts by mass of the first resin material having the shape of small pieces and 400 parts by mass of the second resin material having the shape of small pieces were dry-mixed to prepare a resin mixture.

<Preparation of molded article>
Next, the resin mixture was cured and molded in the same manner as in the preparation of the molded article described above to prepare a 300 mm square flat plate molded article.

The flat plate molded article had a natural marble-like pattern close to that of natural marble. FIG. 2 shows a photograph of the flat plate molded product in plan view.

Claims (4)

preparing a first resin material having a small piece shape;
a step of preparing a second resin material that is different in color and/or color tone from the first resin material and has a liquid state ;
mixing the first resin material and the second resin material to prepare a resin mixture;
Curing and molding the resin mixture,
In the step of preparing the resin mixture, the second resin material is sprayed onto the first resin material, or the surface of the first resin material is coated with the second resin material;
In the step of molding the resin mixture, the first resin material is crushed, and the second resin material having a liquid state flows into the gaps between the first resin materials to form a marble pattern. , are mixed with each other. The step of preparing the first resin material includes:
preparing a first resin molding compound comprising the first resin material;
2. The method for manufacturing a marble-like molded product according to claim 1, further comprising: cutting out the first resin material having a small piece shape from the first resin molding compound. Further comprising the step of preparing a third resin material that is different in color and/or color tone from the first resin material and has a small piece shape,
In the step of preparing the resin mixture, mixing the first resin material, the second resin material, and the third resin material;
In the step of molding the resin mixture, the first resin material and the third resin material are crushed, and the second resin having a liquid state is filled in the gap between the first resin material and the third resin material. 2. The method for producing a marbled molded article according to claim 1 , wherein the materials flow in and mix with each other to form a marbled look. 4. The method of manufacturing a marble-like molded product according to claim 3 , wherein the first resin material and the third resin material have different sizes.

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