Thermosetting resin composition, molding material and molded article

Abstract

To provide a thermosetting resin composition capable of giving a molded article excellent in pattern material discoloration resistance, a molding material containing the thermosetting resin composition, and a molded article obtained using the molding material.SOLUTION: The thermosetting resin composition contains a resin component, a pattern material, and a coupling agent. The resin component contains: at least one selected from the group consisting of an unsaturated polyester, a vinyl ester, and a (meth)acrylic polymer; and a polymerizable monomer. The pattern material has a metal-containing layer containing a metal, and a silica-based film covering the metal-containing layer.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a thermosetting resin composition, a molding material, and a molded article. [Background technology]

[0002] It has been known to add a luster pigment to a thermosetting resin composition. Examples of molded articles made from such thermosetting resin compositions include artificial marble. Examples of luster pigments include inorganic fillers coated on metals.

[0003] More specifically, the following bright pigment is known as a bright pigment. In this bright pigment, the surface of a glass flake is coated with a coating layer containing a metal. The coating layer is further coated with a silica coating containing an inorganic pigment (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-176741 Summary of the Invention [Problem to be solved by the invention]

[0005] However, molded articles of thermosetting resin compositions containing the above-mentioned luster pigments have poor discoloration resistance of the pattern material (hereinafter referred to as "pattern material discoloration resistance"). More specifically, when molded articles of thermosetting resin compositions are used as artificial marble, the molded articles may be washed with chlorine-based detergents. In such cases, the metal contained in the luster pigment is converted into a chloride by the chlorine-based detergent, causing discoloration. As a result, the pattern material in the molded article of the thermosetting resin composition discolors.

[0006] The present invention relates to a thermosetting resin composition capable of producing a molded article having excellent resistance to discoloration of a handle material, a molding material containing the thermosetting resin composition, and a molded article obtained using the molding material. [Means for solving the problem]

[0007] The present invention [1] is a thermosetting resin composition comprising a resin component, a handle material, and a coupling agent, wherein the resin component comprises at least one selected from the group consisting of unsaturated polyester, vinyl ester, and (meth)acrylic polymer, and a polymerizable monomer, and the handle material comprises a thermosetting resin composition having a metal-containing layer containing metal and a silica-based coating coating the metal-containing layer.

[0008] The present invention [2] includes the thermosetting resin composition according to the above [1], wherein the coupling agent contains at least one selected from the group consisting of a silane-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent.

[0009] The present invention [3] includes the thermosetting resin composition according to the above [1] or [2], in which the content ratio of the coupling agent per 1 part by mass of the handle material is 0.030 parts by mass or more.

[0010] The present invention [4] includes a molding material containing the thermosetting resin composition according to any one of the above [1] to [3] and reinforcing fibers.

[0011] The present invention [5] includes a molded article made from a cured product of the molding material described in [4] above.

[0012] The present invention [6] includes the molded article according to the above [5], which is an artificial marble. [Effects of the Invention]

[0013] In the thermosetting resin composition of the present invention, the handle material has a metal-containing layer containing a metal and a silica-based coating coating the metal-containing layer. The thermosetting resin composition also contains a coupling agent. Therefore, the silica-based coating of the handle material is reinforced by the coupling agent, allowing for more reliable coating of the metal-containing layer. As a result, the thermosetting resin composition of the present invention can inhibit metal chloride and discoloration, providing the handle material with excellent discoloration resistance.

[0014] The molding material of the present invention contains the above-mentioned thermosetting resin composition, and therefore has excellent resistance to discoloration of the pattern material.

[0015] The molded article of the present invention is made from the cured product of the molding material described above, and therefore has excellent resistance to discoloration of the pattern material. DETAILED DESCRIPTION OF THE INVENTION

[0016] The thermosetting resin composition of the present invention contains, as essential components, a resin component, a handle material, and a coupling agent.

[0017] The resin component contains, as essential components, a thermosetting resin (polymer component) and a polymerizable monomer (monomer component). The resin component may also contain, as an optional component, a low-profile agent (described below).

[0018] Examples of the thermosetting resin (polymer component) include unsaturated polyester, vinyl ester, and (meth)acrylic polymer. That is, the thermosetting resin contains at least one selected from the group consisting of unsaturated polyester, vinyl ester, and (meth)acrylic polymer.

[0019] Unsaturated polyesters are the polymerization products of polybasic acids and polyhydric alcohols.

[0020] The polybasic acid includes, for example, a polybasic acid having an ethylenically unsaturated double bond (hereinafter referred to as an unsaturated polybasic acid), and preferably further includes a polybasic acid not having an ethylenically unsaturated double bond (hereinafter referred to as a saturated polybasic acid).

[0021] Examples of unsaturated polybasic acids include maleic acid, fumaric acid, and itaconic acid. Also included in the unsaturated polybasic acids are acid anhydrides derived from ethylenically unsaturated aliphatic dibasic acids. Examples of such acid anhydrides include maleic anhydride and itaconic anhydride. Preferred examples of unsaturated polybasic acids include maleic anhydride and fumaric acid, and more preferred examples include fumaric acid.

[0022] Examples of saturated polybasic acids include saturated aliphatic polybasic acids, saturated alicyclic polybasic acids, and aromatic polybasic acids, as well as their anhydrides and halides.

[0023] Examples of saturated aliphatic polybasic acids include saturated aliphatic dibasic acids. Examples of saturated aliphatic dibasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and dimer acid. Saturated aliphatic polybasic acids also include acid anhydrides derived from the above saturated aliphatic dibasic acids. Examples of acid anhydrides include oxalic anhydride and succinic anhydride.

[0024] Examples of saturated alicyclic polybasic acids include saturated alicyclic dibasic acids. Examples of saturated alicyclic dibasic acids include HET acid, 1,2-hexahydrophthalic acid, 1,1-cyclobutanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Saturated alicyclic polybasic acids also include acid anhydrides derived from the above saturated alicyclic dibasic acids. Examples of acid anhydrides include HET acid anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and 4-methylhexahydrophthalic anhydride.

[0025] Examples of aromatic polybasic acids include orthophthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. Also included in the aromatic polybasic acids are acid anhydrides derived from the above aromatic dibasic acids. Examples of acid anhydrides include phthalic anhydride, trimellitic anhydride, and pyromellitic anhydride.

[0026] The saturated polybasic acid is preferably an aromatic saturated polybasic acid, more preferably an aromatic saturated dibasic acid, even more preferably phthalic acid, and particularly preferably isophthalic acid.

[0027] The polybasic acids can be used alone or in combination of two or more. When an unsaturated polybasic acid and a saturated polybasic acid are used in combination, the blending ratio of the unsaturated polybasic acid to the polybasic acids (total amount thereof) is, for example, 50 mol % or more, preferably 70 mol % or more, and, for example, 100 mol % or less.

[0028] Examples of polyhydric alcohols include dihydric alcohols and trihydric alcohols. Examples of dihydric alcohols include aliphatic diols, alicyclic diols, and aromatic diols. Examples of aliphatic diols include alkanediols and ether diols. Examples of alkanediols include ethylene glycol, propylene glycol (1,2- or 1,3-propanediol or a mixture thereof), butylene glycol (1,2-, 1,3-, or 1,4-butylene glycol or a mixture thereof), 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, and 3,3-dimethylolheptane. Examples of ether diols include diethylene glycol, triethylene glycol, and dipropylene glycol. Examples of alicyclic diols include cyclohexanediol, cyclohexanedimethanol, cyclohexanediethanol, and hydrogenated bisphenol A. Examples of aromatic diols include an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A. Examples of trihydric alcohols include glycerin, trimethylolpropane, and triisopropanolamine. The polyhydric alcohols can be used alone or in combination of two or more. Preferred examples of the polyhydric alcohol include propylene glycol, neopentyl glycol, hydrogenated bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A, more preferred examples include hydrogenated bisphenol A, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A, and particularly preferred examples include hydrogenated bisphenol A. When the polyhydric alcohol used as a raw material component of the unsaturated polyester contains hydrogenated bisphenol A, molded articles of the thermosetting resin composition containing the unsaturated polyester have particularly excellent pattern discoloration resistance.

[0029] Unsaturated polyesters are obtained by polycondensation (condensation polymerization) of polybasic acids and polyhydric alcohols.

[0030] To polycondense (condensation polymerization) a polybasic acid and a polyhydric alcohol, they are mixed in an appropriate ratio and reacted under normal pressure in a nitrogen atmosphere. The equivalent ratio of the polyhydric alcohol to the polybasic acid (hydroxyl groups of the polyhydric alcohol / carboxyl groups of the polybasic acid) is, for example, 1.2 or less, preferably 1.1 or less. The reaction temperature is, for example, 150°C or more, preferably 190°C or more. The reaction temperature is, for example, 250°C or less, preferably 230°C or less. In the above reaction, known solvents and known catalysts can also be added as necessary. This results in an unsaturated polyester.

[0031] The acid value of the unsaturated polyester (measurement method: in accordance with JIS K6901 (2008)) is, for example, 10 mgKOH / g or more, preferably 20 mgKOH / g or more, and, for example, less than 50 mgKOH / g, preferably 40 mgKOH / g or less.

[0032] The unsaturated polyesters can be used alone or in combination of two or more kinds.

[0033] Vinyl esters are the reaction products of epoxy resins and unsaturated monobasic acids.

[0034] Examples of the epoxy resin include bisphenol-type epoxy resin and novolac-type epoxy resin, and preferably, the epoxy resin is bisphenol-type epoxy resin.

[0035] The bisphenol-type epoxy resin is represented by the following general formula (1). [ka] (In the formula, Y1 represents any one of -C(CH3)2-, -CH2-, -O-, -S-, and -(O=S=O)-, and n represents an integer of 0 to 5.)

[0036] Examples of bisphenol type epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins. As the bisphenol type epoxy resins, preferably, bisphenol A type epoxy resins are used.

[0037] Epoxy resins can also be modified with phenolic compounds, such as bisphenol A, bisphenol F, and bisphenol S.

[0038] To modify an epoxy resin with a phenolic compound, the epoxy resin is reacted with the phenolic compound. The blending ratio of the phenolic compound is, for example, 0.1 mol or more, preferably 0.2 mol or more, per mol of the epoxy resin. The blending ratio of the phenolic compound is, for example, 0.5 mol or less, per mol of the epoxy resin. The reaction temperature is, for example, 100°C or more, preferably 130°C or more. The reaction temperature is, for example, 180°C or less.

[0039] In addition, a catalyst can be added to the above reaction if necessary. Examples of catalysts include amines, ammonium salts, imidazoles, phosphines, phosphonium salts, and organic metal salts. Examples of amines include triethylamine and benzyldimethylamine. Examples of ammonium salts include tetramethylammonium chloride and triethylbenzylammonium chloride. Examples of imidazoles include 2-ethyl-4-imidazole. Examples of phosphines include triphenylphosphine. Examples of phosphonium salts include tetraphenylphosphonium bromide and ethyltriphenylphosphonium bromide. Examples of organic metal salts include zinc octylate. Examples of catalysts further include amides, pyridines, sulfonium salts, and sulfonic acids. Preferred examples of catalysts include ammonium salts and phosphonium salts, and more preferred examples include triethylbenzylammonium chloride and tetraphenylphosphonium bromide. The catalysts can be used alone or in combination of two or more.

[0040] The catalyst is added in an amount of, for example, 0.1 parts by mass or more, and preferably 3 parts by mass or less, and preferably 1 part by mass or less, per 100 parts by mass of the phenol compound.

[0041] This allows the epoxy resin to be modified with the phenol compound.

[0042] The epoxy resins can be used alone or in combination of two or more.

[0043] The epoxy equivalent of the epoxy resin is, for example, 200 g equivalents or more, preferably 250 g equivalents or more, and for example, 550 g equivalents or less, preferably 500 g equivalents or less.

[0044] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, cinnamic acid, and sorbic acid. (Meth)acrylic is synonymous with methacrylic and / or acrylic. The unsaturated monobasic acids can be used alone or in combination of two or more. As the unsaturated monobasic acid, preferably (meth)acrylic acid is used, and more preferably methacrylic acid is used.

[0045] To obtain a vinyl ester, the above-mentioned epoxy resin or an epoxy resin and a phenol compound-modified epoxy resin are subjected to an addition reaction with an unsaturated monobasic acid. The equivalent weight of the carboxyl group of the unsaturated monobasic acid relative to the epoxy group of the epoxy resin is, for example, 0.8 or more, preferably 0.9 or more. The equivalent weight of the carboxyl group of the unsaturated monobasic acid relative to the epoxy group of the epoxy resin is, for example, 1.5 or less, preferably 1.1 or less. The reaction temperature is, for example, 80°C or more, preferably 100°C or more. The reaction temperature is, for example, 150°C or less, preferably 130°C or less.

[0046] In the above reaction, if necessary, a known solvent and a known catalyst (for example, the above-mentioned catalyst (preferably an ammonium salt, more preferably triethylbenzylammonium chloride)) can be blended. In addition, the above reaction is preferably carried out in the presence of a polymerization inhibitor.

[0047] Examples of polymerization inhibitors include hydroquinone compounds, benzoquinone compounds, phenol compounds, and N-oxyl compounds. Examples of hydroquinone compounds include hydroquinone, methylhydroquinone, and t-butylhydroquinone. Examples of benzoquinone compounds include p-benzoquinone and methyl-p-benzoquinone. Examples of catechol compounds include t-butylcatechol. Examples of phenol compounds include 2,6-di-t-butyl-4-methylphenol and 4-methoxyphenol. Examples of N-oxyl compounds include 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-ol, 4-hydroxy-2,2,6,6-tetrapiperidine-1-oxyl, and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. The polymerization inhibitors can be used alone or in combination. As the polymerization inhibitor, preferably, a hydroquinone compound is used, and more preferably, hydroquinone is used.

[0048] The mixing ratio of the polymerization inhibitor relative to 100 parts by mass of the epoxy resin is, for example, 0.005 parts by mass or more, preferably 0.01 parts by mass or more, and for example, 0.05 parts by mass or less, preferably 0.03 parts by mass or less.

[0049] This gives a vinyl ester.

[0050] Vinyl esters can also be modified with acid anhydrides. That is, vinyl esters may be vinyl esters modified with acid anhydrides (hereinafter referred to as acid-modified vinyl esters) or vinyl esters that are not modified with acid anhydrides (hereinafter referred to as unmodified vinyl esters).

[0051] The acid-modified vinyl ester is a reaction product of a vinyl ester and an acid anhydride. Examples of the acid anhydride include maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride. A preferred example of the acid anhydride is maleic anhydride.

[0052] The proportion of the acid anhydride relative to the hydroxyl groups in the vinyl ester is, for example, 10% or more, preferably 20% or more. The proportion of the acid anhydride relative to the hydroxyl groups in the vinyl ester is, for example, 80% or less, preferably 50% or less. The reaction temperature is, for example, 60°C or more, and, for example, 100°C or less.

[0053] This gives an acid-modified vinyl ester.

[0054] The acid value of the acid-modified vinyl ester (measured according to JIS K6901 (2008)) is, for example, 40 mgKOH / g or more, preferably 50 mgKOH / g or more, and, for example, 100 mgKOH / g or less, preferably 90 mgKOH / g or less.

[0055] The unmodified vinyl ester has an acid value of, for example, 1 mgKOH / g or more, preferably 5 mgKOH / g or more, and for example, 20 mgKOH / g or less, preferably 10 mgKOH / g or less.

[0056] The vinyl esters can be used alone or in combination of two or more. Preferred examples of the vinyl esters include acid-modified vinyl esters.

[0057] Examples of the (meth)acrylic polymer include poly(meth)acrylate and acid-modified poly(meth)acrylate.

[0058] Poly(meth)acrylates are polymerization products of (meth)acrylates, including, for example, mono(meth)acrylates having one (meth)acryloyl group and polyfunctional (meth)acrylates having two or more (meth)acryloyl groups.

[0059] Examples of mono(meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, alkyl (meth)acrylate (having 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 Examples of the mono(meth)acrylate include hydroxyethyl, hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, methyl chloride salt of dimethylaminoethyl (meth)acrylate, benzyl chloride salt of dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, heptadecafluorodecyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. Also, such mono(meth)acrylate may be copolymerized with styrene.

[0060] Examples of polyfunctional (meth)acrylates include alkane glycol di(meth)acrylate and polyoxyalkylene di(meth)acrylate. Examples of alkane glycol di(meth)acrylate include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and neopentyl glycol di(meth)acrylate. Examples of polyoxyalkylene di(meth)acrylate include diethylene glycol di(meth)acrylate and triethylene glycol di(meth)acrylate.

[0061] The (meth)acrylates can be used alone or in combination of two or more. As the (meth)acrylate, preferably, mono(meth)acrylate is used, and more preferably, methyl (meth)acrylate is used.

[0062] The poly(meth)acrylate is prepared, for example, by polymerizing the above-mentioned (meth)acrylate under known reaction conditions.

[0063] Acid-modified poly(meth)acrylates can be obtained, for example, by copolymerizing the addition reaction product obtained by the addition reaction of a hydroxyl group-containing vinyl monomer with an acid anhydride with the above-mentioned (meth)acrylate. Acid-modified poly(meth)acrylates can also be obtained by addition reaction of an acid anhydride with a copolymer of the above-mentioned hydroxyl group-containing vinyl monomer with the above-mentioned (meth)acrylate. Examples of hydroxyl group-containing vinyl monomers include hydroxymethyl methacrylate, hydroxymethyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, hydroxybutyl methacrylate, and hydroxybutyl acrylate. Examples of acid anhydrides include aromatic acid anhydrides, alicyclic acid anhydrides, and aliphatic acid anhydrides. More specifically, examples include maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, succinic anhydride, cyclohexanedicarboxylic anhydride, and cyclopentanedicarboxylic anhydride. Acid-modified poly(meth)acrylate can also be obtained as a copolymer of an unsaturated acid and the above (meth)acrylate. Examples of unsaturated acids include maleic acid, fumaric acid, and (meth)acrylic acid.

[0064] The (meth)acrylic polymer can be used alone or in combination of two or more kinds. As the (meth)acrylic polymer, preferably, an acid-modified poly(meth)acrylate is used, more preferably, a copolymer of an addition reaction product of a hydroxyl group-containing vinyl monomer and an acid anhydride, and a (meth)acrylate, and particularly preferably, a copolymer of an addition reaction product of hydroxymethyl methacrylate and phthalic anhydride, and a methyl (meth)acrylate.

[0065] These thermosetting resins can be used alone or in combination of two or more kinds.

[0066] Examples of the polymerizable monomer include styrene-based monomers and (meth)acrylates. Examples of the styrene-based monomer include styrene, α-methylstyrene, α-ethylstyrene, vinyltoluene, t-butylstyrene, and chlorostyrene. Examples of the (meth)acrylate include the above-mentioned (meth)acrylates.

[0067] The polymerizable monomers can be used alone or in combination of two or more, and are appropriately selected depending on the type of thermosetting resin (unsaturated polyester, vinyl ester, and (meth)acrylic polymer).

[0068] Specifically, when an unsaturated polyester or vinyl ester is used as the thermosetting resin, the polymerizable monomer is preferably a styrene-based monomer, more preferably styrene. When a (meth)acrylic polymer is used as the thermosetting resin, the polymerizable monomer is preferably a (meth)acrylate, more preferably methyl methacrylate.

[0069] The blending ratio of the polymerizable monomer is, for example, 30 parts by mass or more and, for example, 60 parts by mass or less, relative to 100 parts by mass of the total amount of the thermosetting resin (polymer component) and the polymerizable monomer (monomer component).

[0070] The resin component may contain a low-profile agent as an optional component. Examples of low-profile agents include polyvinyl acetate, poly(meth)acrylate resin, cellulose ester resin, polystyrene, cross-linked polystyrene, polyethylene, polyvinyl acetate-polystyrene block copolymer, SBS (rubber), SEPS (rubber), and saturated polyester resin. Among the low-profile agents, preferred are polystyrene, cross-linked polystyrene, polyethylene, and polyvinyl acetate-polystyrene block copolymer, and more preferred are polystyrene and cross-linked polystyrene. The low-profile agents may be used alone or in combination of two or more.

[0071] The low shrinkage agent may be dissolved in the polymerizable monomer as needed. That is, a solution of the low shrinkage agent may be added to the base composition. In the solution of the low shrinkage agent, the blending ratio of the polymerizable monomer (solvent) is, for example, 100 parts by mass or more and 250 parts by mass or less per 100 parts by mass of the low shrinkage agent.

[0072] The amount of the thermosetting resin is, for example, 25 parts by mass or more, preferably 30 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent). The amount of the thermosetting resin is, for example, 50 parts by mass or less, preferably 45 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent).

[0073] The amount of the polymerizable monomer is, for example, 40 parts by mass or more, preferably 45 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent). The amount of the polymerizable monomer is, for example, 75 parts by mass or less, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent).

[0074] The amount of the low shrinkage agent is, for example, 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low shrinkage agent).The amount of the low shrinkage agent is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin components (thermosetting resin, polymerizable monomer, and low shrinkage agent).

[0075] The content of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent) relative to 100 parts by mass of the total of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent), the handle material, and the coupling agent is, for example, 50 parts by mass or more, preferably 70 parts by mass or more. The content of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent) relative to 100 parts by mass of the total of the resin components (thermosetting resin, polymerizable monomer, and low-profile agent), the handle material, and the coupling agent is, for example, 99.9 parts by mass or less, preferably 99 parts by mass or less.

[0076] The pattern material is a filler for imparting luster to a molded product (described later). The pattern material has a substrate, a metal-containing layer containing a metal, and a silica-based coating coating the metal-containing layer.

[0077] The substrate is not particularly limited, but examples thereof include glass flakes, alumina flakes, silica flakes, mica flakes, and aluminum powder. These may be used alone or in combination of two or more. Preferably, the substrate is glass flakes.

[0078] The shape of the substrate is not particularly limited, and examples thereof include granular, block, plate, scale, needle, and spherical shapes. These may be used alone or in combination of two or more. The preferred shape of the substrate is scale.

[0079] These substrates can be used alone or in combination of two or more. From the viewpoint of improving the luster of a molded article (described later) and using the thermosetting resin composition for producing artificial marble (described later), preferably, the substrate is scaly glass flakes.

[0080] The size of the substrate is not particularly limited and is appropriately set depending on the material and shape of the substrate. For example, when the substrate is scaly, the average length is, for example, 1 μm or more, preferably 10 μm or more, and more preferably 30 μm or more. The average length is, for example, 500 μm or less, preferably 400 μm or less, and more preferably 300 μm or less. The average thickness is, for example, 0.1 μm or more and 30 μm or less. In particular, when excellent brilliance is required, the average thickness of the substrate is preferably 0.2 μm or more, and more preferably 0.5 μm or more. The average thickness of the substrate is preferably 15 μm or less, and more preferably 10 μm or less.

[0081] The metal-containing layer is a layer that coats the surface of the substrate and imparts brilliance and / or interference color to the substrate. The metal-containing layer contains a metal and / or a metal oxide, and preferably consists of a metal and / or a metal oxide. Examples of metals include gold, silver, platinum, palladium, copper, iron, aluminum, titanium, cobalt, nickel, and alloys thereof. Examples of metal oxides include oxides of the above metals. These can be used alone or in combination of two or more types.

[0082] The metal-containing layer is formed on the surface of the substrate by a known method. Examples of methods for forming the metal-containing layer include sputtering, sol-gel, electroless plating, and CVD. For example, when the substrate is a scaly glass flake, electroless plating is preferably used. Electroless plating can form a uniform metal-containing layer on the surface of the substrate. The film thickness of the metal-containing layer is not particularly limited and can be appropriately set depending on the purpose and application.

[0083] Substrates coated with a metal-containing layer are also commercially available. Examples of commercially available products include the Metashine (registered trademark) RS series, PS series, TY series, KY series, KB series, and GP series (all manufactured by Nippon Sheet Glass Co., Ltd.), the Paliocrom (registered trademark) series, Lumina (registered trademark) series, Firemist (registered trademark) series, Paliocrom (registered trademark) series, Glacier (registered trademark) series, Metasheen (registered trademark) series, Unique Black series, MagnaPearl (registered trademark) series, and Mearlin (registered trademark) series (all manufactured by BASF), the TWINCLEPEARL (registered trademark) series (manufactured by Nihon Koken Kogyo Co., Ltd.), the Biflair (registered trademark) series, Candurin (registered trademark) series, Colorstream (registered trademark) series, Iriodin (registered trademark) series, Meoxal (registered trademark) series, Miraval (registered trademark) series, Pyrisma (registered trademark) series, Spectraval (registered trademark) series, Thermaval (registered trademark) series, Xirallic (registered trademark) series, and the Sparkle (registered trademark) series (manufactured by Merck).

[0084] The silica-based coating is a protective layer for protecting the metal-containing layer. The silica-based coating contains silicon dioxide as an essential component. The silica-based coating may also contain other metal oxides as optional components. Examples of other metal oxides include titanium oxide and zirconium oxide. The silica-based coating may also contain known pigments as optional components. The content ratios of silicon dioxide, other metal oxides, and pigments in the silica-based coating are not particularly limited and may be appropriately determined depending on the purpose and application.

[0085] The silica-based coating is formed on the surface of the metal-containing layer by a known method. Examples of methods for forming the silica-based coating include the sol-gel method. For example, to form a silica-based coating containing a pigment, a solution of a silicon-containing organometallic compound capable of hydrolysis and polycondensation is first prepared. The substrate coated with the metal-containing layer is then dispersed in the solution, and the organometallic compound is hydrolyzed and polycondensed. The thickness of the silica-based coating is not particularly limited, but is, for example, 10 nm or more, preferably 50 nm or more. The thickness of the silica coating is, for example, 5 μm or less, preferably 1 μm or less.

[0086] Such pattern materials can be produced, for example, according to the method described in JP 2006-176741 A. Pattern materials are also available as commercially available products, such as the Metashine (registered trademark) PTSM series (manufactured by Nippon Sheet Glass Co., Ltd.), the Metashine (registered trademark) TC series (manufactured by Nippon Sheet Glass Co., Ltd.), and the Metashine (registered trademark) RC series (manufactured by Nippon Sheet Glass Co., Ltd.).

[0087] The content of the handle material is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total of the resin component, handle material, and coupling agent. The content of the handle material is, for example, 20.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the total of the resin component, handle material, and coupling agent.

[0088] The content of the pattern material is, for example, 0.01 part by mass or more, preferably 0.03 part by mass or more, more preferably 0.1 part by mass or more, per 100 parts by mass of the resin component. The content of the pattern material is, for example, 20.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, per 100 parts by mass of the resin component.

[0089] The content of the pattern material is, for example, 0.01 parts by mass or more, preferably 0.03 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total amount of the thermosetting resin composition. The content of the pattern material is, for example, 20.0 parts by mass or less, preferably 10.0 parts by mass or less, more preferably 5.0 parts by mass or less, and even more preferably 3.0 parts by mass or less, relative to 100 parts by mass of the total amount of the thermosetting resin composition.

[0090] The coupling agent is a reinforcing agent that reinforces the silica-based coating of the handle material. Examples of coupling agents include silane-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, and zirconium-based coupling agents. The coupling agent preferably contains at least one selected from the group consisting of silane-based coupling agents, titanium-based coupling agents, aluminum-based coupling agents, and zirconium-based coupling agents.

[0091] Examples of silane coupling agents include epoxy silane, amino silane, (meth)acrylic silane, isocyanato silane, vinyl silane, and chloro silane.

[0092] Examples of epoxy silanes include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and di(γ-glycidoxypropyl)dimethoxysilane. Examples of amino silanes include N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-propylmethyldimethoxysilane, n-(dimethoxymethylsilylpropyl)ethylenediamine, n-(triethoxysilylpropyl)ethylenediamine, and N-phenyl-γ-aminopropyltrimethoxysilane. Examples of (meth)acrylsilanes include 3-(meth)acryloxypropyltrimethoxysilane, 3-(meth)acryloxypropylmethyldimethoxysilane, 3-(meth)acryloxypropyltriethoxysilane, and (meth)acryloxypropylmethyldiethoxysilane. Examples of isocyanatosilanes include γ-isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane. Examples of vinylsilanes include vinyltriethoxysilane. Examples of chlorosilanes include vinyltrichlorosilane. These can be used alone or in combination of two or more.

[0093] Examples of titanium-based coupling agents include isopropyl(N-ethylaminoethylamino)titanate, isopropyl triisostearoyl titanate, titanium di(dioctylpyrophosphate)oxyacetate, tetraisopropyl di(dioctylphosphite)titanate, and neoalkoxytri(pN-(β-aminoethyl)aminophenyl)titanate. These can be used alone or in combination of two or more.

[0094] Examples of aluminum coupling agents include ethyl acetoaluminum diisopropylate, alkyl acetoacetate aluminum diisopropylate, Al-acetylacetonate, Al-methacrylate, and Al-propionate. These can be used alone or in combination of two or more.

[0095] Examples of zirconium-based coupling agents include Zr-acetylacetonate, Zr-methacrylate, Zr-propionate, neoalkoxyzirconate, neoalkoxytrisneodecanoylzirconate, neoalkoxytris(dodecanoyl)benzenesulfonylzirconate, neoalkoxytris(ethylenediaminoethyl)zirconate, neoalkoxytris(m-aminophenyl)zirconate, and ammonium zirconium carbonate. These can be used alone or in combination of two or more.

[0096] The coupling agent is not limited to the above, and any known coupling agent can be appropriately selected and used.

[0097] The coupling agent can be used alone or in combination of two or more. From the viewpoint of reinforcing the silica-based coating, the coupling agent preferably includes a silane-based coupling agent, a titanium-based coupling agent, and an aluminum-based coupling agent, more preferably a silane-based coupling agent and a titanium-based coupling agent, even more preferably a silane-based coupling agent, particularly preferably a (meth)acrylsilane, and more preferably 3-(meth)acryloxypropyltrimethoxysilane. Here, (meth)acryl refers to acryl and / or methacryl.

[0098] The content of the coupling agent is, for example, 0.01 parts by mass or more, preferably 0.1 parts by mass or more, relative to 100 parts by mass of the total of the resin component, the handle material, and the coupling agent. The content of the coupling agent is, for example, 10.0 parts by mass or less, preferably 5.0 parts by mass or less, relative to 100 parts by mass of the total of the resin component, the handle material, and the coupling agent.

[0099] The content of the coupling agent relative to 100 parts by mass of the resin component is, for example, 0.01 part by mass or more, or preferably 0.1 part by mass or more, and for example, 10.0 parts by mass or less, or preferably 5.0 parts by mass or less.

[0100] From the viewpoint of the discoloration resistance of the pattern material, the content of the coupling agent is, for example, 0.010 parts by mass or more, preferably 0.030 parts by mass or more, more preferably 0.30 parts by mass or more, even more preferably 1.0 parts by mass or more, and particularly preferably 3.0 parts by mass or more, per part by mass of the pattern material. The content of the coupling agent is, for example, 10.0 parts by mass or less, preferably 8.0 parts by mass or less, more preferably 5.0 parts by mass or less, per part by mass of the pattern material.

[0101] When the blending ratio of the coupling agent is within the above range, the silica-based coating can be more effectively reinforced by the coupling agent. In other words, the metal-containing layer can be more reliably protected by the silica-based coating. Therefore, when the blending ratio of the coupling agent is within the above range, chloride and discoloration of the metal in the handle material can be more effectively suppressed, and excellent discoloration resistance of the handle material can be obtained.

[0102] The thermosetting resin composition may also contain additives as optional components, such as polymerization inhibitors, curing agents, release agents, fillers (excluding handle materials), colorants, thickeners, wetting and dispersing agents, anti-separation agents, and flame retardants.

[0103] Examples of the polymerization inhibitor include the above-mentioned polymerization inhibitors, preferably a benzoquinone compound, more preferably p-benzoquinone.

[0104] The mixing ratio of the polymerization inhibitor relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer is, for example, 0.01 parts by mass or more, and for example, 5 parts by mass or less, preferably 1 part by mass or less.

[0105] Examples of curing agents include peroxides, such as benzoyl peroxide, t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, 1,1-bis(t-butylperoxy)cyclohexane, t-butylperoxy-2-ethylhexanoate, amylperoxy-2-ethylhexanoate, 2-ethylhexylperoxy-2-ethylhexanoate, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-hexylperoxyacetate, and t-hexylperoxy-2-ethylhexanoate. The peroxide preferably includes peroxyisopropyl monocarbonate, more specifically t-butylperoxyisopropyl monocarbonate, t-amylperoxyisopropyl monocarbonate, and t-hexylperoxyisopropyl monocarbonate.The peroxide preferably includes t-butylperoxybenzoate, t-hexylperoxybenzoate, and t-hexylperoxy-2-ethylhexanoate.

[0106] The curing agent can be used alone or in combination of two or more kinds. The blending ratio of the curing agent relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer is, for example, 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and for example, 5 parts by mass or less, preferably 3 parts by mass or less.

[0107] Examples of the release agent include fatty acids and fatty acid metal salts. Examples of the fatty acids include stearic acid and lauric acid. Examples of the fatty acid metal salts include zinc stearate and calcium stearate. Examples of the release agent include paraffin, liquid wax, fluoropolymer, silicon-based polymer, and alkylammonium salt. Examples of the release agent include fatty acid metal salts, and more preferably zinc stearate.

[0108] The release agent can be used alone or in combination of two or more. The blending ratio of the release agent 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, relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0109] Examples of fillers (excluding handle materials) include inorganic fillers. Examples of inorganic fillers include oxides, hydroxides, carbonates, sulfates, silica, glass powder, hollow fillers, silicates, fluorides, phosphates, and clay minerals. Examples of oxides include alumina and titania. Examples of hydroxides include magnesium hydroxide and aluminum hydroxide. Examples of carbonates include calcium carbonate. Examples of sulfates include barium sulfate. Examples of silicas include crystalline silica, fused silica, fumed silica, and dry silica (Aerosil). Examples of hollow fillers include glass balloons, silica balloons, and alumina balloons. Examples of silicates include silica sand, diatomaceous earth, mica, clay, kaolin, and talc. Examples of fluorides include fluorspar. Examples of phosphates include calcium phosphate. Examples of clay minerals include smectite. As the filler, preferably, an inorganic filler is used, more preferably, hydroxide, carbonate, glass powder, and hollow filler are used, still more preferably, aluminum hydroxide, calcium carbonate, glass powder, and hollow filler are used, still more preferably, aluminum hydroxide and calcium carbonate are used, and particularly preferably, aluminum hydroxide is used.

[0110] The filler may be used alone or in combination of two or more kinds. The blending ratio of the filler is, relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer, for example, 1 part by mass or more, preferably 10 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 100 parts by mass or more, and for example, 300 parts by mass or less, preferably 200 parts by mass or less.

[0111] The colorant is not particularly limited, and examples thereof include pigments and polyester toners. Examples of pigments include organic pigments such as titanium oxide, carbon black, red iron oxide, and phthalocyanine blue. Examples of polyester toners include pigment-containing polyester colorants. A preferred colorant is polyester toner.

[0112] The colorant may be used alone or in combination of two or more kinds. The blending ratio of the colorant is, for example, 1 part by mass or more, preferably 3 parts by mass or more, and for example, 20 parts by mass or less, preferably 10 parts by mass or less, per 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0113] The thickener is blended to thicken the thermosetting resin composition to a viscosity suitable for hot compression molding. The thickener is preferably blended before (preferably immediately before) impregnating the thermosetting resin composition into reinforcing fibers (described below). Examples of thickeners include alkaline earth metal oxides, alkaline earth metal hydroxides, and polyisocyanate compounds. Examples of alkaline earth metal oxides include magnesium oxide. Examples of alkaline earth metal hydroxides include magnesium hydroxide and calcium hydroxide. Examples of polyisocyanate compounds include diphenylmethane diisocyanate (MDI). Examples of thickeners include alkaline earth metal oxides, and more preferably magnesium oxide.

[0114] The thickener may be used alone or in combination of two or more kinds. The blending ratio of the thickener is, for example, 0.5 parts by mass or more, preferably 0.7 parts by mass or more, and for example, 5 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0115] The wetting and dispersing agent is blended to improve the wettability of the filler. Examples of the wetting and dispersing agent include known wetting and dispersing agents. Examples of the wetting and dispersing agent include phosphate polyester. Commercially available wetting and dispersing agents can also be used, and examples of commercially available wetting and dispersing agents include BYK-W996 and BYK-W9010 (both manufactured by BYK-Chemie).

[0116] The wetting and dispersing agent can be used alone or in combination of two or more. The blending ratio of the wetting and dispersing agent 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, preferably 3 parts by mass or less, relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0117] The anti-separation agent is blended to prevent separation of the thermosetting resin composition. Examples of the anti-separation agent include a block copolymer of styrene and vinyl acetate. Commercially available anti-separation agents can also be used, and examples of commercially available anti-separation agents include BYK-W972 and BYK-9076 (both manufactured by BYK-Chemie).

[0118] The anti-separation agent can be used alone or in combination of two or more. The blending ratio of the anti-separation agent is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and for example, 10 parts by mass or less, preferably 3 parts by mass or less, relative to 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0119] Examples of the flame retardant include halogen-based flame retardants and non-halogen-based flame retardants. Examples of the halogen-based flame retardant include bromine-based flame retardants. Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, inorganic flame retardants, and nitrogen compound-based flame retardants.

[0120] The flame retardant may be used alone or in combination of two or more. The blending ratio of the flame retardant is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 50 parts by mass or less, preferably 20 parts by mass or less, per 100 parts by mass of the total amount of the thermosetting resin and the polymerizable monomer.

[0121] Furthermore, the thermosetting resin composition may contain other additives in an appropriate proportion, such as an antibacterial agent, a hydrophilic agent, a photocatalyst, an ultraviolet absorber, an ultraviolet stabilizer, an antistatic agent, a thixotropic agent, a thixotropic stabilizer, and a polymerization accelerator.

[0122] In the above-mentioned thermosetting resin composition, the handle material has a metal-containing layer containing a metal and a silica-based coating coating the metal-containing layer. The thermosetting resin composition also contains a coupling agent. Therefore, the silica-based coating of the handle material is reinforced by the coupling agent, and the metal-containing layer can be more reliably coated. As a result, the above-mentioned thermosetting resin composition can suppress chlorination and discoloration of the metal, and has excellent handle material discoloration resistance.

[0123] Therefore, the thermosetting resin composition is preferably used in a molding material. The molding material contains the thermosetting resin composition alone, or contains the thermosetting resin composition and reinforcing fibers. Preferably, the molding material contains the thermosetting resin composition and reinforcing fibers. That is, the molding material is preferably a molding material for a fiber-reinforced molded product.

[0124] Examples of reinforcing fibers include inorganic fibers, organic fibers, and natural fibers. Examples of inorganic fibers include glass fibers, carbon fibers, metal fibers, and ceramic fibers. Examples of organic fibers include polyvinyl alcohol fibers, polyester fibers, polyamide fibers, fluororesin fibers, and phenolic fibers. Examples of natural fibers include hemp and kenaf. Reinforcing fibers can be used alone or in combination of two or more. Among the reinforcing fibers, inorganic fibers are preferred, carbon fibers and glass fibers are more preferred, and glass fibers are even more preferred.

[0125] Examples of the shape of the reinforcing fiber include cloth, mats such as chopped strand mat, preformable mat, continuous strand mat, and surfacing mat, strands, chopped strands, rovings, nonwoven fabrics, and paper. Of the shapes of the reinforcing fiber, rovings are preferred.

[0126] From the viewpoint of smoothness of the molded article, the length of the reinforcing fiber is, for example, 0.1 m or more, preferably 1.5 mm or more. Furthermore, from the viewpoint of strength of the molded article, the length of the reinforcing fiber is more preferably 5 mm or more, more preferably 15 mm or more. Furthermore, from the viewpoint of strength of the molded article, the length of the reinforcing fiber is, for example, 80 mm or less, preferably 40 mm or less.

[0127] The blending ratio of the reinforcing fibers is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the thermosetting resin composition and the reinforcing fibers, and, for example, 50% by mass or less, preferably 40% by mass or less, based on the total amount of the thermosetting resin composition and the reinforcing fibers.

[0128] The molding material can be obtained by a known manufacturing method. Examples of the molding material include resin molding compounds. Examples of the resin molding compounds include sheet molding compounds (SMC), thick molding compounds (TMC), and bulk molding compounds (BMC).

[0129] For example, a sheet-shaped molding material can be obtained by impregnating reinforcing fibers with an unsaturated polyester resin composition. When the molding material is in sheet form, the thickness of the molding material is, for example, 1.0 mm or more and, for example, 15.0 mm or less.

[0130] Such molding materials contain the above-mentioned thermosetting resin composition, which has excellent resistance to discoloration of the pattern material. Therefore, the molding materials have excellent resistance to discoloration of the pattern material. Therefore, the molding materials are suitable for use in the production of any molded product.

[0131] The method for producing the molded article is not particularly limited, and known methods can be used. For example, first, the molding material is thickened. Examples of thickening methods include aging. The aging temperature is, for example, 20°C or higher and 60°C or lower. The aging time is, for example, 8 hours or higher and 120 hours or lower.

[0132] This allows the molding material to be held in a sheet shape, for example. That is, the molding material preferably has a sheet shape.

[0133] The molding material is then heated and compression molded. The molding conditions are appropriately set depending on the purpose and application. More specifically, the molding temperature is, for example, 100°C or higher and 200°C or lower. The molding pressure is, for example, 0.1 MPa or higher, preferably 1 MPa or higher, and more preferably 5 MPa or higher. The molding pressure is, for example, 20 MPa or lower, preferably 15 MPa or lower.

[0134] This causes the molding material to thermally cure, resulting in a molded article made of the cured molding material.

[0135] The molded article is made of the cured product of the molding material and has excellent discoloration resistance, making it suitable for use as a fiber-reinforced plastic (FRP) material in various industrial fields.

[0136] A preferred example of the molded product is artificial marble. Artificial marble is widely used in various industrial fields. Applications of artificial marble include, for example, bathtubs, bathroom components, kitchen countertops, sinks, washbasins, washstand counters, automotive exterior and interior materials, railroad vehicle components, architectural components, and lighting fixture components. In particular, bathroom components include, for example, the washing area of ​​a bathroom unit, a washbasin counter, floors, ceilings, walls, and bathtubs with washing areas. Railroad vehicle components include, for example, lighting cover components, table components, flame-retardant components, window frame components, and walls. Building components include, for example, wall materials, tile materials, skylight materials, and flooring materials. Lighting fixture components include, for example, lighting covers.

[0137] The uses of the molded article are not limited to those mentioned above, and examples of uses of the molded article include elevator ceilings, elevator walls, stained glass substitutes, mobile device bodies, decorative parts for electrical appliances, and flame-retardant materials. [Example]

[0138] Specific numerical values ​​of blending ratios (content ratios), physical property values, parameters, etc. used in the following description can be replaced with the corresponding upper limit values ​​(numeric values ​​defined as "not more than" or "less than") or lower limit values ​​(numeric values ​​defined as "not less than" or "exceeding") of blending ratios (content ratios), physical property values, parameters, etc. described in the above "Description of the Invention." Furthermore, unless otherwise specified in the following description, "parts" and "%" are based on mass.

[0139] Synthesis Example 1 (Unsaturated Polyester) A flask equipped with a thermometer, nitrogen gas inlet tube, partial condenser, and stirrer was used as a reactor. 332 parts by mass of isophthalic acid, 419 parts by mass of propylene glycol, and 521 parts by mass of neopentyl glycol were charged into the reactor, and a polycondensation reaction was carried out at a temperature of 200 to 210°C while stirring under a nitrogen gas atmosphere. When the acid value reached 10 mgKOH / g, the mixture was cooled to 150°C, and 785 parts by mass of maleic anhydride was charged. The reaction was continued at 210 to 220°C, yielding an unsaturated polyester (1) with an acid value of 27.0 mgKOH / g.

[0140] Synthesis Example 2 (Unsaturated Polyester) 50 parts by mass of isophthalic acid, 570 parts by mass of propylene glycol, 720 parts by mass of hydrogenated bisphenol A, and 951 parts by mass of maleic anhydride were charged into a reactor similar to that used in Synthesis Example 1, and the mixture was subjected to a polycondensation reaction at a temperature of 200 to 210°C under a nitrogen gas atmosphere with stirring. An unsaturated polyester (2) with an acid value of 27.0 mgKOH / g was obtained.

[0141] Synthesis Example 3 (Vinyl Ester) In a reactor equipped with a partial condenser similar to that used in Synthesis Example 1, 1,850 parts by weight of bisphenol A epoxy resin (epoxy equivalent weight 185), 317 parts by weight of bisphenol A, and 0.4 parts by weight of triethylbenzylammonium chloride as a catalyst were charged and reacted at 170°C for 5 hours while blowing in nitrogen to obtain an epoxy resin with an epoxy equivalent weight of 300. After cooling to 120°C, 2.0 parts by weight of hydroquinone as a polymerization inhibitor, 2.0 parts by weight of triethylbenzylammonium chloride as a catalyst, and 636 parts by weight of methacrylic acid were charged and subjected to an addition reaction at 120°C while blowing in air. 354 parts by weight of maleic anhydride was added to the resulting vinyl ester with an acid value of 7.0 mgKOH / g, and the reaction was continued at 80°C to obtain an acid-modified vinyl ester with an acid value of 71.2 mgKOH / g.

[0142] Synthesis Example 4 (Acrylic Polymer) 4515 parts by mass of methyl methacrylate and 807 parts by mass of an addition reaction product of hydroxyethyl methacrylate (639 parts by mass) and phthalic anhydride (168 parts by mass) were reacted at 85°C for 8 hours using azobisisobutylnitrile (AIBN) as a polymerization initiator, and the end point was 8 cm using a bubble viscometer. 2 After confirming the temperature was within 1 / second, the mixture was cooled. Next, 100 ppm of 6-tert-butyl-2,4-xylenol was added, and air was bubbled to obtain an acrylic syrup containing 30% acrylic polymer, 70% methyl methacrylate, and an acid value of 12 mgKOH / g.

[0143] Manufacturing Example 1 (Manufacturing of Handle Material A) The glass was classified using a vibrating sieve to obtain scaly glass flakes as the substrate. The glass used was produced from molten glass by a blowing method.

[0144] Meanwhile, 0.20 g of stannous chloride was dissolved in 1 L of pure water, and dilute hydrochloric acid was added to the solution. This resulted in a pretreatment solution with a pH of 2.0. Next, 200 g of the above-mentioned scaly glass flakes were added to the pretreatment solution, and then the scaly glass flakes were taken out and washed with water. In this way, the scaly glass flakes were pretreated.

[0145] Also, 50 g of 25% aqueous ammonia, 30 ml of ethylenediamine, and 30 g of silver nitrate were added to 2 L of pure water and heated at 30° C. to obtain a plating solution.

[0146] A solution was prepared by dissolving 15 g of glucose in 500 mL of pure water. The pretreated scaly glass flakes were added to the glucose solution to obtain a mixed solution. The above plating solution was added to the mixed solution and stirred for 30 minutes. Silver was deposited on the surface of the scaly glass flakes by an electroless plating reaction. As a result, a silver-containing coating as a metal-containing layer was formed on the surface of the scaly glass flakes as the substrate.

[0147] The scaly glass flakes having the silver-containing coating were then filtered, washed with water, dried at 150°C, and heat-treated in an electric furnace at 400°C for 3 hours, thereby obtaining pattern material A having a substrate (scaly glass flakes) and a metal-containing layer (silver-containing coating) covering the substrate. Manufacturing Example 2 (Manufacturing of Handle Material A') A silica-based coating was formed on the surface of the above-mentioned pattern material A. Specifically, 15 mL of tetraethoxysilane, 300 mL of ethyl alcohol, and 600 mL of pure water were mixed to obtain a coating solution. Next, 30 g of the above-mentioned pattern material A was added to the coating solution and mixed with a stirrer. Next, 15 mL of ammonium hydroxide (25%) was added to the mixed solution, and dehydration condensation was carried out while stirring for 3 hours. This resulted in the deposition of a silica-based coating on the surface of the pattern material A. Thereafter, the pattern material A with the silica-based coating was filtered, washed with water, air-dried, and heat-treated. The heat treatment temperature was 180°C, and the heat treatment time was 2 hours. This resulted in the preparation of pattern material A', which included a substrate (scale-like glass flakes), a metal-containing layer (silver-containing coating) coating the substrate, and a silica-based coating coating the metal-containing layer.

[0148] Manufacturing Example 3 (Manufacturing of Handle Material B) Pattern material B was obtained by the following method. That is, a silver-containing film was formed as a metal-containing layer on the surface of scaly glass flakes as a substrate by the same method as pattern material A. The amount of silver-containing film was reduced by about 10% compared to pattern material A. In this way, pattern material B was obtained, which included a substrate (scaly glass flakes) and a metal-containing layer (silver-containing film) covering the substrate.

[0149] Manufacturing Example 4 (Manufacturing of Handle Material B') A silica-based coating was formed on the surface of pattern material B in the same manner as in Production Example 2, except that pattern material B was used instead of pattern material A. This resulted in pattern material B', which included a substrate (scale-like glass flakes), a metal-containing layer (silver-containing coating) covering the substrate, and a silica-based coating covering the metal-containing layer.

[0150] Example 1 4, Reference Example 5, Example 6 9 and Comparative Examples 1 to 6 (1) Thermosetting resin composition and molding material The formulations shown in Tables 1 and 2 consist of resin components (thermosetting resin, polymerizable monomer, and low-shrinkage agent), handle material, coupling agent, polymerization inhibitor, mold release agent, and hardener. 、 The filler, colorant, and thickener were mixed together to obtain a thermosetting resin composition.

[0151] Next, glass fibers cut into continuous 1-inch (25 mm) pieces were added to the thermosetting resin compositions according to the formulations shown in Tables 1 and 2 to obtain molding materials.

[0152] (2) Molded products (artificial marble) The molding material was molded in a flat mold measuring 300 mm x 300 mm x 4 mm thick to obtain a flat molded product. The molded product was then removed from the mold and immediately placed between iron plates to cool. The molding conditions were as follows: Molding temperature: Upper mold / lower mold = 140℃ / 140℃ Molding pressure: 10 MPa Holding time: 420 seconds

[0153] <Evaluation> (1) Flexural strength and flexural modulus Test pieces (length 80 mm, width 10 mm) were cut out from the molded product. The flexural strength and flexural modulus of the test pieces at 23°C were measured in accordance with JIS K 7017 (1999).

[0154] (2) Tensile strength and tensile modulus Test specimens were cut out from the molded articles, and the tensile strength and tensile modulus of the test specimens at 23°C were measured in accordance with JIS K 7164 (2005). (3) Izod impact test Test pieces (length 65 mm, width 10 mm) were cut out from the molded product, and the Izod impact test (flatwise, unnotched) of the test pieces was performed in accordance with JIS K 7062 (1992).

[0155] (4) Discoloration resistance of handle material Test pieces (35 mm square) were cut out from the molded product. The discoloration resistance of the pattern material of the test pieces was evaluated by the following method.

[0156] (a) Detergent A: Domesto (sodium hypochlorite concentration 9% by mass), manufactured by Unilever Japan (b) Detergent B: Strong Mold Haiter (sodium hypochlorite concentration 4% by mass, sulfur concentration 0.2% by mass) manufactured by Kao

[0157] The molded articles were immersed in detergent A or detergent B for 48 hours or 72 hours, after which the color change of the molded articles was visually evaluated.

[0158] The evaluation criteria are as follows: ⊚: No noticeable black dots were found in the test piece. ○: Black spots were barely noticeable in the test piece. △: Black dots were slightly noticeable in the test piece. ×: Black spots were very noticeable in the test piece.

[0159] (5) Boiling property and gloss A 150 mm square test piece cut out from the molded article was immersed in a water bath at 90°C. The time until blisters (swelling) appeared was visually observed. The color tone of the test piece was also measured before and after immersion. A spectrophotometer SE 6000 (manufactured by Denshoku Co., Ltd.) was used for the measurements. This confirmed that the molded articles of each example had sufficient gloss and boiling resistance, with Example 9 being the most excellent.

[0160] [Table 1]

[0161] [Table 2]

[0162] Details of the abbreviations in the table are given below. Pattern material A: Pattern material obtained in Manufacturing Example 1 Handle material A': Handle material obtained in Production Example 2 Handle material B: Handle material obtained in Manufacturing Example 3 Handle material B': Handle material obtained in Production Example 4 Low-profile solution: Polystyrene in styrene PBQ: Polymerization inhibitor, parabenzoquinone Trigonox 129-75: Trade name Trigonox 129-75, hardener, t-amylperoxyisopropyl monocarbonate, manufactured by Nouryon

Claims

1. A thermosetting resin composition containing a resin component, a handle material, and a coupling agent, the resin component contains at least one selected from the group consisting of unsaturated polyesters, vinyl esters, and (meth)acrylic polymers, and a polymerizable monomer; the handle material has a metal-containing layer containing a metal and a silica-based coating coating the metal-containing layer, A thermosetting resin composition in which the content of the coupling agent is 0.30 parts by mass or more per 1 part by mass of the handle material.

2. 2. The thermosetting resin composition according to claim 1, wherein the coupling agent comprises at least one selected from the group consisting of a silane-based coupling agent, a titanium-based coupling agent, an aluminum-based coupling agent, and a zirconium-based coupling agent.

3. A molding material comprising the thermosetting resin composition according to claim 1 or 2 and reinforcing fibers.

4. A molded article comprising a cured product of the molding material according to claim 3.

5. The molded article according to claim 4, which is an artificial marble.

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