JPH0513899B2 - - Google Patents
Info
- Publication number
- JPH0513899B2 JPH0513899B2 JP61185236A JP18523686A JPH0513899B2 JP H0513899 B2 JPH0513899 B2 JP H0513899B2 JP 61185236 A JP61185236 A JP 61185236A JP 18523686 A JP18523686 A JP 18523686A JP H0513899 B2 JPH0513899 B2 JP H0513899B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylate
- meth
- parts
- monomer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 14
- 239000012778 molding material Substances 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 11
- 239000011256 inorganic filler Substances 0.000 claims description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000000113 methacrylic resin Substances 0.000 claims description 9
- 239000004575 stone Substances 0.000 claims description 8
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- -1 alkoxide compounds Chemical class 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 239000004412 Bulk moulding compound Substances 0.000 description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000003677 Sheet moulding compound Substances 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- MJYFYGVCLHNRKB-UHFFFAOYSA-N 1,1,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(F)(F)CF MJYFYGVCLHNRKB-UHFFFAOYSA-N 0.000 description 1
- 150000003923 2,5-pyrrolediones Chemical class 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- IYMZEPRSPLASMS-UHFFFAOYSA-N 3-phenylpyrrole-2,5-dione Chemical compound O=C1NC(=O)C(C=2C=CC=CC=2)=C1 IYMZEPRSPLASMS-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001875 Ebonite Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- WRKRMDNAUJERQT-UHFFFAOYSA-N cumene hydroxyperoxide Chemical compound OOOO.CC(C)C1=CC=CC=C1 WRKRMDNAUJERQT-UHFFFAOYSA-N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KCAMXZBMXVIIQN-UHFFFAOYSA-N octan-3-yl 2-methylprop-2-enoate Chemical compound CCCCCC(CC)OC(=O)C(C)=C KCAMXZBMXVIIQN-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、各種天然石調製品を量産することの
できる方法、特に耐熱性、耐水性、装飾性に富ん
だ天然石調の製品を量産する方法に関するもので
ある。[Detailed Description of the Invention] (Industrial Application Field) The present invention provides a method for mass-producing various natural stone products, particularly a method for mass-producing natural stone-like products that are highly heat resistant, water resistant, and highly decorative. It is related to.
（従来の技術）
従来よりメタクリル酸エステル系樹脂に無機質
充填材を混入した製品は公知であり、メタクリル
酸エステル系単量体を10〜30％予備重合したシラ
ツプに無機質充填材を混練したスラリーを型に注
入して硬化せしめる方法によるものや、更に無機
質充填材を高充填にして押出し成形する方法等に
より製造されている。しかし、これらは、生産に
長時間を要したり、製品の形状が限定されたり、
製品の耐熱性も不足するなどの欠点を有してい
た。(Prior art) Products in which inorganic fillers are mixed into methacrylic acid ester resins have been known for some time. It is manufactured by a method in which it is injected into a mold and allowed to harden, or by a method in which it is further filled with an inorganic filler and extruded. However, these methods require a long time to produce, have limited product shapes, and
The product also had drawbacks such as insufficient heat resistance.
一方、不飽和ポリエステル樹脂に硬化剤、充填
材、補強材、増粘剤などを混練して、粘土状にし
たバルクモールデイングコンパウンド（BMC）
やシート状にしたシートモールデイングコンパウ
ンド（SMC）と呼ばれる成形材料も公知であり、
この成形材料の収縮率を下げる目的のために熱可
塑性のポリマーを加えたBMCやSMCも多用され
ている。しかし、これらは増粘剤として多価金属
酸化物や水酸化物あるいはアルコキシド化合物な
どを用いるので、水分の影響を受けて品質のバラ
ツキが大きく、また、相分離なども起こし易くて
装飾性に富むものではなかつた。 On the other hand, bulk molding compound (BMC) is made by kneading unsaturated polyester resin with curing agents, fillers, reinforcing materials, thickeners, etc.
Molding materials called sheet molding compounds (SMCs) are also known.
BMC and SMC, which contain thermoplastic polymers, are also frequently used to reduce the shrinkage rate of molding materials. However, since these use polyvalent metal oxides, hydroxides, or alkoxide compounds as thickeners, their quality varies widely due to the influence of moisture, and they also tend to undergo phase separation, making them highly decorative. It wasn't something.
（発明が解決しようとする問題点）
本発明者は、前記のような在来技術の現況を改
善するため鋭意研究した結果、本発明に到達し
た。したがつて、本発明の目的は、メタクリル酸
エステル系樹脂シラツプによる注形法での美観や
装飾性を失することなく、BMCやSMCに匹敵す
る製品形状の多様性と量産性を有し且つ耐熱、耐
水性に富む製品を得ることのできる天然石調製品
の製法を提供することにある。(Problems to be Solved by the Invention) The present inventor has arrived at the present invention as a result of intensive research to improve the current state of the conventional technology as described above. Therefore, the object of the present invention is to provide a product with a variety of product shapes and mass productivity comparable to BMC and SMC without losing the beauty and decorative properties of the casting method using methacrylic acid ester resin syrup. An object of the present invention is to provide a method for producing natural stone products that can produce products with high heat resistance and water resistance.
（問題点を解決するための手段）
本発明は、多官能（メタ）アクリレートを20重
量％以上含有する単量体A100重量部に対して、
メタクリル酸エステル類を必須成分として含有す
る単量体から導かれる平均分子量５万〜20万の範
囲で20メツシユ以下の粒度のメタクリル系樹脂粉
末B50〜300重量部、該単量体Ａの硬化剤C0.5〜
２重量部、無機質充填材D100〜500重量部および
必要によりカツプリング剤、着色剤および補強材
を常温又は硬化温度未満の加温下に混練・熟成し
て得られる常温で粘土状ないし固形の成形材料
を、加圧下に加熱して成形・硬化することを特徴
とする天然石調製品の製法である。(Means for Solving the Problems) The present invention provides that, for 100 parts by weight of monomer A containing 20% by weight or more of polyfunctional (meth)acrylate,
50 to 300 parts by weight of methacrylic resin powder B derived from a monomer containing methacrylic acid esters as an essential component and having an average molecular weight in the range of 50,000 to 200,000 and a particle size of 20 mesh or less, and a curing agent for the monomer A. C0.5～
A clay-like or solid molding material at room temperature obtained by kneading and aging 2 parts by weight of inorganic filler D, 100 to 500 parts by weight of inorganic filler D, and if necessary a coupling agent, a coloring agent, and a reinforcing material at room temperature or under heating below the curing temperature. This is a method for producing natural stone preparations, which is characterized by molding and curing by heating under pressure.
（作用）
本発明で用いる多官能（メタ）アクリレートを
20重量％以上含有する単量体Ａは、成形・硬化時
に架橋構造を形成するのに必要な多官能（メタ）
アクリレートを必須成分とし、必要により多官能
（メタ）アクリレートと共重合可能な他の単量体
を配合したものである。(Function) The polyfunctional (meth)acrylate used in the present invention
Monomer A containing 20% by weight or more is a polyfunctional (meta) necessary to form a crosslinked structure during molding and curing.
It contains acrylate as an essential component and, if necessary, contains other monomers copolymerizable with polyfunctional (meth)acrylate.
単量体Ａを構成する多官能（メタ）アクリレー
トとしては、例えばエチレングリコールジ（メ
タ）アクリレート、プロピレングリコールジ（メ
タ）アクリレート、ネオペンチルグリコールジ
（メタ）アクリレート、トリメチロールプロパン
トリ（メタ）アクリレート、ペンタエリスリトー
ルテトラ（メタ）アクリレート、ジペンタエリス
リトールヘキサ（メタ）アクリレートなどが使用
でき、また、単量体Ａとして必要により使用でき
る他の単量体としては、比較的硬質の重合体を与
える単量体が有効であり、メタクリル系樹脂粉末
Ｂの樹脂組成により適宜選択して使用でき、例え
ばメチルメタクリレート、エチルメタクリレー
ト、シクロヘキシルメタクリレート、ベンジルメ
タクリレートなどのメタクリル酸エステル類、ス
チレン、ｏ，ｍ，ｐ−メチルスチレン、α−メチ
ルスチレンなどの芳香族ビニル化合物、ヒドロキ
シエチル（メタ）アクリレート、ヒドロキシプロ
ピル（メタ）アクリレート、グリシジル（メタ）
アクリレート、（メタ）アクリロニトリルなどを
挙げることができる。 Examples of the polyfunctional (meth)acrylate constituting monomer A include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. , pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. can be used.Other monomers that can be used as monomer A if necessary include monomers that give relatively hard polymers. methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, styrene, o, m, p- Aromatic vinyl compounds such as methylstyrene and α-methylstyrene, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)
Examples include acrylate and (meth)acrylonitrile.
単量体Ａ中の多官能（メタ）アクリレートの量
は、得られる天然石調製品の耐熱性等の性能を考
慮すれば、20重量％以上であることが必要であ
る。 The amount of polyfunctional (meth)acrylate in monomer A needs to be 20% by weight or more, considering the performance such as heat resistance of the natural stone preparation obtained.
多官能（メタ）アクリレートの量が20重量％未
満の少量では、天然石調製品を構成する他の成分
との組合わせによつては、硬化して十分な架橋構
造とはならず、耐熱性や耐水性に劣つた製品しか
得られない。 If the amount of polyfunctional (meth)acrylate is less than 20% by weight, depending on the combination with other components that make up the natural stone preparation, it may not harden to form a sufficient crosslinked structure, resulting in poor heat resistance and Only products with poor water resistance can be obtained.
本発明で用いるメタクリル系樹樹脂粉末Ｂは、
メチルメタクリレート、エチルメタクリレート、
iso−プロピルメタクリレート、ｎ−ブチルメタ
クリレート、iso−ブチルメタクリレート、２−
エチルヘキシルメタクリレートなどのアルキルメ
タクリレート；シクロヘキシルメタクリレートな
どのシクロアルキルメタクリレート；ベンジルメ
タクリレートなどのアルキルメタクリレートの中
から選ばれた１種以上のメタクリル酸エステル類
を必須成分とし、必要によりメタクリル酸エステ
ル類と共重合可能な他の単量体を配合してなる単
量体を、懸濁重合又は外部界面活性剤の使用なし
に乳化重合して、ポリマーを沈降などの方法で分
別して取出すか、塊状重合により重合したポリマ
ーを微粉砕することにより得られる熱可塑性ない
し部分的に架橋構造を有する粒状物である。その
粒径は２〜３mmに及ぶものも目的によつては選択
できるが、通常は100μm以下のものが好ましい。
樹脂粉末Ｂを構成するポリマーの平均分子量は５
万〜20万のものが好適に使用され、特に10万以上
のものが作業性に優れた成形材料を得る上で好ま
しい特性を発揮する。 The methacrylic resin powder B used in the present invention is
Methyl methacrylate, ethyl methacrylate,
iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, 2-
One or more methacrylic acid esters selected from alkyl methacrylates such as ethylhexyl methacrylate; cycloalkyl methacrylates such as cyclohexyl methacrylate; and alkyl methacrylates such as benzyl methacrylate are essential components, and can be copolymerized with methacrylic esters if necessary. A monomer prepared by blending with other monomers is subjected to suspension polymerization or emulsion polymerization without the use of an external surfactant, and the polymer is separated out by a method such as sedimentation, or polymerized by bulk polymerization. It is a granular material having a thermoplastic or partially crosslinked structure obtained by finely pulverizing a polymer. The particle size may range from 2 to 3 mm depending on the purpose, but it is usually preferred to have a particle size of 100 μm or less.
The average molecular weight of the polymer constituting resin powder B is 5
A number of 10,000 to 200,000 is preferably used, and a number of 100,000 or more exhibits preferable characteristics in obtaining a molding material with excellent workability.
メタクリル系樹脂粉末Ｂを得る際に使用できる
メタクリル酸エステル類と共重合可能な他の単量
体としては、メチルアクリレート、エチルアクリ
レート、ブチルアクリレート、２−エチルヘキシ
ルアクリレート、シクロヘキシルアクリレートな
どのアルキル又はシクロアルキルアクリレート
類、ヒドロキシエチル（メタ）アクリレート、ヒ
ドロキシプロピル（メタ）アクリレート、グリシ
ジル（メタ）アクリレート、
一般式
（Ｒは水素又はメチル基であり、ｎは２〜10で
ある。）などのポリグリコールのモノ（メタ）ア
クリレート類、一般式
（Ｒは水素又はメチル基、R′はアルキル基で
あり、ｎは２〜10である。）などのポリグリコー
ルエーテルのモノ（メタ）アクリレート類、ネオ
ペンチルグリコールモノ（メタ）アクリレートな
どのグリコールモノ（メタ）アクリレート類、エ
チレングリコールジ（メタ）アクリレート、プロ
ピレングリコールジ（メタ）アクリレート、ネオ
ペンチルグリコールジ（メタ）アクリレート、ト
リメチロールプロパントリ（メタ）アクリレー
ト、ペンタエリスリトールテトラ（メタ）アクリ
レート、ジペンタエリスリトールヘキサ（メタ）
アクリレートなどの多官能（メタ）アクリレート
類、スチレン、ｏ，ｍ，ｐ−メチルスチレン、α
−メチルスチレンなどの芳香族ビニル化合物、ト
リフルオロエチル（メタ）アクリレートなどの含
弗素不飽和化合物、フエニルマレイミドなどのマ
レイミド化合物等を挙げることができ、これらの
中から選んだ１種以上の単量体を使用できる。 Other monomers copolymerizable with methacrylic acid esters that can be used to obtain methacrylic resin powder B include alkyl or cycloalkyl such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. Acrylates, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, general formula Polyglycol mono(meth)acrylates such as (R is hydrogen or a methyl group, and n is 2 to 10), general formula (R is hydrogen or a methyl group, R' is an alkyl group, and n is 2 to 10.) Glycol mono(meth)acrylates such as polyglycol ether mono(meth)acrylate, neopentyl glycol mono(meth)acrylate, etc. (meth)acrylates, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipenta Erythritol hexa (meth)
Polyfunctional (meth)acrylates such as acrylate, styrene, o, m, p-methylstyrene, α
- Aromatic vinyl compounds such as methylstyrene, fluorine-containing unsaturated compounds such as trifluoroethyl (meth)acrylate, maleimide compounds such as phenylmaleimide, and one or more monomers selected from these. Quantity can be used.
メタクリル系樹脂粉末Ｂの使用量は、単量体
A100重量部に対して50〜300重量％の割合が好ま
しい。メタクリル系樹脂粉末Ｂの使用量がこの割
合をはずれると、混練・熟成して常温で粘土状な
いし固形の、成形硬化時の作業性に優れた成形材
料が得難くなる。 The amount of methacrylic resin powder B used is
The ratio is preferably 50 to 300% by weight based on 100 parts by weight of A. If the amount of methacrylic resin powder B used exceeds this ratio, it will be difficult to obtain a molding material that is clay-like or solid at room temperature after kneading and aging and has excellent workability during molding and curing.
本発明における硬化剤Ｃは、単量体Ａのラジカ
ル重合開始剤であるアゾビス化合物や有機過酸化
物、例えばアゾビスイソブチロニトリル、ベンゾ
イルパーオキサイド、ｔ−ブチルパーオキサイ
ド、クメンヒドロキシパーオキサイド、ｔ−ブチ
ルヒドロパーオキサイド、ジクミルパーオキサイ
ドなどの一種以上を単量体Ａに溶解して用いるこ
とができる。硬化剤Ｃの使用量は、単量体A100
重量部に対して0.5〜２重量部の割合が好ましい。 Curing agent C in the present invention is a radical polymerization initiator for monomer A, such as an azobis compound or an organic peroxide, such as azobisisobutyronitrile, benzoyl peroxide, t-butyl peroxide, cumene hydroxy peroxide, One or more types of t-butyl hydroperoxide, dicumyl peroxide, etc. can be dissolved in monomer A and used. The amount of curing agent C used is 100% of monomer A.
A ratio of 0.5 to 2 parts by weight is preferred.
無機質充填材Ｄとしては、炭酸カルシウム、カ
オリン、クレー、アルミナ、シリカ、酸化マグネ
シウムなど種々あるが、水酸化アルミニウムや水
酸化マグネシウムなどは製品に難燃性を与え、且
つ美観的にも好ましいものである。粒径は100μm
以下が好ましいが、特に補強材にガラス繊維など
を用いたり、高充填を行うためには、平均粒径は
5μm以下が好ましい。無機質充填材Ｄの使用量
は、単量体A100重量部に対して100〜500重量部
の割合が好ましい。 There are various types of inorganic filler D, such as calcium carbonate, kaolin, clay, alumina, silica, and magnesium oxide, but aluminum hydroxide, magnesium hydroxide, etc. impart flame retardancy to the product and are aesthetically pleasing. be. Particle size is 100μm
The average particle size is preferably
It is preferably 5 μm or less. The amount of inorganic filler D used is preferably 100 to 500 parts by weight per 100 parts by weight of monomer A.
カツプリング剤は種々なものが用いられるが特
にシラン系のものは好ましい。着色材は有機・無
機の顔料が用いられるのが好ましいには金属酸化
物系の顔料である。補強材としては、ガラス繊
維、カーボン繊維、アラミド繊維などの有機系の
繊維類を用いることができる。 Various coupling agents can be used, but silane-based coupling agents are particularly preferred. The colorant is preferably an organic or inorganic pigment, preferably a metal oxide pigment. As the reinforcing material, organic fibers such as glass fibers, carbon fibers, and aramid fibers can be used.
本発明では、前記の単量体Ａ、メタクリル系樹
脂粉末Ｂ、硬化剤Ｃ、無機質充填材Ｄに、必要に
よりカツプリング剤；着色剤；補強材等を配合し
て、常温又は硬化温度未満の加温下に混練・熟成
を行う。混練・熟成は、前記の成分が常温で粘土
状ないし固形状物となるまで行う必要があるが、
混練分散を十分に達成するためには、メタクリル
系樹脂粉末Ｂの混練に先立つて無機質充填材Ｄの
分散を行つておくのが好ましい。この混練・熟成
は、各種混練機、例えばコニーダー、Σブレード
捏和機、押出機などを用いて一気に行うことがで
き、また、混練を前記混練機で行つた後、得られ
た高粘性スラリー又は湿つた粉末状物を熟成室に
て常温又は硬化温度未満の加温下に保持して熟成
を完結して行うこともできる。 In the present invention, the monomer A, methacrylic resin powder B, curing agent C, and inorganic filler D are blended with a coupling agent, a coloring agent, a reinforcing material, etc., if necessary, and then heated at room temperature or below the curing temperature. Knead and mature at warm temperature. Kneading and aging must be carried out until the above ingredients become clay-like or solid at room temperature.
In order to achieve sufficient kneading and dispersion, it is preferable to disperse the inorganic filler D prior to kneading the methacrylic resin powder B. This kneading and maturation can be carried out all at once using various kneaders, such as a co-kneader, a Σ blade kneader, an extruder, etc. After kneading is carried out in the kneader, the resulting high viscosity slurry or It is also possible to complete the ripening by keeping the wet powdered material in a ripening room at room temperature or under heating below the curing temperature.
本発明実施の典型的な方法を次に記述する。ま
ず単量体A100重量部に硬化剤Ｃを0.5〜２重量部
溶解し、ついで無機質充填材Ｄを100〜500重量部
を混練分散し、最後に50〜300重量部のメタクリ
ル系樹脂粉末Ｂを加えて混練すると、常温で高粘
性のスラリー又は湿つた粉末状になるので、これ
を常温又は硬化温度未満の加温により熟成すると
常温で粘土状ないし固形状の成形材料が得られ
る。 A typical method of implementing the invention will now be described. First, 0.5 to 2 parts by weight of curing agent C is dissolved in 100 parts by weight of monomer A, then 100 to 500 parts by weight of inorganic filler D are kneaded and dispersed, and finally 50 to 300 parts by weight of methacrylic resin powder B is added. When added and kneaded, it becomes a highly viscous slurry or wet powder at room temperature, so if this is aged at room temperature or by heating below the curing temperature, a clay-like or solid molding material can be obtained at room temperature.
このようにして得られた成形材料はベタつきが
なく、ナイフ等によるカツトができて計量容易で
あり、圧縮、トランスフアー、射出、押出しなど
の方法で形状を与えつつ硬化温度に加熱すること
により、硬化を進め天然石調の成形品を得ること
ができる。成形時の圧力は10〜100Kg／cm2、温度
は80〜160℃程度で成形時間も数十分以下の短時
間で良い。したがつて、比較的高分子量の樹脂粉
末も分解を受けることなく成形され、製品の各種
物性の向上にも役立つものである。 The molding material obtained in this way is non-sticky, can be cut with a knife, etc., and is easy to measure, and can be shaped by compression, transfer, injection, extrusion, etc. and heated to a curing temperature. By proceeding with curing, it is possible to obtain a molded product that looks like natural stone. The pressure during molding may be 10 to 100 kg/cm 2 , the temperature may be approximately 80 to 160°C, and the molding time may be as short as several tens of minutes or less. Therefore, even relatively high molecular weight resin powders can be molded without decomposition, which is useful for improving various physical properties of products.
以下、具体例について更に詳細に説明するが、
これらは本発明の全てを包括するものではない。 Specific examples will be explained in more detail below.
These are not all-inclusive of the invention.
実施例 １
エチレングリコールジメタクリレート500g、
トリメチロールプロパントリメタクリレート
500g、ジクミルパーオキサイド10gおよびγ−メ
タクリロキシトリメトキシシラン20gの混合液
に、平均粒径3μmの水酸化アルミニウム粉末
3000gを加えて、コニーダーにて分散させた。次
いで、20メツシユ以下の粒度であるメチルメタク
リレート／メチルアクリレートが９対１の割合の
樹脂粉末（平均分子量10万）1000gを加えて、60
℃で60分間混練・熟成したのち、常温まで冷却し
て固いゴム粘土状の成形材料を得た。次に、この
成形材料よりカツターナイフで500gを切り出し、
トレー成形の圧縮成形用型を用いて120℃で50
Kg／cm2の加圧下に30分間保持して、大きさが25cm
×15cm×0.8cmのトレーを得た。このトレーは透
明感が白大理石調で美しく、このトレーから切出
した試験片で測定したアイゾツト衝撃強さ（JIS
Ｋ 6911に準じて測定）は3.5Kg・cm／cmで熱変
形温度（ASTM Ｄ−648に準じて測定）は130℃
であつた。Example 1 500g of ethylene glycol dimethacrylate,
Trimethylolpropane trimethacrylate
500g, aluminum hydroxide powder with an average particle size of 3μm in a mixture of 10g dicumyl peroxide and 20g γ-methacryloxytrimethoxysilane.
3000g was added and dispersed using a co-kneader. Next, 1000g of resin powder (average molecular weight 100,000) with a particle size of 20 mesh or less and a ratio of 9:1 methyl methacrylate/methyl acrylate was added,
After kneading and aging at ℃ for 60 minutes, the mixture was cooled to room temperature to obtain a hard rubber clay-like molding material. Next, cut out 500g from this molding material with a cutter knife,
50 at 120℃ using a compression molding mold for tray molding.
Hold under pressure of Kg/ cm2 for 30 minutes, size 25cm
A tray of x15cm x 0.8cm was obtained. This tray has a beautiful white marble-like transparency, and the Izot impact strength (JIS
The heat distortion temperature (measured according to ASTM D-648) is 130℃.
It was hot.
実施例 ２
トリメチロールプロパントリメタクリレート
500g、スチレン500g、ジ−ｔ−ブチルパーオキ
サイド10gおよびγ−メタクリロキシトリメトキ
シシラン20gの混合液に、平均粒径3μmの水酸化
アルミニウム粉末4000gを加えて、コニーダーに
て分散させた。次いで、20メツシユ以下の粒度を
有するメチルメタクリレート／スチレンが７対３
の割合の樹脂粉末（平均分子量20万）1500gを加
えて、60℃で30分間混練・熟成したのち、押出し
て常温に冷却し、弾性のある固形板状の成形材料
を得た。この成形材料500gを実施例１と同じ金
型を用いて140℃、70Kg／cm2の加圧下に20分間保
持して25cm×15cm×0.75cmのトレーを得た。この
トレーは白色オニツクス調の透明感があつて美し
く、このトレーから切出した試験片で測定したア
イゾツト衝撃強さは３Kg・cm／cmで熱変形温度は
120℃であつた。Example 2 Trimethylolpropane trimethacrylate
500 g of aluminum hydroxide powder having an average particle size of 3 μm was added to a mixed solution of 500 g of styrene, 500 g of styrene, 10 g of di-t-butyl peroxide, and 20 g of γ-methacryloxytrimethoxysilane, and dispersed in a co-kneader. Then 7:3 methyl methacrylate/styrene with a particle size of 20 mesh or less
1,500 g of resin powder (average molecular weight: 200,000) was added thereto, and after kneading and aging at 60°C for 30 minutes, it was extruded and cooled to room temperature to obtain an elastic solid plate-shaped molding material. Using the same mold as in Example 1, 500 g of this molding material was held at 140° C. under a pressure of 70 kg/cm 2 for 20 minutes to obtain a tray of 25 cm x 15 cm x 0.75 cm. This tray has a beautiful white onyx-like transparency, and the Izot impact strength measured with a test piece cut from this tray was 3Kg・cm/cm, and the heat distortion temperature was 3Kg・cm/cm.
It was 120℃.
（発明の効果）
本発明は、美麗な耐熱性に富んだ天然石調製品
を形状に関係なく容易に生産することを可能にす
る優れた方法である。(Effects of the Invention) The present invention is an excellent method that makes it possible to easily produce beautiful and highly heat-resistant natural stone preparations regardless of their shape.
Claims (1)
含有する単量体A100重量部に対して、 メタクリル酸エステル類を必須成分として含有
する単量体から導かれる平均分子量５万〜20万の
範囲で20メツシユ以下の粒度のメタクリル系樹脂
粉末B50〜300重量部、 該単量体Ａの硬化剤C0.5〜２重量部、 無機質充填材D100〜500重量部 および必要によりカツプリング剤、着色剤およ
び補強材を常温又は硬化温度未満の加温下に混
練・熟成して得られる常温で粘土状ないし固形の
成形材料を、加圧下に加熱して成形・硬化するこ
とを特徴とする天然石調製品の製法。[Claims] 1. An average molecular weight of 50,000 derived from a monomer containing methacrylic acid esters as an essential component, based on 100 parts by weight of monomer A containing 20% by weight or more of polyfunctional (meth)acrylate. 50 to 300 parts by weight of methacrylic resin powder B with a particle size of 20 mesh or less in the range of ~200,000, 0.5 to 2 parts by weight of the curing agent C of the monomer A, 100 to 500 parts by weight of the inorganic filler D, and coupling as necessary. A molding material that is clay-like or solid at room temperature, which is obtained by kneading and maturing additives, colorants, and reinforcing materials at room temperature or under heating below the curing temperature, is molded and hardened by heating under pressure. A manufacturing method for natural stone products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18523686A JPS6345160A (en) | 1986-08-08 | 1986-08-08 | Manufacture of natural stone-like product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18523686A JPS6345160A (en) | 1986-08-08 | 1986-08-08 | Manufacture of natural stone-like product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6345160A JPS6345160A (en) | 1988-02-26 |
| JPH0513899B2 true JPH0513899B2 (en) | 1993-02-23 |
Family
ID=16167265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18523686A Granted JPS6345160A (en) | 1986-08-08 | 1986-08-08 | Manufacture of natural stone-like product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6345160A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174954B1 (en) | 1997-10-29 | 2001-01-16 | Sumitomo Chemical Company, Limited | Resin composition, artificial marble obtained by molding composition and production thereof |
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|---|---|---|---|---|
| JPH0717423B2 (en) * | 1989-04-17 | 1995-03-01 | 千尋 黒川 | Natural stone pattern plastic molding material |
| JP3366540B2 (en) * | 1996-11-29 | 2003-01-14 | 株式会社クラレ | Method for producing acrylic syrup |
| KR20010108295A (en) * | 1999-03-03 | 2001-12-07 | 나가이 야타로 | Method for Producing Acrylic BMC, Method for Producing Acrylic Syrup, and Method for Producing Acrylic Molded Article |
| JP5486340B2 (en) * | 2010-02-23 | 2014-05-07 | パナソニック株式会社 | Thermosetting (meth) acrylic resin composition |
| JP5486341B2 (en) * | 2010-02-23 | 2014-05-07 | パナソニック株式会社 | Thermosetting (meth) acrylic resin composition and sheet molding compound, bulk molding compound and molded product using the same |
| WO2017126661A1 (en) * | 2016-01-22 | 2017-07-27 | 住友化学株式会社 | Resin composition, molded article, and method for manufacturing molded article |
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| JPS57212248A (en) * | 1981-06-15 | 1982-12-27 | Du Pont | Methacrylate polymer concrete mixture with little curing shrinkage |
| JPS59133254A (en) * | 1983-01-20 | 1984-07-31 | Kyowa Gas Chem Ind Co Ltd | Patterned cured article |
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1986
- 1986-08-08 JP JP18523686A patent/JPS6345160A/en active Granted
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|---|---|---|---|---|
| GB983826A (en) * | 1962-06-16 | 1965-02-17 | Roehm & Haas Gmbh | Surfacing materials for roads and the like |
| JPS57212248A (en) * | 1981-06-15 | 1982-12-27 | Du Pont | Methacrylate polymer concrete mixture with little curing shrinkage |
| JPS59133254A (en) * | 1983-01-20 | 1984-07-31 | Kyowa Gas Chem Ind Co Ltd | Patterned cured article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6174954B1 (en) | 1997-10-29 | 2001-01-16 | Sumitomo Chemical Company, Limited | Resin composition, artificial marble obtained by molding composition and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6345160A (en) | 1988-02-26 |
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