JPH0257086B2 - - Google Patents
Info
- Publication number
- JPH0257086B2 JPH0257086B2 JP61273026A JP27302686A JPH0257086B2 JP H0257086 B2 JPH0257086 B2 JP H0257086B2 JP 61273026 A JP61273026 A JP 61273026A JP 27302686 A JP27302686 A JP 27302686A JP H0257086 B2 JPH0257086 B2 JP H0257086B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- weight
- unsaturated polyester
- aluminum hydroxide
- resin
- 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 18
- 239000011342 resin composition Substances 0.000 claims description 16
- 239000002928 artificial marble Substances 0.000 claims description 15
- 229920006305 unsaturated polyester Polymers 0.000 claims description 15
- 239000004793 Polystyrene Substances 0.000 claims description 14
- 229920002223 polystyrene Polymers 0.000 claims description 14
- 239000000178 monomer Substances 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- IISBACLAFKSPIT-UHFFFAOYSA-N Bisphenol A Natural products C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 21
- 238000000465 moulding Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- 229920006337 unsaturated polyester resin Polymers 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- -1 amine compound Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 150000002689 maleic acids Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- DSPZRAREZHBQMV-UHFFFAOYSA-N (4-butylcyclohexyl) (4-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(CCCC)CCC1OC(=O)OOC(=O)OC1CCC(CCCC)CC1 DSPZRAREZHBQMV-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- VNGLVZLEUDIDQH-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;2-methyloxirane Chemical compound CC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 VNGLVZLEUDIDQH-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920002978 Vinylon Polymers 0.000 description 1
- JUDXBRVLWDGRBC-UHFFFAOYSA-N [2-(hydroxymethyl)-3-(2-methylprop-2-enoyloxy)-2-(2-methylprop-2-enoyloxymethyl)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(CO)(COC(=O)C(C)=C)COC(=O)C(C)=C JUDXBRVLWDGRBC-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000001746 injection moulding Methods 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
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、人造大理石物品の製法に関し、詳し
くは、クラツクや歪のない、美麗に光を散乱する
半透明性の人造大理石物品の製法に関するもので
ある。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing an artificial marble article, and more particularly, to a method for manufacturing a translucent artificial marble article that is free from cracks and distortions and beautifully scatters light. It is something.
（従来の技術）
従来より不飽和ポリエステル樹脂と水酸化アル
ミニウムとよりなる重合性シロツプを注型法にて
常圧硬化して、大理石調の物品を製造することは
公知であり、その優れた外観等の性能ゆえに需要
が増えてきている。しかし、注型法では生産性が
悪く、プレス成形法等の加熱加圧硬化による方法
が望まれている。(Prior art) It has been known to manufacture marble-like articles by curing polymerizable syrup made of unsaturated polyester resin and aluminum hydroxide using a casting method under normal pressure, and the excellent appearance thereof has been known. Demand is increasing due to its performance. However, the casting method has poor productivity, and methods using heat and pressure curing, such as press molding, are desired.
プレス成形法では、特開昭58−90921号にみら
れるような水酸化アルミニウム等の充填剤を配合
したSMCを80〜120℃という低温で成形して人造
大理石を得る方法が提案されているが、未だ透明
性劣り、本格的には採用されていない。 In the press molding method, a method has been proposed in which artificial marble is obtained by molding SMC containing fillers such as aluminum hydroxide at a low temperature of 80 to 120 degrees Celsius, as seen in Japanese Patent Application Laid-open No. 58-90921. , it still lacks transparency and has not been adopted in earnest.
（発明が解決しようとする問題点）
加熱加圧成形法によつて半透明性の美麗な人造
大理石物品を得るのは非常に困難であつた。その
理由としては、１）樹脂の収縮（硬化収縮及び熱
収縮）に起因する樹脂と充填剤や補強材との界面
の接着不良による不透明化、２）樹脂の低収縮化
による樹脂自体の不透明化という一見相容れない
要因が考えられる。(Problems to be Solved by the Invention) It has been extremely difficult to obtain beautiful translucent artificial marble articles by hot-pressure molding. The reasons for this are: 1) opacity due to poor adhesion at the interface between the resin and filler or reinforcing material due to resin shrinkage (curing shrinkage and heat shrinkage); 2) opacity of the resin itself due to low resin shrinkage. There are several seemingly contradictory factors that can be considered.
本発明者らは、これらのことを考慮し、鋭意研
究した結果、特定の不飽和ポリエステル樹脂、ポ
リスチレン系重合体および充填剤としての水酸化
アルミニウムを特定の比率で組合せて用いること
により、透明感がありしかもクラツクや歪のない
人造大理石物品を加熱加圧成形できることを見出
して、本発明を完成するに至つた。 The inventors of the present invention have taken these matters into consideration and have conducted intensive research. By using a specific combination of a specific unsaturated polyester resin, a polystyrene polymer, and aluminum hydroxide as a filler in a specific ratio, the inventors have achieved a transparent appearance. The present invention has been completed by discovering that it is possible to heat and press mold an artificial marble article without cracks or distortions.
従つて、本発明の目的は、生産性の良い加熱加
圧成形法により、クラツクや歪のない半透明性の
美麗な人造大理石物品を提供することにある。 Therefore, an object of the present invention is to provide a beautiful, translucent artificial marble article free from cracks and distortions by a heat-pressing molding method with good productivity.
（問題点を解決するための手段および作用）
本発明は、一般式
（ただし式中、R1およびR2はそれぞれ同一でも
異なつていてもよい炭素数２〜３のアルキレン基
を示し、ｍおよびｎはそれぞれ０又は１〜10の整
数であり且つｍ＋ｎは２〜10の整数である。）で
表わされるビスフエノールＡアルキレンオキシド
付加物を10〜100モル％含有する多価アルコール
を、必須成分として導かれるα，β−エチレン性
不飽和ポリエステル(A)30〜50重量％、架橋性単量
体(B)20〜50重量％およびポリスチレン系重合体(C)
20〜40重量％（ただし、(A)、(B)および(C)成分の合
計は100重量％である。）からなる樹脂組成物(I)
100重量部に対して、水酸化アルミニウム20〜300
重量部を分散した後、135〜160℃の温度で加圧成
形・硬化することを特徴とする人造大理石物品の
製法に関するものである。(Means and effects for solving the problems) The present invention is based on the general formula (However, in the formula, R 1 and R 2 each represent an alkylene group having 2 to 3 carbon atoms, which may be the same or different, m and n are each an integer of 0 or 1 to 10, and m+n is 2 to 10. α,β-ethylenically unsaturated polyester (A) containing 10 to 100 mol% of a bisphenol A alkylene oxide adduct represented by (an integer of 10) as an essential component. Weight%, crosslinkable monomer (B) 20-50% by weight and polystyrene polymer (C)
Resin composition (I) consisting of 20 to 40% by weight (however, the total of components (A), (B) and (C) is 100% by weight)
20-300 parts of aluminum hydroxide per 100 parts by weight
The present invention relates to a method for producing an artificial marble article, which is characterized in that after dispersing parts by weight, pressure molding and curing are performed at a temperature of 135 to 160°C.
本発明におけるα，β−エチレン性不飽和ポリ
エステル(A)は、通常の方法、例えばα，β−不飽
和二塩基酸に必要に応じて飽和二塩基酸を混合し
て得た酸成分と多価アルコールとを不活性ガス気
流中で150〜250℃の温度範囲で縮合反応せしめて
得られる酸価５〜50の範囲、分子量800〜10000の
範囲のものであるが、前記一般式で表わされるビ
スフエノールＡアルキレンオキシド付加物を多価
アルコール中10〜100モル％の範囲の量で用いて
導かれるものである。α，β−エチレン性不飽和
ポリエステル(A)を得るための必須成分の１つであ
る多価アルコール中のビスフエノールＡアルキレ
ンオキシド付加物の含有量が10モル％より少ない
量では、成形硬化して得られる物品の透明性が悪
くなり、しかも硬化時にポリスチレン系重合体(C)
が分離して、物品の表面が汚染されるため好まし
くない。 The α,β-ethylenically unsaturated polyester (A) in the present invention can be obtained by a conventional method, for example, by mixing an α,β-unsaturated dibasic acid with a saturated dibasic acid as required. It has an acid value in the range of 5 to 50 and a molecular weight in the range of 800 to 10,000, which is obtained by condensation reaction with a hydric alcohol at a temperature range of 150 to 250°C in an inert gas stream, and is represented by the general formula above. It is derived using a bisphenol A alkylene oxide adduct in an amount ranging from 10 to 100 mole percent in a polyhydric alcohol. If the content of the bisphenol A alkylene oxide adduct in the polyhydric alcohol, which is one of the essential components for obtaining α,β-ethylenically unsaturated polyester (A), is less than 10 mol%, molding hardening will not occur. The transparency of the resulting product is poor, and the polystyrene polymer (C) is removed during curing.
is undesirable because it separates and contaminates the surface of the article.
α，β−エチレン性不飽和ポリエステル(A)を調
製する際に用いられるビスフエノールＡアルキレ
ンオキシド付加物は、前記一般式で表わされるも
のであり、普通、ビスフエノールA1モルに対し
て２〜10モルの酸化エチレンおよび／または酸化
プロピレンを、必要によりアミン化合物等の付加
反応触媒の存在下に反応させて得られる。 The bisphenol A alkylene oxide adduct used in preparing the α,β-ethylenically unsaturated polyester (A) is represented by the above general formula, and is usually used in an amount of 2 to 10 per mole of bisphenol A. It is obtained by reacting moles of ethylene oxide and/or propylene oxide in the presence of an addition reaction catalyst such as an amine compound, if necessary.
α，β−エチレン性不飽和ポリエステル(A)を得
るために使用されるα，β−不飽和二塩基酸とし
ては、例えばマレイン酸、ハロゲン化マレイン
酸、フマル酸、無水マレイン酸などを挙げること
ができ、飽和二塩基酸としては、例えばフタル
酸、無水フタル酸、イソフタル酸、テレフタル
酸、テトラヒドロ無水フタル酸、コハク酸、アジ
ピン酸、セバシン酸などを挙げることができる。 Examples of the α,β-unsaturated dibasic acid used to obtain the α,β-ethylenically unsaturated polyester (A) include maleic acid, halogenated maleic acid, fumaric acid, maleic anhydride, etc. Examples of the saturated dibasic acids include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, succinic acid, adipic acid, and sebacic acid.
また、α，β−エチレン性不飽和ポリエステル
(A)を得るための多価アルコールとしては、前記の
ビスフエノールＡアルキレンオキシド付加物以外
に必要ならばエチレングリコール、１，２−プロ
ピレングリコール、１，３−プロピレングリコー
ル、ジエチレングリコール、トリエチレングリコ
ール、ジプロピレングリコール、１，３−ブタン
ジオール、ネオペンチルグリコール、水素化ビス
フエノールＡ、グリセリン、ペンタエリスリトー
ルなどが使用できる。 In addition, α,β-ethylenically unsaturated polyester
In addition to the above bisphenol A alkylene oxide adduct, the polyhydric alcohol for obtaining (A) may include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, if necessary. Dipropylene glycol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, glycerin, pentaerythritol, etc. can be used.
この不飽和ポリエステル(A)の使用量は、樹脂組
成物(I)中30〜50重量％の範囲である。この範囲外
では、樹脂組成物(I)の粘度が高くなり、水酸化ア
ルミニウム分散時の作業性が悪くなつたり、硬化
して得られる物品の透明性が悪くなり人造大理石
物品として価値の低いものしか得られない。 The amount of this unsaturated polyester (A) used is in the range of 30 to 50% by weight in the resin composition (I). If it is outside this range, the viscosity of the resin composition (I) will be high, and the workability during dispersion of aluminum hydroxide will be poor, and the transparency of the product obtained by curing will be poor, resulting in low value as an artificial marble product. I can only get it.
本発明における架橋性単量体(B)としては、例え
ばスチレン、α−メチルスチレン、クロロスチレ
ン、ビニルトルエン、アクリル酸エステル類、メ
タクリル酸エステル類、ジアリルフタレート、ジ
ビニルベンゼン、トリメチロールプロパントリメ
タクリレート、トリメチロールプロパントリアク
リレート、ペンタエリスリトールトリメタクリレ
ート、ペンタエリスリトールトリアクリレートな
どを挙げることができ、特にスチレンが有効であ
り、単独あるいは他の単量体と併用して使用する
ことが好ましい。 Examples of the crosslinkable monomer (B) in the present invention include styrene, α-methylstyrene, chlorostyrene, vinyltoluene, acrylic esters, methacrylic esters, diallylphthalate, divinylbenzene, trimethylolpropane trimethacrylate, Examples include trimethylolpropane triacrylate, pentaerythritol trimethacrylate, and pentaerythritol triacrylate. Styrene is particularly effective and is preferably used alone or in combination with other monomers.
架橋性単量体(B)の使用範囲としては樹脂組成物
(I)中20〜50重量％である。20重量％より少ないと
樹脂組成物(I)の粘度が高くなり水酸化アルミニウ
ム分散時の作業性が悪くなり、50重量％を超える
多量になると硬化して得られる物品の透明性が悪
くなる。 The crosslinking monomer (B) can be used in resin compositions.
It is 20 to 50% by weight in (I). When the amount is less than 20% by weight, the viscosity of the resin composition (I) becomes high and the workability during dispersion of aluminum hydroxide becomes poor, and when the amount exceeds 50% by weight, the transparency of the cured article becomes poor.
本発明におけるポリスチレン系重合体(C)として
は、スチレン単独又はスチレンを70重量％以上含
んでなる単量体混合物を重合して得られるポリス
チレン又はポリスチレン系共重合体であり、その
分子量は5000〜100万程度である。ポリスチレン
系重合体(C)の使用量としては、樹脂組成物(I)中20
〜40重量％の範囲である。20重量％より少ない
と、成形硬化時の収縮が大きくなりクラツクや歪
が発生しやすくなり、また得られる物品の表面平
滑性や透明性が悪くなる。逆に40重量％より多く
なると、樹脂組成物(I)の粘度が高くなり水酸化ア
ルミニウム分散時の作業性が悪くなつたり、硬化
して得られる物品の表面光沢が悪くなる。 The polystyrene polymer (C) in the present invention is a polystyrene or polystyrene copolymer obtained by polymerizing styrene alone or a monomer mixture containing 70% by weight or more of styrene, and has a molecular weight of 5000 to 5000. It is about 1 million. The amount of polystyrene polymer (C) used is 20% in the resin composition (I).
~40% by weight. If it is less than 20% by weight, shrinkage during molding and curing will increase, making cracks and distortions more likely to occur, and the surface smoothness and transparency of the resulting article will deteriorate. On the other hand, if the amount exceeds 40% by weight, the viscosity of the resin composition (I) increases, resulting in poor workability during dispersion of aluminum hydroxide and poor surface gloss of the cured article.
ポリスチレン系重合体(C)を得るに際し、スチレ
ンと必要により共重合される単量体成分として
は、例えばメタクリル酸又はそのエステル類、ア
クリル酸又はそのエステル類、無水マレイン酸、
マレイン酸エステル類、ブタジエンなどを挙げる
ことができるが、そのような単量体成分の使用量
は、ポリスチレン系重合体(C)を構成する全単量体
中30重量％以下にする必要がある。スチレン以外
の単量体成分を30重量％より多量に用いて得られ
た重合体では、成形硬化して得られる物品の透明
性が悪くなる。 When obtaining the polystyrene polymer (C), monomer components to be optionally copolymerized with styrene include, for example, methacrylic acid or its esters, acrylic acid or its esters, maleic anhydride,
Examples include maleic acid esters and butadiene, but the amount of such monomer components used must be 30% by weight or less based on the total monomers constituting the polystyrene polymer (C). . A polymer obtained by using a monomer component other than styrene in an amount greater than 30% by weight deteriorates the transparency of the article obtained by molding and curing.
本発明で用いられる樹脂組成物(I)は、前記した
α，β−エチレン性不飽和ポリエステル(A)、架橋
性単量体(B)およびポリスチレン系重合体(C)からな
り、例えばこれらの３成分を撹拌下に混合して得
られる。 The resin composition (I) used in the present invention consists of the above-described α,β-ethylenically unsaturated polyester (A), a crosslinkable monomer (B), and a polystyrene polymer (C), such as It is obtained by mixing the three components under stirring.
このようにして得られる樹脂組成物(I)に水酸化
アルミニウムを分散するが、水酸化アルミニウム
の使用量は、樹脂組成物(I)100重量部に対して20
〜300重量部の範囲の割合である。この使用量が
20重量部より少ないと、成形硬化時の収縮率が大
きくなり、得られる物品に歪や艷むらが生じやす
くなる。また、300重量部より多くなると、水酸
化アルミニウム分散時の作業性が悪くなり、得ら
れる物品の透明性も悪くなる。 Aluminum hydroxide is dispersed in the resin composition (I) obtained in this way, and the amount of aluminum hydroxide used is 20 parts by weight per 100 parts by weight of the resin composition (I).
The proportion ranges from ~300 parts by weight. This usage is
If the amount is less than 20 parts by weight, the shrinkage rate during molding and curing will increase, making it easy for the resulting article to be distorted or uneven. Moreover, if the amount exceeds 300 parts by weight, the workability during dispersion of aluminum hydroxide will deteriorate, and the transparency of the obtained article will also deteriorate.
水酸化アルミニウムを分散するには、例えばバ
ンバリー型ニーダー等の低速混練機、デイスパー
等の高速撹拌機、塗料製造用の顔料分散機あるい
は混練ロールなどを用いれば良いが、中でも混練
力の強い低速混練機が好ましい。 To disperse aluminum hydroxide, for example, a low-speed kneader such as a Banbury-type kneader, a high-speed stirrer such as a disper, a pigment dispersion machine for paint manufacturing, or a kneading roll may be used, but among these, a low-speed kneader with a strong kneading power can be used. machine is preferred.
樹脂組成物(I)に水酸化アルミニウムを分散する
に際し、分散工程の前後あるいは分散中に、必要
に応じて本発明の効果を阻害しない範囲の各種充
填剤、内部離型剤、重合禁止剤、増粘剤、繊維状
補強材、揺変剤、可塑剤、難燃剤や耐炎剤、着色
剤などを加えてもよい。 When dispersing aluminum hydroxide in the resin composition (I), various fillers, internal mold release agents, polymerization inhibitors, Thickeners, fibrous reinforcing agents, thixotropic agents, plasticizers, flame retardants, colorants, and the like may be added.
水酸化アルミニウムと併用可能な充填剤として
は、例えば水酸化マグネシウム、水酸化カルシウ
ム、炭酸カルシウム、タルク、クレー、シリカ、
アルミナ、石英、ケイ酸カルシウム、ガラスパウ
ダーなどを挙げることができる。内部離型剤とし
ては、例えばステアリン酸、ステアリン酸亜鉛、
ステアリン酸カルシウムなどを使用できる。重合
禁止剤としては、例えばハイドロキノン、ベンゾ
キノン、ｔ−ブチルハイドロキノンなどが使用で
きる。増粘剤としては、例えば酸化マグネシウ
ム、酸化カルシウム、水酸化マグネシウム、水酸
化カルシウムなどが使用できる。繊維状補強材と
しては、例えばガラス繊維、ミルドフアイバー、
ビニロン繊維、アルミナウイスカーなどが使用で
きる。 Examples of fillers that can be used in combination with aluminum hydroxide include magnesium hydroxide, calcium hydroxide, calcium carbonate, talc, clay, silica,
Examples include alumina, quartz, calcium silicate, and glass powder. Examples of internal mold release agents include stearic acid, zinc stearate,
Calcium stearate etc. can be used. As the polymerization inhibitor, for example, hydroquinone, benzoquinone, t-butylhydroquinone, etc. can be used. As the thickener, for example, magnesium oxide, calcium oxide, magnesium hydroxide, calcium hydroxide, etc. can be used. Examples of fibrous reinforcing materials include glass fiber, milled fiber,
Vinylon fiber, alumina whiskers, etc. can be used.
本発明において、樹脂組成物(I)に水酸化アルミ
ニウムを分散した後に加圧成形硬化するには、硬
化剤を添加配合して、プレス成形、射出成形、ト
ランスフアー成形、押出成形等の加熱加圧成形法
によつて成形硬化すればよく、特に135〜160℃に
加熱された合せ金型内や押圧機で成形すると、表
面光沢にすぐれクラツクや歪のない半透明の美麗
な人造大理石物品を単純なものから複雑なものま
でその形状のいかんにかかわらず生産性良く製造
することができる。 In the present invention, in order to perform pressure molding curing after dispersing aluminum hydroxide in the resin composition (I), a curing agent is added and blended, and heat processing such as press molding, injection molding, transfer molding, extrusion molding, etc. It can be molded and hardened using a compression molding method, especially when molded in a mold heated to 135-160°C or in a press machine, it can produce beautiful translucent artificial marble products with excellent surface gloss and no cracks or distortions. It can be manufactured with high productivity regardless of its shape, from simple to complex.
硬化剤としては、例えばｔ−ブチルパーオキシ
ベンゾエート、ラウロイルパーオキサイド、ビス
−（４−ブチルシクロヘキシル）パーオキシジカ
ーボネート、１，１，３，３−テトラメチルブチ
ルパーオキシ２−エチルヘキサノエート、ｔ−ブ
チルパーオクトエートなど通常のものを使用する
ことができる。硬化剤の添加時期は特に制限な
く、水酸化アルミニウムの分散工程の前後あるい
は分散中のいずれでもよく、硬化剤の添加量は樹
脂組成物(I)の重量を基準として0.3〜3.0％に相当
する量とするのが普通である。 Examples of the curing agent include t-butyl peroxybenzoate, lauroyl peroxide, bis-(4-butylcyclohexyl) peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, Common materials such as t-butyl peroctoate can be used. The timing of addition of the curing agent is not particularly limited, and may be before or after the dispersion step of aluminum hydroxide, or during dispersion, and the amount of curing agent added is equivalent to 0.3 to 3.0% based on the weight of the resin composition (I). It is usually expressed as quantity.
（発明の効果）
本発明の人造大理石物品の製法によれば単純な
ものから複雑なものまでその形状のいかんにかか
わらず加熱加圧成形法により生産性良く製造さ
れ、しかも従来の加熱加圧成形法による人造大理
石物品にみられたクラツクや歪あるいは表面光沢
の欠如といつた欠点が全くない半透明性の美麗な
ものが得られる。(Effects of the Invention) According to the manufacturing method of the artificial marble article of the present invention, regardless of the shape of the article, from simple to complex, it can be manufactured with high productivity by the hot press molding method, and moreover, it can be manufactured with high productivity by the hot press molding method. A beautiful translucent product can be obtained that is completely free of defects such as cracks, distortion, and lack of surface gloss that are found in artificial marble products produced by the method.
したがつて、本発明の製造法で得られる人造大
理石物品は、浴槽・キツチンカウンター・洗面化
粧台等の住宅機材、釦生地、建材、車輛部品等の
FRP用途に広く用いられるものである。 Therefore, the artificial marble articles obtained by the manufacturing method of the present invention can be used for housing equipment such as bathtubs, kitchen counters, washstands, button fabrics, building materials, vehicle parts, etc.
It is widely used for FRP applications.
（実施例）
以下、実施例を挙げて本発明を具体的に示す。
なお、以下に用いる部は特にことわりのないかぎ
り重合部を意味する。(Example) Hereinafter, the present invention will be specifically illustrated by giving examples.
Note that the parts used below mean polymerization parts unless otherwise specified.
実施例 １
無水マレイン酸78.4部、イソフタル酸33.2部、
プロピレングリコール41.8部（0.55モル）および
ビスフエノールＡエチレンオキシド付加物（エチ
レンオキシドの平均付加モル数は2.7、平均分子
量348）174部（0.50モル）を常法により不活性気
流中150〜230℃の温度で20時間縮合反応させ、酸
価25の不飽和ポリエステルを得た。Example 1 78.4 parts of maleic anhydride, 33.2 parts of isophthalic acid,
41.8 parts (0.55 mol) of propylene glycol and 174 parts (0.50 mol) of bisphenol A ethylene oxide adduct (average number of added moles of ethylene oxide is 2.7, average molecular weight 348) were added in a conventional manner at a temperature of 150 to 230°C in an inert gas stream. A condensation reaction was carried out for 20 hours to obtain an unsaturated polyester with an acid value of 25.
次いで、この不飽和ポリエステル55部、スチレ
ン45部およびハイドロキノン0.01部を混合して相
互溶解せしめ、不飽和ポリエステル樹脂（以下、
樹脂(1)という。）を得た。この樹脂(1)100部とポリ
スチレン（分子量約10万）40部とを混合して得た
樹脂組成物140部、水酸化アルミニウム（昭和軽
金属(株)製、ハイジライトＨ−310）300部、硬化剤
のｔ−ブチルパーオキシベンゾエート1.3部、ス
テアリン酸亜鉛４部およびガラス繊維（６mm長）
20部をバンバリー型ニーダーにて混合し、加熱加
圧成形用材料を得た。 Next, 55 parts of this unsaturated polyester, 45 parts of styrene, and 0.01 part of hydroquinone were mixed and dissolved together to form an unsaturated polyester resin (hereinafter referred to as
It is called resin (1). ) was obtained. 140 parts of a resin composition obtained by mixing 100 parts of this resin (1) and 40 parts of polystyrene (molecular weight approximately 100,000), 300 parts of aluminum hydroxide (Hygilite H-310, manufactured by Showa Light Metal Co., Ltd.), Curing agent t-butyl peroxybenzoate 1.3 parts, zinc stearate 4 parts and glass fiber (6 mm length)
20 parts were mixed in a Banbury-type kneader to obtain a material for hot-press molding.
この材料750gを300×300mmの金型内に入れ、
135℃、５分間、70トンの圧力条件で成形した。
その結果、光透過率15％で美麗に光を散乱する半
透明性であり、収縮率0.15％でクラツクやそり歪
のない、厚さ５mmの人造大理石成形品を得た。 Put 750g of this material into a 300x300mm mold,
Molding was carried out at 135°C for 5 minutes and at a pressure of 70 tons.
As a result, we obtained an artificial marble molded product with a thickness of 5 mm, which had a translucency that beautifully scattered light with a light transmittance of 15%, a shrinkage rate of 0.15%, and no cracks or warpage.
実施例 ２
無水マレイン酸98部およびビスフエノールＡプ
ロピレンオキシド付加物（プロピレンオキシドの
平均付加モル数は2.2、平均分子量356）374部よ
り実施例１と同様にして、酸価30の不飽和ポリエ
ステルを得た。この不飽和ポリエステル50部、ス
チレン50部およびハイドロキノン0.01部を混合し
て相互溶解せしめ、不飽和ポリエステル樹脂（以
下、樹脂(2)という。）を得た。この樹脂(2)100部と
スチレン系共重合体（共重合組成スチレン95％、
アクリル酸５％、分子量約15万）35部とを混合し
て得た樹脂組成物135部、水酸化アルミニウム
（昭和軽金属(株)製ハイジライトＨ−310）200部、
硬化剤のｔ−ブチルパーオキシオクトエート1.3
部、ステアリン酸亜鉛３部およびガラス繊維（６
mm長）20部より、実施例１と同様にして加熱加圧
成形用材料を得た。この材料を実施例１と同様に
して成形したところ、光透過率18％で美麗に光を
散乱する半透明性であり、収縮率0.16％でクラツ
クやそり歪のない、厚さ５mmの人造大理石成形品
を得た。Example 2 An unsaturated polyester with an acid value of 30 was prepared in the same manner as in Example 1 from 98 parts of maleic anhydride and 374 parts of bisphenol A propylene oxide adduct (average number of moles of propylene oxide added was 2.2, average molecular weight 356). Obtained. 50 parts of this unsaturated polyester, 50 parts of styrene, and 0.01 part of hydroquinone were mixed and mutually dissolved to obtain an unsaturated polyester resin (hereinafter referred to as resin (2)). 100 parts of this resin (2) and a styrene copolymer (copolymer composition 95% styrene,
135 parts of a resin composition obtained by mixing 35 parts of acrylic acid (5%, molecular weight approximately 150,000), 200 parts of aluminum hydroxide (Hygilite H-310 manufactured by Showa Light Metal Co., Ltd.),
Curing agent t-butyl peroxyoctoate 1.3
part, 3 parts zinc stearate and glass fiber (6 parts
A material for hot-press molding was obtained in the same manner as in Example 1 from 20 parts (mm length). When this material was molded in the same manner as in Example 1, it was found to be a 5 mm thick artificial marble with a light transmittance of 18%, a translucent structure that beautifully scatters light, a shrinkage rate of 0.16%, and no cracks or warpage. A molded product was obtained.
比較例 １
無水マレイン酸78.4部、イソフタル酸33.2部お
よびプロピレングリコール79.8部より実施例１と
同様にして、酸価35の不飽和ポリエステルを得
た。この不飽和ポリエステル55部、スチレン45部
およびハイドロキノン0.01部を混合して相互溶解
せしめ、不飽和ポリエステル樹脂（以下、比較用
樹脂(1)という。）を得た。Comparative Example 1 An unsaturated polyester having an acid value of 35 was obtained in the same manner as in Example 1 from 78.4 parts of maleic anhydride, 33.2 parts of isophthalic acid and 79.8 parts of propylene glycol. 55 parts of this unsaturated polyester, 45 parts of styrene, and 0.01 part of hydroquinone were mixed and mutually dissolved to obtain an unsaturated polyester resin (hereinafter referred to as comparative resin (1)).
実施例１における樹脂(1)の代わりに比較用樹脂
(1)を同量使用する以外は実施例１と同様にして比
較用成形品を得た。得られた比較用成形品は、光
透過率７％で白色不透明の外観を有し、収縮率は
0.15％であるが、表面にポリスチレン様の樹脂が
浮き出して表面光沢に欠けたものであつた。 Comparative resin instead of resin (1) in Example 1
Comparative molded products were obtained in the same manner as in Example 1 except that the same amount of (1) was used. The comparative molded product obtained had a light transmittance of 7%, a white opaque appearance, and a shrinkage rate of
Although it was 0.15%, polystyrene-like resin stood out on the surface and the surface lacked gloss.
比較例 ２
実施例１におけるポリスチレンを使用しなかつ
た以外は実施例１と同様にして比較用成形品を得
た。この比較用成形品は、光透過率４％で白色不
透明の外観を有し、全面に艷むらを示した。Comparative Example 2 A comparative molded article was obtained in the same manner as in Example 1, except that the polystyrene in Example 1 was not used. This comparative molded product had a light transmittance of 4%, a white opaque appearance, and showed unevenness on the entire surface.
実施例 ３
実施例１におけるポリスチレンの量を10部とす
る他は実施例１と同様にして比較用成形品を得
た。この比較用成形品は、光透過率５％で白色不
透明の外観を有し、艷むらを示した。Example 3 A molded article for comparison was obtained in the same manner as in Example 1 except that the amount of polystyrene in Example 1 was changed to 10 parts. This comparative molded product had a light transmittance of 5%, a white opaque appearance, and exhibited unevenness.
Claims (1)
異なつていてもよい炭素数２〜３のアルキレン基
を示し、ｍおよびｎはそれぞれ０又は１〜10の整
数であり且つｍ＋ｎは２〜10の整数である。）で
表わされるビスフエノールＡアルキレンオキシド
付加物を10〜100モル％含有する多価アルコール
を、必須成分として導かれるα，β−エチレン性
不飽和ポリエステル(A)30〜50重量％、架橋性単量
体(B)20〜50重量％およびポリスチレン系重合体(C)
20〜40重量％（ただし、(A)、(B)および(C)成分の合
計は100重量％である。）からなる樹脂組成物(I)
100重量部に対して、水酸化アルミニウム20〜300
重量部を分散した後、135〜160℃の温度で加圧成
形・硬化することを特徴とする人造大理石物品の
製法。[Claims] 1. General formula (However, in the formula, R 1 and R 2 each represent an alkylene group having 2 to 3 carbon atoms, which may be the same or different, m and n are each an integer of 0 or 1 to 10, and m+n is 2 to α,β-ethylenically unsaturated polyester (A) containing 10 to 100 mol% of a bisphenol A alkylene oxide adduct represented by (an integer of 10) as an essential component. Weight%, crosslinkable monomer (B) 20-50% by weight and polystyrene polymer (C)
Resin composition (I) consisting of 20 to 40% by weight (however, the total of components (A), (B) and (C) is 100% by weight)
20-300 parts of aluminum hydroxide per 100 parts by weight
A method for producing an artificial marble article, which comprises dispersing parts by weight and then pressure forming and curing at a temperature of 135 to 160°C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61273026A JPS63128057A (en) | 1986-11-18 | 1986-11-18 | Artificial marble article |
| KR1019870005012A KR920008577B1 (en) | 1986-05-20 | 1987-05-20 | Marble-like material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61273026A JPS63128057A (en) | 1986-11-18 | 1986-11-18 | Artificial marble article |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63128057A JPS63128057A (en) | 1988-05-31 |
| JPH0257086B2 true JPH0257086B2 (en) | 1990-12-04 |
Family
ID=17522129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61273026A Granted JPS63128057A (en) | 1986-05-20 | 1986-11-18 | Artificial marble article |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63128057A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0653376B2 (en) * | 1988-09-02 | 1994-07-20 | 富士電機株式会社 | Polyester premix for injection molding |
| JP4245751B2 (en) * | 1999-10-18 | 2009-04-02 | ジャパンコンポジット株式会社 | Unsaturated polyester resin and composition for molding material |
| JP6137726B2 (en) * | 2013-03-25 | 2017-05-31 | Toto株式会社 | Artificial marble, bathtub, and method of manufacturing artificial marble |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141890A (en) * | 1976-05-21 | 1977-11-26 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition |
| JPS5890921A (en) * | 1981-11-25 | 1983-05-30 | Hitachi Chem Co Ltd | Manufacture of artificial marble |
-
1986
- 1986-11-18 JP JP61273026A patent/JPS63128057A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52141890A (en) * | 1976-05-21 | 1977-11-26 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition |
| JPS5890921A (en) * | 1981-11-25 | 1983-05-30 | Hitachi Chem Co Ltd | Manufacture of artificial marble |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63128057A (en) | 1988-05-31 |
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