JP2020100753A - Solid molding material and its molded product - Google Patents
Solid molding material and its molded product Download PDFInfo
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- 239000012778 molding material Substances 0.000 title claims abstract description 38
- 239000007787 solid Substances 0.000 title claims abstract description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 42
- 229920005989 resin Polymers 0.000 claims abstract description 34
- 239000011347 resin Substances 0.000 claims abstract description 34
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 23
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims description 16
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002928 artificial marble Substances 0.000 abstract description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 32
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 239000003112 inhibitor Substances 0.000 description 10
- 239000003505 polymerization initiator Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002562 thickening agent Substances 0.000 description 10
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 9
- 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 8
- 239000000395 magnesium oxide Substances 0.000 description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 8
- -1 methacryloyl group Chemical group 0.000 description 8
- NLSFWPFWEPGCJJ-UHFFFAOYSA-N 2-methylprop-2-enoyloxysilicon Chemical compound CC(=C)C(=O)O[Si] NLSFWPFWEPGCJJ-UHFFFAOYSA-N 0.000 description 7
- 239000004412 Bulk moulding compound Substances 0.000 description 7
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 239000003677 Sheet moulding compound Substances 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000010954 inorganic particle Substances 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920006284 nylon film Polymers 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-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
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 230000000052 comparative effect Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011344 liquid material Substances 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
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 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
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide 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
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012948 isocyanate 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 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
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229910052628 phlogopite Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- 230000008719 thickening Effects 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、人造大理石等の成形に使用可能な固体状成形材料に関するものであり、より詳細には、耐擦傷性等の表面特性に優れた人造大理石をプレス成形により生産性良く成形可能な固体状成形材料及びその成形品に関する。 The present invention relates to a solid molding material that can be used for molding artificial marble and the like. More specifically, a solid molding material that is excellent in surface characteristics such as scratch resistance and can be molded with high productivity by press molding. A molding material and a molded product thereof.
人造大理石として、メタクリレート等を主成分とするアクリル系シロップに、水酸化アルミニウム、ガラス粉等の無機充填剤を添加して成るものが、従来より広く知られている。このようなアクリル系樹脂を使用した人造大理石は、美観や耐候性に優れていると共に、加工性や成形性にも優れていることから、システムキッチンや洗面化粧台等の天板、家具の面材、洗面カウンター或いはバスタブ等の種々の用途に好適に使用されている。
また、成形材料を液状ではなく固体状にしてハンドリング性を上げ、さらに生産性が上がるプレス成形が可能な材料として、不飽和ポリエステル樹脂に水酸化アルミニウム、ガラス粉等の無機充填剤を添加して成る成形材料（ＢＭＣ（バルクモールディングコンパウンド）及び／又はＳＭＣ（シートモールディングコンパウンド））も上記用途に好適に使用されている。
しかしながら、これらの人造大理石は摩擦等によって表面に傷がつきやすく、耐擦傷性の点で未だ十分満足するものではなかった。
BACKGROUND ART As an artificial marble, an acrylic syrup containing methacrylate as a main component and an inorganic filler such as aluminum hydroxide or glass powder added thereto has been widely known. Artificial marble using such acrylic resin has excellent aesthetics and weather resistance, as well as excellent workability and moldability. It is preferably used for various purposes such as wood, wash counters and bathtubs.
Further, as a material capable of press molding in which the molding material is in a solid state rather than a liquid state to improve the handling property and further increase the productivity, aluminum hydroxide, an inorganic filler such as glass powder is added to the unsaturated polyester resin. The molding material (BMC (bulk molding compound) and/or SMC (sheet molding compound)) is also suitably used for the above applications.
However, these artificial marbles are apt to be scratched on the surface due to friction or the like, and are not yet sufficiently satisfactory in terms of scratch resistance.
このような従来の人造大理石の問題を解決するものとして、例えば、下記特許文献１には、露呈面及び後面において比重の異なる無機充填剤をアクリレートポリマー等のポリマーマトリックスに配合して成る二層構成の一体ボード状部材が記載されている。
更に、下記特許文献２には、樹脂と、無機粒子とを備える人工大理石であって、前記無機粒子が、１０段階モース硬度５以上の硬質粒子を、無機粒子全体に対して３０ｖｏｌ％を超えて含み、前記人工大理石表面において前記無機粒子が占める面積の割合が４８％を超え９９％未満であり、且つ前記人工大理石全体において前記無機粒子が占める体積割合が３０ｖｏｌ％を超え５３ｖｏｌ％未満であることを特徴とする人工大理石が記載されている。
As a means for solving such a problem of the conventional artificial marble, for example, in Patent Document 1 below, a two-layer structure formed by blending an inorganic filler having a different specific gravity on the exposed surface and the rear surface into a polymer matrix such as an acrylate polymer , An integral board-shaped member is described.
Further, in Patent Document 2 below, an artificial marble comprising a resin and inorganic particles, wherein the inorganic particles are hard particles having a 10-step Mohs hardness of 5 or more in an amount of more than 30 vol% with respect to the entire inorganic particles. Including, the ratio of the area occupied by the inorganic particles on the surface of the artificial marble is more than 48% and less than 99%, and the volume ratio of the inorganic particles in the entire artificial marble is more than 30 vol% and less than 53 vol%. An artificial marble characterized by is described.
しかしながら、上記特許文献１に記載されたボート状部材及び特許文献２に記載された人造大理石は、いずれも液状の成形材料を金型に注ぎ込んで加熱硬化して成形されるものであり、さらに生産工程が多く、金型一型当たりの生産性が劣るというものであり、ハンドリング性の良いＢＭＣやＳＭＣのような固体状材料を用い、生産性に優れたプレス成形等で成形できるものではない。 However, both the boat-shaped member described in Patent Document 1 and the artificial marble described in Patent Document 2 are molded by pouring a liquid molding material into a mold and heating and curing the molding material. This is because the number of steps is large and the productivity per mold is inferior, and solid materials such as BMC and SMC, which have good handling properties, are used, and they cannot be molded by press molding or the like with excellent productivity.
従って本発明の目的は、液状原料の注型成形によらず、固体原料を使いプレス成形により人造大理石等を成形可能であり、耐擦傷性に優れた人造大理石を提供することである。 Therefore, an object of the present invention is to provide an artificial marble excellent in scratch resistance, which is capable of forming an artificial marble or the like by press molding using a solid material instead of cast molding of a liquid material.
本発明によれば、不飽和ポリエステル樹脂及び／又はビニルエステル樹脂を含有する成形材料に対し、シリカを７４〜８５重量％の量で含有することを特徴とする固体状成形材料が提供される。 According to the present invention, there is provided a solid molding material characterized by containing silica in an amount of 74 to 85% by weight based on a molding material containing an unsaturated polyester resin and/or a vinyl ester resin.
本発明の固体状成形材料においては、
１．前記シリカが、表面処理された結晶性シリカであること、
２．前記シリカの平均粒径が、５〜１５０μｍの範囲にあること、
３．前記シリカが、平均粒径の異なる２種類以上のシリカをブレンドしたものであること、
４．耐擦傷性の評価はＪＩＳＫ５６００、引っかき硬度（鉛筆法）での鉛筆硬度およびＪＩＳＫ６９１１の成形品の硬さであるバーコル硬度での評価とした場合、成形品は鉛筆硬度が９Ｈ以上且つバーコル硬さが７５以上であること、
が好適である。
本発明によればまた、上記固体状成形材料をプレス成形して成ることを特徴とする成形品が提供される。
In the solid molding material of the present invention,
1. The silica is a surface-treated crystalline silica,
2. The average particle diameter of the silica is in the range of 5 to 150 μm,
3. The silica is a blend of two or more kinds of silica having different average particle diameters,
4. The scratch resistance is evaluated according to JIS K5600, pencil hardness according to scratch hardness (pencil method) and bark hardness according to JIS K6911, which is the hardness of the molded product. 75 or more,
Is preferred.
According to the present invention, there is also provided a molded product characterized by being press-molded from the above solid molding material.
本発明品は、ハンドリング性に優れた固体状成形材料であり、プレス成形により人造大理石等の成形品を成形可能であることから、従来の液状原料の注型成形に比して、生産性が顕著に優れている。例えば、前述した特許文献２においては、金型内での硬化時間が９０分と記載されているが、本発明品では硬化時間が肉厚１ｍｍあたり１〜２分であるため、１５ｍｍの成形でも金型内での硬化が１５〜３０分と特許文献２よりも一つの金型における単位時間での生産数が多くなる。 The product of the present invention is a solid molding material having excellent handleability, and since it is possible to mold a molded product such as artificial marble by press molding, productivity is higher than that of conventional liquid material casting molding. Remarkably excellent. For example, in the above-mentioned Patent Document 2, the curing time in the mold is described as 90 minutes, but in the product of the present invention, since the curing time is 1 to 2 minutes per 1 mm of wall thickness, even with molding of 15 mm. Curing in the mold is 15 to 30 minutes, which means that the number of products produced in one mold per unit time is larger than in Patent Document 2.
（マトリックス樹脂）
本発明の固体状成形材料において、マトリックス樹脂としては、不飽和ポリエステル樹脂及び／又はビニルエステル樹脂を使用する。これらの樹脂は、それぞれ単独でも使用できるが、ブレンドして用いることもできる。
(Matrix resin)
In the solid molding material of the present invention, an unsaturated polyester resin and/or a vinyl ester resin is used as the matrix resin. These resins can be used alone or in a blend.
不飽和ポリエステル樹脂は、一般に無水マレイン酸またはフマル酸のような不飽和酸と無水フタル酸、イソフタル酸、テレフタル酸、アジピン酸、セバシン酸、コハク酸、グルコン酸等の飽和塩基酸を併用して、プロピレングリコール、エチレングリコール、ジエチレングリコール、ネオペンチルグリコール、水素添加ビスフェノールＡ等のグリコール類などをエステル化して得られる不飽和アルキドをスチレンモノマー、ビニルトルエン、トリアリルシアヌレート、ジアリルフタレート、メチルメタクリレートモノマーなどのビニルモノマーに溶解して得られるものである。
ビニルエステル樹脂は、分子内に複数のエポキシ基を有する化合物、例えばビスフェノールＡ型エポキシ樹脂やノボラック型エポキシ樹脂と、アクリル酸あるいはメタクリル酸を反応させることにより得られる、分子内に複数のアクリロイル基あるいはメタクリロイル基を有する化合物である。
不飽和ポリエステル樹脂及びビニルエステル樹脂は、従来のＳＭＣおよび／またはＢＭＣの製造に用いられていたグレードのものを使用することが好適である。
The unsaturated polyester resin is generally a combination of an unsaturated acid such as maleic anhydride or fumaric acid and a saturated basic acid such as phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, succinic acid, and gluconic acid. Unsaturated alkyds obtained by esterifying glycols such as propylene glycol, ethylene glycol, diethylene glycol, neopentyl glycol, hydrogenated bisphenol A, etc. are styrene monomer, vinyltoluene, triallyl cyanurate, diallyl phthalate, methyl methacrylate monomer, etc. It is obtained by dissolving it in the vinyl monomer.
The vinyl ester resin is a compound having a plurality of epoxy groups in the molecule, for example, a bisphenol A type epoxy resin or a novolac type epoxy resin, and a plurality of acryloyl groups or acryloyl groups in the molecule obtained by reacting acrylic acid or methacrylic acid. It is a compound having a methacryloyl group.
As the unsaturated polyester resin and the vinyl ester resin, it is preferable to use the grades that have been used in the conventional production of SMC and/or BMC.
また、通常のＢＭＣ、ＳＭＣの低収縮剤も使用することができ、不飽和ポリエステル樹脂及び／又はビニルエステル樹脂の配合量の５〜５０重量％、を低収縮剤に置き換えることができる。
低収縮剤は、スチレン系モノマー、ビニルトルエン、トリアリルシアヌレート、ジアリルフタレート、メチルメタクリレート等のビニルモノマーに、ポリスチレン樹脂、スチレン−アクリル酸共重合体、スチレン−酢酸ビニル共重合体、スチレン−ブタジエン共重合体、スチレン−オレフィン共重合体、ポリ（メタ）アクリル酸エステル等の熱可塑性樹脂を溶解したものであり、低収縮剤に占める熱可塑性樹脂の濃度は５〜５０重量％である。
また低収縮剤として０．０１〜５％の架橋密度で三次元化されたスチレン系、アクリル系、酢酸ビニル系、及びこれらの共重合体系の樹脂粉末を使用してもよい。
Further, a general BMC or SMC low-shrinking agent can be used, and 5 to 50% by weight of the blending amount of the unsaturated polyester resin and/or the vinyl ester resin can be replaced with the low-shrinking agent.
The low-shrinking agent is a styrene-based monomer, vinyltoluene, triallyl cyanurate, diallyl phthalate, methyl methacrylate, or another vinyl monomer, and polystyrene resin, styrene-acrylic acid copolymer, styrene-vinyl acetate copolymer, styrene-butadiene. A thermoplastic resin such as a copolymer, a styrene-olefin copolymer and a poly(meth)acrylic acid ester is dissolved, and the concentration of the thermoplastic resin in the low-shrinking agent is 5 to 50% by weight.
Further, as the low-shrinking agent, a styrene-based resin, an acrylic resin-based resin, a vinyl acetate-based resin powder having a three-dimensional structure with a crosslinking density of 0.01 to 5%, or a copolymer powder thereof may be used.
（シリカ）
本発明に用いるシリカとしては、耐擦傷性向上の点から結晶性シリカを使うことが好適であり、特に表面処理が施された結晶性シリカが好適である。
シリカが、カップリング剤等の表面処理剤によって表面処理されていることにより、樹脂とシリカ間の結合が強まり、機械的強度が向上すると共に、混練粘度が下がるためシリカの添加量も多くすることができ、耐擦傷性が向上する。
表面処理剤としては、シランカップリング剤、チタネートカップリング剤、アルミニウムカップリング剤等が挙げられるが、樹脂とシリカ間との結合を強くすることから、ビニルシラン、（メタ）アクリル酸シラン等ビニル基を含むシランカップリング剤であることが好ましい。
表面処理されたシリカは、１種のみが用いられていてもよいし、表面処理剤の異なる２種以上が組み合わせて使用されてもよい。
(silica)
As the silica used in the present invention, it is preferable to use crystalline silica from the viewpoint of improving scratch resistance, and particularly surface-treated crystalline silica is preferable.
Since silica is surface-treated with a surface-treating agent such as a coupling agent, the bond between the resin and silica is strengthened, the mechanical strength is improved, and the kneading viscosity is lowered, so the amount of silica added should be increased. And the scratch resistance is improved.
Examples of the surface treatment agent include a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc., but since they strengthen the bond between the resin and silica, vinyl silane, (meth)acrylic acid silane, etc. A silane coupling agent containing is preferable.
As the surface-treated silica, only one type may be used, or two or more types having different surface-treating agents may be used in combination.
シリカの平均粒径は、５〜１５０μｍの範囲、特に１０〜１００μｍの範囲にあることが好適である。上記範囲にあることにより、混練物は粘調であるが、その粘度が低いため混練がしやすくなる。尚、上記シリカの平均粒径は、レーザー回折散乱方式の粒度分布測定装置を用いて測定した、メディアン径（ｄ５０）の値である。
本発明においては、シリカの平均粒径が上記範囲内にあることを条件として、平均粒径の異なる２種類以上のシリカをブレンドしたものを特に好適に使用することができる。２種の場合は、これに限定されないが、平均粒径が５〜８０μｍの範囲内にあるシリカと、３０〜１７０μｍの範囲にあるシリカを組み合わせることが望ましい。これにより、シリカの充填量を多くすることができ、得られる成形品の耐擦傷性を向上することができる。２種のシリカのブレンド比率は、ブレンドするシリカの平均粒径によって異なり、ブレンドするシリカの平均粒径の差異が大きいほど、平均粒径の大きいシリカを加えることができる。ブレンド比率（重量比、平均粒径の小さいシリカ：平均粒径の大きいシリカ）は、９９：１〜２０：８０の範囲、さらに好ましくは９０：１０〜３０：７０の範囲であることが好ましい。
シリカは、成形材料に対し７４〜８５重量％の範囲、特に７７〜８３重量％の範囲で含有することが好適である。上記範囲よりもシリカの含有量が少ない場合には、鉛筆硬度が９Ｈ未満となることが多く、耐擦傷性が悪くなる一方、上記範囲よりもシリカの含有量が多い場合には混練機で混練しにくくなり、配合物の分散不良を起こしやすくなる。
The average particle diameter of silica is preferably in the range of 5 to 150 μm, particularly preferably 10 to 100 μm. When the content is in the above range, the kneaded product has a viscous viscosity, but since the viscosity is low, the kneading becomes easy. The average particle size of the silica is the value of the median diameter (d50) measured using a particle size distribution analyzer of the laser diffraction scattering method.
In the present invention, a blend of two or more kinds of silica having different average particle diameters can be used particularly preferably, provided that the average particle diameter of silica is within the above range. In the case of two kinds, although not limited to this, it is desirable to combine silica having an average particle diameter of 5 to 80 μm and silica having an average particle diameter of 30 to 170 μm in combination. As a result, the filling amount of silica can be increased, and the scratch resistance of the resulting molded article can be improved. The blending ratio of the two kinds of silica differs depending on the average particle size of the silica to be blended, and the larger the difference in the average particle size of the silica to be blended, the larger the average particle size of the silica can be added. The blending ratio (weight ratio, silica having a small average particle diameter:silica having a large average particle diameter) is preferably in the range of 99:1 to 20:80, more preferably 90:10 to 30:70.
Silica is preferably contained in the range of 74 to 85% by weight, particularly 77 to 83% by weight based on the molding material. When the silica content is less than the above range, the pencil hardness is often less than 9H, and the scratch resistance is deteriorated. On the other hand, when the silica content is more than the above range, kneading is performed by a kneader. It becomes difficult to do so, and the poor dispersion of the compound is likely to occur.
（その他）
本発明の固体状成形材料には、上記マトリックス樹脂及びシリカの他、重合開始剤、重合禁止剤、内部離型剤、増粘剤、顔料、ガラス繊維等、従来よりＳＭＣ及び／又はＢＭＣに配合されていた各種添加剤を公知の処方に従って含有することができる。
重合開始剤としては公知のものを使用することができ、例えば、ジアシルパーオキサイド系、パーオキシエステル系、アルキルパーオキサイド系、パーオキシケタール系等の有機過酸化物を例示できる。
重合禁止剤としては公知のものを使用することができ、ハイドロキノン、トリメチルハイドロキノン、ｐ−ｔ−ブチルカテコール、トルハイドロキノン、ｐ−ベンゾキノン等を例示できる。
内部離型剤としては公知のものを使用することができ、例えば、ステアリン酸等の脂肪酸、ステアリン酸亜鉛等の脂肪酸塩、パラフィンワックス、カルナバワックス等を例示できる。
成形材料を固体にするために使用する増粘剤は公知のものを使用することができ、例えば、酸化マグネシウム、水酸化マグネシウム、酸化カルシウム、水酸化カルシウム等の金属酸化物や金属水酸化物、イソシアネート化合物等を例示できる。
ガラス繊維は主に成形品の強度及び／又は耐衝撃性を上げるために配合される。ガラスの種類としてはＥガラス、Ｃガラス、Ｔガラス等があり、繊維径も５〜２５μｍあり、表面処理剤も原料として酢酸ビニル樹脂、アクリル樹脂、エポキシ樹脂、シランカップリング剤等が使われている。必要に応じガラス繊維を配合する場合は、通常のＢＭＣに使用されるものが好適である。
(Other)
In the solid molding material of the present invention, in addition to the above matrix resin and silica, a polymerization initiator, a polymerization inhibitor, an internal release agent, a thickener, a pigment, glass fiber, etc. have been conventionally compounded in SMC and/or BMC. The various additives that have been described can be contained according to a known formulation.
As the polymerization initiator, known ones can be used, and examples thereof include diacyl peroxide-based, peroxy ester-based, alkyl peroxide-based, and peroxyketal-based organic peroxides.
As the polymerization inhibitor, known compounds can be used, and examples thereof include hydroquinone, trimethylhydroquinone, pt-butylcatechol, tolhydroquinone and p-benzoquinone.
Known internal release agents can be used, and examples thereof include fatty acids such as stearic acid, fatty acid salts such as zinc stearate, paraffin wax, and carnauba wax.
As the thickener used for making the molding material solid, known ones can be used, for example, magnesium oxide, magnesium hydroxide, calcium oxide, metal oxides and hydroxides such as calcium hydroxide, An isocyanate compound etc. can be illustrated.
The glass fiber is mainly added to improve the strength and/or impact resistance of the molded product. Types of glass include E-glass, C-glass, T-glass, etc., fiber diameter is 5 to 25 μm, and vinyl acetate resin, acrylic resin, epoxy resin, silane coupling agent, etc. are used as raw materials for the surface treatment agent. There is. When glass fiber is blended as necessary, those used for ordinary BMC are suitable.
本発明の固体状成形材料においては、充填剤としてシリカが必須の成分であるが、シリカの特性を損なわない範囲で他の無機充填材を併用することもでき、これに限定されないが、例えば、酸化アルミニウム、水酸化アルミニウム、水酸化マグネシウム、アルミン酸カルシウム、炭酸カルシウム、炭酸マグネシウム、雲母、合成金雲母、タルク、カオリン、マイカ、セリサイト、無水珪酸、硫酸バリウム等を併用できる。
シリカよりも硬い材料の場合、例えば酸化アルミニウムはシリカの一部として含有させることができ、得られる成形品の表面硬度をさらに向上することができる。酸化アルミニウムの含有量は限定されないが、シリカの１〜７５重量％の範囲で置き換えることができる。
In the solid molding material of the present invention, silica is an essential component as a filler, but other inorganic fillers can also be used in combination within the range not impairing the properties of silica, but are not limited thereto. Aluminum oxide, aluminum hydroxide, magnesium hydroxide, calcium aluminate, calcium carbonate, magnesium carbonate, mica, synthetic phlogopite, talc, kaolin, mica, sericite, anhydrous silicic acid, barium sulfate and the like can be used in combination.
In the case of a material harder than silica, for example, aluminum oxide can be contained as a part of silica, and the surface hardness of the obtained molded article can be further improved. Although the content of aluminum oxide is not limited, it can be replaced within the range of 1 to 75% by weight of silica.
（固体状成形材料の製造）
本発明の固体状成形材料は、シリカを上述した条件で用いる以外は、従来公知の製造方法により製造することができる。すなわち、上述した不飽和ポリエステル樹脂及び／又はビニルエステル樹脂を含有する成形材料に、シリカ及び増粘剤等の添加剤を所定の割合で添加し、ニーダーやプラネタリーミキサー等の従来公知の混練装置で混練物を作製する。次いで、必要により混練物を混練物に含まれるビニルモノマーのガス遮断性を有する包材で外包する。その後必要に応じ、常温〜５０℃の温度条件下で１６〜４８時間加熱することにより増粘させて、固体状成形材料として製造する。
(Manufacture of solid molding material)
The solid molding material of the present invention can be manufactured by a conventionally known manufacturing method, except that silica is used under the conditions described above. That is, to the molding material containing the unsaturated polyester resin and/or vinyl ester resin described above, additives such as silica and a thickener are added at a predetermined ratio, and a conventionally known kneading device such as a kneader or a planetary mixer is used. Make a kneaded product. Next, if necessary, the kneaded product is externally wrapped with a packaging material having a gas blocking property for the vinyl monomer contained in the kneaded product. Then, if necessary, the mixture is heated at room temperature to 50° C. for 16 to 48 hours to increase the viscosity, thereby producing a solid molding material.
（成形品）
本発明の固体状成形材料を用いて人造大理石等の成形品を成型するには、１２０〜１６０℃の温度に調節された金型内に、本発明の固体状成形材料を設置する。次いで、金型を閉じて、成形圧力１〜１５ＭＰａの圧力で肉厚１ｍｍあたり１〜２分の間加圧することにより、成形品が得られる。得られた成形品は、鉛筆硬度（ＪＩＳ Ｋ５６００準拠）が９Ｈ以上且つバーコル硬度（ＪＩＳ Ｋ６９１１準拠）が７５以上の表面硬度を有しており、優れた耐擦傷性を有している。
(Molding)
In order to mold a molded article such as artificial marble using the solid molding material of the present invention, the solid molding material of the present invention is placed in a mold adjusted to a temperature of 120 to 160°C. Next, the mold is closed, and a molded product is obtained by applying a molding pressure of 1 to 15 MPa for 1 to 2 minutes per 1 mm of wall thickness. The obtained molded product has a pencil hardness (JIS K5600 compliant) of 9H or higher and a Barcol hardness (JIS K6911 compliant) of 75 or higher, and has excellent scratch resistance.
以下に具体的な実施例を挙げて説明する。
（実施例１）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、平均粒径１０μｍ）３１０重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
Specific examples will be described below.
(Example 1)
To 100 parts of Resin A consisting of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene) in a weight ratio of 80:20, crystalline silica (east) Kan Material Technology Co., Ltd. prototype, average particle size 10 μm) 310 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent ( 6 parts by weight of zinc stearate and 1 part by weight of a thickener (magnesium oxide) were mixed and kneaded with a kneader.
（実施例２）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、平均粒径１０μｍ）３２５重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
(Example 2)
To 100 parts of Resin A, which is a weight ratio of 80:20 of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene), crystalline silica (east) is used. Can Material Technology Co., Ltd. prototype, average particle size 10 μm) 325 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent ( 6 parts by weight of zinc stearate and 1 part by weight of a thickener (magnesium oxide) were mixed and kneaded with a kneader.
（実施例３）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径２５μｍ）３３５重量部、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径１００μｍ）１００重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
(Example 3)
To 100 parts of Resin A consisting of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene) in a weight ratio of 80:20, crystalline silica (east) Can Material Technology Co., Ltd. Prototype, Methacryloxy Silane Coupling Product, Average Particle Size 25 μm 335 parts by weight, Crystalline Silica (Tokan Material Technology Co. Prototype, Methacryloxy Silane Coupling Product, Average Grain Diameter 100 μm) 100 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent (zinc stearate) 6 parts by weight, thickener 1 part by weight of (magnesium oxide) was mixed and kneaded with a kneader.
（実施例４）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径２５μｍ）５１５重量部、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径１００μｍ）１００重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
(Example 4)
To 100 parts of Resin A consisting of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene) in a weight ratio of 80:20, crystalline silica (east) Can Material Technology Co., Ltd. prototype, methacryloxy silane coupling treated product, average particle size 25 μm 515 parts by weight, crystalline silica (Tokan Material Technology Co. prototype, methacryloxy silane coupling treated product, average particle Diameter 100 μm) 100 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent (zinc stearate) 6 parts by weight, thickener 1 part by weight of (magnesium oxide) was mixed and kneaded with a kneader.
（実施例５）
不飽和ポリエステル樹脂（ビス系不飽和ポリエステル樹脂、スチレン希釈）１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、平均粒径２５μｍ）３３５重量部、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径１００μｍ）１００重量部、重合禁止剤（ｐ−ベンゾキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
(Example 5)
To 100 parts of unsaturated polyester resin (bis unsaturated polyester resin, diluted with styrene), 335 parts by weight of crystalline silica (Tokan Material Technology Co., Ltd. prototype, average particle size 25 μm), crystalline silica (Tokan Material)・Technology Co., Ltd. prototype, methacryloxy silane coupling treated product, average particle size 100 μm) 100 parts by weight, polymerization inhibitor (p-benzoquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 By weight, 6 parts by weight of an internal mold release agent (zinc stearate) and 1 part by weight of a thickener (magnesium oxide) were mixed and kneaded with a kneader.
（実施例６）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径２５μｍ）３６０重量部、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、メタクリロキシ系シランカップリング処理品、平均粒径１００μｍ）１００重量部、重合禁止剤（ｐ−ベンゾキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（ヘキサメチレンジイソシアネートビウレット）８重量部、を配合しニーダーで混練した。
(Example 6)
To 100 parts of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene), 360 parts by weight of crystalline silica (Tokan Material Technology Co., Ltd. prototype, methacryloxy silane coupling treated product, average particle size 25 μm), Crystalline silica (Tokan Material Technology Co., Ltd. prototype, methacryloxy silane coupling treated product, average particle size 100 μm) 100 parts by weight, polymerization inhibitor (p-benzoquinone) 0.03 parts by weight, polymerization initiator (t -Butyl peroxybenzoate) 1 part by weight, an internal release agent (zinc stearate) 6 parts by weight, and a thickener (hexamethylene diisocyanate biuret) 8 parts by weight were mixed and kneaded with a kneader.
実施例１〜６の成形材料をナイロンフィルムで包装し、４５℃の温度条件下で２４時間加熱した。
得られた固形状成形材料を、成形面の温度が１４５℃、裏面の温度が１３０℃に調節された金型内にセットし７ＭＰａの圧力で８分加圧して肉厚６ｍｍの成形板を得た。
得られた成形品の鉛筆硬度（ＪＩＳ Ｋ５６００準拠）を測定した。また表面についてバーコル硬度（ＪＩＳ Ｋ６９１１準拠）を測定した。結果を表１に併せて示す。すべて鉛筆硬度が９Ｈ、バーコル硬度が７５以上である。
The molding materials of Examples 1 to 6 were wrapped with a nylon film and heated under a temperature condition of 45° C. for 24 hours.
The obtained solid molding material is set in a mold in which the temperature of the molding surface is adjusted to 145° C. and the temperature of the back surface is adjusted to 130° C., and a pressure of 7 MPa is applied for 8 minutes to obtain a molding plate having a wall thickness of 6 mm. It was
The pencil hardness (according to JIS K5600) of the obtained molded product was measured. Barcol hardness (according to JIS K6911) was measured on the surface. The results are also shown in Table 1. All have a pencil hardness of 9H and a Barcol hardness of 75 or more.
（比較例１）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、水酸化アルミニウム（平均粒径２５μｍ）４３５重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
混練物をナイロンフィルムで包装し、４５℃の温度条件下で２４時間加熱し熟成した。
得られた固形状成形材料を、成形面の温度が１４５℃、裏面の温度が１３０℃に調節された金型内にセットし７ＭＰａの圧力で８分加圧して肉厚６ｍｍの成形板を得た。
得られた成形品の鉛筆硬度（ＪＩＳ Ｋ５６００準拠）を測定した。また表面についてバーコル硬度（ＪＩＳ Ｋ６９１１準拠）を測定した。結果を表１に併せて示す。鉛筆硬度が５Ｈ、バーコル硬度が６３と、鉛筆硬度９Ｈ未満、バーコル硬度７５未満であった。
(Comparative Example 1)
Aluminum hydroxide (average) is added to 100 parts of resin A consisting of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene) in a weight ratio of 80:20. Particle size 25 μm) 435 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent (zinc stearate) 6 parts by weight, thickening 1 part by weight of the agent (magnesium oxide) was mixed and kneaded with a kneader.
The kneaded product was wrapped with a nylon film, and heated and aged at a temperature of 45° C. for 24 hours.
The obtained solid molding material is set in a mold having a molding surface temperature of 145° C. and a rear surface temperature of 130° C. and pressed at a pressure of 7 MPa for 8 minutes to obtain a molding plate having a thickness of 6 mm. It was
The pencil hardness (according to JIS K5600) of the obtained molded product was measured. Barcol hardness (according to JIS K6911) was measured on the surface. The results are also shown in Table 1. The pencil hardness was 5H and the barcol hardness was 63, which was less than 9H and less than 75.
（比較例２）
ビニルエステル樹脂（ビスフェノールＡ型ビニルエステル樹脂、スチレン希釈）及び不飽和ポリエステル樹脂（イソ系不飽和ポリエステル樹脂、スチレン希釈）の８０：２０の重量比から成る樹脂Ａ１００部に対し、結晶性シリカ（東罐マテリアル・テクノロジー株式会社試作品、平均粒径１０μｍ）２９５重量部、重合禁止剤（ハイドロキノン）０．０３重量部、重合開始剤（ｔ−ブチルパーオキシベンゾエート）１重量部、内部離型剤（ステアリン酸亜鉛）６重量部、増粘剤（酸化マグネシウム）１重量部、を配合しニーダーで混練した。
混練物をナイロンフィルムで包装し、４５℃の温度条件下で２４時間加熱し熟成した。
得られた固形状成形材料を、成形面の温度が１４５℃、裏面の温度が１３０℃に調節された金型内にセットし７ＭＰａの圧力で８分加圧して肉厚６ｍｍの成形板を得た。
得られた成形品の鉛筆硬度（ＪＩＳ Ｋ５６００準拠）を測定した。また表面についてバーコル硬度（ＪＩＳ Ｋ６９１１準拠）を測定した。結果を表１に併せて示す。鉛筆硬度が８Ｈ、バーコル硬度が７４と、鉛筆硬度９Ｈ未満、バーコル硬度７５未満であった。
(Comparative example 2)
To 100 parts of Resin A consisting of vinyl ester resin (bisphenol A type vinyl ester resin, diluted with styrene) and unsaturated polyester resin (iso unsaturated polyester resin, diluted with styrene) in a weight ratio of 80:20, crystalline silica (east) Can Material Technology Co., Ltd. prototype, average particle size 10 μm) 295 parts by weight, polymerization inhibitor (hydroquinone) 0.03 parts by weight, polymerization initiator (t-butylperoxybenzoate) 1 part by weight, internal release agent ( 6 parts by weight of zinc stearate and 1 part by weight of a thickener (magnesium oxide) were mixed and kneaded with a kneader.
The kneaded product was wrapped with a nylon film, and heated and aged at a temperature of 45° C. for 24 hours.
The obtained solid molding material is set in a mold having a molding surface temperature of 145° C. and a rear surface temperature of 130° C. and pressed at a pressure of 7 MPa for 8 minutes to obtain a molding plate having a thickness of 6 mm. It was
The pencil hardness (according to JIS K5600) of the obtained molded product was measured. Barcol hardness (according to JIS K6911) was measured on the surface. The results are also shown in Table 1. The pencil hardness was 8H and the barcol hardness was 74, which was less than 9H and less than 75.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309935A (en) * | 1994-05-16 | 1995-11-28 | Showa Highpolymer Co Ltd | High-molecular-weight unsaturated polyester resin composition and its cured item |
| JP2000234050A (en) * | 1999-02-15 | 2000-08-29 | Matsushita Electric Works Ltd | Unsaturated polyester resin molding material and molded product |
| JP2005097068A (en) * | 2003-08-26 | 2005-04-14 | Matsushita Electric Works Ltd | Resin composition for artificial marble, and artificial marble obtained by heating and curing the composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07309935A (en) * | 1994-05-16 | 1995-11-28 | Showa Highpolymer Co Ltd | High-molecular-weight unsaturated polyester resin composition and its cured item |
| JP2000234050A (en) * | 1999-02-15 | 2000-08-29 | Matsushita Electric Works Ltd | Unsaturated polyester resin molding material and molded product |
| JP2005097068A (en) * | 2003-08-26 | 2005-04-14 | Matsushita Electric Works Ltd | Resin composition for artificial marble, and artificial marble obtained by heating and curing the composition |
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