KR100596935B1 - Composition for artificial marble with excellent mechanical properties and method for producing same - Google Patents
Composition for artificial marble with excellent mechanical properties and method for producing same Download PDFInfo
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- KR100596935B1 KR100596935B1 KR1020020081063A KR20020081063A KR100596935B1 KR 100596935 B1 KR100596935 B1 KR 100596935B1 KR 1020020081063 A KR1020020081063 A KR 1020020081063A KR 20020081063 A KR20020081063 A KR 20020081063A KR 100596935 B1 KR100596935 B1 KR 100596935B1
- Authority
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- South Korea
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- weight
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- coupling agent
- phosphate
- artificial marble
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Links
- 239000002928 artificial marble Substances 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000007822 coupling agent Substances 0.000 claims abstract description 65
- 239000011256 inorganic filler Substances 0.000 claims abstract description 19
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 19
- 239000006188 syrup Substances 0.000 claims abstract description 19
- 235000020357 syrup Nutrition 0.000 claims abstract description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 16
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 15
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 15
- 125000000524 functional group Chemical group 0.000 claims abstract description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- 239000010452 phosphate Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 13
- 239000004579 marble Substances 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229920000058 polyacrylate Polymers 0.000 claims description 4
- GDOBGDUGIFUCJV-UHFFFAOYSA-N 2,2-dimethylbutane;2-methylprop-2-enoic acid Chemical compound CCC(C)(C)C.CC(=C)C(O)=O.CC(=C)C(O)=O.CC(=C)C(O)=O GDOBGDUGIFUCJV-UHFFFAOYSA-N 0.000 claims description 3
- POLZHVHESHDZRD-UHFFFAOYSA-N 2-hydroxyethyl 2-methylprop-2-enoate;phosphoric acid Chemical compound OP(O)(O)=O.CC(=C)C(=O)OCCO POLZHVHESHDZRD-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 claims description 2
- JJBFVQSGPLGDNX-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)COC(=O)C(C)=C JJBFVQSGPLGDNX-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- FSKGUHXQWFRTOQ-UHFFFAOYSA-N P(=O)(O)(O)O.OCOC(C(=C)C)=O Chemical compound P(=O)(O)(O)O.OCOC(C(=C)C)=O FSKGUHXQWFRTOQ-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- HLKMEIITONDPGG-UHFFFAOYSA-L barium(2+);2-hydroxypropanoate Chemical compound [Ba+2].CC(O)C([O-])=O.CC(O)C([O-])=O HLKMEIITONDPGG-UHFFFAOYSA-L 0.000 claims description 2
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- -1 mechanical strength Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- 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 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HTEAGOMAXMOFFS-UHFFFAOYSA-N methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C HTEAGOMAXMOFFS-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B18/00—Use of agglomerated or waste materials or refuse as fillers for mortars, concrete or artificial stone; Treatment of agglomerated or waste materials or refuse, specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B18/02—Agglomerated materials, e.g. artificial aggregates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/003—Phosphorus-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/54—Substitutes for natural stone, artistic materials or the like
- C04B2111/542—Artificial natural stone
- C04B2111/545—Artificial marble
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
본 발명의 기계적 물성이 우수한 인조 대리석은 (A) 아크릴 수지 시럽 100 중량부, (B) 가교제 0.3 내지 10 중량부, 무기 충전물 100 내지 300 중량부, 중합 개시제 0.1 내지 10 중량부, 마블칩 0 내지 150 중량부 및 (ⅰ)실란계 커플링제와 (ⅱ)산(acid)이나 알코올을 관능기로 갖는 포스페이트계 커플링제의 혼합물 0.5 내지 1.5 중량부로 이루어진다.The artificial marble having excellent mechanical properties of the present invention includes (A) 100 parts by weight of an acrylic resin syrup, (B) 0.3 to 10 parts by weight of a crosslinking agent, 100 to 300 parts by weight of an inorganic filler, 0.1 to 10 parts by weight of a polymerization initiator, and 0 to Marble Chips. 150 parts by weight and a mixture of (iii) a silane coupling agent and (ii) a phosphate-based coupling agent having an acid or an alcohol as a functional group.
인조 대리석, 실란계 커플링제, 기계적 강도, 포스페이트계 커플링제Artificial marble, silane coupling agent, mechanical strength, phosphate coupling agent
Description
발명의 분야Field of invention
본 발명은 기계적 강도가 우수한 인조 대리석 조성물에 관한 것이다. 보다 구체적으로, 본 발명은 인조대리석용 조성물에 상호 보완 작용을 할 수 있는 서로 다른 종류의 커플링제를 적정비율로 혼합하여 사용함으로써, 복잡한 커플링제의 전처리 과정이 없이 소량의 커플링제를 사용하고도 기계적 강도가 우수한 인조 대리석에 관한 것이다. The present invention relates to an artificial marble composition having excellent mechanical strength. More specifically, the present invention uses a mixture of different types of coupling agents that can complement each other in the composition for artificial marble in an appropriate ratio, so that even a small amount of coupling agent is used without a complicated pretreatment process of the coupling agent. The present invention relates to an artificial marble having excellent mechanical strength.
발명의 배경Background of the Invention
인조대리석은 최근 건축 내장재로 많이 사용되고 있으며, 그 사용되는 베이스 레진(Base resin)에 따라 크게 아크릴계와 불포화폴리에스터계의 두 가지 종류로 구분된다. 이 중 아크릴계 인조 대리석은 수지 자체의 은은한 투명성과 고급스 러운 질감 및 우수한 내후성 등의 장점으로 인해 여러 가지 용도로 사용되고 있으며, 그 수요가 계속 증가하고 있다.Artificial marble is widely used as a building interior material in recent years, and largely divided into two types, acrylic and unsaturated polyester, depending on the base resin used. Among them, acrylic artificial marble is used for various purposes due to its soft transparency, luxurious texture, and excellent weather resistance, and its demand is continuously increasing.
예를 들면, 씽크대 상판, 세면 화장대의 상판, 은행 및 일반 매장의 접수대 등 각종 카운터의 상판, 상품 매장의 내벽재, 욕조, 싱크 보울(sink bowl) 및 각종 인테리어 조형물의 소재로서 전 세계적으로 그 사용이 확대되고 있다.For example, it is used worldwide as sink tops, vanity tops, counter tops such as banks and general shops, interior walls of commodity stores, bathtubs, sink bowls and various interior sculptures. This is expanding.
이러한 인조 대리석은 운송이나 가공하는 과정에서 외부 충격에 의해 쉽게 파손되는 특징이 있다.Such artificial marble is characterized by being easily damaged by external impact during transportation or processing.
이처럼 충격에 쉽게 파손되는 문제를 해결하기 위해 여러 가지 종류의 커플링제를 사용하여 기계적 강도를 향상시킨다. 일반적으로 상기 커플링제로는 중심 원소가 실란(Si)으로 구성된 커플링제나, 포스페이트(PO4)로 구성된 커플링제를 사용한다. 또한 커플링제에는 커플링작용을 할 수 있는 관능기인 산(-COOH)이나 알코올(-OH)을 함유하고 있는 경우와 관능기 부분이 -O-R형태(R : Methyl, Ethyl, Amono-alkyl, etc.)로 구성되는 경우가 있다. 전자의 경우 별도의 전처리 과정이 필요로 하지 않기 때문에 커플링제를 효율적으로 사용할 수 있지만 반응 개시 역할을 하는 라디칼에 대해 스캐빈져로 작용하여 충분한 량을 투입할 수 없다는 단점이 있으며, 후자의 경우 복잡한 전처리 과정을 거처 커플링제를 커플링 작용을 쉽게할 수 있는 형태로 바꾸어 투입하거나, 커플링제를 과량투입해야 하는 단점이 있다. In order to solve the problem of being easily damaged by impact, various types of coupling agents are used to improve mechanical strength. In general, a coupling agent composed of a silane (Si) or a phosphate (PO 4 ) is used as the coupling agent. In addition, the coupling agent contains an acid (-COOH) or alcohol (-OH), which is a functional group capable of coupling, and the functional group portion is -OR form (R: Methyl, Ethyl, Amono-alkyl, etc.) It may consist of. In the former case, the coupling agent can be used efficiently because no separate pretreatment is required. However, in the latter case, a sufficient amount cannot be added by acting as a scavenger to the radical that serves as a reaction initiation. Through the pretreatment process, the coupling agent may be changed into a form that facilitates the coupling action, or the coupling agent may be excessively added.
여러 제조사에서는 기계적 강도를 향상하기 위한 커플링제를 사용함에 있어 초기 설비 투자비가 많이 소요되며, 추가적인 공정이 요구되는 전처리 방법보다는 추가적 공정이 필요로 하지 않으며, 반응에 영향이 상대적으로 적은 -O-R형태의 커플링제를 과량 투입하는 방법을 이용하고 있다. 그러나, 상대적으로 고가인 커플링제를 과량 사용함에 따라 제조 원가의 상승이 유발되는 단점과 더불어, 온도나 습도와 같은 공정 조건에 따른 품질 편차가 발생할 수 있는 단점이 있다.Many manufacturers have a high initial capital investment in using coupling agents to improve mechanical strength, do not require additional processes than pretreatment methods that require additional processes, and have a relatively low impact on the reaction. The method of adding an excessive amount of coupling agents is used. However, the excessive use of a relatively expensive coupling agent has the disadvantage of causing an increase in the manufacturing cost, there is a disadvantage that a quality deviation depending on the process conditions such as temperature or humidity.
상기와 같은 단점을 보완하기 위해서는 커플링제가 충분하게 작용할 수 있는 형태로 바꾸는 커플링제의 전처리 방법을 가능한 단순화하여야 한다.In order to make up for the above disadvantages, the pretreatment method of the coupling agent to be changed into a form in which the coupling agent can function sufficiently should be simplified as much as possible.
따라서, 본 발명자들은 상기의 문제점을 극복하기 위하여, 커플링제로서 실란 커플링제와 산(acid)이나 알코올(alcohol)을 관능기로 갖는 포스페이트계 커플링제의 적정비율로 혼합하여 사용함으로써, 하나가 다른 커플링제의 전처리과정에 필요로 하는 촉매 역할을 동시에 수행할 수 있도록 하여 커플링제의 효율을 향상시켜, 커플링제가 반응에 미치는 영향은 최소화하고 별도의 전처리나, 과량을 투입하지 않고도 기계적 물성이 우수한 인조 대리석 조성물을 개발하기에 이른 것이다. Therefore, the present inventors, in order to overcome the above problems, by using a silane coupling agent as a coupling agent in a proper ratio of a phosphate-based coupling agent having an acid or an alcohol (alcohol) as a functional group, one of the other couple It improves the efficiency of the coupling agent by simultaneously performing the catalyst role required for the pretreatment of the ring agent, thereby minimizing the influence of the coupling agent on the reaction, and having excellent mechanical properties without additional pretreatment or excessive input. It is early to develop the marble composition.
본 발명의 목적은 기계적 물성이 우수한 인조 대리석 조성물을 제공하기 위한 것이다.An object of the present invention is to provide an artificial marble composition excellent in mechanical properties.
본 발명의 다른 목적은 별도의 전처리나, 과량을 투입하지 않고도 우수한 기계적 물성을 갖는 인조 대리석의 제조방법을 제공하기 위한 것이다.Another object of the present invention is to provide a method for producing artificial marble having excellent mechanical properties without additional pretreatment or excessive input.
본 발명의 상기 목적 및 기타의 목적들은 하기 설명되는 본 발명에 의해 모두 달성될 수 있다. The above and other objects of the present invention can be achieved by the present invention described below.
이하, 본 발명의 내용을 하기에 상세히 설명한다.
Hereinafter, the content of the present invention will be described in detail below.
본 발명의 기계적 물성이 우수한 인조 대리석 조성물은 (A) 아크릴 수지 시럽 100 중량부, (B) 가교제 0.3 내지 10 중량부, (C) 무기 충전물 100 내지 300 중량부, (D) 중합 개시제 0.1 내지 10 중량부, (E) 마블칩 0 내지 150 중량부 및 (F) (ⅰ)실란 커플링제 및 (ⅱ)산(acid) 또는 알코올을 관능기로 갖는 포스페이트계 커플링제의 혼합물 0.5 내지 1.5 중량부로 이루어진다. 이하, 본 발명의 각 성분을 하기에 상세히 설명한다. The artificial marble composition having excellent mechanical properties of the present invention comprises (A) 100 parts by weight of an acrylic resin syrup, (B) 0.3 to 10 parts by weight of a crosslinking agent, (C) 100 to 300 parts by weight of an inorganic filler, and (D) 0.1 to 10 polymerization initiators. It consists of 0.5-1.5 weight part of mixtures of a weight part, (E) 0-150 weight part of marble chips, and (F) (iii) a silane coupling agent, and (ii) a phosphate type coupling agent which has an acid or an alcohol as a functional group. Hereinafter, each component of this invention is demonstrated in detail below.
(A) 아크릴 수지 시럽 (A) acrylic resin syrup
본 발명에 사용되는 아크릴 수지 시럽은 아크릴계 단량체와 이들의 중합물인 폴리아크릴레이트가 용해되어 있는 수지 시럽이다. The acrylic resin syrup used in the present invention is a resin syrup in which an acrylic monomer and a polyacrylate which is a polymer thereof are dissolved.
상기 아크릴계 단량체로는 메타 아크릴산, 메틸 메타 아크릴레이트, 에틸 메타 아크릴레이트, 이소 프로필 메타 아크릴레이트, n-부틸 메타 아크릴레이트, 2-에틸 헥실 메타 아클릴레이트 등이 있다. The acrylic monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate, and the like.
본 발명의 아크릴 수지 시럽은 아크릴 단량체의 함량이 65 중량% 이상이고, 아크릴 중합물 함량이 35 중량% 이하인 것이 바람직하다.The acrylic resin syrup of the present invention preferably has an acrylic monomer content of 65% by weight or more and an acrylic polymer content of 35% by weight or less.
(B) 가교제(B) crosslinking agent
본 발명의 가교제는 다 관능성 메타 아크릴레이트가 사용되며, 구체적인 예로는 에틸렌 글리콜 디 메타 아크릴레이트, 프로필렌 글리콜 디 메타 아크릴레이트, 글리세롤 트리 메타 아크릴레이트, 트리메틸 프로판 트리 메타 아크릴레이트 및 비스페놀 A 디 메타 아크릴레이트를 들 수 있다.As the crosslinking agent of the present invention, polyfunctional methacrylate is used, and specific examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, glycerol trimethacrylate, trimethyl propane trimethacrylate and bisphenol A dimethacrylate. The rate is mentioned.
상기 다 관능성 단량체는 아크릴 수지 시럽 100 중량부를 기준으로 0.1 내지 30 중량부로 첨가하며, 바람직하기로는 0.3 내지 10 중량부이다. The polyfunctional monomer is added in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the acrylic resin syrup, preferably 0.3 to 10 parts by weight.
(C) 무기 충전물(C) inorganic filler
본 발명의 무기 충전물은 탄산칼슘, 수산화 알루미늄, 실리카, 알루미나, 유산바륨, 수산화 마그네슘과 같이 당 분야에서 통상적으로 사용되는 무기 분말 중 어느 것도 사용 가능하며, 1 내지 100 ㎛의 크기를 갖는 것이 바람직하다. The inorganic filler of the present invention may be any of inorganic powders commonly used in the art, such as calcium carbonate, aluminum hydroxide, silica, alumina, barium lactate, magnesium hydroxide, and preferably has a size of 1 to 100 μm. .
상기 무기 분말 중 특히, 수산화 알루미늄은 투명하고 미려한 대리석 형상의 외관을 갖는 인조대리석을 제조 할 수 있다는 점에서 바람직하다.Among the inorganic powders, aluminum hydroxide is particularly preferable in that it can produce artificial marble having a transparent and beautiful marble appearance.
본 발명의 무기 충전물의 혼합비는 인조 대리석 슬러리의 경우, 아크릴 수지 시럽 100 중량부를 기준으로 무기 충전물이 100∼300 중량부, 더욱 바람직하기로는 120∼200 중량부로 첨가되는 것이 바람직하다. 또한, 마블칩의 경우에는 아크릴 수지 시럽 100 중량부를 기준으로 무기 충전물이 80∼200 중량부, 바람직하게는 100∼150 중량부로 첨가되는 것이 바람직하다. In the case of the artificial marble slurry, the mixing ratio of the inorganic filler of the present invention is preferably 100 to 300 parts by weight, more preferably 120 to 200 parts by weight, based on 100 parts by weight of the acrylic resin syrup. In the case of the marble chip, the inorganic filler is preferably added in an amount of 80 to 200 parts by weight, preferably 100 to 150 parts by weight, based on 100 parts by weight of the acrylic resin syrup.
(D) 중합 개시제(D) polymerization initiator
본 발명의 중합 개시제로는 벤조일 퍼옥사이드, 라우로일 퍼옥사이드, 부틸 하이드로 퍼옥사이드, 큐밀 하이드로 퍼옥사이드등의 과산화물 또는 아조비스이소부틸로니트릴과 같은 아조 화합물을 사용한다.As the polymerization initiator of the present invention, peroxides such as benzoyl peroxide, lauroyl peroxide, butyl hydroperoxide, cumyl hydroperoxide or azo compounds such as azobisisobutylonitrile are used.
여기에 중합 속도를 빠르게 하는 유기 금속염이나, 유기아민과 같은 가속제를 사용할 수 있다.An organic metal salt for accelerating the polymerization rate or an accelerator such as an organic amine can be used here.
상기 중합개시제의 함량은 아크릴 수지 시럽 100 중량부 기준으로 0.1∼10 중량부가 바람직하다.The content of the polymerization initiator is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the acrylic resin syrup.
(E) 마블칩 (E) Marble Chip
본 발명의 마블칩은 천연석의 질감을 발현하기 위한 입자로서, 아크릴 수지 시럽 100 중량부에 대하여, 무기 충전물 100 내지 150 중량부, 가교제 2 내지 10 중량부 및 개시제 0.1 내지 10 중량부를 혼합, 경화한 다음, 이를 햄머밀 타입의 파쇄기 또는 커터 타입의 파쇄기를 이용하여 파쇄한 후 다양한 크기의 채를 이용하여 0.1∼5mm크기로 분류한 것이다.Marble chips of the present invention is a particle for expressing the texture of natural stone, 100 to 150 parts by weight of the inorganic filler, 100 to 150 parts by weight of the inorganic filler, 2 to 10 parts by weight of the crosslinking agent and 0.1 to 10 parts by weight of the initiator is cured Next, this was broken using a hammer mill type shredder or cutter type shredder and then classified into 0.1 to 5 mm size using various sizes of shreds.
본 발명에서 마블 칩의 혼합비는 아크릴 수지 시럽 100 중량부를 기준으로 0∼150 중량부 더욱 바람직하기로는 0∼70 중량부가 바람직하다.In the present invention, the mixing ratio of the marble chip is 0 to 150 parts by weight, and more preferably 0 to 70 parts by weight, based on 100 parts by weight of the acrylic resin syrup.
(F) 커플링제(F) coupling agent
커플링제는 분자내에 수지와 결합할 수 있는 소수성 관능기와 무기충전물과 결합할 수 있는 친수성 관능기를 동시에 갖는 물질이다. The coupling agent is a substance having both a hydrophobic functional group capable of binding to a resin and a hydrophilic functional group capable of binding to an inorganic filler in a molecule.
본 발명의 커플링제는 베타-3,4에폭시사이클로헥실에틸트리메톡시실란, 감마-글리시독시프로필트리메톡시실란, 감마-메타크릴옥시프로필트리메톡시실란 및 감마-아미노프러필트리메톡시실란과 같은 Si를 중심원소로 하며, 가수분해와 같은 전처리과정을 통하여 실란올(Si-OH) 형태로 바뀌어 무기 충전물과 결합하게 되는 실란계 커플링제(ⅰ)와 하이드록시에틸메타크릴레이트엑시드포스페이트 등과 같이 별도의 전처리가 필요 없이 무기충전물과 직접 결합할 수 있는 산(acid) 또는 알코올을 관능기로 갖는 포스페이트계 커플링제(ⅱ)을 함께 사용한다. Coupling agents of the invention are beta-3,4-epoxycyclohexylethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and gamma-aminopropyltrimethoxy A silane coupling agent and a hydroxyethyl methacrylate phosphate, which are made of Si such as silane and are converted into silanol (Si-OH) form through pretreatment such as hydrolysis and combined with an inorganic filler. A phosphate-based coupling agent (ii) having an acid or alcohol as a functional group that can be directly bonded to the inorganic filler without separate pretreatment is used together.
상기 실란계 커플링제(ⅰ)의 구체적인 예로는 β-3,4에폭시사이클로헥실에틸트리메톡시실란, γ-글리시독시프로필트리메톡시실란, γ-메타크릴옥시프로필트리메톡시실란 및 γ-아미노프러필트리메톡시실란 등이 있다. 또한 상기 산(acid) 또는 알코올을 관능기로 갖는 포스페이트계 커플링제(ⅱ)의 구체적인 예로는 하이드록시에틸메타크릴레이트엑시드포스페이트, 하이드록시메틸메타크릴레이트엑시드포스페이트 등이 있다. Specific examples of the silane coupling agent (ⅰ) include β-3,4 epoxycyclohexylethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane and γ- Aminopropyltrimethoxysilane and the like. Specific examples of the phosphate coupling agent (ii) having an acid or an alcohol as a functional group include hydroxyethyl methacrylate phosphate, hydroxymethyl methacrylate phosphate, and the like.
실란계 커플링제의 경우 산 촉매를 이용한 가수분해과정을 거쳐서 무기충전물과 결합이 가능한 알콜(-OH) 형태의 관능기를 포함하는 상태에서 커플링제로써 작용이 가능한데, 일반적으로 아세트산과 같은 약산을 묽게 희석한 수용액을 커플링제와 혼합하여 가수분해를 진행시킨 다음 무기 충전물에 스프레이나 무기충전물을 혼합 용액에 담근 후 무기충전물을 다시 건조하는 과정을 필요로 한다. 이와 같은 과정이 너무 복잡하므로 실란계 커플링제를 사용하는 경우 과량을 투입하여 사용한다. In the case of a silane coupling agent, a hydrolysis process using an acid catalyst can be used as a coupling agent in the state of containing an alcohol (-OH) functional group capable of binding to an inorganic filler. Generally, a weak acid such as acetic acid is diluted thinly. Hydrolysis is performed by mixing an aqueous solution with a coupling agent, and then a process of drying the inorganic filler again after dipping the inorganic filler with the spray or the inorganic filler in the mixed solution. Since such a process is too complicated, an excess amount is used when a silane coupling agent is used.
그러나 본 발명에서는 스스로 커플링제로 작용이 가능하면서, 강산(Strong acid)의 특징을 갖는 산(acid)을 관능기로 갖는 포스페이트계 커플링제를 함께 사용함으로써 실란계 커플링제가 가수분해하는데 필요한 촉매역할을 동시에 할 수 있도록 하여 커플링제의 효율을 향상시킨 것이다.However, in the present invention, it is possible to act as a coupling agent on its own, and by using a phosphate coupling agent having an acid having a strong acid as a functional group, the silane coupling agent plays a catalytic role necessary for hydrolysis. The efficiency of a coupling agent was improved by making it possible to carry out simultaneously.
본 발명에서 커플링제의 혼합비는 아크릴 수지 시럽 100 중량부를 기준으로 (ⅰ),(ⅱ)종류의 커플링제 각각 0.2 내지 1.0 중량부 더욱 바람직하기로는 0.3 내지 0.6 중량부가 바람직하다. 두 가지 커플링제의 합은 0.5 내지 1.5 중량부가 바람직하다. 커플링제 투입량이 0.5중량부 이하의 경우 충분한 기계적 물성 개선 효과를 기대할 수 없으며, 1.5 중량부 이상을 투입하는 경우 추가적인 기계적 물성의 향상 효과를 기대할 수 없다. In the present invention, the mixing ratio of the coupling agent is 0.2 to 1.0 parts by weight, and more preferably 0.3 to 0.6 parts by weight, based on 100 parts by weight of the acrylic resin syrup. The sum of the two coupling agents is preferably 0.5 to 1.5 parts by weight. When the amount of the coupling agent is 0.5 parts by weight or less, sufficient mechanical properties cannot be expected to be improved. When the amount of the coupling agent is added by 1.5 parts by weight or more, the effect of improving the mechanical properties cannot be expected.
또한, (ⅰ),(ⅱ)커플링제의 상대적 비율은 (ⅰ)커플링제 대비 (ⅱ)커플링제가 0.5 내지 1.5배가 바람직하다. (ⅱ)커플링제의 혼합비율이 (ⅰ)커플링제의 0.5배 이하인 경우 (ⅰ)커플링제가 충분하게 가수분해를 할 수 없게 되어 기계적 물성 효과가 충분하지 않고, 1.5배 이상인 경우 (ⅱ)커플링제에 의한 반응에 미치는 영향이 커져 반응속도가 크게 저하된다.Moreover, as for the relative ratio of (iii) and (ii) coupling agent, (ii) coupling agent is 0.5-1.5 times as compared with (iv) coupling agent. (Ii) When the mixing ratio of the coupling agent is (0.5) or less than that of the coupling agent (i) The coupling agent is unable to sufficiently hydrolyze and the mechanical properties are not sufficient, and when the coupling agent is 1.5 times or more (ii) Couple The influence on the reaction by the ring agent is increased, and the reaction rate is greatly reduced.
본 발명의 기계적 물성이 우수한 인조 대리석은 상기로부터 제조된 마블 칩과 인조대리석 슬러리를 각각 제조한 후 성형 셀에 뿌린 다음 45∼120 ℃의 열풍 오븐에서 경화시켜 제조된다. Artificial marble having excellent mechanical properties of the present invention is prepared by manufacturing the marble chip and artificial marble slurry prepared from the above, sprinkled in a molding cell and then cured in a hot air oven at 45 to 120 ℃.
본 발명의 기계적 물성이 우수한 인조대리석은 기계적 물성을 향상시키기 위 한 커플링제를 별도의 전처리 과정 없이 소량을 사용함으로써 커플링제의 전처리를 위한 별도의 공정을 추가하는 문제점을 해결할 수 있을 뿐만 아니라, 고가인 커플링제를 과량 사용함에 따른 제조 원가를 상승시키는 문제점을 해결할 수 있다Artificial marble having excellent mechanical properties of the present invention can solve the problem of adding a separate process for the pretreatment of the coupling agent by using a small amount of the coupling agent to improve the mechanical properties without a separate pretreatment process, as well as expensive It can solve the problem of increasing the manufacturing cost due to the excessive use of the phosphorus coupling agent
본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이며 첨부된 특허 청구 범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
실시예Example
30 %의 폴리메틸 메타 아크릴레이트와 70 %의 메틸메타 아크릴레이트의 혼합물로 이루어진 메틸메타 아크릴레이트 시럽(이하, 수지 시럽으로 칭함) 100 중량부, 수산화 알루미늄 100 중량부, 트리메틸 프로판 트리 메타 아크릴레이트 2 중량부, 라우로일 퍼옥사이드 2 중량부, 실란계 커플링제로서 γ-메타크릴옥시프로필트리메톡시실란과 포스페이트계 커플링제로서 하이드록시에틸메타크릴레이트엑시드포스페이트를 표 1과 같이 혼합하여 인조대리석 슬러리를 제조하여 300×600×15 ㎜의 유리 성형 셀에 뿌린 후 45 ℃ 열풍오븐에 넣고, 단계적으로 오븐의 온도를 100까지 올려 경화를 시켰다. 경화가 완료된 후 상온까지 냉각하여 평판상의 인조대리석판을 얻었다. 제조된 각각의 인조대리석 시편에 대하여 굴곡강도 및 충격 강도를 측정하였으며 측정 결과를 표 2에 나타내었다. 100 parts by weight of methylmethacrylate acrylate syrup (hereinafter referred to as resin syrup) consisting of a mixture of 30% polymethyl methacrylate and 70% methylmethacrylate, 100 parts by weight of aluminum hydroxide, trimethyl propane trimethacrylate 2 Parts by weight, 2 parts by weight of lauroyl peroxide, γ-methacryloxypropyltrimethoxysilane as the silane coupling agent, and hydroxyethyl methacrylate acid phosphate as the phosphate coupling agent as shown in Table 1 The slurry was prepared, sprinkled in a glass forming cell of 300 × 600 × 15 mm, put in a 45 ° C. hot air oven, and the oven temperature was raised to 100 to cure stepwise. After curing was completed, the mixture was cooled to room temperature to obtain a plate-like artificial marble plate. Flexural strength and impact strength of each manufactured artificial marble specimen were measured and the results are shown in Table 2.
상기 표 2에서 나타난 바와 같이, 전체 커플링제의 량이 0.5 중량부 이하로 사용한 경우 및 실란계 커플링제 함량 대비 포스페이트계 커플링제의 함량이 과도하게 적은 경우에는 커플링제에 의한 기계적 물성의 향상 효과가 크게 감소하며, 한가지 종류만을 사용하는 경우와 비교시 소량을 사용하여도 보다 큰 물성 향상 효과를 기대할 수 있으며, 두 가지 커플링제의 합이 1.5 중량부 이상을 혼합하여도 추가적인 향상 효과가 작은 것으로 나타났다.As shown in Table 2, when the total amount of the coupling agent is used at 0.5 parts by weight or less, and when the content of the phosphate-based coupling agent is excessively small relative to the content of the silane coupling agent, the effect of improving the mechanical properties by the coupling agent is greatly increased. In comparison with the case where only one type is used, even when a small amount is used, a greater physical property improvement effect can be expected, and even when the sum of the two coupling agents is mixed by 1.5 parts by weight or more, the additional improvement effect is small.
본 발명의 기계적 물성이 우수한 인조 대리석은 서로 다른 종류의 커플링제를 적정 비율로 혼합 사용함으로써, 별도의 커플링제 전처리 공정을 거치거나, 과량의 커플링제를 혼합하지 않고도 기계적 물성이 우수한 인조 대리석을 제공하는 발명의 효과를 갖는다. The artificial marble of the present invention having excellent mechanical properties is mixed with different types of coupling agents in an appropriate ratio, thereby providing an artificial marble having excellent mechanical properties without undergoing a separate coupling agent pretreatment process or mixing excess coupling agent. It has the effect of the invention.
본 발명의 단순한 변형 내지 변경은 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며, 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다.
Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
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