KR19990039632A - Artificial marble having a natural stone texture and its manufacturing method - Google Patents

Artificial marble having a natural stone texture and its manufacturing method Download PDF

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Publication number
KR19990039632A
KR19990039632A KR1019970059795A KR19970059795A KR19990039632A KR 19990039632 A KR19990039632 A KR 19990039632A KR 1019970059795 A KR1019970059795 A KR 1019970059795A KR 19970059795 A KR19970059795 A KR 19970059795A KR 19990039632 A KR19990039632 A KR 19990039632A
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South Korea
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natural stone
weight
parts
artificial marble
stone texture
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KR1019970059795A
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Korean (ko)
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이동원
박경남
이성인
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전원중
주식회사 효성
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Priority to KR1019970059795A priority Critical patent/KR19990039632A/en
Publication of KR19990039632A publication Critical patent/KR19990039632A/en

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    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B26/00Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
    • C04B26/02Macromolecular compounds
    • C04B26/10Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B26/18Polyesters; Polycarbonates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/04Silica-rich materials; Silicates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B14/00Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/02Granular materials, e.g. microballoons
    • C04B14/36Inorganic materials not provided for in groups C04B14/022 and C04B14/04 - C04B14/34
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B24/00Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
    • C04B24/24Macromolecular compounds
    • C04B24/26Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B24/2676Polystyrenes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B28WORKING CEMENT, CLAY, OR STONE
    • B28BSHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00Producing shaped prefabricated articles from the material
    • B28B1/26Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor
    • B28B1/265Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor pressure being applied on the slip in the filled mould or on the moulded article in the mould, e.g. pneumatically, by compressing slip in a closed mould
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2103/00Function or property of ingredients for mortars, concrete or artificial stone
    • C04B2103/44Thickening, gelling or viscosity increasing agents
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/54Substitutes for natural stone, artistic materials or the like
    • C04B2111/542Artificial natural stone

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

본 발명은 열경화성 수지와 천연석 파쇄물 등을 사용하여 제조하는 천연석 질감을 가지는 인조 대리석 및 그 제조방법에 관한 것으로, 열경화성 수지(A) 100중량부, 무기 충전재(B) 150∼700중량부, 직경 3∼20 mm 의 천연석 파쇄물(C) 300∼700 중량부, 저수축제(D) 1∼50중량부로 구성되는 것을 특징으로 하며, 본 발명의 인조대리석은 기계적 물성이 우수하고 천연석 질감을 가지므로 카운터 테이블탑, 벽재, 바닥재 등에 사용가능하다.The present invention relates to artificial marble having a natural stone texture prepared using a thermosetting resin and natural stone crushed products, and a method for manufacturing the same, 100 parts by weight of a thermosetting resin (A), 150 to 700 parts by weight of an inorganic filler (B), diameter 3 It is characterized by consisting of 300 to 700 parts by weight of the natural stone crushed material (C) of 1 ~ 20 mm, 1 to 50 parts by weight of the low shrinkage agent (D), the artificial marble of the present invention has excellent mechanical properties and has a natural stone texture counter table It can be used for towers, walls, floors, etc.

Description

천연석 질감을 가지는 인조대리석 및 그 제조방법Artificial marble having a natural stone texture and its manufacturing method

본 발명은 열경화성 수지와 천연석 파쇄물 등을 사용하여 제조되는 천연석 질감을 가지는 인조 대리석 및 그 제조방법에 관한 것이다.The present invention relates to an artificial marble having a natural stone texture produced using a thermosetting resin and natural stone crushed products and the like and a method of manufacturing the same.

천연석인 화강석 및 대리석은 바닥재, 벽재 등으로 사용되어지고 있지만, 강도가 약해서 얇은 대형 제품을 얻을 수 없을 뿐만 아니라 동일한 모양으로 생산하는 데 한계가 있기 때문에 천연석 질감을 가지는 인조대리석을 천연석 대신에 사용하는 것이 행해지고 있다.Granite and marble, which are natural stones, are used as flooring and walling materials, but because they are weak in strength, they cannot produce thin and large products, and there is a limit to producing them in the same shape. Is done.

천연석 질감을 가지는 인조대리석은 천연석의 파쇄물과 무기충전재를 열경화성 수지와 같이 성형한 후 성형품의 표면을 연마하는 인조대리석이다. 그러나 상기 천연석 파쇄물을 사용한 성형품은 천연의 질감을 발현하기 위해 비교적 큰 입자를 사용해야 하나 큰 입자를 사용할 경우에는 혼합물의 유동성이 나빠져서 성형이 어려울 뿐만 아니라 성형시에 균열, 깨짐, 휨 등이 발생해서 양호한 성형품을 얻기에 쉽지 않다는 문제점이 있다.Artificial marble having a natural stone texture is an artificial marble for shaping the surface of the molded product after molding the crushed material and the inorganic filler with the thermosetting resin. However, the molded article using the natural stone crushed product should use relatively large particles to express the natural texture, but when the large particles are used, the fluidity of the mixture is poor, so that the molding is difficult, and cracks, cracks, warpage, etc. occur during molding. There is a problem that it is not easy to obtain a molded article.

그래서 종래는 무기충전재 만을 사용하거나(대한민국 특허 공개 제96-4288호, 공개 제93-5942호), 천연석 파쇄물중 작은 입자를 소량 첨가하거나 (대한민국 특허공개 제96-4267호), 혹은 수지 함량이 높은 경우 주형법과 같이 상온에서 금형의 중간에 혼합물을 부어 넣어서 성형한 후 표면을 연마하는 것(일본 특허공개 평 5-330884호)에 의하여 천연석의 질감을 내는 방법이 채택되어지고 있다.Thus, conventionally, only inorganic fillers are used (Korean Patent Publication Nos. 96-4288, Publication No. 93-5942), small amounts of small particles in natural stone crushed materials (Korean Patent Publication No. 96-4267), or resin content is high. In a high case, a method of forming a natural stone texture is adopted by pouring a mixture in the middle of a mold at room temperature and then polishing the surface after molding, such as the casting method.

그러나 무기 충전재만을 사용하거나 천연석 파쇄물 중 작은 입자만은 소량 첨가할 경우는 천연석과 같은 질감을 얻을 수 없고, 수지함량이 높은 성형품의 경우 20 mm 이하의 천연석 파쇄물을 첨가하면 입자들이 가라앉는 문제가 있어 주형법에는 적합치 않다. 또한 소량의 열경화성 수지와 천연석 파쇄물 중 큰 입자를 혼합할 경우는 앞에서도 언급한 바와 같이 혼합물의 유동성이 떨어져 가압 성형시 충진 불량 및 깨짐 등이 발생하는 문제가 있다.However, if only inorganic filler is used or only small particles of natural stone crushed particles are not added, the same texture as natural stone cannot be obtained. In the case of molded products having a high resin content, particles having 20 mm or less of natural stone crushed particles may sink. It is not suitable for the casting method. In addition, when mixing a small amount of thermosetting resin and large particles of the natural stone crushed material, as mentioned above, there is a problem that poor filling and cracking occurs during the press molding due to the poor fluidity of the mixture.

본 발명의 목적은 천연석의 질감을 잃지 않으면서 강도도 천연석의 2∼3배 정도로 커지는 양호한 천연석 질감을 가지는 인조대리석 및 그 제조방법을 제공하는 것이다.An object of the present invention is to provide an artificial marble having a good natural stone texture that is about two to three times greater than that of natural stone without losing the texture of the natural stone, and a method of manufacturing the same.

본 발명은 상기 과제를 해결하기 위해서 열경화성 수지(A)에 무기 충전재(B)와 3∼20 mm 인 천연석 파쇄물(C)을 함유하는 수지 성분에 대해서 저수축제(D)가 첨가되는 것을 특징으로 하며, 필요한 경우 20 mm 이하의 섬유상 강화제(E), 경화촉매(F) 및 중점제(G) 중 선택된 1 종이상을 함유하는 것을 특징으로 한다.The present invention is characterized in that a low shrinkage agent (D) is added to a resin component containing an inorganic filler (B) and a natural stone crushed product (C) of 3 to 20 mm in order to solve the above problems. It is characterized by containing one paper form selected from fibrous reinforcement (E), a curing catalyst (F), and a midpoint agent (G) of 20 mm or less if necessary.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명에서 사용될 수 있는 열경화성 수지(A)는 불포화 폴리에스테르 수지, 에폭시 수지, 요소 수지, 멜라민 수지, 디아릴프탈레이트 수지 등을 들 수 있다. 불포화 폴리에스테르 수지는 α,β-불포화 이염산기와, 그 산 무수물, 방향족 포화 이염기산과 그 산무물, 글리콜류의 축중합에 의하여 제조되어지고, 경우에 따라서는 지방족 또는 방향족 포화 이염기산을 병용하여 제조된 불포화 폴리에스테르 30∼80 중량부를 α,β-불포화 단량제 70∼20 중량부에 용해하여 얻을 수 있다.The thermosetting resin (A) that can be used in the present invention includes unsaturated polyester resins, epoxy resins, urea resins, melamine resins, diaryl phthalate resins, and the like. Unsaturated polyester resins are prepared by condensation polymerization of an α, β-unsaturated dihydrochloric acid group with an acid anhydride, an aromatic saturated dibasic acid, an acid anhydride, and glycols, and in combination with an aliphatic or aromatic saturated dibasic acid. 30 to 80 parts by weight of the unsaturated polyester produced by dissolving to obtain 70 to 20 parts by weight of the α, β-unsaturated monomer.

그 외에도 불포화 폴리에스테르 말단을 비닐로 변경시키거나 에폭시 수지 골격 말단을 비닐 변성한 비닐 에스테르 등도 사용할 수 있다. 상기 α,β-불포화 이염기산과 그 산무수물로서는 말레인산, 무수 말레인산, 푸말산, 이타콘산, 시로라콘산, 클로로말레인산 및 그의 에스테르 등이 있고, 방향족 포화 이염기산과 그의 산 무수물로서는 푸탈산, 무수푸탈산, 이소푸탈산, 테레푸탈산, 니트로 푸탈산, 디프엔산, 테트라 히드로 무수 푸탈산, 할로겐화 무수 푸탈산과 그의 에스테르 등이 있다.In addition, the vinyl ester which changed the unsaturated polyester terminal into vinyl, or vinyl-modified the epoxy resin backbone terminal can also be used. The α, β-unsaturated dibasic acids and acid anhydrides thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, siroraconic acid, chloromaleic acid and esters thereof, and the like. Butyric acid, isophthalic acid, terephthalic acid, nitrophthalic acid, diproic acid, tetrahydrophthalic anhydride, halogenated phthalic anhydride and esters thereof.

글리콜류는 에틸렌 글리콜, 프로필렌 글리콜, 디에틸렌 글리콜, 1,4-브탄디올, 1,3-브탄디올, 2,3-브탄디올, 디프로필렌 글리콜, 트리메틸렌 글리콜, 트리에틸렌 글리콜, 네오펜틸 글리콜, 1,5-펜탄디올, 1,6-헥사디올, 수소화 비스페놀A 등이 있다.Glycols include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, dipropylene glycol, trimethylene glycol, triethylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexadiol, hydrogenated bisphenol A, and the like.

또한 모노머는 스틸렌 비닐톨루엔, 클로로스틸렌, α-메틸스틸렌, 디비닐벤젠, 메타크릴산메틸, 아크릴산 메틸, 염산비닐, 디알릴프탈레이트, 트리알릴시아누레이트, 디알릴벤젠포스포네이트, N-비닐피톨리돈, 말레아미드 등이 있으며, 이들은 불포화 에스테르 수지나 비닐 에스테르 수지와 가교 결합을 형성한다. 상기의 모노머는 단독 혹은 병용해서 사용가능하지만, 일반적으로 스틸렌이 사용된다.Monomers include styrene vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, methyl methacrylate, methyl acrylate, vinyl hydrochloride, diallyl phthalate, triallyl cyanurate, diallyl benzene phosphonate, and N-vinyl. Phytolidone, maleamide, and the like, which form a crosslink with an unsaturated ester resin or a vinyl ester resin. Although said monomer can be used individually or in combination, styrene is generally used.

본 발명에서 사용될 수 있는 무기 충전재(B)로서는 실리카, 탄산칼슘, 수산화 알루미늄, 알루미나 글라스, 글라스 비드, 마이카, 황산바륨 등이 있으며, 그 적절한 사용량은 열경화성 수지 (A) 100 중량부에 100 내지 700 중량부이며, 바람직하게는 550 내지 650 중량부 범위이다. 무기 충전재의 평균 입경은 60 마이크론 이하의 것이 바람직하다.Inorganic fillers (B) that can be used in the present invention include silica, calcium carbonate, aluminum hydroxide, alumina glass, glass beads, mica, barium sulfate, and the like. The appropriate amount is 100 to 700 parts by weight of the thermosetting resin (A). It is part by weight, preferably in the range of 550 to 650 parts by weight. The average particle diameter of the inorganic filler is preferably 60 microns or less.

본 발명에서 사용될 수 있는 천연석 파쇄물(C) 중 바람직한 것으로는 국내 각 석재 채석장에서 원석을 채굴하여 건축용 석판재로 가공하기까지 발생되는 석재 폐기물이다. 국내화강석(포천석, 신북석, 일동석, 거창석, 진안석, 운천석, 문경석, 철원석 등), 대리석, 유리조각 등도 파쇄해서 건조, 체질하여 사용할 수 있으며, 입자크기는 원하는 패턴에 따라 다양하게 선택할 수 있다. 천연석에 가까운 성형물을 제조하려면 천연석 파쇄물의 평균 입자 직경을 3∼20 mm 내에서 선택하며, 다양한 크기의 영역을 적절하게 배합하여 사용할 수 있다. 이들은 원하는 패턴에 따라 상기 종류를 단독 혹은 둘 이상의 혼합물 형태로 사용할 수 있다.Among the natural stone crushed material (C) that can be used in the present invention is a stone waste that is generated until the raw stone is mined in each domestic stone quarry to be processed into building slabs. Domestic granite (Pocheon stone, Sinbuk stone, Ildong stone, Geochang stone, Jinan stone, Uncheon stone, Mungyeong stone, Cheorwon stone, etc.), marble, glass pieces, etc. can also be crushed, dried and sieved, and the particle size varies according to the desired pattern. You can choose to. To produce moldings close to natural stone, the average particle diameter of natural stone crushed is selected within 3 to 20 mm, and various sized regions can be appropriately combined. These may be used alone or in the form of a mixture of two or more depending on the desired pattern.

사용되는 천연석 파쇄물 (C)의 양은 열경화성 수지 (A) 100 중량부에 대하여 300 내지 700 중량부이며 원하는 패턴에 따라 바람직하게는 400 내지 600 중량부의 범위에 있는 것을 사용한다.The amount of the natural stone crushed material (C) to be used is 300 to 700 parts by weight with respect to 100 parts by weight of the thermosetting resin (A) and preferably in the range of 400 to 600 parts by weight depending on the desired pattern.

본 발명에서 사용되어지는 저수축제(D)로서는 열가소성 수지를 들수 있다. 그 구체적인 예로는 폴리메틸메타크릴레이트(PMMA), 폴리스티렌(PS), 폴리비닐 아세테이트(PVAC), 폴리에틸렌(PE), 폴리비닐클로라이드(PVC), 폴리에스테르, 변성 폴리우레탄 등이 있다. 사용되는 저수축제 (D)의 양은 열경화성 수지 100 중량부에 대하여 5∼50중량부, 바람직하게는 15∼35 중량부이다.As the low shrinkage agent (D) used in the present invention, thermoplastic resins may be mentioned. Specific examples thereof include polymethyl methacrylate (PMMA), polystyrene (PS), polyvinyl acetate (PVAC), polyethylene (PE), polyvinyl chloride (PVC), polyester, modified polyurethane, and the like. The amount of the low shrinkage agent (D) used is 5 to 50 parts by weight, preferably 15 to 35 parts by weight, based on 100 parts by weight of the thermosetting resin.

본 발명에서 사용될 수 있는 섬유 강화제(E)는 일반적으로 글라스 섬유(Glass Fiber)가 사용되지만, 그 외의 비닐론 섬유, 폴리에스테르 섬유, 페놀 섬유 등의 유기섬유, 아스베스토, 카본 섬유 등도 사용 가능하다. 성유 강화제의 길이는 20 mm 이하의 것이 사용된다. 바람직하게는 3∼18mm 이고, 그 첨가량은 불포화 열경화성 수지 100 중량부에 대해서 0∼100 중량부, 바람직하게는 0∼60 중량부이다.As the fiber reinforcing agent (E) that can be used in the present invention, glass fiber is generally used, but other organic fibers such as vinylon fiber, polyester fiber, phenol fiber, asbestos, carbon fiber, and the like can also be used. The oil reinforcing agent is used with a length of 20 mm or less. Preferably it is 3-18 mm, and the addition amount is 0-100 weight part with respect to 100 weight part of unsaturated thermosetting resins, Preferably it is 0-60 weight part.

본 발명에서 사용될 수 있는 경화 촉매(F)는 불포화 폴리에스테르 수지, 비닐 에스테르 수지 등에 작용하는 것으로, 예를 들면 아조이소부틸니트릴과 같은 아조 화합물, 고온경화용으로 바람직하게는 TBPB (t-부틸퍼옥시벤조에이트)와 TBHP (t-부틸하이드로퍼어옥사이드) 이외에 10 여가지 종류이다. 또한 경화효과를 높히기 위하여 필요에 따라 경화 촉진제도 병용할 수 있는 데 이것에는 유기산의 금속염, 특히 코발트염, 예를 들면 나프탈렌염 코발트, 옥틸염 코발트, 아세틸아세톤코발트 등이 사용된다. 사용되는 경화 촉매와 경화 촉진제 (F)의 양은 열경화성 수지 A) 100 중량부에 통상 0.3 내지 3 중량부이며, 바람직하게는 0.1 내지 2 중량부이다.The curing catalyst (F) which can be used in the present invention acts on unsaturated polyester resins, vinyl ester resins, and the like, for example, azo compounds such as azoisobutylnitrile, and for high temperature curing, preferably TBPB (t-butylper In addition to oxybenzoate) and TBHP (t-butylhydroperoxide), there are about 10 kinds. Moreover, a hardening accelerator can also be used together as needed in order to raise hardening effect, The metal salt of organic acid, especially cobalt salt, for example, naphthalene salt cobalt, octyl salt cobalt, acetylacetone cobalt, etc. are used. The amount of the curing catalyst and the curing accelerator (F) used is usually 0.3 to 3 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the thermosetting resin A).

본 발명에서 사용가능한 중점제(G)는 불포화 폴리에스테르에 있는 수산기, 카르복실기와 에스테르 결합, 특히 일부 교차결합을 해서 분자량을 증가시켜 불포화 폴리에스테르 수지의 점도를 증가시키는 성질을 가지고 있는 것이다. 사용되는 중점제의 예로는 산화 마그네슘(MgO), 산화 칼슘(CaO), 산화 아연(ZnO), 수산화 마그네슘(Mg(OH)2), 수산화 칼슘(Ca(OH)2) 등이 있다. 일반적으로 산화 마그네슘이 사용된다.The midpoint agent (G) usable in the present invention has the property of increasing the molecular weight of the unsaturated polyester resin by increasing the molecular weight by performing some crosslinking with the hydroxyl group, the carboxyl group and the ester bond in the unsaturated polyester. Examples of medium used include magnesium oxide (MgO), calcium oxide (CaO), zinc oxide (ZnO), magnesium hydroxide (Mg (OH) 2 ), calcium hydroxide (Ca (OH) 2 ), and the like. In general, magnesium oxide is used.

사용되는 중점제 (G)의 양은 열경화성 수지 100 중량부에 통상 0.2∼5 중량부, 바람직하게는 2∼4 중량부이다. 그리고 필요하다면 물과 같은 강한 극성의 물질을 중점제로 소량 사용할 수 있다.The amount of the medium agent (G) to be used is usually 0.2 to 5 parts by weight, preferably 2 to 4 parts by weight, in 100 parts by weight of the thermosetting resin. If necessary, small amounts of strong polar substances such as water can be used.

이 외에 본 발명에서는 아래와 같은 기타 첨가제를 사용할 수 있다.In addition, the present invention may use other additives as follows.

내부 이형제는 스테아린산염, 스테아린산염 아연 등과 같은 고급 지방염이나 고급 지방염 에스테르, 알킬린염 에스테르 등이 있다. 사용되는 내부 이형제는 열경화성 수지 (A) 100 중량부에 통산 0.5 내지 5 중량부이며, 바람직하게는 1 내지 3 중량부이다. 또한 착색제인 유기안료 및 무기안료도 사용할 수 있으며, 내열성, 투명성에 뛰어난 열경화성 수지의 경화를 방해하지 않는 것이 바람직하다.Internal mold release agents include higher fatty salts such as stearic acid salts and zinc stearate salts, higher fatty acid esters, and alkylin salt esters. The internal mold release agent to be used is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, in 100 parts by weight of the thermosetting resin (A). In addition, organic pigments and inorganic pigments, which are colorants, may also be used, and it is preferable not to interfere with curing of the thermosetting resin having excellent heat resistance and transparency.

본 발명의 천연석 질감을 가지는 인조대리석을 제조하는 것에는 상기의 각 성분을 혼합하고, 그 혼합물을 시트상에 프리폼(Preform)한다. 그리고 증점된 후 상온에서 숙성 과정을 거쳐 110∼170℃에서 가열된 평판용 금형에 충전하고 가업하여 경화한다.In preparing the artificial marble having the natural stone texture of the present invention, the above components are mixed and the mixture is preformed on a sheet. Then, after thickening, the mixture is filled in a flat mold heated at 110 to 170 ° C. through a aging process at room temperature, and cured by heating.

이하 본 발명의 실시예 및 비교예를 설명하면 다음과 같으나 이들 실시예 및 비교예 등이 본 발명의 보호 범위를 제한하는 것은 아니다.Hereinafter, examples and comparative examples of the present invention will be described as follows, but these examples and comparative examples do not limit the protection scope of the present invention.

표에 나오는 물성치, 성형수축물, 굴국강도, 샤르피 충격치는 JIS 6911의 표준을 기준으로 측정하였으며, 성형품 외관은 육안으로 관찰하여 기록하였다.Physical properties, molded shrinkage, flexural strength and Charpy impact value shown in the table were measured based on the standard of JIS 6911, and the appearance of the molded product was recorded by visual observation.

<실시예 1∼4><Examples 1-4>

다음 표 1 에 나타낸 성분 및 조성비대로 성형을 한후 시편을 제작하였다.The specimens were prepared after molding according to the components and composition ratios shown in Table 1 below.

먼저 표 1 의 성분을 조성비대로 니더(kneader)에서 혼합을 하고, 이 혼합물을 시트상에 프리폼(perform)한 다음, 상온에서 24시간 숙성시킨 후 150℃로 가열된 금형내에 충진시킨 후 성형 압력이 90 kgf/cm2의 조건하에서 20 분간 가압 성형하였다. 완성된 성형품은 두께 15 mm 로 크랙이나 휨이 없는 것을 얻을 수 있었다. 이 성형품의 표면을 연마기로 1 mm 정도 연마를 하였다.First, the ingredients of Table 1 are mixed in a kneader according to the composition ratio, and the mixture is preformed on a sheet, aged at room temperature for 24 hours, and then filled into a mold heated to 150 ° C., and then the molding pressure is increased. Press molding was carried out for 20 minutes under the conditions of 90 kgf / cm 2 . The finished molded article was 15 mm thick and was free of cracks or warpage. The surface of this molded article was polished by about 1 mm with a polishing machine.

기계적 강도 및 성형품 외관을 평가하여 그 결과는 다음 표 2 에 나타내었다.The mechanical strength and the appearance of the molded article were evaluated and the results are shown in Table 2 below.

<비교예 1∼3><Comparative Examples 1 to 3>

다음 표 1 에 사용된 성분 및 조성비를 나타내었는 데, 천연석 파쇄물의 입경을 바꿔가면서 비교하였다. 성형방법은 실시예와 동일하게 실시하였다. 비교예 2 는 작은 천연석 파쇄물을 이용하여 성형을 했는 데 성형성은 좋았으나 천연석의 질감을 얻지 못했다. 또한 수축률이 크고 기계적 강도도 낮았다. 비교예 3 은 천연석 파쇄물의 큰 입자를 사용해서 성형을 했으나 입경이 커서 유동성이 작을 뿐만 아니라 성형불량으로 인해 성형품 외관도 좋지 않았다. 또한 수축률이 크고 기계적 강도도 작았다. 기계적 강도 및 성형품 외관을 평가하여 그 결과를 다음 표 1 에 나타내었다.The components and composition ratios used in Table 1 are shown, and the comparison was made while changing the particle sizes of natural stone crushed products. The molding method was performed in the same manner as in Example. Comparative Example 2 was molded using a small natural stone crushed, but the formability was good, but the texture of the natural stone was not obtained. In addition, the shrinkage was large and the mechanical strength was low. Comparative Example 3 was molded using large particles of natural stone crushed, but the particle size was large, not only the fluidity is small, but also the appearance of the molded product was not good due to poor molding. In addition, the shrinkage was large and the mechanical strength was small. Mechanical strength and the appearance of the molded article were evaluated and the results are shown in Table 1 below.

성 분ingredient 실 시 예Example 비 교 예Comparative Example 1One 22 33 44 1One 22 33 불포화 폴리에스테르 수지Unsaturated polyester resin 올소타입Allso type 100100 100100 100100 100100 100100 100100 100100 무기충전재(수산화 알루미늄)Inorganic fillers (aluminum hydroxide) 200200 200200 200200 200200 200200 200200 200200 천연석(포천석)파쇄물Natural Stones 3∼7 mm3-7 mm 500500 500500 500500 500500 500500 -- -- 0.1∼1.0 mm0.1-1.0 mm -- -- -- -- -- 500500 -- 25∼30 mm25-30 mm -- -- -- -- -- -- 500500 저수축제(폴리스티렌)Low Concentrate (Polystyrene) 3030 3030 3030 3030 -- 3030 3030 섬유상보강재(글라스섬유)Fibrous reinforcement (glass fiber) 12mm12 mm -- 4040 -- -- -- -- -- 30mm30 mm -- -- -- -- -- -- 4040 경화촉매(TBPB)Curing Catalyst (TBPB) 1One 1One 1One 1One 1One 1One 1One 증점제(산화마그네슘)Thickener (Magnesium Oxide) -- -- -- 1One -- -- --

기계적 강도 및 성형품 외관Mechanical strength and molding appearance 실 시 예Example 비 교 예Comparative Example 1One 22 33 44 1One 22 33 성형수축율(%)Mold Shrinkage (%) 0.100.10 0.110.11 0.100.10 0.100.10 0.350.35 0.110.11 0.120.12 굴곡강도(kgf/mm2)Flexural Strength (kgf / mm 2 ) 2.82.8 4.14.1 3.03.0 4.44.4 1.81.8 2.02.0 1.91.9 샤르치충격치(kgf·cm/cm2)Charl impact value (kgfcm / cm 2 ) 3.03.0 5.25.2 3.33.3 6.06.0 2.22.2 3.33.3 2.02.0 성형품 외관Molded product appearance 충진성Fillability ×× 크랙crack Nil Nil Nil Nil With Nil With 질감Texture ××

본 발명의 인조대리석은 기계적 물성이 우수하고 천연석 질감을 가지므로 카운터 테이블탑, 벽재, 바닥재 등에 사용가능하다.The artificial marble of the present invention has excellent mechanical properties and natural stone texture, so that it can be used for counter table tops, wall materials, floor materials, and the like.

Claims (5)

열경화성 수지(A) 100중량부, 무기 충전재(B) 150∼700중량부, 직경 3∼20 mm 의 천연석 파쇄물(C) 300∼700 중량부, 저수축제(D) 1∼50중량부로 구성되는 것을 특징으로 하는 천연석 질감을 가지는 인조대리석.Consisting of 100 parts by weight of the thermosetting resin (A), 150 to 700 parts by weight of the inorganic filler (B), 300 to 700 parts by weight of the natural stone crushed material (C) having a diameter of 3 to 20 mm, and 1 to 50 parts by weight of the low shrinkage agent (D). Artificial marble with natural stone texture characterized by. 제 1 항에 있어서, 직경 20mm 이내의 섬유상강화제(E)가 100중량부 이내 첨가된 것을 특징으로 하는 천연석 질감을 가지는 인조대리석.The artificial marble having a natural stone texture according to claim 1, wherein a fibrous reinforcing agent (E) having a diameter of 20 mm or less is added within 100 parts by weight. 제 1 항에 있어서, 경화촉매(F)가 0.3∼3.0중량부 첨가되는 것을 특징으로 하는 천연석 질감을 가지는 인조대리석.The artificial marble having a natural stone texture according to claim 1, wherein 0.3 to 3.0 parts by weight of a curing catalyst (F) is added. 제 1 항에 있어서, 증점제(G)가 0.2∼5중량부 첨가되는 것을 특징으로 하는 천연석 질감을 가지는 인조대리석.The artificial marble having a natural stone texture according to claim 1, wherein the thickener (G) is added in an amount of 0.2 to 5 parts by weight. 제 1 항의 조성물을 중점시킨 후 금형내에 투입하고 110∼170℃에서 가압 성형하고, 더욱이 성형품 표면을 0.5∼1.0 mm 연마하는 것을 특징으로 하는 천연석 질감을 가지는 인조대리석의 제조방법.A method for producing artificial marble having a natural stone texture, wherein the composition of claim 1 is placed in a mold, pressure molded at 110 to 170 ° C., and the surface of the molded product is polished to 0.5 to 1.0 mm.
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KR20010079127A (en) * 2001-06-15 2001-08-22 이영대 Method of forming stone injection method of natural stone headstone and top seedling
KR100492253B1 (en) * 2002-01-29 2005-05-31 서성오 Fiber resin complex panel with color stone
WO2006062363A1 (en) * 2004-12-08 2006-06-15 Cheil Industries Inc. Method and apparatus for making composite solid surface article and composite solid surface article containing large particles
WO2006062362A1 (en) * 2004-12-08 2006-06-15 Cheil Industries Inc. Composite solid surface article comprising at least one of randomly shaped fibers and powder particles
WO2009102091A1 (en) * 2008-02-14 2009-08-20 Hanwha L & C Corp. Native rock combined with resin having multi color vein and manufacturing method thereof
KR101147395B1 (en) * 2009-11-13 2012-05-22 한국생산기술연구원 Method of manufacturing polymer composite material using natural stone
KR101471399B1 (en) * 2014-03-07 2014-12-10 주식회사 에코스톤코리아 Fence manufactured from artificial stone using paste composition for manufacturing artificial stone of corrosion-resistance
WO2015160011A1 (en) * 2014-04-17 2015-10-22 월드씨엠엠에이(주) Environment-friendly artificial marble with coffee scent using brewed coffee powder and coffee by-products and method for manufacturing same
KR20190066595A (en) * 2017-12-05 2019-06-13 (주)엘지하우시스 An artificial stone
KR102243646B1 (en) * 2020-10-23 2021-04-23 주식회사 주안 Ultra high strength fiber reinforced plastics using natural fiber and preparing method thereof
WO2021145472A1 (en) * 2020-01-14 2021-07-22 월드비앰씨 주식회사 Eco-friendly artificial marble using peel and method for manufacturing same

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990084009A (en) * 1999-09-06 1999-12-06 이재일 Nature Type Mixed Stone using the Waste Stone
KR20010079127A (en) * 2001-06-15 2001-08-22 이영대 Method of forming stone injection method of natural stone headstone and top seedling
KR100492253B1 (en) * 2002-01-29 2005-05-31 서성오 Fiber resin complex panel with color stone
US8476339B2 (en) 2004-12-08 2013-07-02 Cheil Industries Inc. Method and apparatus for making composite solid surface article and composite solid surface article containing large particles
WO2006062363A1 (en) * 2004-12-08 2006-06-15 Cheil Industries Inc. Method and apparatus for making composite solid surface article and composite solid surface article containing large particles
WO2006062362A1 (en) * 2004-12-08 2006-06-15 Cheil Industries Inc. Composite solid surface article comprising at least one of randomly shaped fibers and powder particles
US8211536B2 (en) 2004-12-08 2012-07-03 Cheil Industries Inc. Composite solid surface article comprising at least one of randomly shaped fibers and powder particles
WO2009102091A1 (en) * 2008-02-14 2009-08-20 Hanwha L & C Corp. Native rock combined with resin having multi color vein and manufacturing method thereof
KR101147395B1 (en) * 2009-11-13 2012-05-22 한국생산기술연구원 Method of manufacturing polymer composite material using natural stone
KR101471399B1 (en) * 2014-03-07 2014-12-10 주식회사 에코스톤코리아 Fence manufactured from artificial stone using paste composition for manufacturing artificial stone of corrosion-resistance
WO2015160011A1 (en) * 2014-04-17 2015-10-22 월드씨엠엠에이(주) Environment-friendly artificial marble with coffee scent using brewed coffee powder and coffee by-products and method for manufacturing same
KR20190066595A (en) * 2017-12-05 2019-06-13 (주)엘지하우시스 An artificial stone
WO2021145472A1 (en) * 2020-01-14 2021-07-22 월드비앰씨 주식회사 Eco-friendly artificial marble using peel and method for manufacturing same
KR102243646B1 (en) * 2020-10-23 2021-04-23 주식회사 주안 Ultra high strength fiber reinforced plastics using natural fiber and preparing method thereof

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