KR20050102798A - The artificial marble used by bone ash and manufacture thereof - Google Patents
The artificial marble used by bone ash and manufacture thereof Download PDFInfo
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- KR20050102798A KR20050102798A KR1020040028072A KR20040028072A KR20050102798A KR 20050102798 A KR20050102798 A KR 20050102798A KR 1020040028072 A KR1020040028072 A KR 1020040028072A KR 20040028072 A KR20040028072 A KR 20040028072A KR 20050102798 A KR20050102798 A KR 20050102798A
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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
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/06—Acrylates
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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
- C04B18/04—Waste materials; Refuse
- C04B18/06—Combustion residues, e.g. purification products of smoke, fumes or exhaust gases
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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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
- C04B20/008—Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder
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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
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
본 발명은 인조대리석을 제조함에 있어서 아크릴 수지와 골회를 주재로 한 조성과 그 제조방법에 대한 것이다. 아크릴 수지 시럽(a) 20 내지 50중량%, 골회(b) 50 내지 80중량%, (a)+(b)100 중량부에 대하여 각각 가교제 0.5 내지 8중량부, 라디칼 개시제 0.05 내지 3중량부와 소량의 기타첨가제로 이루어진 아크릴계 인조대리석 조성물을 통하여 내흡습성과 내열성이 향상되며 미백의 효과가 탁월한 인조대리석을 얻을 수 있는 것이다.The present invention relates to a composition based on acrylic resins and bone ash in the manufacture of artificial marble and a method of manufacturing the same. 20 to 50% by weight of acrylic resin syrup (a), 50 to 80% by weight of bone ash (b), 0.5 to 8 parts by weight of crosslinking agent, and 0.05 to 3 parts by weight of radical initiator, respectively, based on 100 parts by weight of (a) + (b) Through the acrylic artificial marble composition composed of a small amount of other additives, the hygroscopicity and heat resistance are improved, and the artificial marble having excellent whitening effect can be obtained.
Description
일반적으로 주방의 외장판, 건축재, 욕실의 배수관 및 실내장식품 등을 중심으로 충진재를 함유하는 합성수지가 널리 사용되고 있는데 그 중에서도 수요에 비하여 훨씬 공급이 제한되고 성형가공이 곤란한 대리석에 관해서는 특히 충진재 함유 플라스틱으로 천연대리석을 대용하고자하는 요구가 크다. 그러나 천연대리석이 가지는 외관은 적당한 투명성에 기인하는 깊이와 은폐성과의 기묘한 조화에 의하여 생기는 것으로 충진재 함유 플라스틱으로 구성되는 인조대리석에 재현하기는 곤란하다. In general, synthetic resins containing fillers are widely used, especially in exterior panels of kitchens, building materials, bathroom drainage pipes, and interior decorations. Among them, fillers containing plastics, which are much more limited than demand and difficult to form, are especially used for plastics containing fillers. As a result, there is a great demand to substitute natural marble. However, the appearance of natural marble is caused by a strange combination of depth and concealability due to proper transparency, and it is difficult to reproduce it in artificial marble composed of filler-containing plastic.
따라서 대리석이 가지는 외관상의 깊이를 부여하기 위해서는 사용되는 합성수지 자체가 투명성이 요구될 뿐만 아니라 그 합성수지와 여기에 혼재된 충진재의 분산에 의해 백색 유사성에 기인하는 은폐성이 매우 중요하다. 이와 같은 필수요건을 구비하지 않으면 제조된 인조대리석은 대리석 같이 보이지 않는다. 또한 인조대리석은 어느 정도의 경도를 역시 가져야 한다. 왜냐하면 인조대리석의 경도가 불충분하면 천연대리석에서는 별로 생기지 않는 마모가 표면에 쉽게 생겨서 외관 및 질감을 현저하게 손상하기 때문이다.Therefore, in order to give the appearance depth of marble, not only transparency is required of the synthetic resin itself, but also the concealability due to white similarity is very important due to the dispersion of the synthetic resin and the filler mixed therein. Without these requirements, the artificial marble produced does not look like marble. Artificial marble should also have some hardness. Because of insufficient hardness of artificial marble, wear that is rarely produced in natural marble easily occurs on the surface, which significantly damages the appearance and texture.
현재까지 인조대리석의 결합재로써 사용된 합성수지는 불포화 폴리에스테르 수지 아크릴 수지 등이 포함되는데 상기의 합성수지중 아크릴 수지가 투명성 내후성 경도 및 내열특성에 있어서 다른 수지보다 우수하다. 종래의 인조대리석은 대부분의 경우 결합재로써 아크릴 수지 시럽과 충진재로써 SiO2, CaCO3, Al(OH)3 등을 사용하고 있다.To date, synthetic resins used as binders of artificial marble include unsaturated polyester resins, acrylic resins, and the like, of which acrylic resins are superior to other resins in transparency weatherability hardness and heat resistance properties. Conventional artificial marble is in most cases using an acrylic resin syrup and a filler SiO 2 , CaCO 3 , Al (OH) 3 and the like as a binder.
본 발명은 아크릴수지에 생체적합성을 지닌 골회를 충진재로 사용함으로써 친환경성 인조대리석을 제조하는 방법을 제공하는 것을 목적으로 한다. It is an object of the present invention to provide a method for producing environmentally friendly artificial marble by using a biocompatible bone ash as a filler in acrylic resin.
또한 본 발명은 골회를 사용하여 기존의 인조대리석에 비하여 상아빛의 흰색을 띄어 미백성이 뛰어나며, 미관이 미려한 효과가 있고, 내흡습성과 내열성이 향상된 인조 대리석을 제공하고자 한다. In another aspect, the present invention is to provide an artificial marble with ivory white compared to the existing artificial marble with excellent whitening, beautiful appearance, and improved hygroscopicity and heat resistance using bone ash.
본 발명은 인조대리석을 제조하기 위한 혼합조성물과 이를 사용한 인조대리석에 관한 것으로, 본 발명의 혼합조성물에 사용되는 충진재는 골회를 사용하는 것을 특징으로 한다. The present invention relates to a mixed composition for preparing artificial marble and an artificial marble using the same, characterized in that the filler used in the mixed composition of the present invention uses bone ash.
본 발명에 사용되는 혼합조성물은,The mixed composition used in the present invention,
(a) 아크릴 수지 시럽 20 내지 50 중량%;(a) 20-50% by weight of acrylic resin syrup;
(b) 골회 50 내지 80 중량%(b) 50 to 80% by weight of bone ash
(c) (a)+(b)100중량부에 대하여 각각 가교제 0.5 내지 8 중량부, 개시제 0.05 내지 3 중량부;(c) 0.5 to 8 parts by weight of crosslinking agent and 0.05 to 3 parts by weight of initiator, respectively, based on 100 parts by weight of (a) + (b);
로 구성된다.It consists of.
본 발명에서 혼합조성물을 구성하는 성분 중 아크릴 수지 시럽에 대해 설명한다. 아크릴 수지 시럽은 메틸메타크릴레이트 단량체 72 내지 87 중량%와 폴리메틸메타크릴레이트 폴리머 13 내지 28 중량%를 혼합하여 제조된다.The acrylic resin syrup among the components constituting the mixed composition in the present invention will be described. Acrylic resin syrups are prepared by mixing 72-87% by weight of methyl methacrylate monomers and 13-28% by weight of polymethylmethacrylate polymers.
상기 아크릴 수지 시럽의 구성물 중 폴리메틸메타크릴레이트 폴리머는 메틸메타크릴레이트 100 내지 94 중량%와 에틸 아크릴레이트, 부틸 아크릴레이트, 2-에틸헥실 아크릴레이트, 아크릴로 니트릴, 에틸메타크릴레이트, 부틸메타크릴레이트, 2-에틸헥실 메타크릴레이트, 메타크릴로니트릴 등의 아크릴계 단량체로부터 선택되는 하나 또는 혼합물을 0 내지 6 중량% 사용하여 중합하는 공중합체 혹은 동종고분자이다. 호모중합체의 경우는 투명성과 클리어런스가 좋고, 공중합체를 사용하는 경우는 충격성과 분산성 등에서 우수한 효과를 얻을 수 있다.Polymethyl methacrylate polymer in the composition of the acrylic resin syrup is 100 to 94% by weight of methyl methacrylate and ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, acrylonitrile, ethyl methacrylate, butyl meth It is a copolymer or homopolymer which polymerizes using 0-6 weight% of 1 or mixtures chosen from acryl-type monomers, such as a acrylate, 2-ethylhexyl methacrylate, and methacrylonitrile. In the case of the homopolymer, transparency and clearance are good, and in the case of using a copolymer, excellent effects can be obtained in impact and dispersibility.
본 발명에서 혼합조성물을 구성하는 성분 중 충진재에 대해서 설명한다. 본 발명에서 충진재는 골회(인산염칼슘Ca2P2O7, X-ray를 통한 분석)를 사용하며 입자크기가 5 내지 50 ㎛인 것이 바람직하고, 20 내지 80 중량%를 사용하는 천연 혹은 인조 골회 모두 사용가능하다.Filler in the components constituting the mixed composition in the present invention will be described. In the present invention, the filler uses bone ash (calcium phosphate Ca 2 P 2 O 7 , analysis through X-ray) and the particle size is preferably 5 to 50 ㎛, natural or artificial bone using 20 to 80% by weight All are available.
골회의 함량이 20 중량% 이하를 사용하면 투명성이 너무 크고 경도가 부족하며 80 중량% 이상이 되면 충전제 분말의 흐름성이 저하하여 성형용 혼합물의 유동성이 불충분하여 20 내지 80 중량%를 사용하는 것이 가장 바람직하다.If the content of bone ash is less than 20% by weight, the transparency is too large, the hardness is insufficient, and if it is more than 80% by weight, the flowability of the filler powder decreases, and the fluidity of the molding mixture is insufficient, so that the use of 20 to 80% by weight is used. Most preferred.
상기 구성성분 중 골회는 인조골회나 천연골회를 모두 사용할 수 있으며, 천연골회는 아교질이나 지방질을 제거한 동물의 뼈를 약 1000℃에서 소성하여 분말로 만든 가루를 지칭하는 것으로 원료의 융제 역할을 하며, 소재의 백색도와 투광성을 증가시키는 역할을 한다. 골회는 유럽인들이 홍차를 마실 때 홍차의 색을 돋보이게 하기 위하여 흰색의 도자기를 만들어 낸 것에서 유래하고 영국에서 처음으로 본차이나(bone china)에 적용하였다. 본차이나는 일반적으로 식생활에 중요한 부분을 차지하고 있는 도자기 제품으로서 골회, 점토, 코니시 스톤 등을 혼합 성형하여 고온에서 소성 제조한 제품이다. 본차이나의 주재인 골회는 내흡습성 및 내열성 향상뿐만 아니라 상아빛 흰색을 띔으로서 미려한 외양을 제공함으로써 본차이나는 가장 고급 도자기 제품으로 사용되어지고 있다. Among the components, bone ash can be used for both artificial bone and natural bone, and natural bone refers to the powder made by sintering the bones of animals from which gelatin or fat is removed at about 1000 ° C. It increases the whiteness and light transmittance of the material. The skeletal conjugation derives from the creation of white porcelain to enhance the color of black tea when Europeans drink it and applied it to bone china for the first time in Britain. Bone China is a porcelain product that generally plays an important part in the diet, and it is a product made by mixing and molding bone ash, clay, and polish stone at high temperature. Bongol, the presiding of Bone China, is not only improved hygroscopicity and heat resistance but also ivory white to provide a beautiful appearance.
인조 골회는 소량의 Ca2P2O7와 다량의 칼슘 히드록시 아파타이트의 혼합물을 주 구성으로 하는 것으로 비철금속 제품의 몰드 이형성을 향상시키기 위하여 적용되고 있으며 천연골회와 혼용이 가능한 인공적으로 제조된 골회이다(삼조실업, 뮬린케미칼)Artificial bone is composed of a mixture of small amount of Ca 2 P 2 O 7 and a large amount of calcium hydroxyapatite, which is applied to improve mold release properties of nonferrous metal products. Samjo Unemployment, Mullin Chemical
본 발명에서 혼합조성물을 구성하는 성분 중 가교제에 대해서 설명한다. 가교제는 에틸렌 글리콜 디메타크릴레이트, 에틸렌 글리콜 트리메타크릴레이트, 트리메틸올프로판 트리메타크릴레이트, 트리아릴시아네이트, 디아릴프탈레이트, 아릴 메타크릴레이트와 같이 분자 내에 2 내지 3개의 이중결합을 포함하는 화합물을 하나 또는 하나 이상을 혼합하여 사용할 수 있으며, 상기 아크릴 수지 시럽에 대하여 0.5 내지 8 중량% 사용하는 것이 바람직하다.The crosslinking agent of the component which comprises a mixed composition in this invention is demonstrated. The crosslinking agent contains two to three double bonds in the molecule, such as ethylene glycol dimethacrylate, ethylene glycol trimethacrylate, trimethylolpropane trimethacrylate, triarylcyanate, diarylphthalate, aryl methacrylate. One or more compounds may be used in combination, and it is preferable to use 0.5 to 8% by weight based on the acrylic resin syrup.
본 발명에서 혼합조성물을 구성하는 성분 중 개시제에 대해서 설명한다. 개시제는 벤조일퍼옥사이드, 디큐밀 퍼옥사이드, 디-터셔리 부틸퍼옥사이드 등과 같은 유기과산화물이나 아조이소부티로비스니트릴 등과 같은 아조 개시제를 단독 혹은 복합으로 사용하며 이러한 중합개시제의 첨가량은 상기 아크릴 수지 시럽과 골회의 총중량부에 대해 0.05 내지 8 중량부 바람직하다.In the present invention, an initiator among the components constituting the mixed composition will be described. The initiator is used alone or in combination with an organic peroxide such as benzoyl peroxide, dicumyl peroxide, di-butyl butyl peroxide or azo initiator such as azoisobutyronibisnitrile, and the like. 0.05 to 8 parts by weight relative to the total weight of the bone and bone are preferred.
또한 본 발명의 혼합조성물은 필요에 의해서 첨가제들을 선택적으로 사용할 수 있다. 본 발명에 사용할 수 있는 첨가제로서는 중합조절제, 자외선 안정제, 개시제의 분해를 촉진하는 분해촉진제, 이형성과 혼화성을 증진시키는 활제, 골회를 수지 내에 분산을 용이하게 하는 커플링 에이전트, 등을 사용할 수 있다.In addition, the mixed composition of the present invention may optionally use additives as necessary. As the additive which can be used in the present invention, a polymerization regulator, an ultraviolet stabilizer, a decomposition accelerator for promoting decomposition of the initiator, a lubricant for promoting releasability and miscibility, a coupling agent for easily dispersing bone in the resin, and the like can be used. .
하기는 본 발명의 바람직한 일실시예에 대해서 기재하는 바, 본 발명이 하기의 실시예에 의하여 제한되는 것은 아니다.The following describes a preferred embodiment of the present invention, the present invention is not limited by the following examples.
[실시예 1]Example 1
메틸메타크릴레이트 75중량부 폴리메틸메타크릴레이트 25중량부를 혼합하여 아크릴 수지 시럽을 제조한 후, 아크릴 수지 시럽 100중량부에 가교제로서 에틸렌 디메틸메타크릴레이트 2중량부, 라디칼 개시제로 1,1,3,3-테트라메틸부틸퍼옥시-2-에틸헥사노에이트를 1중량부를 상온에서 혼합한다. 상기 혼합 조성물에 평균입경이 22㎛인 천연골회(삼조실업 제품)를 아크릴수지 시럽과 골회의 비가 35:65중량%가 되도록 투입한 후 교반하여 분산시킨 후 진공 탈포한다. 다음에 SUS몰드에 혼합물을 붓고 70℃에서 2시간 경화반응을 수행한다. 그 후 150℃에서 1시간동안 후 경화를 수행한 후 탈형하여 최종제품을 수득하였다. After mixing 75 parts by weight of methyl methacrylate and 25 parts by weight of polymethyl methacrylate to prepare an acrylic resin syrup, 2 parts by weight of ethylene dimethyl methacrylate as a crosslinking agent to 100 parts by weight of acrylic resin syrup, 1,1, as a radical initiator 1 part by weight of 3,3-tetramethylbutylperoxy-2-ethylhexanoate is mixed at room temperature. Into the mixed composition is added to the natural bone (average product of Samjo Industrial Co., Ltd.) having a particle size of 22㎛ so that the ratio of acrylic resin syrup and bone ash to 35: 65% by weight, stirred and dispersed and then vacuum degassed. Next, the mixture is poured into a SUS mold and cured for 2 hours at 70 ° C. Thereafter, curing was performed at 150 ° C. for 1 hour and then demolded to obtain a final product.
제조된 인조대리석판의 열전이 온도(Tg)를 측정하여 본 결과 105 ℃로서 내열성이 우수하였으며, 또한 표면의 외관이 미려하여 자연스러운 느낌을 주었고 표면 광택도 우수하였다.The heat transfer temperature (T g ) of the manufactured artificial marble plate was measured, and as a result, it was excellent in heat resistance as 105 ° C., and the surface appearance was beautiful to give a natural feeling and surface gloss.
[실시예 2]Example 2
상기 실시예 1에서 천연골회 대신 합성골회(삼조실업)를 사용한 것을 제외하고는 동일한 방법과 동일한 함량으로 수행하였다.The same method as in Example 1, except that synthetic bone (soybean industry) instead of natural bone was used in the same amount.
제조된 인조대리석판의 열전이 온도(Tg)를 측정하여 본 결과 105 ℃이었다. 또한 표면의 외관이 미려하여 자연스러운 느낌을 주었고, 표면광택도 우수하였다.The thermal transition temperature (T g ) of the manufactured artificial marble plate was measured and found to be 105 ° C. In addition, the appearance of the surface was beautiful and gave a natural feeling, the surface gloss was also excellent.
[비교예 1]Comparative Example 1
상기 실시예 1에서 천연골회 대신 평균입경 20㎛인 수산화 알루미늄을 사용한 것을 제외하고는 동일한 방법과 동일한 함량으로 수행하였다.The same method as in Example 1, except that aluminum hydroxide having an average particle diameter of 20 ㎛ instead of natural bone was used.
제조된 인조대리석판의 열전이 온도(Tg)를 측정하여 본 결과 102 ℃로서 다소 내열성이 열세로 나타났다.As a result of measuring the heat transition temperature (T g ) of the manufactured artificial marble plate, the heat resistance was slightly inferior as 102 ° C.
본 발명에 따른 인조대리석의 색상은 골회를 사용하여 기존의 인조대리석에 비하여 상아빛의 흰색을 띄어 미백성이 뛰어나며, 미관이 미려한 효과가 있어 이를 이용한 인조대리석을 욕조 등에 응용 시 고급스러운 느낌을 준다. 또한 본 발명에 따른 인조대리석은 내열성에서도 기존의 첨가제에 의한 것보다 우수하고 기존 제품 대비 내흡습성도 유사하거나 향상되는 효과가 있다. The color of the artificial marble according to the present invention has whitening of ivory white color compared to the existing artificial marble using bone ash and has excellent whitening ability, and has a beautiful effect to give a luxurious feeling when applying artificial marble using the same to a bathtub. . In addition, the artificial marble according to the present invention is excellent in heat resistance than the conventional additives and has the effect of similar or improved hygroscopicity compared to the existing products.
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KR20190054349A (en) * | 2017-11-13 | 2019-05-22 | (주)이지켐 | Artificial marble having a themal storage and the manufacturing method thereof |
CN115974455A (en) * | 2022-12-15 | 2023-04-18 | 清远戈兰迪高分子材料有限公司 | Ultraviolet aging resistant quartz stone plate and preparation method thereof |
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KR20190054349A (en) * | 2017-11-13 | 2019-05-22 | (주)이지켐 | Artificial marble having a themal storage and the manufacturing method thereof |
CN115974455A (en) * | 2022-12-15 | 2023-04-18 | 清远戈兰迪高分子材料有限公司 | Ultraviolet aging resistant quartz stone plate and preparation method thereof |
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