KR950002387B1 - Acrylic resin composition for artificial marble manufacture - Google Patents
Acrylic resin composition for artificial marble manufacture Download PDFInfo
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- KR950002387B1 KR950002387B1 KR1019910015536A KR910015536A KR950002387B1 KR 950002387 B1 KR950002387 B1 KR 950002387B1 KR 1019910015536 A KR1019910015536 A KR 1019910015536A KR 910015536 A KR910015536 A KR 910015536A KR 950002387 B1 KR950002387 B1 KR 950002387B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
Abstract
Description
본 발명은 외관과 경도를 개량한 인조대리석의 제조방법에 관한 것으로 더욱 상세히 설명하면 합성수지 생성물로 구성되고 충전재로써 적당한 입자 크기의 Al(OH)3분말과, 표면 개질제로써 바륨 설페이트를 소량 첨가하여 중합하므로써 천연대리석과 유사한 외관과 우수한 내스크래치성을 보유함과 동시에 내열성 및 이형성이 개선된 인조대리석을 제조하는 방법에 관한 것이다.The present invention relates to a method of manufacturing artificial marble with improved appearance and hardness. More specifically, the present invention relates to polymerization of Al (OH) 3 powder having a suitable particle size as a filler and a small amount of barium sulfate as a surface modifier. Therefore, the present invention relates to a method of manufacturing artificial marble having a similar appearance and excellent scratch resistance to natural marble and improved heat resistance and releasability.
일반적으로 건축재, 주방의 외장판, 욕실의 배수관 및 실내 장식품 등을 중심으로 충전재를 함유하는 합성수지가 널리 사용되고 있는데 그 중에서도 수요에 비하여 훨씬 공급이 제한되고 성형가공이 곤란한 대리석에 관해서는 특히, 충전재 함유 플라스틱으로 천연 대리석을 대용하고자 하는 요구가 크다. 그러나, 천연 대리석이 가지는 외관은 적당한 투명성에 기인하는 깊이와 은폐성과의 기묘한 조화에 의하여 생기는 것으로 충전재 함유 플라스틱으로 구성되는 인조 대리석에 재현하기는 곤란하다.In general, synthetic resins containing fillers are mainly used for building materials, exterior panels of kitchens, drainage pipes and upholstery in bathrooms. Among them, fillers, which are more limited in supply than demand and difficult to form, are especially included. There is a great demand to replace natural marble with plastic. However, the appearance of natural marble is caused by a strange combination of depth and concealability due to proper transparency and is difficult to reproduce 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 충전재와의 굴절률이 유사할 필요가 있으며, 또한, 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 impart the apparent depth that marble has, not only transparency is required but also the refractive index between the synthetic resin and the filler mixed therein needs to be similar, and also, concealment due to white similarity is required. Sex is very important. Without these requirements, the artificial marble produced does not look like marble. In addition, the artificial marble must 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 결합제로써 사용된 합성수지는 불포화폴리에스테르수지, 아클릴수지 등이 포함되는데 상기의 합성수지 중 아크릴 수지가 투명성, 내후성, 경도 및 내열특성에 있어서 다른 수지보다 우수하다. 종래의 인조대리석은 대부분의 경우 결합제로써 아크릴수지 시럽과 충전재로써 SiO2, CaCO3, Al(OH)3등을 포함한다.To date, synthetic resins used as binders of artificial marble include unsaturated polyester resins and acryl resins. Among the synthetic resins, acrylic resins are superior to other resins in transparency, weather resistance, hardness, and heat resistance. Conventional artificial marble in most cases includes an acrylic resin syrup as a binder and SiO 2 , CaCO 3 , Al (OH) 3 and the like as a filler.
그러나, SiO2를 충전재로 사용할 경우 높은 경도를 가지고 있지만 절단가공이 곤란한 문제가 있으며, CaCO3입자를 사용하면 수지 성형체의 색체가 열약하게 되고 광굴절률의 차이가 상대적으로 커서 색의 깊이가 없다. 즉, 은폐력은 충분하나 투명성이 떨어진다는 결점을 가지고 있다.However, when SiO 2 is used as a filler, it has a high hardness, but there is a problem in that cutting is difficult. When CaCO 3 particles are used, the color of the resin molded product is weak and the difference in light refractive index is relatively large, so that there is no depth of color. In other words, the concealment power is sufficient, but the transparency has a drawback.
한편, Al(OH)3분말을 사용하는 경우에는 제품의 깊이는 상당히 개선되었으나 Al(OH)3나 SiO2에 비해 비표면적이 크고 수지의 흡유량이 커서 고충전시 혼합물의 점도가 너무 높아져 성형이 곤란하므로 다량으로 아크릴수지 시럽에 가할 수 없다. 인조대리석에서 수지의 양이 충전재의 양보다 커서 충전재에 대한 수지의 비율이 높으면 중합과정 중에 조성물 내에 실질적인 수축이 일어나며 이로 인해 제품의 표면에 요철현상을 발생시켜 불규칙한 표면을 갖게 되고 만족할만한 표면경도도 가지지 못한다.On the other hand, when Al (OH) 3 powder is used, the depth of the product is considerably improved, but the specific surface area is larger than that of Al (OH) 3 or SiO 2 , and the oil absorption amount of the resin is large, so that the viscosity of the mixture is too high for high filling, making molding difficult. Therefore, a large amount cannot be added to the acrylic resin syrup. If the amount of resin in the artificial marble is higher than that of the filler and the ratio of the resin to the filler is high, a substantial shrinkage occurs in the composition during the polymerization process, which causes irregularities on the surface of the product, resulting in an irregular surface and a satisfactory surface hardness. Don't have
따라서, 본 발명은 충전재로써 Al(OH)3를 사용하는 경우 소량의 바륨설페이트를 첨가하여 표면을 개질하므로서 불규칙한 표면과 표면경도가 부족한 결점을 제거함과 동시에 바륨설페이트의 역할로 인한 내열성 및 이형성의 향상을 도모코자 하는 것이다.Therefore, the present invention improves the heat resistance and releasability due to the role of barium sulfate while eliminating the defects of irregular surface and surface hardness by modifying the surface by adding a small amount of barium sulfate when using Al (OH) 3 as a filler. I want to try.
본 발명에 있어서, 바륨설페이트는 2중량부 내지 10중량부로 사용되며, 바람직하게는 약 5중량부의 양으로 사용된다. 2중량부 이하로 사용되면 표면개질의 효과가 충분하지 못하며 10중량부를 초과하면 충격강도등의 물성저하가 초래된다.In the present invention, barium sulfate is used in 2 to 10 parts by weight, preferably in an amount of about 5 parts by weight. When used in 2 parts by weight or less, the effect of surface modification is not sufficient, and when it exceeds 10 parts by weight, physical properties such as impact strength are reduced.
본 발명의 인조대리석은 아크릴계 수지 시럽에 충전재로써 Al(OH)3분말을 가하고 바륨설페이트를 첨가하여 균일 혼합한 후, 유기 과산화물과 제 3 급 아민 존재하에 중합한 것을 특징으로 하는 것이다.The artificial marble of the present invention is characterized in that Al (OH) 3 powder is added to an acrylic resin syrup as a filler, barium sulfate is added, homogeneously mixed, and then polymerized in the presence of an organic peroxide and a tertiary amine.
본 발명에서 사용되는 아크릴계 수지시럽으로는 중합된 상태에서 Al(OH)3입자와 유사한 굴절률을 가지는 것이면 사용될 수 있으나 투명성, 경도 및 열적 특성이 특히 우수한 메틸메타크릴레이트의 호모중합체 또는 메타크릴산과 공중합 가능한,-에틸렌성 불포화 단량체와의 공중합체로 된 아크릴계 수지가 사용된다. 아크릴계 수지 시럽은 상기의 아클릴계 수지 단량체를 개시제 및 연쇄이동제의 존재하에 부분 중합하여 점도 2-10포아즈(POISE)의 수지액을 얻는다.The acrylic resin syrup used in the present invention may be used as long as it has a refractive index similar to that of Al (OH) 3 particles in a polymerized state, but copolymerizes with homopolymer or methacrylic acid of methyl methacrylate having excellent transparency, hardness and thermal properties. possible , Acrylic resins made of copolymers with ethylenically unsaturated monomers are used. The acrylic resin syrup partially polymerizes the above-described acrylic resin monomer in the presence of an initiator and a chain transfer agent to obtain a resin liquid having a viscosity of 2-10 poise.
상기의 아크릴수지 시럽에 Al(OH)2분말을 가하고 과산화벤조일, 과산화라우릴, 아조비스이소부티로니트릴 등의 유기 산화물과 N, N-디알킬톨루이딘, N, N-디알킬아닐린, N, N-디하드록시톨루이딘 등의 3급 아민으로 된 중합 개시제계에서 필요에 따라 연쇄이동제와 임의의 색조를 가진 착색제를 첨가하며 본발명에서 목적하는 바륨설페이트를 첨가하여 균일하게 혼합한 후 기포를 제거하여 금형에 주입시키고 50 내지 100℃ 범위의 온도에서 2 내지 5시간 동안 중합시킨 다음 120℃ 온도로 1시간 동안 후경화하여 탈형하면 성형품을 얻는다.Al (OH) 2 powder was added to the acrylic resin syrup and organic oxides such as benzoyl peroxide, lauryl peroxide and azobisisobutyronitrile, and N, N-dialkyltoluidine, N, N-dialkylaniline, N, In the polymerization initiator system consisting of tertiary amines such as N-dihydroxytoluidine, a chain transfer agent and a coloring agent having an arbitrary color tone are added as necessary, and barium sulfate as desired in the present invention is added to uniformly mix to remove bubbles. After injection into the mold and polymerized for 2 to 5 hours at a temperature in the range of 50 to 100 ℃ and post-cured for 1 hour at 120 ℃ temperature to obtain a molded article.
Al(OH)3분말을 조화된 깊이와 은폐성을 부여하기 위하여 1 내지 50㎛의 입자경을 가지는 것으로 20 내지 80중량부 첨가하는 것이 바람직하며, 더욱 좋기로는 50 내지 75중량부가 첨가된다. 20% 미만에서는 투명성이 너무 크고 또한 경도가 부족하며 80%를 넘으면 충전재 분말의 흐름성이 저하하여 성형용 혼합물의 유동성이 불충분하게 된다.It is preferable to add 20 to 80 parts by weight of Al (OH) 3 powder to have a particle size of 1 to 50 µm in order to provide a harmonized depth and concealability, and more preferably to 50 to 75 parts by weight. If it is less than 20%, transparency is too large and hardness is insufficient, and if it exceeds 80%, the flowability of the filler powder will fall and the fluidity of the molding mixture will be insufficient.
성형용 복합물의 유동성은 주형용으로서는 약 100포이즈 이하일 필요가 있고 이것을 초과하면 형캐비티의 전면에 흘러 들어가지 않게 된다. 상기 대리석 모양물을 제조함에 있어 수지액과 충전재와의 혼합방법을 연구하므로서 보다 천연대리석에 가까운 외관을 가지는 인조대리석을 얻을 수 있다.The flowability of the molding composite needs to be about 100 poise or less for casting, and if it exceeds this, it will not flow into the front of the mold cavity. In preparing the marble-like material, by studying the mixing method of the resin liquid and the filler, it is possible to obtain an artificial marble having an appearance closer to natural marble.
본 발명의 전형적인 실시예는 다음과 같다.Typical embodiments of the invention are as follows.
[실시예 1-5 및 비교예 1]Example 1-5 and Comparative Example 1
메틸메타크릴레이트 부분 중합체 시럽(중합율 30%, 점도 6 포아즈) 35중량부에 Al(OH)3분말(입경20㎛) 65중량부와 바륨설페이트를 0-12중량부 가하고 과산화벤조일 0.2중량부 N, N-디히드록시-P-톨루이딘 0.2 중량부와 함께 균일하게 혼합한다. 액상 혼합물의 기포를 제거하고 탈포된 혼합물을 조립된 유리판의 가스킷 사이로 주입하고 가스킷을 봉한 후, 60℃의 수조에서 3시간 동안 중합시킨다. 중합이 끝난 주형판을 120℃의 오븐에서 1시간 동안 후 경화시켜 잔류 모노머를 제거시킨다.To 35 parts by weight of methyl methacrylate partial polymer syrup (30% polymerization rate, viscosity 6 poise), 65 parts by weight of Al (OH) 3 powder (particle size: 20 µm) and 0-12 parts by weight of barium sulfate were added, and 0.2 weight of benzoyl peroxide. Part N, mix uniformly with 0.2 parts by weight of N-dihydroxy-P-toluidine. The bubbles of the liquid mixture are removed, the degassed mixture is injected between the gaskets of the assembled glass plates, the gaskets are sealed, and then polymerized in a 60 占 폚 water bath for 3 hours. After completion of the polymerization, the template was cured in an oven at 120 ° C. for 1 hour to remove residual monomer.
첨가된 바륨셀페이트의 양에 따른 시료의 물성시험결과는 아래의 표 1과 같다. 본 실시예 및 비교예를 통하여 알 수 있는 바와 같이 물성의 손상을 최소화하면서 표면개질 효과를 발휘하기 위한 적당한 바륨설페이트의 첨가량은 2-10중량부이다.The physical property test results of the samples according to the amount of barium sulphate added are shown in Table 1 below. As can be seen from the examples and comparative examples, the addition amount of a suitable barium sulfate for exerting a surface modification effect while minimizing damage to physical properties is 2 to 10 parts by weight.
[표 1]TABLE 1
[시험방법][Test Methods]
경도 : 로크웰 ASTM D-785Hardness: Rockwell ASTM D-785
열변형온도 : 18.6㎏ ASTM D-648Heat Deflection Temperature: 18.6㎏ ASTM D-648
표면 조도 : MITUTOYO SURFTEST 501(평균조도 Ra)Surface Roughness: MITUTOYO SURFTEST 501 (Average Roughness Ra)
아이조도충격강도 : ASTM D-256Eye roughness impact strength: ASTM D-256
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| Application Number | Priority Date | Filing Date | Title |
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| KR1019910015536A KR950002387B1 (en) | 1991-09-06 | 1991-09-06 | Acrylic resin composition for artificial marble manufacture |
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| KR1019910015536A KR950002387B1 (en) | 1991-09-06 | 1991-09-06 | Acrylic resin composition for artificial marble manufacture |
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| KR950002387B1 true KR950002387B1 (en) | 1995-03-17 |
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