KR20140025895A - Addition curable silicone rebber composition and cured silicon rebber - Google Patents
Addition curable silicone rebber composition and cured silicon rebber Download PDFInfo
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Abstract
Description
본 발명은 부가경화형 실리콘 고무 조성물 및 실리콘 고무 경화물에 관한 것으로서, 높은 인열 강도와 우수한 성형 안정성을 가지고 식품용 또는 의료용에 적합한 부가경화형 실리콘 고무 조성물 및 이로부터 얻은 실리콘 고무 경화물에 관한 것이다. The present invention relates to an addition-curable silicone rubber composition and a silicone rubber cured product, and more particularly to an addition-curable silicone rubber composition and a silicone rubber cured product obtained therefrom having a high tear strength and excellent molding stability.
실리콘 고무는 내열성, 내한성, 안정성, 전기절연성 및 내후성이 우수하며, 이러한 유리한 특성들 때문에 다양한 분야에서 여러 용도로 사용되고 있다. 이러한 실리콘 고무는 유기과산화물 경화타입으로 성형하는 것이 전형적이었으나, 2000년대 들어 친환경 제품에 대한 관심 및 성형품 외관, 냄새 등의 감성품질이 이슈화되면서 백금 촉매를 이용한 부가경화 타입이 각광받는 경화방식으로 자리매김하고 있다.Silicone rubber is excellent in heat resistance, cold resistance, stability, electrical insulation and weather resistance, and because of these advantageous properties, it is used in various applications in various fields. Such silicone rubber was typically molded into an organic peroxide cured type, but since the interest of eco-friendly products and emotional quality such as appearance and smell of molded products have been raised in the 2000s, the addition curing type using platinum catalysts has become a popular curing method. Doing.
본 발명은 위와 같은 친환경 부가경화형 실리콘 고무를 만들기 위해서 실리콘 베이스를 제조하기 위한 비닐 폴리머 조합 및 백금 촉매와 지연제의 조합하는 신규 기술을 배경으로 한다. The present invention is based on a novel technique of combining a vinyl polymer and a platinum catalyst and a retarder to produce a silicone base to make an eco-friendly addition-curable silicone rubber as described above.
본 발명의 목적은 특정 비닐기 함량을 보유한 실리콘 폴리머와 유기 실란 화합물의 비율을 특정함으로써 인열강도를 향상시키고, 가사시간 및 성형안정성이 우수한 부가경화형 실리콘 고무 조성물을 제공하고자 하는 것이다.It is an object of the present invention to improve the tear strength by specifying the ratio of the silicone polymer and the organic silane compound having a specific vinyl group content, and to provide an addition-curable silicone rubber composition having excellent pot life and molding stability.
본 발명의 또 다른 목적은 백금 촉매와 특정 지연제를 일정 비율로 사용하여 경화시킴으로써 가사시간 및 성형안정성이 우수한 실리콘 고무 경화물을 제공하고자 하는 것이다. Another object of the present invention is to provide a silicone rubber cured product having excellent pot life and molding stability by curing by using a platinum catalyst and a specific retarder in a certain ratio.
상기 목적을 달성하기 위하여, 본 발명은 비닐기 함량이 0.01∼8.5 몰퍼센트인 비닐 실리콘 검 100 중량부에 대하여, BET법에 의한 비표면적이 200 ㎡/g 이상인 보강성 실리카 10 내지 100 중량부; 유기 실란 화합물 0.1 내지 1.0 중량부; 양 말단에 하이드록시기를 가지고, 측쇄에 메틸기 또는 메틸비닐기를 가지는 저점도 가공조제 1.0 내지 15.0 중량부; 하이드로젠 실리콘 폴리머 0.5 내지 2.0 중량부를 포함하는 부가경화형 실리콘 고무 조성물을 제공한다.In order to achieve the above object, the present invention is 10 to 100 parts by weight of reinforcing silica having a specific surface area of 200 m 2 / g or more by BET method with respect to 100 parts by weight of vinyl silicon gum having a vinyl group content of 0.01 to 8.5 mole percent; 0.1 to 1.0 parts by weight of the organosilane compound; 1.0 to 15.0 parts by weight of a low viscosity processing aid having a hydroxy group at both ends and a methyl group or a methylvinyl group at the side chain; It provides an addition-curable silicone rubber composition comprising 0.5 to 2.0 parts by weight of hydrogen silicone polymer.
또한, 본 발명은 본 발명의 부가경화형 실리콘 고무 조성물 100 중량부에 대하여, C8H18OPtSi2로 표시되는 액상 백금촉매 1 내지 10 ppm; 및 지연제로서, 트리스(2,4-디터셔리-부틸페닐)포스파이트 5 내지 100 ppm을 사용하여 경화시켜 얻은 실리콘 고무를 제공한다.In addition, the present invention is 1 to 10 ppm of a liquid platinum catalyst represented by C 8 H 18 OPtSi 2 with respect to 100 parts by weight of the addition-curable silicone rubber composition of the present invention; And a silicone rubber obtained by curing using 5 to 100 ppm of tris (2,4-di-butylphenyl) phosphite as a retardant.
본 발명의 부가 경화형 실리콘 고무 조성물은 식품 및 의료용품의 중요 물성인 인열강도를 향상시키고, 성형성 및 가사시간을 극대화시킬 수 있어, 식품용 및 의료용으로 매우 적합하다. The addition-curable silicone rubber composition of the present invention can improve tear strength, which is an important property of food and medical products, maximize moldability and pot life, and is very suitable for food and medical use.
이하, 본 발명에 따른 부가경화형 실리콘 고무 조성물을 성분별로 더욱 상세하게 설명한다.
Hereinafter, the addition-curable silicone rubber composition according to the present invention will be described in more detail by component.
(1) 비닐 실리콘 검(GUM)(1) vinyl silicone gum (GUM)
본 발명의 부가경화형 실리콘 고무 조성물은 비닐기 함량이 0.01∼8.5 몰퍼센트인 비닐 실리콘 검 100 중량부를 포함한다. 상기 비닐기 함량 범위 내에서 열경화시 기본적인 경화 성질을 가질 수 있다. The addition-curable silicone rubber composition of the present invention contains 100 parts by weight of vinyl silicone gum having a vinyl group content of 0.01 to 8.5 mole percent. It may have a basic curing properties during thermosetting within the vinyl group content range.
본 발명에 따른 비닐 실리콘 검은 분자량이 400,000 내지 700,000이며, 점도가 수백만 센티포아즈 이상의 고중합(2,000~10,000의 실록산 단위)된 선형 오가노폴리실록산으로서, 양 말단, 양말단과 측쇄 또는 측쇄에 메틸기 또는 메틸비닐기를 함유하는 것이다. The vinyl silicone gum according to the present invention is a linear organopolysiloxane having a molecular weight of 400,000 to 700,000 and a viscosity of several million centipoise or more (2,000 to 10,000 siloxane units), and has a methyl group or methyl group at both ends, both ends and side or side chains. It contains a vinyl group.
특히, 본 발명의 부가경화형 실리콘 고무 조성물은 하기 화학식 1로 표시되는 반복 단위를 가지는 것이 바람직하다: In particular, the addition-curable silicone rubber composition of the present invention preferably has a repeating unit represented by the following general formula (1):
[화학식 1][Chemical Formula 1]
RaSiO(4-a)/2 R a SiO (4-a) / 2
화학식 1에서, R은 탄소 수 1 내지 10, 바람직하게는 1 내지 8의 비치환 또는 치환된 1가의 탄화수소기이지만, R 중 2개 이상은 비닐기이고, a는 1.90 내지 2.05이다.In formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, but at least two of R are vinyl groups and a is 1.90 to 2.05.
여기서, 상기 R로 표시되는 규소 원자에 결합한 비치환 또는 치환된 1가의 탄화수소기로는, 예를 들면 메틸기, 에틸기, 프로필기, 이소프로필기, 부틸기, 이소부틸기, tert-부틸기, 펜틸기, 네오펜틸기, 헥실기, 시클로헥실기, 옥틸기, 노닐기, 데실기 등의 알킬기, 페닐기, 톨릴기, 크실릴기, 나프틸기 등의 아릴기, 벤질기, 페닐에틸기, 페닐프로필기 등의 아랄킬기, 비닐기, 알릴기, 프로페닐기, 이소프로페닐기, 부테닐기, 헥세닐기, 시클로헥세닐기, 옥테닐기 등의 알케닐기나, 이들 기의 수소 원자의 일부 또는 전부를 불소, 브롬, 염소 등의 할로겐 원자, 시아노기 등으로 치환한 것, 예를 들면 클로로메틸기, 클로로프로필기, 브로모에틸기, 트리플루오로프로필기, 시아노에틸기 등을 들 수 있지만, 전체 R의 90 몰％ 이상이 메틸기인 것이 바람직하다.Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group Alkyl groups such as neopentyl, hexyl, cyclohexyl, octyl, nonyl and decyl groups, aryl groups such as phenyl, tolyl, xylyl and naphthyl, benzyl, phenylethyl and phenylpropyl Alkenyl groups such as aralkyl groups, vinyl groups, allyl groups, propenyl groups, isopropenyl groups, butenyl groups, hexenyl groups, cyclohexenyl groups, octenyl groups, and some or all of the hydrogen atoms of these groups are fluorine and bromine Substituted by halogen atoms, such as chlorine, and a cyano group, for example, chloromethyl group, chloropropyl group, bromoethyl group, trifluoropropyl group, cyanoethyl group, etc. are mentioned, 90 mol% of all R's It is preferable that the above is a methyl group.
본 발명에 따른 비닐 실리콘 검은 0.01∼8.5 몰퍼센트의 비닐기 함량 범위 내에서 한 종류의 비닐 실리콘 검을 사용할 수 있고, 비닐기 함량이 상이한 실리콘 검의 혼합물을 사용할 수도 있다, 바람직하게는 저비닐 함량의 실리콘 검과 고비닐 함량의 실리콘 검의 혼합물을 사용할 수 있다. 특히 바람직하게는, 본 발명에 따른 비닐 실리콘 검 100 중량부는 비닐기 함량이 0.1 몰퍼센트인 비닐 실리콘 검 20~80 중량부와 비닐기 함량이 0.2 몰퍼센트인 비닐 실리콘 검 20~80 중량부로 이루어질 수 있다.
The vinyl silicone gum according to the present invention may use one kind of vinyl silicone gum within the vinyl group content range of 0.01 to 8.5 mole percent, and a mixture of silicone gums having different vinyl group contents may be used, preferably a low vinyl content Mixtures of silicone gums and high vinyl silicone gums can be used. Particularly preferably, 100 parts by weight of vinyl silicone gum according to the present invention may be composed of 20 to 80 parts by weight of vinyl silicone gum having a vinyl group content of 0.1 mol percent and 20 to 80 parts by weight of vinyl silicone gum having a vinyl group content of 0.2 mol percent. have.
(2) 보강성 실리카(2) reinforcing silica
본 발명의 부가경화형 실리콘 고무 조성물에 포함되는 보강성 실리카는 무정형 실리카로서 BET법에 의한 비표면적이 200 ㎡/g 이상인 습식 실리카 또는 건식 실리카(fumed silica)를 사용할 수 있다. BET법에 의한 비표면적이 200 ㎡/g 이상인 것을 사용함으로써 기계적 성질을 보강할 수 있다. The reinforcing silica included in the addition-curable silicone rubber composition of the present invention may be wet silica or fumed silica having a specific surface area of 200 m 2 / g or more by BET as amorphous silica. By using a specific surface area of 200 m 2 / g or more by the BET method, mechanical properties can be reinforced.
바람직하게는, 평균입자크기가 7 내지 22 ㎚이고, 비중이 1.9 내지 2.2 g/㎤인 건식 실리카(fumed silica)를 사용한다. Preferably, fumed silica having an average particle size of 7 to 22 nm and specific gravity of 1.9 to 2.2 g / cm 3 is used.
본 발명에 따른 보강성 실리카는 상기 실리콘 검 100 중량부에 대하여, 10 내지 100 중량부로 사용된다. 사용량이 10 중량부 미만이면 기계적 물성 보강이 어렵고, 100 중량부를 초과하면 실리카 분산의 어려움과 고 모듈러스로 인해 기계적 물성이 약화한다. 본 발명에 따라 인열강도를 최대화하기 위해서는, 보강성 실리카를 40 내지 55 중량부로 사용하는 것이 바람직하다.
The reinforcing silica according to the present invention is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the silicon gum. If the amount is less than 10 parts by weight, it is difficult to reinforce mechanical properties. If the amount is more than 100 parts by weight, mechanical properties are weakened due to the difficulty of dispersion of silica and high modulus. In order to maximize the tear strength according to the invention, it is preferred to use 40 to 55 parts by weight of reinforcing silica.
(3) 유기 실란 화합물(3) organosilane compound
본 발명의 부가경화형 실리콘 고무 조성물에 포함되는 유기 실란 화합물은 보유하는 하이드로젠기가 실리콘 검의 비닐기와 가교를 형성함으로써 하이드로젠기를 갖는 실리콘 폴리머의 하이드로젠기와 실리콘 검의 비닐기의 가교 결합과 함께 가교 밀도를 더욱 높여 인장강도 및 경도를 향상시키는데 기여한다. The organosilane compound included in the addition-curable silicone rubber composition of the present invention crosslinks together with the crosslinking bond between the hydrogen group of the silicone polymer having a hydrogen group and the vinyl group of the silicone gum by forming a crosslink with the vinyl group of the silicone gum. Higher density contributes to improved tensile strength and hardness.
바람직하게는, 본 발명의 유기 실란 화합물은 3-(메타크릴옥시프로필)트라이메톡시실란을 사용할 수 있다.Preferably, the organosilane compound of the present invention may use 3- (methacryloxypropyl) trimethoxysilane.
본 발명에 유기 실란 화합물은 상기 실리콘 검 100 중량부에 대하여, 0.1 내지 1.0 중량부로 사용된다. 사용량이 0.1 중량부 미만이면 가교밀도 증진 효과가 떨어지며, 1.0 중량부를 초과하면 제품 외관 및 냄새에 영향을 준다.
In the present invention, the organosilane compound is used in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the silicon gum. If the amount is less than 0.1 part by weight, the effect of improving crosslinking density is lowered. If the amount is more than 1.0 part by weight, the product appearance and smell are affected.
(4) 가공조제 (4) Processing aid
본 발명의 부가경화형 실리콘 고무 조성물에 포함되는 가공조제는 양 말단에 하이드록시기를 가지고, 측쇄에 메틸기 또는 메틸비닐기를 가지는 저점도 가공조제이다. 이러한 가공조제는 당업계에 공지된 방법에 기초하여 적절하게 합성하여 사용할 수 있으며, 양 말단에 하이드록시기를 가지고, 측쇄에 메틸기 또는 메틸비닐기를 가지는 것이라면, 특별하게 한정되지 않는다. 양 말단에 존재하는 하이드록시기가 실리카와의 수소 결합을 형성하여 실리카들이 실리콘 검에 직접 결합되어 가공 공정상 거칠게 갈라지는 현상의 발생을 억제하고, 또한 보강성 실리카의 분산력을 높임으로써 균일한 기계적 물성을 유지하고자 사용되는 것이다. The processing aid included in the addition-curable silicone rubber composition of the present invention is a low viscosity processing aid having a hydroxyl group at both ends and a methyl group or methylvinyl group at the side chain. Such processing aids can be suitably synthesized and used based on methods known in the art, and are not particularly limited as long as they have a hydroxyl group at both ends and a methyl group or methylvinyl group at the side chain. Hydroxyl groups present at both ends form hydrogen bonds with silica to prevent the silica from being directly bonded to the silicon gum, resulting in rough cracking in the processing process, and also to increase the dispersibility of the reinforcing silica, resulting in uniform mechanical properties. It is used to maintain.
바람직하게는, 양 말단에 하이드록시기를 가지고, 측쇄에 메틸기 또는 메틸비닐기를 가지는 저점도 가공조제는 실리콘 폴리머로서 점도가 25℃에서 100 센티포아즈 이하, 바람직하게는 30~50 센티포아즈인 것이다. Preferably, the low viscosity processing aid having a hydroxy group at both ends and a methyl group or methylvinyl group at the side chain is a silicone polymer having a viscosity of 100 centipoise or less at 25 ° C. or less, preferably 30 to 50 centipoise. .
본 발명에 따른 저점도 가공조제는 수산화기(-OH) 함량이 약 5~8% 사이인 것이 바람직하나, 이에 한정되는 것은 아니다. The low viscosity processing aid according to the invention preferably has a hydroxyl (-OH) content of about 5 to 8%, but is not limited thereto.
본 발명에 따른 가공조제는 상기 실리콘 검 100 중량부에 대하여, 1.0 내지 15.0 중량부로 사용된다. 사용량이 1.0 중량부 미만이면 실리카 분산이 힘들고, 15.0 중량부를 초과하면 컴파운드의 끈적거림으로 인하여 투롤밀 작업이 힘들어진다.
The processing aid according to the present invention is used in an amount of 1.0 to 15.0 parts by weight based on 100 parts by weight of the silicon gum. If the amount is less than 1.0 parts by weight, it is difficult to disperse silica, and if it exceeds 15.0 parts by weight, the two-roll mill operation becomes difficult due to the stickiness of the compound.
(5) 하이드로젠 실리콘 폴리머(5) hydrogen silicone polymer
본 발명의 부가경화형 실리콘 고무 조성물에 포함되는 하이드로젠 실리콘 폴리머는 경화제로 작용한다. Si-H 결합을 보유하는 하이드로젠 실리콘 폴리머는 백금과 실리콘 고무 조성물에 포함되는 성분이 보유하는 비닐기와 반응하여 가교를 촉진시킨다. The hydrogen silicone polymer included in the addition-curable silicone rubber composition of the present invention acts as a curing agent. Hydrogen silicone polymers having Si—H bonds react with the vinyl groups possessed by the components contained in the platinum and silicone rubber compositions to promote crosslinking.
바람직하게는, 본 발명에 따른 하이드로젠 실리콘 폴리머는 하기 화학식 2로 표시되는 구조이다:Preferably, the hydrogen silicone polymer according to the present invention has a structure represented by the following Chemical Formula 2:
[화학식 2](2)
식 중, n은 10 내지 40의 정수이고, m은 0 내지 140의 정수이다. In formula, n is an integer of 10-40 and m is an integer of 0-140.
또한, 본 발명에 따른 하이드로젠 실리콘 폴리머는 Si-H의 농도가 1.40∼15.5 mmol/g 범위인 것이 바람직하다. 상기 농도 범위 내에서 경화가 진행된다. In addition, the hydrogen silicone polymer according to the present invention preferably has a concentration of Si-H in the range of 1.40 to 15.5 mmol / g. Curing proceeds within the concentration range.
본 발명에 따른 하이드로젠 실리콘 폴리머는 상기 실리콘 검 100 중량부에 대하여, 0.5 내지 2.0 중량부로 사용된다. 사용량이 0.5 중량부 미만이면 반응일 일어나지 않고, 2.0 중량부를 초과하면 실리콘 고무에 끈적임을 유발할 수 있다.
Hydrogen silicone polymer according to the present invention is used in 0.5 to 2.0 parts by weight based on 100 parts by weight of the silicone gum. If the amount is less than 0.5 parts by weight, no reaction occurs, and if it is more than 2.0 parts by weight, it may cause stickiness to the silicone rubber.
한편, 본 발명에 따른 부가경화형 실리콘 고무 조성물은 백금 촉매 및 지연제를 사용하여 경화된 실리콘 고무 경화물을 제공한다. 보다 구체적으로는, 상기 부가경화형 실리콘 고무 조성물 100 중량부에 대하여, C8H18OPtSi2로 표시되는 액상 백금촉매 1 내지 10 ppm; 및 지연제로서, 트리스(2,4-디터셔리-부틸페닐)포스파이트 5 내지 100 ppm을 사용하여 경화시켜 얻을 수 있다. On the other hand, the addition-curable silicone rubber composition according to the present invention provides a cured silicone rubber cured using a platinum catalyst and a retarder. More specifically, 1 to 10 ppm of a liquid platinum catalyst represented by C 8 H 18 OPtSi 2 with respect to 100 parts by weight of the addition-curable silicone rubber composition; And 5 to 100 ppm of tris (2,4-di-butylphenyl) phosphite as a retardant.
본 발명에 따른 백금 촉매는 C8H18OPtSi2로 표시되는 액상 백금 촉매이며(하기 화학식 참조), 하이드로젠 실리콘 폴리머와의 반응을 통하여 부가경화형 실리콘 고무 조성물 내 비닐기와 경화를 이룬다.The platinum catalyst according to the present invention is a liquid platinum catalyst represented by C 8 H 18 OPtSi 2 (see the following chemical formula) and forms a vinyl group in the addition-curable silicone rubber composition through reaction with a hydrogen silicone polymer.
본 발명에 따른 백금 촉매는 상기 부가경화형 실리콘 고무 조성물 100 중량부에 대하여, 1 내지 10 ppm으로 사용되어야 한다. 그 사용량이 1 ppm 미만이면 경화속도가 현저히 느려지며, 10 ppm을 초과하면, 과가류 및 원가상승으로 인해 상품성이 없어진다. The platinum catalyst according to the present invention should be used at 1 to 10 ppm based on 100 parts by weight of the addition-curable silicone rubber composition. If the amount used is less than 1 ppm, the curing rate is significantly slowed, and if it is more than 10 ppm, the mercury property is lost due to excessive vulcanization and cost increase.
본 발명에 따른 지연제는 하기 화학식으로 표시되는 트리스(2,4-디터셔리-부틸페닐)포스파이트([[(CH3)3C]2C6H3O]3P)로서, 상온에서의 백금 촉매의 활성을 억제시키는 작용을 하여 부가경화형 실리콘 고무 조성물(제품 베이스)에 촉매를 혼입한 뒤의 작업가능시간(가사시간) 및 성형 안정성을 부여한다: The retardant according to the present invention is tris (2,4-di-butylphenyl) phosphite ([[(CH 3 ) 3 C] 2 C 6 H 3 O] 3 P) represented by the following formula, and at room temperature It acts to inhibit the activity of the platinum catalyst of and imparts working time (household time) and molding stability after incorporation of the catalyst into the addition-curable silicone rubber composition (product base):
본 발명에 따른 트리스(2,4-디터셔리-부틸페닐)포스파이트는 상기 부가경화형 실리콘 고무 조성물 100 중량부에 대하여, 5 내지 100 ppm으로 사용되어야 한다. 그 사용량이 5 ppm 미만이면, 경화 지연 효과가 불충분하고, 100 ppm을 초과하면, 경화 지연 효과가 강하여 경화 진행이 불가능하다.
Tris (2,4-di-butylphenyl) phosphite according to the present invention should be used at 5 to 100 ppm based on 100 parts by weight of the addition-curable silicone rubber composition. If the amount is less than 5 ppm, the curing delay effect is insufficient. If the amount is more than 100 ppm, the curing delay effect is strong and curing progression is impossible.
이하 실시예 및 비교예를 통해 좀 더 구체적으로 살펴보지만, 이에 본 발명의 범주가 한정되는 것은 아니다.
The following Examples and Comparative Examples will be described in more detail, but the scope of the present invention is not limited thereto.
실시예Example 1 내지 3, 1 to 3, 비교예Comparative Example 1 내지 3: 1 to 3: 부가경화형Addition hardening type 실리콘 고무 조성물의 제조 Preparation of Silicone Rubber Compositions
실시예Example 1 One
실시예 1의 조성물은 하기와 같은 배합으로 제조하였다. 배합에 투입된 조성물은 비닐 실리콘 검(0.1몰 퍼센트) 100 중량부에 대하여 비표면적이 200 ㎡/g이고, 평균 입자 사이즈가 12 ㎚인 건식 실리카(상품명 Reolosil CP-102, 혹은 KCC D-200) 48 중량부, 양 말단이 하이드록시 그룹이며 측쇄에 메틸비닐기를 가지는 저점도 가공조제를 7 중량부, 유기실란 화합물(3-(메타크릴옥시프로필)트라이메톡시실란) 0.3 중량부, 폴리디메틸-메틸하이드로젠 실리콘폴리머(하이드로젠함량 7.3 mmol/g) 1.0 중량부 투입 후 니더에서 교반/분산/가열/냉각 후 취출하였다.
The composition of Example 1 was prepared in the following formulation. The composition added to the formulation was dry silica (trade name Reolosil CP-102 or KCC D-200) having a specific surface area of 200 m 2 / g and an average particle size of 12 nm with respect to 100 parts by weight of vinyl silicone gum (0.1 mole percent). 7 parts by weight of a low-viscosity processing aid having a hydroxyl group at both ends and a methylvinyl group on the side chain, 0.3 parts by weight of an organosilane compound (3- (methacryloxypropyl) trimethoxysilane), polydimethyl-methyl 1.0 parts by weight of hydrogen silicone polymer (hydrogen content 7.3 mmol / g) was added thereto, followed by stirring / dispersion / heating / cooling in a kneader.
비교예Comparative Example 1 One
비교예 1의 조성물은 실시예 1의 조성물에서 유기실란 화합물을 제거하여 동일공정으로 제조하였다.
The composition of Comparative Example 1 was prepared in the same process by removing the organosilane compound from the composition of Example 1.
실시예Example 2 2
실시예 2의 조성물은 하기와 같은 배합으로 제조하였다. 배합에 투입된 조성물은 다이비닐 실리콘 검(0.2 몰퍼센트) 100 중량부에 대하여 비표면적이 200 ㎡/g이고, 평균 입자 사이즈가 12 ㎚인 건식 실리카 (상품명 Reolosil CP-102, 혹은 KCC D-200) 48 중량부, 양 말단이 하이드록시 그룹이며 측쇄에 메틸비닐기를 가지는 저점도 가공조제를 7 중량부, 유기실란 화합물(3-(메타크릴옥시프로필)트라이메톡시실란) 0.3 중량부, 폴리디메틸-메틸하이드로젠 실리콘폴리머(하이드로젠함량 7.3 mmol/g) 1.0 중량부 투입 후 니더에서 교반/분산/가열/냉각 후 취출하였다.
The composition of Example 2 was prepared in the following formulation. The composition added to the formulation was dry silica (trade name Reolosil CP-102, or KCC D-200) having a specific surface area of 200 m 2 / g and an average particle size of 12 nm with respect to 100 parts by weight of divinyl silicon gum (0.2 mol%). 48 parts by weight, 7 parts by weight of a low-viscosity processing aid having a hydroxyl group at both ends and a methylvinyl group, 0.3 parts by weight of an organosilane compound (3- (methacryloxypropyl) trimethoxysilane), polydimethyl- 1.0 parts by weight of methylhydrogen silicone polymer (hydrogen content 7.3 mmol / g) was added thereto, and then the mixture was taken out of the kneader after stirring / dispersion / heating / cooling.
비교예Comparative Example 2 2
비교예 2의 조성물은 실시예 2의 조성물에서 유기실란 화합물을 제거하여 동일공정으로 제조하였다.
The composition of Comparative Example 2 was prepared in the same process by removing the organosilane compound from the composition of Example 2.
실시예Example 3 3
실시예 3의 조성물은 하기와 같은 배합으로 제조하였다. 배합에 투입된 조성물은 다이비닐 실리콘 검(0.1 몰퍼센트, 0.2 몰퍼센트) 100 중량부에 대하여 비표면적이 200 ㎡/g이고, 평균 입자 사이즈가 12 ㎚인 건식 실리카(상품명 Reolosil CP-102, 혹은 KCC D-200) 48 중량부, 양 말단이 하이드록시 그룹이며 측쇄에 메틸비닐기를 가지는 저점도 가공조제를 7 중량부, 유기실란 화합물(3-(메타크릴옥시프로필)트라이메톡시실란) 0.3 중량부, 폴리디메틸-메틸하이드로젠 실리콘폴리머(하이드로젠함량 7.3 mmol/g) 1.0 중량부 투입 후 니더에서 교반/분산/가열/냉각 후 취출하였다.
The composition of Example 3 was prepared in the following formulation. The composition added to the formulation was dry silica (trade name Reolosil CP-102, or KCC) having a specific surface area of 200 m 2 / g and an average particle size of 12 nm based on 100 parts by weight of divinyl silicon gum (0.1 mol%, 0.2 mol%). D-200) 48 parts by weight, 7 parts by weight of a low-viscosity processing aid having a hydroxyl group at both ends and a methylvinyl group, and 0.3 parts by weight of an organosilane compound (3- (methacryloxypropyl) trimethoxysilane) , 1.0 parts by weight of polydimethyl-methylhydrogen silicone polymer (hydrogen content of 7.3 mmol / g) was added thereto, followed by stirring / dispersion / heating / cooling in a kneader.
비교예Comparative Example 3 3
비교예 3의 조성물은 실시예 3의 조성물에서 유기실란 화합물을 제거하여 동일공정으로 제조하였다.
The composition of Comparative Example 3 was prepared in the same process by removing the organosilane compound from the composition of Example 3.
상기 실시예와 비교예에서 제조한 미경화 실리콘 고무 조성물 각각을 투롤 밀에서 충분히 가소화시킨 후 상기 미경화 실리콘 고무 조성물 100 중량부에 대하여 백금촉매 5 ppm, 지연제(트리스(2,4-디-터셔리-부틸페닐)포스파이트) 20 ppm을 첨가하여 충분히 분산시켰다. 그 후 탈포 공정을 거친 프리폼을 성형 몰드에서 120℃ 10분 동안 가압하여 두께 2 ㎜ 시트를 만들고, 열풍 순환식 오븐에서 200℃ 4시간 동안 후 경화를 행하여 분해된 유기 과산화물을 제거하여 경화 퇴행성이 일어나는 현상을 방지하였다.
After fully plasticizing each of the uncured silicone rubber compositions prepared in Examples and Comparative Examples in a two-roll mill, 5 ppm of a platinum catalyst and a retardant (tris (2,4-di) were added to 100 parts by weight of the uncured silicone rubber composition. 20 parts of tertiary-butylphenyl) phosphite) were added and dispersed sufficiently. Thereafter, the preform subjected to the defoaming process was pressed in a molding mold at 120 ° C. for 10 minutes to form a 2 mm thick sheet, followed by curing at 200 ° C. for 4 hours in a hot air circulation oven to remove decomposed organic peroxides, thereby causing hardening degeneration. The phenomenon was prevented.
실시예와 비교예의 조성물의 성분 및 경화 후 특성을 표 1에 나타냈다. The components and the properties after curing of the compositions of Examples and Comparative Examples are shown in Table 1.
실리콘 검0.1 mol%
Silicone sword
실리콘 검0.2 mol%
Silicone sword
실리콘 폴리머Hydrogen
Silicone polymer
상기 표 1로부터, 본 발명에 따라 유기실란 화합물이 첨가된 조성물(실시예)의 경우, 첨가되지 않은 조성물(비교예)에 비해 인열강도가 개선됨을 확인하였고, 특히, 비닐기 함량이 상이한 실리콘 검의 혼합물과 유리실란 화합물을 사용한 실시예 3의 경우, 인열강도가 현저하게 높음을 확인할 수 있다.
From Table 1, in the case of the composition (Example) to which the organosilane compound is added according to the present invention, it was confirmed that the tear strength is improved compared to the composition (Comparative Example) not added, in particular, the vinyl group content is different In the case of Example 3 using the mixture of the gum and the free silane compound, it can be seen that the tear strength is remarkably high.
실시예Example 4 내지 6, 4 to 6, 비교예Comparative Example 4 내지 5: 실리콘 고무 4 to 5: silicone rubber 경화물의Cured product 제조 Produce
실시예Example 4 4
실시예 4는 실시예 3에 따른 실리콘 고무 조성물 100 중량부에 대하여 C8H18OPtSi2 백금촉매 1 ppm, 트리스(2,4-디-터셔리-부틸페닐)포스파이트([[(CH3)3C]2C6H3O]3P) 5 ppm을 적용하여 성형안정성, 경화속도 및 가사시간을 측정하였다.
Example 4 is based on 100 parts by weight of the silicone rubber composition according to Example 3, 1 ppm C 8 H 18 OPtSi 2 platinum catalyst, tris (2,4-di-tert-butylphenyl) phosphite ([[(CH 3 ) 3 C] 2 C 6 H 3 O] 3 P) 5 ppm was applied to determine the molding stability, curing rate and pot life.
실시예Example 5 5
실시예 5는 실시예 3에 따른 실리콘 고무 조성물 100 중량부에 대하여 C8H18OPtSi2 백금촉매 5 ppm, 트리스(2,4-디-터셔리-부틸페닐)포스파이트 10 ppm을 적용하여 성형안정성, 경화속도 및 가사시간을 측정하였다.
Example 5 was molded by applying 5 ppm of C 8 H 18 OPtSi 2 platinum catalyst and 10 ppm of tris (2,4-di-tert-butylphenyl) phosphite to 100 parts by weight of the silicone rubber composition according to Example 3 Stability, cure rate and pot life were measured.
실시예Example 6 6
실시예 6은 실시예 3에 따른 실리콘 고무 조성물 100 중량부에 대하여 C8H18OPtSi2 백금촉매 10 ppm, 트리스(2,4-디-터셔리-부틸페닐)포스파이트 70ppm 을 적용하여 성형안정성, 경화속도 및 가사시간을 측정하였다.
Example 6 was applied to 100 parts by weight of the silicone rubber composition according to Example 3 by applying 10 ppm C 8 H 18 OPtSi 2 platinum catalyst, 70 ppm of tris (2,4-di- tert-butylphenyl) phosphite molding stability , Curing rate and pot life were measured.
비교예Comparative Example 4 4
비교예 4는 실시예 3에 따른 실리콘 고무 조성물 100 중량부에 대하여 C8H18OPtSi2 백금촉매 5 ppm, 1-에틴일-1-시클로헥사놀(C8H12O) 25 ppm을 적용하여 성형안정성, 경화속도 및 가사시간을 측정하였다.
Comparative Example 4 was applied to 100 parts by weight of the silicone rubber composition according to Example 3 by applying 5 ppm C 8 H 18 OPtSi 2 platinum catalyst, 25 ppm 1-ethynyl-1-cyclohexanol (C 8 H 12 O) Molding stability, curing rate and pot life were measured.
비교예Comparative Example 5 5
비교예 5는 실시예 3에 따른 실리콘 고무 조성물 100 중량부에 대하여 C8H18OPtSi2 백금촉매 5 ppm, 트리알릴 이소시아누레이트(C12H15N3O3) 100 ppm을 적용하여 성형안정성, 경화속도 및 가사시간을 측정하였다.
Comparative Example 5 was formed by applying 5 ppm of C 8 H 18 OPtSi 2 platinum catalyst and 100 ppm of triallyl isocyanurate (C 12 H 15 N 3 O 3 ) to 100 parts by weight of the silicone rubber composition according to Example 3 Stability, cure rate and pot life were measured.
실시예 4 내지 6 및 비교예 4 내지 5의 조성물을 충분히 분산시켰다. 그 후 탈포 공정을 거친 프리폼의 7g 가량을 취하여 레오미터에서 120℃ 5분 동안 가압하여 경화속도를 측정하였다. 또한 프리폼한 컴파운드를 항온항습실 25℃에 공기 중 방치시켜 제품의 경화 유무를 하루 간격으로 측정함으로써 가사시간을 측정하였다. 그 결과를 표 2에 나타낸다. The compositions of Examples 4-6 and Comparative Examples 4-5 were sufficiently dispersed. Then, about 7 g of the preform subjected to the defoaming process was taken, and pressed at 120 ° C. for 5 minutes on a rheometer to measure the curing rate. In addition, the preformed compound was left in air in a constant temperature and humidity room at 25 ° C., and the pot life was measured by measuring the presence or absence of product curing at a daily interval. The results are shown in Table 2.
조성물
(실시예 3)Silicone rubber
Composition
(Example 3)
* 성형안정성은 외경 10 ㎜ 내경 8 ㎜ 실리콘 고무 호스 제조시 치수가 외경 10 ㎜±0.05 ㎜ 유지시 양호, 10 ㎜±0.10 ㎜ 유지시 중간, 10 ㎜±0.10 ㎜ 초과시 불량으로 판정하였다.* Molding stability was determined to be 10 mm ± 0.15 mm in diameter, 10 mm ± 0.05 mm in diameter, and 10 mm ± 0.10 mm in case of silicone rubber hose manufacturing.
* 경화속도는 레오미터 측정기기를 통해 고무 경화시 60% 경화시점의 시간을 측정한 것이다(120℃, 5분 측정).* Curing rate is measured by Rheometer measuring device at 60% curing time (120 ℃, 5 minutes).
* 가사시간은 실시예 3에 따른 실리콘 고무 조성물에 백금촉매와 지연제를 첨가한 후 상온에서의 BASE 유지상태를 측정한 것이다. 이 BASE 상태를 유지하지 못할 경우 첨가 뒤 상온에서의 경화가 일어나게 되어 장기간 보관 시 사용하지 못하게 된다.
* Pot life is the BASE holding state at room temperature after the addition of the platinum catalyst and the retardant to the silicone rubber composition according to Example 3. Failure to maintain this BASE will result in hardening at room temperature after addition, making it unusable for long-term storage.
상기 표 2로부터 확인할 수 있는 바와 같이, 실시예 4 내지 6에 따른 백금 촉매-포스파이트(지연제) 조합 사용에 의해 성형 안정성 및 안정적인 가사시간 확보가 가능하였다.
As can be seen from Table 2, by using the platinum catalyst-phosphite (delay agent) combination according to Examples 4 to 6 it was possible to ensure the molding stability and stable pot life.
Claims (9)
BET법에 의한 비표면적이 200 ㎡/g 이상인 보강성 실리카 10 내지 100 중량부;
유기 실란 화합물 0.1 내지 1.0 중량부;
양 말단에 하이드록시기를 가지고, 측쇄에 메틸기 또는 메틸비닐기를 가지는 저점도 가공조제 1.0 내지 15.0 중량부;
하이드로젠 실리콘 폴리머 0.5 내지 2.0 중량부를 포함하는 부가경화형 실리콘 고무 조성물.To 100 parts by weight of vinyl silicone gum having a vinyl group content of 0.01 to 8.5 mole percent,
10 to 100 parts by weight of reinforcing silica having a specific surface area of 200 m 2 / g or more by BET method;
0.1 to 1.0 parts by weight of the organosilane compound;
1.0 to 15.0 parts by weight of a low viscosity processing aid having a hydroxy group at both ends and a methyl group or a methylvinyl group at the side chain;
An addition-curable silicone rubber composition comprising 0.5 to 2.0 parts by weight of hydrogen silicone polymer.
상기 비닐 실리콘 검 100 중량부는,
비닐기 함량이 0.1 몰퍼센트인 비닐 실리콘 검 20~80 중량부와 비닐기 함량이 0.2 몰퍼센트인 비닐 실리콘 검 20~80 중량부로 이루어지는 것을 특징으로 하는 부가경화형 실리콘 고무 조성물. The method according to claim 1,
100 parts by weight of the vinyl silicone gum,
An addition-curable silicone rubber composition comprising 20 to 80 parts by weight of vinyl silicone gum having a vinyl group content of 0.1 mol percent and 20 to 80 parts by weight of vinyl silicone gum having a vinyl group content of 0.2 mol percent.
상기 비닐 실리콘 검은 하기 화학식 1로 표시되는 반복 단위를 가지는 것을 특징으로 하는 부가경화영 의료용 실리콘 고무 조성물.
[화학식 1]
RaSiO(4-a)/2
화학식 1에서, R은 탄소 수 1 내지 10의 비치환 또는 치환된 1가의 탄화수소기이지만, R 중 2개 이상은 비닐기이고, a는 1.90 내지 2.05이다. The method according to claim 1,
Said vinyl silicone gum has a repeating unit represented by the following formula (1).
[Chemical Formula 1]
R a SiO (4-a) / 2
In formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, but at least two of R are vinyl groups, and a is 1.90 to 2.05.
상기 유기 실란 화합물은 3-(메타크릴옥시프로필)트라이메톡시실란인 것을 특징으로 하는 부가경화형 실리콘 고무 조성물. The method according to claim 1,
The organosilane compound is an addition-curable silicone rubber composition, characterized in that 3- (methacryloxypropyl) trimethoxysilane.
상기 저점도 가공조제는 OH 함량이 5~8% 사이로 이루어지는 것을 특징으로 하는 부가경화형 실리콘 고무 조성물. The method according to claim 1,
The low-viscosity processing aid is an addition-curable silicone rubber composition, characterized in that the OH content is comprised between 5-8%.
상기 보강성 실리카는 평균입자크기가 7 내지 22 ㎚이고, 비중이 1.9 내지 2.2 g/㎤인 건식 실리카(fumed silica)인 것을 특징으로 하는 부가경화형 실리콘 고무 조성물. The method according to claim 1,
Said reinforcing silica is fumed silica having an average particle size of 7 to 22 nm and specific gravity of 1.9 to 2.2 g / cm 3.
상기 하이드로젠 실리콘 폴리머는 하기 화학식 2로 표시되는 것을 특징으로 하는 부가경화형 실리콘 고무 조성물.
[화학식 2]
식 중, n은 10 내지 40의 정수이고, m은 0 내지 140의 정수이다. The method according to claim 1,
The hydrogen silicone polymer is an addition-curable silicone rubber composition, characterized in that represented by the formula (2).
(2)
In formula, n is an integer of 10-40 and m is an integer of 0-140.
상기 하이드로젠 실리콘 폴리머는 Si-H의 농도가 1.40∼15.5 mmol/g 범위인 것을 특징으로 하는 부가경화형 실리콘 고무 조성물. The method according to claim 1,
The hydrogen silicone polymer is an addition-curable silicone rubber composition, characterized in that the concentration of Si-H ranges from 1.40 to 15.5 mmol / g.
C8H18OPtSi2로 표시되는 액상 백금촉매 1 내지 10 ppm; 및
지연제로서, 트리스(2,4-디터셔리-부틸페닐)포스파이트 5 내지 100 ppm을 사용하여 경화시켜 얻은 실리콘 고무 경화물.10 parts by weight of the addition-curable silicone rubber composition according to any one of claims 1 to 8,
1 to 10 ppm of a liquid platinum catalyst represented by C 8 H 18 OPtSi 2 ; And
A silicone rubber cured product obtained by curing using 5 to 100 ppm of tris (2,4-di-butylphenyl) phosphite as a retardant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109390A (en) * | 2014-06-19 | 2014-10-22 | 滁州天成有机硅高分子材料有限公司 | Food-contacting silicone rubber compound |
| KR20230172699A (en) * | 2022-06-16 | 2023-12-26 | 주식회사 밸런스테크 | Dental correction device having silicon and propolis |
| KR20230173237A (en) * | 2022-06-16 | 2023-12-27 | 주식회사 밸런스테크 | Dental correction device having silicon and silver nano particles |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040032867A (en) * | 2001-07-26 | 2004-04-17 | 다우 코닝 도레이 실리콘 캄파니 리미티드 | Room-temperature-curable organopolysiloxane composition |
| KR20050070924A (en) * | 2003-12-31 | 2005-07-07 | 주식회사 케이씨씨 | Thermosetting silicone rubber composition with high tear strength |
| JP2006083237A (en) * | 2004-09-14 | 2006-03-30 | Shin Etsu Chem Co Ltd | Silicone rubber sponge composition and silicone rubber sponge |
| KR20070076315A (en) * | 2006-01-18 | 2007-07-24 | 주식회사 케이씨씨 | High temperature vulcanizing silicone rubber composition having excellent physical property |
| KR20110121376A (en) * | 2010-04-30 | 2011-11-07 | 주식회사 케이씨씨 | Heat-vulcanizable silicon sponge rubber composition having uniformeded anc closed cell, process for the preparation thereof and sponge rubber product produced therefrom |
-
2012
- 2012-08-23 KR KR1020120092394A patent/KR101905190B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20040032867A (en) * | 2001-07-26 | 2004-04-17 | 다우 코닝 도레이 실리콘 캄파니 리미티드 | Room-temperature-curable organopolysiloxane composition |
| KR20050070924A (en) * | 2003-12-31 | 2005-07-07 | 주식회사 케이씨씨 | Thermosetting silicone rubber composition with high tear strength |
| JP2006083237A (en) * | 2004-09-14 | 2006-03-30 | Shin Etsu Chem Co Ltd | Silicone rubber sponge composition and silicone rubber sponge |
| KR20070076315A (en) * | 2006-01-18 | 2007-07-24 | 주식회사 케이씨씨 | High temperature vulcanizing silicone rubber composition having excellent physical property |
| KR20110121376A (en) * | 2010-04-30 | 2011-11-07 | 주식회사 케이씨씨 | Heat-vulcanizable silicon sponge rubber composition having uniformeded anc closed cell, process for the preparation thereof and sponge rubber product produced therefrom |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104109390A (en) * | 2014-06-19 | 2014-10-22 | 滁州天成有机硅高分子材料有限公司 | Food-contacting silicone rubber compound |
| KR20230172699A (en) * | 2022-06-16 | 2023-12-26 | 주식회사 밸런스테크 | Dental correction device having silicon and propolis |
| KR20230173237A (en) * | 2022-06-16 | 2023-12-27 | 주식회사 밸런스테크 | Dental correction device having silicon and silver nano particles |
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