KR101875883B1 - Foam composition of low density resins - Google Patents

Foam composition of low density resins Download PDF

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KR101875883B1
KR101875883B1 KR1020160142253A KR20160142253A KR101875883B1 KR 101875883 B1 KR101875883 B1 KR 101875883B1 KR 1020160142253 A KR1020160142253 A KR 1020160142253A KR 20160142253 A KR20160142253 A KR 20160142253A KR 101875883 B1 KR101875883 B1 KR 101875883B1
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low
parts
foam composition
foam
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KR20180046722A (en
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왕은진
허지수
이용관
임성욱
박은영
김옥배
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(주)타이리젠
한국신발피혁연구원
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066Use of inorganic compounding ingredients
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/011Crosslinking or vulcanising agents, e.g. accelerators
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025Crosslinking or vulcanising agents; including accelerators
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/16Solid spheres
    • C08K7/18Solid spheres inorganic
    • C08K7/20Glass
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/06Polyethene
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0846Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853Vinylacetate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/005Additives being defined by their particle size in general
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00Properties characterising the ingredient of the composition
    • C08L2207/06Properties of polyethylene
    • C08L2207/066LDPE (radical process)

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Abstract

본발명은 저밀도 수지 발포체 조성물에 관한 것으로, 보다 구체적으로는 저밀도 수지에 글래스버블(glass bubble)을 다량 적용함으로써, 저발포율에서도 낮은 밀도를 유지하여 부력성을 향상시키는 동시에 저밀도 수지의 낮은 파괴한계를 보강하여 내파열성, 내압축성 등의 내구성을 향상시킬 수 있도록 한다. 즉, 본 발명은 발포율을 낮춰 내구성을 높이는 동시에 글래스버블의 적용으로 인해 저발포율에서도 발포체의 밀도를 낮춰 부력성을 극대화 할 수 있도록 하는, 저밀도 수지 발포체 조성물에 관한 것이다.The present invention relates to a low-density resin foam composition, and more particularly to a low-density resin foam composition which is produced by applying glass bubbles to a low-density resin in a large amount to maintain a low density even at a low foaming rate to improve buoyancy, So that durability such as resistance to rupture resistance and compressibility can be improved. That is, the present invention relates to a low-density resin foam composition capable of maximizing buoyancy by lowering the density of the foam even at a low foaming rate due to application of glass bubbles while increasing the durability by lowering the foaming ratio.

Description

저밀도 수지 발포체 조성물{FOAM COMPOSITION OF LOW DENSITY RESINS}[0001] FOAM COMPOSITION OF LOW DENSITY RESINS [0002]

본 발명은 저발포율에서도 낮은 밀도를 유지하여 발포체의 내구성과 부력성을 동시에 향상시킬 수 있도록 하는, 저밀도 폴리에틸렌 발포체 조성물에 관한 것이다.
The present invention relates to a low density polyethylene foam composition which maintains a low density even at low foaming rates, thereby simultaneously improving durability and buoyancy of the foam.

일반적으로 '발포체'란 고체상태의 고분자 내에 기포가 공존하고 있는 이종상태의 물체를 말한다. 대부분의 고분자물은 발포체로 만들어질 수는 있지만 상업적으로 개발된 것은 소수에 불과하며 폴리우레탄, 폴리스티렌, 폴리염화비닐 또는 폴리올레핀계 발포체가 주로 사용되고 있다.
Generally, "foam" refers to a heterogeneous material in which bubbles coexist in a solid state polymer. Although most of the polymer water can be made into foam, only a few are commercially developed, and polyurethane, polystyrene, polyvinyl chloride or polyolefin based foams are mainly used.

아울러, 상기와 같은 발포체는 물질 속에 수많은 기포가 분산되어 있는 구조적 특징으로 인해 부력성, 내파열성, 내압축성 등을 가지며, 이러한 기능을 바탕으로 각종 스포츠 및 레져용품의 소재와 각종 부력재로 사용되고 있다.
In addition, such a foam has buoyancy, frictional resistance, compressibility and the like due to a structural characteristic in which a large number of bubbles are dispersed in a material. Based on these functions, the foam is used as a material for various sports and leisure products and various buoyancy materials.

한편, 발포체의 부력성을 극대화하기 위해서는 발포율을 높여 밀도를 낮추어야 하지만, 발포율이 높아지면 내파열성, 내압측성 등이 급격히 저하되어 내구성이 떨어지는 문제점이 있었다.
On the other hand, in order to maximize the buoyancy of the foam, it is necessary to increase the foaming rate to lower the density. However, when the foaming ratio is increased, there is a problem that the durability is deteriorated due to rapid deterioration of the resistance to rupture and pressure resistance.

이를 해결하기 위하여, 특허문헌 1에서는 산업용 발포체 조성물에 있어서, 서로 다른 유리전이온도를 가지는 2종 이상의 스티렌-포화탄화수소계 열가소성 고분자 기재 또는 필요에 따라 폴리에틸렌, 에틸렌 비닐아세테이트 공중합체, 에틸렌-올레핀 공중합체, 고무 등을 블렌드한 블렌드물을 기재로 하고 충전제, 가교제, 발포제 및 기타 첨가제를 투입하여 프레스 성형함으로서 비중이 낮고 영구압축줄음율 등의 내구성이 우수하면서 다양한 온도영역에서 우수한 충격흡수성을 갖는 것을 특징으로 하는 다양한 온도영역에서 우수한 충격흡수성을 갖는 산업용 발포체 조성물에 관한 것으로, 기존의 충격흡수 재료보다 환경적인 측면 혹은 비용적인 측면에서 유리하고 충격흡수성 특성을 갖는 산업용 발포체로서, 특히, 기존 충격흡수 소재가 상온영역에서만 충격흡수 특성이 발현되는데 비해 다양한 온도영역에서도 우수한 충격흡수성 발현되도록 기능성을 부여함으로써 기존에 사용 범위가 제한되어있던 소재의 한계를 극복하는 신규 기능 소재를 제공하여 스포츠용품, 건설용품 등의 산업에 다양한 용도에 적용이 가능하며, 또한, 기존의 충격흡수 재료인 폴리비닐클로라이드와 폴리우레탄을 대체할 수 있어 상기소재 사용으로 인하여 발생되었던 환경오염 문제를 해결할 수 있도록 하는, 산업용 발포체 조성물을 제안하였다.
In order to solve this problem, Patent Document 1 discloses an industrial foam composition comprising two or more styrene-saturated hydrocarbon-based thermoplastic polymer substrates having different glass transition temperatures or, if necessary, polyethylene, ethylene vinyl acetate copolymer, ethylene-olefin copolymer It is characterized by having low specific gravity, excellent durability such as permanent compression toughness and excellent shock absorbing property in various temperature range by applying a filler, a crosslinking agent, a foaming agent and other additive into a blend which is a blend of rubber, , Which is superior in terms of environment or cost to existing shock absorbing materials and has impact absorbing properties. Especially, it is an object of the present invention to provide an industrial foam composition having excellent impact absorbing properties In the room temperature region It provides new functional materials that overcome the limitation of the material that was limited in the range of use in the past, so that it can be used in industries such as sporting goods and construction products The present invention also provides an industrial foam composition capable of being applied to various applications and capable of replacing polyvinyl chloride and polyurethane, which are conventional shock absorbing materials, to solve environmental pollution problems caused by use of the above materials.

하지만, 상기 특허문헌 1의 경우 영구압축줄음율 등의 내구성은 우수하지만 이는 발포율을 낮추어 밀도를 높임에 따라 구현되는 것으로, 저발포율에서 높은 밀도를 가짐에 따라 부력성이 미비하게 되는 문제점이 있었다.
However, in the case of Patent Document 1, the durability such as the permanent compressive strain rate is excellent, but it is realized by increasing the density by lowering the expansion ratio, and there is a problem that the buoyancy is insufficient due to high density at low expansion rate there was.

특허문헌 1 : 대한민국 등록특허공보 제10-0980028호 "다양한 온도영역에서 우수한 충격흡수성을 갖는 산업용 발포체 조성물"Patent Document 1: Korean Patent Registration No. 10-0980028 "Industrial Foam Composition Having Excellent Shock Absorbency in Various Temperature Regions"

본 발명은 상기와 같은 문제점을 해결하기 위한 것으로, 저밀도 수지에 글래스버블(glass bubble)을 다량 적용함으로써, 저발포율에서도 낮은 밀도를 유지하여 부력성을 향상시키는 동시에 저밀도 수지의 낮은 파괴한계를 보강하여 내파열성, 내압축성 등의 내구성을 향상시킴을 과제로 한다.
Disclosure of the Invention The present invention has been made to solve the above problems and it is an object of the present invention to improve the buoyancy by maintaining a low density even at a low foaming rate by applying a large amount of glass bubble to a low density resin, Thereby improving durability such as resistance to rupture and compression resistance.

즉, 본 발명은 발포율을 낮춰 내구성을 높이는 동시에 글래스버블의 적용으로 인해 저발포율에서도 발포체의 밀도를 낮춰 부력성을 극대화함을 과제로 한다.
That is, the present invention aims at maximizing the buoyancy by lowering the density of the foam even at a low foaming rate by applying the glass bubble while increasing the durability by lowering the foaming ratio.

본 발명은 저밀도 수지 발포체 조성물에 있어서, 저밀도 수지, 글래스버블, 가교제 및 발포체용 첨가제를 포함하여 이루어지는 것을 특징으로 하는, 저밀도 수지 발포체 조성물을 과제의 해결 수단으로 한다.
Disclosed is a low-density resin foam composition comprising a low-density resin, a glass bubble, a crosslinking agent, and an additive for a foam in a low-density resin foam composition.

보다 구체적으로 상기 저밀도 수지 발포체 조성물은, 선형 저밀도 폴리에틸렌 80 ~ 90 중량% 및 에틸렌비닐아세테이트 10 ~ 20 중량%로 이루어지는 저밀도 수지 100 중량부에 대하여, 글래스버블 10 ~ 30 중량부, 가교제 0.1 ~ 1.5 중량부 및 발포체용 첨가제가 포함되어 이루어지는 것이 바람직하다.
More specifically, the low-density resin foam composition comprises 10 to 30 parts by weight of a glass bubble, 0.1 to 1.5 parts by weight of a cross-linking agent, 10 to 30 parts by weight of a cross-linking agent, 100 parts by weight of a low-density resin comprising 80 to 90% by weight of a linear low density polyethylene and 10 to 20% by weight of ethylene- And an additive for the foam and the foam.

한편, 상기 글래스버블은 평균입자가 0.38 ~ 0.60mm이고, 크러쉬(crush) 강도가 16,000 ~ 28,000 psi인 것을 사용하는 것이 바람직하다.
Meanwhile, the glass bubble preferably has an average particle size of 0.38 to 0.60 mm and a crush strength of 16,000 to 28,000 psi.

아울러, 상기 가교제는, 황 가교제, 유기과산화물 가교제 또는 레진 가교제 중에서 단독 또는 2종 이상 병용하여 사용하는 것이 바람직하다.
The crosslinking agent is preferably used alone or in combination of two or more among a sulfur crosslinking agent, an organic peroxide crosslinking agent and a resin crosslinking agent.

본 발명은 저밀도 수지에 글래스버블을 적용함으로써, 저발포율에서도 낮은 밀도를 유지하여 부력성을 향상시키는 동시에 저밀도 수지의 낮은 파괴한계를 보강하여 내파열성, 내압축성 등의 내구성을 향상시킬 수 있는 효과를 가진다. 아울러 상기와 같은 효과로 인해 각종 스포츠 및 레져용품의 재료나 벽, 방수부재 및 각종 부력재로 다양하게 활용될 수 있는 효과를 가진다.
The present invention relates to an improvement in durability such as resistance to rupture resistance and resistance to compression by reinforcing the low fracture limit of the low density resin while improving the buoyancy by maintaining a low density even at a low foaming rate by applying a glass bubble to the low density resin . In addition, due to the above-mentioned effects, it can be utilized variously as materials and walls of various sports and leisure goods, waterproof members and various buoyancy materials.

도 1은 본 발명에 따른 글래스버블이 포함된 저밀도 수지 발포체의 주사전자현미경(SEM)사진(50배율)1 is a scanning electron microscope (SEM) photograph (50 magnification) of a low density resin foam containing a glass bubble according to the present invention;

상기의 효과를 달성하기 위한 본 발명은 저밀도 수지 발포체 조성물체에 관한 것으로서, 본 발명의 기술적 구성을 이해하는데 필요한 부분만이 설명되며 그 이외 부분의 설명은 본 발명의 요지를 흩트리지 않도록 생략될 것이라는 것을 유의하여야 한다.
In order to achieve the above effects, the present invention relates to a low-density resin foam composition body, wherein only parts necessary for understanding the technical structure of the present invention are described, and descriptions of other parts are omitted so as not to disturb the gist of the present invention .

이하, 본 발명에 따른 저밀도 수지 발포체 조성물을 도 1을 참조하여 상세히 설명하면 다음과 같다.
Hereinafter, the low-density resin foam composition according to the present invention will be described in detail with reference to FIG.

본 발명에 따른 저밀도 수지 발포체 조성물은, 저밀도 수지, 글래스버블, 가교제 및 발포체용 첨가제를 포함하여 이루어지며, 저밀도 수지는 선형 저밀도 폴리에틸렌과 에틸렌비닐아세테이트를 혼합하여 적용하는 것이 바람직하지만 여기에 한정되는 것은 아니고 발포체 조성물의 사용 용도나 사용 환경을 고려하여 이미 공지된 다양한 수지를 적용할 수 있다.
The low density resin foam composition according to the present invention preferably comprises a low density resin, a glass bubble, a crosslinking agent, and an additive for foam, and the low density resin is preferably a mixture of linear low density polyethylene and ethylene vinyl acetate, But various known resins can be applied in consideration of the intended use and the use environment of the foam composition.

보다 구체적으로 상기 저밀도 수지 발포체 조성물은, 선형 저밀도 폴리에틸렌 80 ~ 90 중량% 및 에틸렌비닐아세테이트 10 ~ 20 중량%로 이루어지는 저밀도 수지 100 중량부에 대하여, 글래스버블 10 ~ 30 중량부, 가교제 0.1 ~ 1.5 중량부 및 발포체용 첨가제가 포함되어 이루어진다.
More specifically, the low-density resin foam composition comprises 10 to 30 parts by weight of a glass bubble, 0.1 to 1.5 parts by weight of a cross-linking agent, 10 to 30 parts by weight of a cross-linking agent, 100 parts by weight of a low-density resin comprising 80 to 90% by weight of a linear low density polyethylene and 10 to 20% by weight of ethylene- And an additive for the foam and the foam.

상기 저밀도 수지는, 부력성을 향상시키기 위해 사용되는 기재로써 상술한 바와 같이, 선형 저밀도 폴리에틸렌 80 ~ 90 중량% 및 에틸렌비닐아세테이트 10 ~ 20 중량%를 혼합하여 적용한다.
The low-density resin is a mixture of 80 to 90% by weight of linear low-density polyethylene and 10 to 20% by weight of ethylene vinyl acetate as a base material used for improving buoyancy.

여기서, 상기 선형 저밀도 폴리에틸렌의 함량이 80 중량% 미만이거나 에틸렌비닐아세테이트의 함량이 20 중량%를 초과할 경우, 부력성이 저하될 우려가 있으며, 선형 저밀도 폴리에틸렌의 함량이 90 중량%를 초과하거나 에틸렌비닐아세테이트의 함량이 10 중량% 미만일 경우, 내구성이 저하될 우려가 있다.
If the content of the linear low density polyethylene is less than 80% by weight or the content of ethylene vinyl acetate is more than 20% by weight, the buoyancy may be lowered. If the content of the linear low density polyethylene exceeds 90% If the content of vinyl acetate is less than 10% by weight, durability may be deteriorated.

상기 글래스버블은, 속이 빈 중공구조를 갖는 3차원의 미소구형의 필러(filler)의 한 종류이며, 저발포율에서도 낮은 밀도를 유지하여 부력성을 향상시키는 동시에 저밀도 수지의 낮은 파괴한계를 보강하여 내파열성, 내압축성 등의 내구성을 향상시키기 위해 첨가되는 것으로, 그 함량이 10 중량부 미만일 경우, 상기 효과가 미비해질 우려가 있으며, 30 중량부를 초과할 경우, 가공성이 저하될 우려가 있고 또한 사용량 대비 효과의 향상효율이 미비하여 비경제적일 우려가 있다.
The glass bubble is one kind of three-dimensional micro-spherical filler having a hollow hollow structure. The glass bubble maintains a low density even at a low foaming rate, thereby improving buoyancy and reinforcing the low fracture limit of the low density resin The effect is insufficient when the content is less than 10 parts by weight, and when the content is more than 30 parts by weight, there is a possibility that the workability is lowered, There is a possibility that the improvement efficiency of the contrast effect is insufficient, which is uneconomical.

한편, 상기 글래스버블은, 부력성과 내구성의 동시 향상효율을 고려하여 평균입자가 0.38 ~ 0.60mm이고, 크러쉬(crush) 강도가 16,000 ~ 28,000 psi인 것을 사용하는 것이 바람직하지만, 여기에 한정되는 것은 아니고 발포체 조성물의 사용 용도나 사용 환경 등에 따라 다양한 물성의 글래스버블을 사용할 수 있다.
The glass bubble preferably has an average particle size of 0.38 to 0.60 mm and a crush strength of 16,000 to 28,000 psi in consideration of the simultaneous improvement in buoyancy and durability, but is not limited thereto Glass bubbles of various physical properties can be used depending on the intended use of the foam composition, the use environment, and the like.

상기 가교제는, 황 가교제, 유기과산화물 가교제 또는 레진 가교제 중에서 단독 또는 2종 이상 병용하여 사용하며, 유기과산화물 가교제는 사이클로헥사논퍼옥사이드, t-부틸퍼옥시이소프로필카르보네이트, t-부틸퍼옥시라우릴레이트, t-부틸퍼옥시아세테이트, 디-t-부틸디퍼옥시프탈레이트, t-디브틸퍼옥시말레인산, t-부틸큐밀퍼옥사이드, t-부틸하이드로퍼옥사이드, t-부틸퍼옥시벤조에이트, 디벤조일퍼옥사이드, 디큐밀퍼옥사이드, 1,3-비스(t-부틸퍼옥시이소프로필)벤젠, 메틸에틸케톤퍼옥사이드, 디-(2,4-디클로로벤조일)퍼옥사이드, 1,1-디(t-부틸퍼옥시)-3,3,5-트리메틸사이클로헥산, 2,5-디메틸-2,5-디(벤조일퍼옥시)헥산, 2,5-디메틸-2,5-디(t-부틸퍼옥시)헥산, 디-t-부틸퍼옥사이드, 2,5-디메틸-2,5-(t-부틸퍼옥시)-3-헥신, n-부틸-4,4-비스(t-부틸퍼옥시)발러레이트 또는 α,α'-비스(t-부틸퍼옥시)디이소프로필벤젠 등을 적용할 수 있고, 레진 가교제는 메틸올(methylol)기를 5 ~ 20% 함유한 변성 페놀 수지를 적용할 수 있으며, 본 발명의 효과를 고려할 때 99% 이상의 유기과산화물 가교제를 사용하는 것이 바람직하다.
The crosslinking agent may be used singly or in combination of two or more of a sulfur crosslinking agent, an organic peroxide crosslinking agent or a resin crosslinking agent. The organic peroxide crosslinking agent may be selected from cyclohexanone peroxide, t-butyl peroxyisopropyl carbonate, Butyl peroxy benzoate, dibutyl peroxy benzoate, t-butyl peroxy benzoate, t-butyl peroxy benzoate, t-butyl peroxy benzoate, t- (T-butylperoxyisopropyl) benzene, methyl ethyl ketone peroxide, di- (2,4-dichlorobenzoyl) peroxide, 1,1-di (t- Butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl- Butyl peroxide, 2,5-dimethyl-2,5- (t-butylperoxy) -3-hexyne, n-butyl- Rare And?,? '- bis (t-butylperoxy) diisopropylbenzene, and the resin crosslinking agent may be a modified phenol resin containing 5 to 20% of methylol groups, Considering the effects of the present invention, it is preferable to use 99% or more of an organic peroxide crosslinking agent.

그리고, 상기 가교제의 함량이 0.1 중량부 미만일 경우, 가교점도가 낮아 정상적인 발포체 성형이 어렵고 1.5 중량부를 초과할 경우, 가교점도가 높아 가공상의 문제가 있다.
If the content of the crosslinking agent is less than 0.1 part by weight, it is difficult to form a normal foam because the crosslinking viscosity is low. When the amount is more than 1.5 parts by weight, the crosslinking viscosity is high and there is a problem in processing.

한편, 상기 발포체용 첨가제는, 발포체를 이루기 위한 통상의 첨가제로써, 발포제, 금속산화물, 스테아린산, 충전제, 촉진제 등을 적용할 수 있으며, 좀 더 구체적으로는 기재 100 중량부에 대하여, 발포제는 아조디카르본아미드(ADCA), 디니트로소펜타메틸렌테트라민(DPT) 등을 1 ~ 10 중량부, 금속산화물은 산화아연, 산화마그네슘 등을 1 ~ 5 중량부, 스테아린산은 1 ~ 5 중량부, 충전제는 탄산칼슘, 탄산마그네슘, 산화티타늄, 실리카 등을 0.5 ~ 10 중량부, 촉진제는 트리알릴시아누르산염(TAC), 메르캅토벤조티아졸(MBT), 디벤조티아졸디술피드(MBTS), 디펜타메틸렌티우람테프라설파이드(DPTT) 등을 0.1 ~ 0.5 중량부로 사용할 수 있으며, 발포체 성형 조건은 150 ~ 200℃, 100 ~ 150kg/cm2의 조건하에서 5 ~ 20분간 성형하여 발포체를 제조할 수 있지만, 상술한 바와 같이 여기에 한정되는 것은 아니고, 발포체 조성물의 사용 용도나 사용 환경에 대응하여 이미 공지된 다양한 종류의 발포체용 첨가제를 목적에 맞게 적용할 수 있으며, 그 함량 역시 이미 공지된 범위 내에서 제한없이 사용할 수 있다. 아울러 발포체를 제조하기 위한 조건 역시 발포체 조성물의 사용 용도나 사용 환경에 따라 가변적이므로 특정 조건에 한정하지는 않고 이미 공지된 다양한 조건 범위를 적용할 수 있다.
As the additive for the foam, a foaming agent, a metal oxide, stearic acid, a filler, an accelerator and the like can be applied as a typical additive for forming a foam. More specifically, for the 100 parts by weight of the base material, 1 to 5 parts by weight of zinc oxide, magnesium oxide and the like, 1 to 5 parts by weight of stearic acid, and the filler is, for example, (TAC), mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), dipentaerythritol hexafluorophosphate (DMSO), triphenylmethane diisocyanate (DPTT) may be used in an amount of 0.1 to 0.5 parts by weight. The foaming may be performed under the conditions of 150 to 200 DEG C and 100 to 150 kg / cm < 2 > for 5 to 20 minutes to prepare a foam. As described above, Various known foaming additives can be applied according to the use purpose and the use environment of the foam composition, and the content thereof can be also used within the known range without limitation. In addition, the conditions for producing the foam may also vary depending on the use of the foam composition or the use environment, so that various known ranges of conditions can be applied without being limited to specific conditions.

이하, 본 발명을 아래 실시예에 의거하여 더욱 상세히 설명하겠는바 본 발명이 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

1. 발포체 조성물의 제조
1. Preparation of foam composition

(실시예 1)(Example 1)

선형 저밀도 폴리에틸렌 90 중량% 및 에틸렌비닐아세테이트 10 중량%로 이루어지는 저밀도 수지 100 중량부에 대하여, 평균입자가 0.38 ~ 0.60mm이고, 크러쉬 강도가 16,000 psi인 글래스버블 30 중량부, 디큐밀퍼옥사이드 가교제 1.5 중량부, 발포체용 첨가제인 스테아린산 0.7 중량부와 산화아연 2 중량부, 트리알릴시아누르산염(TAC) 촉진제 0.1 중량부, 아조디카본아마이드 발포제 4 중량부를 투입하여 충분히 혼련시켜 혼련물 쉬트를 제조한 후, 상기 쉬트상 혼련물을 170℃, 120kg/cm2의 조건하에서 7분간 성형하여 발포체를 제조하였다.
30 parts by weight of a glass bubble having an average particle size of 0.38 to 0.60 mm and a crushing strength of 16,000 psi, 30 parts by weight of a dicumylperoxide crosslinking agent 1.5 parts by weight based on 100 parts by weight of a low density resin comprising 90% by weight of linear low density polyethylene and 10% by weight of ethylene vinyl acetate , 0.7 part by weight of stearic acid as an additive for foams, 2 parts by weight of zinc oxide, 0.1 part by weight of triallyl cyanurate (TAC) promoter and 4 parts by weight of azodicarbonamide blowing agent were added and sufficiently kneaded to prepare a kneaded product sheet , And the sheet-like kneaded product was molded for 7 minutes under the conditions of 170 캜 and 120 kg / cm 2 to prepare a foam.

(실시예 2)(Example 2)

선형 저밀도 폴리에틸렌 80 중량% 및 에틸렌비닐아세테이트 20 중량%로 이루어지는 저밀도 수지 100 중량부에 대하여, 평균입자가 0.38 ~ 0.60mm이고, 크러쉬 강도가 28,000 psi인 글래스버블 10 중량부, 디큐밀퍼옥사이드 가교제 0.1 중량부, 발포체용 첨가제인 스테아린산 0.7 중량부와 산화아연 2 중량부, 트리알릴시아누르산염(TAC) 촉진제 0.1 중량부, 아조디카본아마이드 발포제 4 중량부를 투입하여 충분히 혼련시켜 혼련물 쉬트를 제조한 후, 상기 쉬트상 혼련물을 170℃, 120kg/cm2의 조건하에서 7분간 성형하여 발포체를 제조하였다.
10 parts by weight of a glass bubble having an average particle size of 0.38 to 0.60 mm and a crushing strength of 28,000 psi, 10 parts by weight of a dicumylperoxide crosslinking agent, 0.1 parts by weight of a low density polyethylene resin, , 0.7 part by weight of stearic acid as an additive for foams, 2 parts by weight of zinc oxide, 0.1 part by weight of triallyl cyanurate (TAC) promoter and 4 parts by weight of azodicarbonamide blowing agent were added and sufficiently kneaded to prepare a kneaded product sheet , And the sheet-like kneaded product was molded for 7 minutes under the conditions of 170 캜 and 120 kg / cm 2 to prepare a foam.

(비교예 1)(Comparative Example 1)

실시예 1과 동일하게 제조하되, 글래스버블을 첨가하지 않았다.
Was prepared in the same manner as in Example 1, but no glass bubble was added.

(비교예 2)(Comparative Example 2)

실시예 2와 동일하게 제조하되, 선형 저밀도 폴리에틸렌을 사용하지 않고 에틸렌비닐아세테이트 100 중량%를 사용하였다.
The same procedure as in Example 2 was carried out except that 100 weight% of ethylene vinyl acetate was used without using linear low density polyethylene.

2. 발포체 조성물의 평가
2. Evaluation of Foam Composition

(1) 비중(1) Specific gravity

KS M6519에 준하여 우에시마(Ueshima)사의 자동비중 측정 장치인 모델DMA-3을 이용하여 측정하였다.
Was measured using Model DMA-3, an automatic specific gravity measuring apparatus of Ueshima, according to KS M6519.

(2) 경도(2) Hardness

KS M6784에 준하여 아스커(Asker) C형 경도계를 사용하여 측정하였다.
Was measured using an Asker C type hardness meter according to KS M6784.

(3) 영구압축줄음율(3) Permanent compression ratio

발포체를 두께가 10mm가 되도록 절단한 후, 지름이 30±0.05mm인 원기둥 형태로 제조한 시험편을 KS M6660에 준하여 측정하였다. 2장의 평행금속판 사이에 시험편을 넣고, 시험편 두께의 50%에 해당하는 스페이서를 끼운 후 압축시켜 50±0.1℃로 유지되는 오픈에서 6시간 열처리한 후 압축상태를 해제하고 실온에서 30분간 방치한 후 시험편의 두께를 측정하였으며, 영구압축줄음율은 다음 수학식 1에 의하여 계산하였다.
The foams were cut to a thickness of 10 mm, and then the test pieces prepared in the form of cylinders having a diameter of 30 ± 0.05 mm were measured according to KS M6660. The test specimens were placed between two parallel metal plates, and the spacers corresponding to 50% of the thickness of the specimen were inserted. The specimens were compressed and heat-treated for 6 hours at 50 ° C ± 0.1 ° C. The specimens were uncompressed and left at room temperature for 30 minutes The thickness of the test piece was measured, and the permanent compressive strain rate was calculated by the following equation (1).

(수학식 1)(1)

Figure 112016105481763-pat00001

Figure 112016105481763-pat00001

t0 : 시험편의 초기 두께t 0 : initial thickness of specimen

tf : 열처리 후 냉각되었을 때 시험편의 두께t f : thickness of specimen when cooled after heat treatment

tx : 스페이서의 두께
t x : thickness of spacer

(4) 인장강도(4) Tensile strength

시편을 약 3mm 두께로 만든 후 KS M6518에 따른 2호형을 커터(cutter)로 시험편을 제작하여 KS M6518에 준하여 인장강도를 측정하였다.
The test specimens were cut to a thickness of about 3 mm, cut into two pieces according to KS M6518, and measured for tensile strength according to KS M6518.

(5) 인열강도(5) Tear strength

KS M6518에 따라 측정을 하였다.
Measured according to KS M6518.

(6) 반발탄성(6) Resilience

ASTM D2632에 준하여 측정하였다.
Measured according to ASTM D2632.

구분division 실시예 1Example 1 실시예 2Example 2 비교예 1Comparative Example 1 비교예 2Comparative Example 2 비중(Sp.Gr.)Specific gravity (Sp.Gr.) 0.320.32 0.360.36 0.450.45 0.380.38 경도(Asker C)Hardness (Asker C) 9090 9191 9292 8585 인장강도
(kg/cm2)
The tensile strength
(kg / cm 2 )
35.535.5 36.736.7 37.637.6 25.125.1
인열강도
(kg/cm)
Phosphorus strength
(kg / cm)
15.915.9 16.116.1 17.017.0 12.912.9
영구압축줄음율
(C/set, %)
Permanent Compression Row
(C / set,%)
5757 5959 6060 6464
반발탄성(%)Resilience (%) 2828 2727 2525 3030

상기 [표 1]에 나타낸 바와 같이 본 발명에 따른 실시예 1 및 2는 비교예 1 및 2에 비하여, 부력성과 내구성이 동시에 향상됨을 알 수 있다.
As shown in Table 1, Examples 1 and 2 according to the present invention show improved buoyancy and durability at the same time as Comparative Examples 1 and 2.

상술한 바와 같이, 본 발명에 따른 저밀도 수지 발포체 조성물은 상기의 바람직한 실시 예를 통해 설명하고, 그 우수성을 확인하였지만 해당 기술 분야의 당업자라면 하기의 특허 청구 범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.As described above, the low-density resin foam composition according to the present invention is described through the above-described preferred embodiments and its superiority is confirmed. However, those skilled in the art will understand that the present invention is not limited to the above- It will be understood that various modifications and changes may be made thereto without departing from the scope of the present invention.

Claims (5)

저밀도 수지 발포체 조성물에 있어서,
선형 저밀도 폴리에틸렌 80 ~ 90 중량% 및 에틸렌비닐아세테이트 10 ~ 20 중량%로 이루어지는 저밀도 수지 100 중량부에 대하여, 글래스버블 10 ~ 30 중량부, 가교제 0.1 ~ 1.5 중량부 및 발포체용 첨가제가 포함되어 이루어지되,
상기 글래스버블은 평균입자가 0.38 ~ 0.60mm이고, 크러쉬(crush) 강도가 16,000 ~ 28,000 psi이며,
상기 가교제는 황 가교제, 유기과산화물 가교제 또는 레진 가교제 중에서 단독 또는 2종 이상 병용하여 사용하는 것을 특징으로 하는, 저밀도 수지 발포체 조성물.
In the low-density resin foam composition,
10 to 30 parts by weight of a glass bubble, 0.1 to 1.5 parts by weight of a cross-linking agent and 0.1 to 1.5 parts by weight of an additive for a foam, relative to 100 parts by weight of a low-density resin comprising 80 to 90% by weight of linear low density polyethylene and 10 to 20% by weight of ethylene vinyl acetate ,
The glass bubble has an average particle size of 0.38 to 0.60 mm, a crush strength of 16,000 to 28,000 psi,
Wherein the cross-linking agent is used alone or in combination of two or more of a sulfur cross-linking agent, an organic peroxide cross-linking agent, or a resin cross-linking agent.
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