KR960022737A - Manufacturing method of composite material composition made from rubber powder and plastic resin and product manufactured using the composition - Google Patents

Manufacturing method of composite material composition made from rubber powder and plastic resin and product manufactured using the composition Download PDF

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KR960022737A
KR960022737A KR1019940035798A KR19940035798A KR960022737A KR 960022737 A KR960022737 A KR 960022737A KR 1019940035798 A KR1019940035798 A KR 1019940035798A KR 19940035798 A KR19940035798 A KR 19940035798A KR 960022737 A KR960022737 A KR 960022737A
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gtr
upe
ratio
eva
epdm
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KR1019940035798A
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KR0180216B1 (en
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조병욱
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정병휴
학교법인 조선대학교
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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
    • C08L21/00—Compositions of unspecified rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/20—Recycled plastic
    • C08L2207/24—Recycled plastic recycling of old tyres and caoutchouc and addition of caoutchouc particles

Abstract

본 발명은 폐타이어분말(Rubber powder)과 플라스틱수지로부터 제조된 복합재료조성물의 제조방법 및 이 조성물을 이용한 제품에 관한 것으로써, 라버파우다(Grounding tire rubber;GTR)와 플라스틱 (또는 재생수지 및 첨가제)을 블렌드하여 고온에서 라디칼화하는 큐멘히드로퍼옥사이드 및 과산화디큐밀등의 가교제를 적당한 고온에서 순간적으로 가교시켜 사출 또는 압출시켜 제조하는 발명이다.The present invention relates to a method for producing a composite composition prepared from rubber powder and plastic resin, and to a product using the composition, and includes grounding tire rubber (GTR) and plastics (or recycled resins and additives). The present invention is produced by injecting or extruding a crosslinking agent such as cumene hydroperoxide and dicumyl peroxide that are radicalized at high temperature by blending).

폐타이어를 재활용하는 통상적인 방법으로는 재생타이어나 재생고무, 분말고무, 오일추출 또는 골프장용보도블럭제 또는 충격완화제로 사용되고 있으나, 가교결합으로 인한 열경화성 때문에 완전한 재사용은 힘들었다.Conventional methods for recycling waste tires are used as recycled tires, recycled rubbers, powdered rubbers, oil extractions, or footpaths for golf courses or shock absorbers. However, it is difficult to reuse completely due to thermosetting due to crosslinking.

또한, 골프장용 보도블럭의 경우 폴리우레탄수지를 바인더로 하여 압축성형한 것으로 옥외에 장기간 노출시 자외선 흡수 후의 화학구조변형이 생겨 내구성 및 내후성이 좋지 않고 재료의 코스트가 높아 실용성이 없었다.In addition, the press block for golf course was compression molded using polyurethane resin as a chemical structural deformation after ultraviolet absorption after prolonged exposure to the outdoors, so that the durability and weather resistance were not good, and the cost of the material was not high and practical.

본 발명은 위와 같은 점을 감안하여, 상기와 같은 방법으로 제조된 복합재료조성물은 상간접착력이 증진되거나 분산된 라버파우다의 응집을 방지하여 두 조성간의 상 안정성을 증진시켜 저렴한 원가의 보도블럭 또는 장판바닥하지재나 철근대용 구조물등으로 활용되도록 한 유용한 발명에 관한 것이다.In view of the above, the present invention, the composite composition prepared by the above method is to promote the phase stability between the two compositions by improving the adhesion between the phases or prevent the agglomeration of the dispersed rubber powder inexpensive press block or floorboard It relates to a useful invention to be utilized as a flooring material or a structure for rebar.

Description

타이어분말(Rubber powder)과 플라스틱수지로부터 제조된 복합재료 조성물의 제조 방법 및 이 조성물을 이용하여 제조된 제품Manufacturing method of composite material composition made from rubber powder and plastic resin and product manufactured using the composition

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음As this is a public information case, the full text was not included.

Claims (20)

라버파우더 (GTR)-재생 폴리에틸렌(UPE)를 일정비율로 혼합한 후 유동제로써 에틸렌비닐아세테이트 코폴리머(EVA), 상용성증진제로는 에틸렌프로필렌디엔(EPDM)를 첨가하고, 가교제로 큐멘히드로퍼옥사이드(Cumene hydroperoxide) 또는 과산화디큐밀(Dicumyl peroxide;DCP)를 0~5 PHR 투입하여 혼합기로 혼련한 후 각 성분의 다중결합부분간에 [-CH2CH2-]의 라디칼 짝지움에 의한 가교반응이 일어나도록 일정 고온에서 0.5~5분동안에 순간 사출 또는 압출하여 제조함을 특징으로 하는 타이어 분말(Rubber powder)과 플라스틱 수지로부터 제조된 복합재료 조성물의 제조방법.After mixing rubber powder (GTR) -regenerated polyethylene (UPE) in a certain ratio, ethylene vinyl acetate copolymer (EVA) is added as a flow agent, and ethylene propylene diene (EPDM) is added as a compatibility enhancer, and cumene hydroper is used as a crosslinking agent. Crosslinking reaction by radical pairing of [-CH 2 CH 2- ] in the multiple bonds of each component after kneading with a mixer by adding 0-5 PHR of oxide (Cumene hydroperoxide) or Dicumyl peroxide (DCP) Method of producing a composite material prepared from a rubber powder and a plastic resin, characterized in that the instant injection or extrusion at a predetermined high temperature for 0.5 to 5 minutes to occur. 제1항에 있어서, 라버파우더-플라스틱수지 및 유동제와 상용성증진제와 가교제를 일시에 혼합하여 사출하거나 또는 압축시킴을 특징으로 하는 타이어 분말과 플라스틱 수지로부터 제조된 복합재료 조성물의 제조방법.The method of claim 1, wherein the rubber powder-plastic resin, a flow agent, a compatibility enhancer, and a crosslinking agent are mixed or injected at a time to compress or compress the composite material prepared from the tire powder and the plastic resin. 제2항에 있어서, 일시에 혼합하는 라버파우더-플라스틱수지 및 유동제와 상용성 증진제와 가교제를 압출기로 펄렛팅 (Pelletizing)하여 이를 압착성형 하거나 사출성형함을 특징으로 하는 타이어분말과 플라스틱수지로부터 제조된 복합재료 조성물의 제조방법.The tire powder and the plastic resin according to claim 2, wherein the rubber powder and the plastic resin which are mixed at one time are pelletized with an extruder and a compatibility agent and a crosslinking agent by compression molding or injection molding. Method for producing a composite material composition prepared. 제1항에 있어서, 라버파우더(Grouding tire rubber: GTR)는 폐타이어를 실온에서 그라인더(Grinder)로 분쇄한 것으로 직경 7mm이하의 입자로서 스틸코드(Steel Cord)나 폴리에스테르(또는 나일론)코드가 제거됨을 특징으로 하는 방법.The rubber tire (GTR) according to claim 1, wherein the rubber tire (GTR) is obtained by grinding waste tires into a grinder at room temperature. The rubber tire or polyester (or nylon) cord is formed as particles having a diameter of 7 mm or less. Removed. 제1항에 있어서, 재생폴리에틸렌 (UPE)은 저밀도 폴리에틸렌 (LDPE)과 고밀도 폴리에틸렌 (HDPE)이 혼합된 제품을 사용함을 특징으로 하는 방법.The method of claim 1 wherein the recycled polyethylene (UPE) uses a product in which low density polyethylene (LDPE) and high density polyethylene (HDPE) are mixed. 제1항에 있어서, 다른 첨가물 없이 GTR/UPE의 혼합비를 70/30으로만 하여 압출 또는 사출 제조함을 특징으로 하는 방법.The method according to claim 1, characterized in that extrusion or injection production is carried out at a mixing ratio of GTR / UPE of only 70/30 without other additives. 제1항에 있어서, 다른 첨가물 없이 GTR/UPE의 혼합비를 50/50으로만 압출 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 1, wherein the mixing ratio of the GTR / UPE is only 50/50 without any other additives. 제1항에 있어서, 다른 첨가물 없이 GTR/UPE의 혼합비를 60/40으로만 압출 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 1, wherein the mixing ratio of the GTR / UPE is only 60/40 without any other additives. 제1항에 있어서, GTR/UPE의 혼합비를 60/40으로 하고, EPDM/EVA/DCP를 5/5/0.5 비율로 첨가하여 압출 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 1, wherein the mixing ratio of GTR / UPE is 60/40, and EPDM / EVA / DCP is added at a ratio of 5/5 / 0.5 to produce extrusion or injection. 제9항에 있어서, 첨가제인 EPDM/EVA/DCP이 0/5/0.5의 비율로 첨가되어 압출, 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 9, wherein the additive EPDM / EVA / DCP is added at a ratio of 0/5 / 0.5 to produce extrusion or injection. 제9항에 있어서, 첨가제인 EPDM/EVA/BCP이 3/7/0.5의 비율로 첨가되어 압출, 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 9, wherein an additive, EPDM / EVA / BCP, is added at a ratio of 3/7 / 0.5 to produce extrusion or injection. 제9항에 있어서, 첨가제인 EPDM/EVA/BCP이 3/7/1.0의 비율로 첨가되어 압출, 또는 사출 제조함을 특징으로 하는 보도블럭.The press block according to claim 9, wherein an additive, EPDM / EVA / BCP, is added at a ratio of 3/7 / 1.0 to produce extrusion or injection. 제1항에 있어서, GTR/UPE/EPDM/EVA/DCP의 혼합비를 60/40/5/5/0.5로 하여, 씰렌(Silane) 화합물을 연결제 (Coupling agent)로 사용할 경우 시멘트 콘크리트와의 젖음성이 증진됨을 특징으로 하는 철근대용 제품.The wettability with cement concrete according to claim 1, wherein the mixing ratio of GTR / UPE / EPDM / EVA / DCP is set to 60/40/5/5 / 0.5, and when a Silane compound is used as a coupling agent. A product for rebar, characterized in that it is enhanced. 제1항에 있어서, 가교제로 첨가되는 과산화디큐밀(DCP) 대신에, cumenehydroperoxide[C6H5C(CH3)2OOH]를 사용하여 평균 4%의 인장 강도가 증진될 수 있도록 함을 특징으로 하는 방법.The cumulative hydroperoxide [C 6 H 5 C (CH 3 ) 2 OOH] is used instead of dicumyl peroxide (DCP) added as a crosslinking agent, so that an average tensile strength of 4% can be enhanced. How to. 제1항에 있어서, 혼합기(Haake rheomix)에 GTR/UPE의 혼합을 100~25/O~75 비율로 넣고 블랜드 온도는 200℃ 혼합기로터 (rotor)의 회전수 40rpm으로 10분간 블랜드시켜 저가로 압착성형됨을 특징으로 하는 보도블럭, 장판하지 또는 바닥재 하지제품.According to claim 1, Hake rheomix is mixed with GTR / UPE at a ratio of 100 ~ 25/0 ~ 75 and the blend temperature is blended for 10 minutes by blending at a rotational speed 40rpm of 200 ℃ mixer rotor for 10 minutes A press block, floor covering or floor covering product characterized in that it is molded. 제15항에 있어서, 압착 성형되는 블랜드 시트를 강판하지 또는 바닥재 하지로 접합 사용하기 위하여는 염소화폴리에틸렌(CPE) 필름이나, 폴리에틸렌(PE)과 CPE 혼합필름을 부착 필름으로 채택하며, 70~l3O℃ 온도에서, 5㎏f/㎠~15㎏f/㎠의 압력으로 열융착함을 특징으로 하는 방법.16. The method of claim 15, wherein in order to bond the blend sheet to be press-molded with a steel sheet or a bottom sheet, a chlorinated polyethylene (CPE) film or a polyethylene (PE) and CPE mixed film is used as an adhesive film. At a temperature of 5 kgf / cm 2 to 15 kgf / cm 2. 제1항에 있어서, GTR/UPE/EPDM/EVA률 일정비율로 섞어 텀블러 혼합기에서 20~30rpm으로 10분 정도 혼련시킨 후, 온도 230~265℃로된 사출성형기 중간부위에 DCP 또는 큐멘 히드로퍼옥사이드(cumenehydroperoxide)를 투입하여 0.5~5분만에 사출 제조함을 특징으로 하는 방법.According to claim 1, GTR / UPE / EPDM / EVA rate of mixing in a constant ratio of 20 ~ 30rpm in a tumbler mixer for about 10 minutes, DCP or cumene hydroperoxide in the middle of the injection molding machine at a temperature of 230 ~ 265 ℃ (cumenehydroperoxide) is added to the injection molding method in 0.5 to 5 minutes. 제 17항에 있어서, GTR/UPE/EPOM/EVA/cumene hydroperoxide의 혼합 조성비를 60/40/5/5/0.5 사출 제조함으로써, GTR과 UPE 사이의 계면이 완전 밀각가교 시킴을 특징으로 하는 방법.18. The method according to claim 17, wherein the interface between the GTR and the UPE is completely tightly crosslinked by 60/40/5/5 / 0.5 injection preparation of a mixed composition ratio of GTR / UPE / EPOM / EVA / cumene hydroperoxide. 제18항에 있어서, GTR/UPE/EPDM/EVA/cumene hydroperoxide의 혼합조성비가 60/40/5/5/0.5로 하고 피그멘트(Pigment)로서 TiO2, ZnO 또는 ZnS, 칙색제로써 phthalocyanine blue, phthalocyanine green 및 산화철, 윤활제로 스테아린산칼슘이나 스테아린산아연등을 사용함을 특징으로 하는 방법.19. The method of claim 18, wherein the mixing ratio of GTR / UPE / EPDM / EVA / cumene hydroperoxide is 60/40/5/5 / 0.5, and TiO 2 , ZnO or ZnS as pigment, phthalocyanine blue, phthalocyanine green, iron oxide, calcium stearate or zinc stearate. 제19항에 있어서, GTR/UPE/EPDM/EVA/cumene hydroperoxide의 혼합조성비가 60/40/5/5/0.5로 하고 피그멘트(Pigment)로서 TiO2, ZnO 또는 ZnS, 착색제로써 phthalocyanine blue, phthalocyanine green 및 산화철, 윤활제로 스테아린산칼슘이나 스테아린산아연등을 첨가시켜 압출 제조함을 특징으로 하는 건축용 타일.20. The method according to claim 19, wherein the mixing composition ratio of GTR / UPE / EPDM / EVA / cumene hydroperoxide is 60/40/5/5 / 0.5, and TiO 2 , ZnO or ZnS as a pigment, phthalocyanine blue as a colorant, phthalocyanine Green and iron oxides, architectural tiles characterized in that the extrusion by adding calcium stearate or zinc stearate as a lubricant. ※ 참고사항 :최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
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KR100408704B1 (en) * 2001-03-05 2003-12-06 문성철 A composition of foams with waste materials and ground tire rubber and foams thereof
KR100431887B1 (en) * 2001-06-27 2004-05-17 김진국 Rubber Sidewalk Block Having Layers
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