WO2021230439A1 - Composition, article moulé formé à partir de cette dernière et procédé de moulage l'utilisant - Google Patents

Composition, article moulé formé à partir de cette dernière et procédé de moulage l'utilisant Download PDF

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WO2021230439A1
WO2021230439A1 PCT/KR2020/014704 KR2020014704W WO2021230439A1 WO 2021230439 A1 WO2021230439 A1 WO 2021230439A1 KR 2020014704 W KR2020014704 W KR 2020014704W WO 2021230439 A1 WO2021230439 A1 WO 2021230439A1
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weight
foaming
parts
composition
based elastomer
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PCT/KR2020/014704
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Korean (ko)
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이지은
이종환
정상옥
박상영
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(주)나노텍세라믹스
한국신발피혁연구원
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • 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
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0066—Use of inorganic compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • 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
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    • C08K5/14—Peroxides
    • 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
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    • 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
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene

Definitions

  • the present invention relates to a non-foaming low specific gravity polyolefin-based elastomer composition having a low specific gravity without a foaming process to realize weight reduction and excellent dimensional stabilization by not performing a foaming process, and a molded article formed therefrom.
  • the present invention relates to a foaming composition capable of minimizing the denaturation of additives and thus exhibiting excellent foaming uniformity and heat resistance of foams, and a foam molding method using the same.
  • Rubber-based materials are being used in various ways as materials for shoes themselves or for outsoles. Although the main component of the material varies depending on the use of the shoe, rubber-based materials such as natural rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and butyl rubber are mainly used.
  • the material of the rubber-based foam used for this is a compound based on chlorosulfonated polyethylene (CSM) containing chlorine, a halogen component.
  • CSM chlorosulfonated polyethylene
  • dioxin which is a carcinogen and a target of environmental pollutants, is generated and pollutes the environment. This occurs, and there is a problem in that various harmful gases such as ammonia gas are emitted during the foaming process.
  • a foaming method using a chemical foaming agent is a method of preparing a composition by mixing a heat-resistant polymer resin, various additives, and a chemical foaming agent that generates gas, and heating it at a decomposition temperature of the foaming agent or higher.
  • Korean Patent Laid-Open No. 10-2016-0081587 it was attempted to provide a stable foaming composition and a foam molding method through a foaming agent master.
  • the prior patent provides a foaming agent masterbatch prepared by adding 100 to 300 parts by weight of a blowing agent to 100 parts by weight of a thermoplastic polymer, dispersing it in a kneader mixer and pelletizing it in an extruder, thereby avoiding the concern that additives are denatured under high temperature conditions. was to be minimized.
  • the heat resistance of the foam could not be expressed to a desired level as the foaming was performed in a state where crosslinking was not sufficiently achieved.
  • the problem to be solved by the present invention is that it is possible to reduce the weight without a foaming process, so that pollutants such as harmful gases are not generated during the foaming process, and there is no fear of shrinkage, so a non-foaming low specific gravity polyolefin-based elastomer composition excellent in dimensional stability and therefrom To provide a molded article formed.
  • a second object to be solved by the present invention is to provide a foaming composition capable of minimizing the denaturation of additives and thus exhibiting excellent foaming uniformity and excellent heat resistance of the foam, and a foam molding method using the same.
  • the third problem to be solved by the present invention is to use the independently formed foamed masterbatch chip together with the high heat-resistance resin chip to form a foam, thereby omitting the processing process for the high-heat-resistance resin chip, so that the process efficiency is improved.
  • the present invention provides a non-foaming low specific gravity polyolefin-based elastomer composition
  • a non-foaming low specific gravity polyolefin-based elastomer composition comprising a low specific gravity hollow filler and a plasticizer on a substrate made of a polyolefin-based elastomer.
  • the polyolefin-based elastomer is ethylene octene copolymer (EOR), propylene-based elastomer (PBE), ethylene butene copolymer (EBR), ethylene propylene copolymer (EPR), ethylene propylene diene It may be made of any one or more selected from the group consisting of monomers (EPDM), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE).
  • EOR ethylene octene copolymer
  • PBE propylene-based elastomer
  • EBR ethylene butene copolymer
  • EPR ethylene propylene copolymer
  • EPDM linear low-density polyethylene
  • LLDPE low-density polyethylene
  • HDPE high-density polyethylene
  • the polyolefin-based elastomer may be composed of an ethylene octene copolymer (EOR) and a propylene-based elastomer (PBE).
  • EOR ethylene octene copolymer
  • PBE propylene-based elastomer
  • the propylene-based elastomer (PBE) may be included in an amount of 300 to 500 parts by weight based on 100 parts by weight of the propylene-based elastomer (PBE).
  • the plasticizer may be included in an amount of 5 to 20 parts by weight based on 100 parts by weight of the polyolefin-based elastomer.
  • the low specific gravity hollow filler may be included in an amount of 2 to 30 parts by weight based on 100 parts by weight of the polyolefin-based elastomer.
  • the plasticizer may be a paraffinic oil.
  • the low specific gravity hollow filler may be a glass bubble (Glass Bubble).
  • the crosslinking agent is dicumyl peroxide (DCP, Dicumyl peroxide), dibenzoyl peroxide (Dibenzoyl peroxide), cyclohexanone peroxide (Cyclohexanone peroxide) , t-Butyl peroxy isopropyl carbonate, t-Butyl peroxy laurylate, t-Butyl peroxy acetate, di- t-butyldiperoxyphthalate (Di-t-Butyl peroxyphthalate), t-butylperoxymaleic acid (t-Butyl peroxy maleic acid), t-butylcumyl peroxide (t-Butylcumyl peroxide), t-butyl hydroperoxide ( t-Butyl hydroperoxide), 1,3-bis(t-butyl peroxyisopropyl) benzene (1,3-d
  • the present invention provides a molded article formed from any one of the compositions described above.
  • the present invention comprises a foamed masterbatch chip and a high heat resistant resin chip in a weight ratio of 10 to 40: 60 to 90, and the foamed masterbatch chip contains 5 to 15 parts by weight of a foaming agent and 15 parts by weight of an additive based on 100 parts by weight of a polymer resin. It provides a foaming composition, characterized in that it contains ⁇ 25 parts by weight.
  • the foaming composition may satisfy Relational Equation 1.
  • HDT p heat deflection temperature of the high heat resistant resin contained in the high heat resistant resin chip
  • HDT mb the heat deflection temperature of the polymer resin contained in the foamed masterbatch chip
  • the polymer resin may be any one or more selected from the group consisting of ethylene vinyl acetate copolymer, low density polyethylene, olefin block copolymer, and isotactic polypropylene.
  • the blowing agent is azodicarbonamide, 4,4'-oxydibenzenesulfonyl hydrazide, dinitroso pentamethylene tetramine, P-toluenesulfonyl hydrazide, P -It may be any one or more selected from the group consisting of toluenesulfonyl semicarbazide.
  • the additive may be any one or more selected from the group consisting of a crosslinking agent, a crosslinking activator, a heat stabilizer, an additive for preventing premature foaming, a metal oxide, stearic acid, and a reactive additive.
  • the additive may include 05 to 6 parts by weight of metal oxide, 05 to 6 parts by weight of stearic acid, and 5 to 15 parts by weight of a crosslinking agent.
  • the present invention comprises the steps of preparing a foamed masterbatch chip; forming a foamed composition by blending the foamed masterbatch chip with a high heat-resistant resin chip in a weight ratio of 10 to 40: 60 to 90; and processing the foaming composition to form a foam; the foamed masterbatch chip provides a foam molding method comprising 5 to 15 parts by weight of a foaming agent and 15 to 25 parts by weight of an additive based on 100 parts by weight of a polymer resin do.
  • the step of preparing the foamed masterbatch chip includes mixing 5 to 15 parts by weight of a foaming agent and 15 to 20 parts by weight of an additive with respect to 100 parts by weight of a polymer resin, and then extruding the same. can be performed.
  • the step of preparing the foamed masterbatch chip may be performed by first adding the additive to the polymer resin, then secondly adding the foaming agent and sequentially mixing.
  • forming the composition may be performed by blending the foamed masterbatch chip and the high heat resistant resin chip in a weight ratio of 10 to 30: 70 to 90.
  • the blending of the step of forming the foam composition may be performed through dry blending.
  • the present invention can provide a non-foaming low specific gravity polyolefin-based elastomer composition having excellent dimensional stability because it does not generate contaminants such as harmful gases during the foaming process, and there is no fear of shrinkage.
  • the present invention can provide a non-foaming low specific gravity polyolefin-based elastomer composition capable of reducing weight and exhibiting excellent physical properties.
  • the present invention can provide a foaming composition and a foam molding method using the same, which can minimize the denaturation of the additive under high-temperature conditions, so that the foaming is performed stably and the foaming uniformity of the foam is stable.
  • the present invention can provide a foaming composition capable of providing a foam capable of excellently expressing the desired heat resistance and a foam molding method using the same, since it is foamed after sufficient crosslinking.
  • the present invention uses the independently formed foamed masterbatch chip together with the high heat-resistance resin chip to mold the foam, thereby omitting the processing process for the high-heat-resistance resin chip. method can be provided.
  • FIG. 1 is a flowchart of a foam molding method according to a preferred embodiment of the present invention.
  • FIG. 2 is an external image of a foam according to a preferred embodiment of the present invention.
  • FIG 3 is an image comparing the appearance of a foam and a commercialized foam according to a preferred embodiment of the present invention.
  • 'chip' refers to a solidified shape of a masterbatch for the purpose of foaming consisting of components and contents as described below, and there is no particular limitation on the shape, and is replaced with 'pellet' can be
  • the present invention sought to solve the above-mentioned limitations by providing a non-foaming, low specific gravity polyolefin-based elastomer composition including a low specific gravity hollow filler and a plasticizer on a substrate made of a polyolefin-based elastomer.
  • the present invention enables weight reduction without a foaming process, pollutants such as harmful gases do not occur during the foaming process, and there is no fear of shrinkage, so there is an effect of excellent dimensional stability.
  • pollutants such as harmful gases do not occur during the foaming process, and there is no fear of shrinkage, so there is an effect of excellent dimensional stability.
  • it is possible to reduce the weight and exhibit excellent physical properties there is an effect suitable for being used as a material for shoes, shoe outsoles, and the like.
  • Thermoplastic elastomer is a polymer material that has the same rubber elasticity as vulcanized rubber at room temperature, melts and plasticizes when heated to a high temperature, and can be molded by a general plastic molding machine.
  • a polyolefin-based elastomer is used as a base material, and a low specific gravity hollow filler, a plasticizer, and the like are added thereto to form a composition, so that it can be easily molded through melt plasticization.
  • a low specific gravity hollow filler, a plasticizer, and the like are added thereto to form a composition, so that it can be easily molded through melt plasticization.
  • the polyolefin-based elastomer is ethylene octene copolymer (EOR), propylene-based elastomer (PBE), ethylene butene copolymer (EBR), ethylene propylene copolymer (EPR), ethylene propylene diene It may be any one or more selected from the group consisting of monomers (EPDM), linear low-density polyethylene (LLDPE), low-density polyethylene (LDPE), and high-density polyethylene (HDPE).
  • EOR ethylene octene copolymer
  • PBE propylene-based elastomer
  • EBR ethylene butene copolymer
  • EPR ethylene propylene copolymer
  • EPDM linear low-density polyethylene
  • LLDPE low-density polyethylene
  • HDPE high-density polyethylene
  • the meaning of ' may be any one or more' means that the substrate may be formed with only one, or two or more may be mixed to form the substrate.
  • the substrate is made of the above-described polyolefin-based elastomer, excellent physical properties such as strength and viscosity can be expressed, and at the same time, there is an effect of reducing the weight without a foaming process.
  • it may consist of an ethylene octene copolymer (EOR) and a propylene-based elastomer (PBE).
  • EOR ethylene octene copolymer
  • PBE propylene-based elastomer
  • the content ratio of the ethylene octene copolymer (EOR) and the propylene-based elastomer (PBE) may be appropriately selected according to the purpose and use of the molded article, but is preferably the propylene-based elastomer (PBE) in 100 parts by weight. It may be included in an amount of 300 to 500 parts by weight. More preferably, 350 to 450 parts by weight based on 100 parts by weight of the propylene-based elastomer (PBE) may be included.
  • the low specific gravity hollow filler may mean a lightweight filler having a hollow shape and a low specific gravity, and may be used in various ways as long as it is a material that is lightweight and has a hollow shape but can function as a filler.
  • a low specific gravity hollow filler it is easy to reduce the weight, and at the same time, there is an effect that the buffer effect is also improved by the 'hollow shape'.
  • the low specific gravity hollow filler may be a glass bubble (Glass Bubble).
  • Glass Bubble Glass Bubble
  • the specific gravity of the composition can be significantly reduced, and dimensional stability can be improved to meet dimensional tolerances.
  • a low injection pressure and rapid cooling are possible, thereby improving the yield.
  • the low specific gravity hollow filler may be mixed in an appropriate content ratio in consideration of weight reduction and physical properties such as strength and viscosity, but preferably 2 to 30 parts by weight based on 100 parts by weight of the polyolefin-based elastomer. More preferably, it may be included in an amount of 2 to 20 parts by weight based on 100 parts by weight of the polyolefin-based elastomer, more preferably in an amount of 2 to 15 parts by weight, and most preferably in an amount of 2 to 10 parts by weight.
  • the plasticizer may be mixed with the elastomer to improve flexibility, processability, and the like, and may refer to an additive that acts as an intermolecular lubricant to promote relaxation of the polymer.
  • the composition of the present invention may have improved flowability by including a plasticizer.
  • the plasticizer may improve flowability, and a polyolefin-based elastomer having good compatibility and plasticizing efficiency may be used.
  • the plasticizer may be a paraffinic oil (Paraffinic Process Oil).
  • Paraffinic oil has advantages of excellent heat resistance and stain resistance.
  • the plasticizer may be mixed in an appropriate content ratio to be uniformly mixed in the composition to improve flowability, processability, etc., but preferably 5 to 20 parts by weight based on 100 parts by weight of the polyolefin-based elastomer. More preferably, it may be included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the polyolefin-based elastomer, and more preferably, it may be included in an amount of 7 to 12 parts by weight based on 100 parts by weight of the polyolefin-based elastomer.
  • a crosslinking agent may be further included.
  • properties such as heat resistance and cohesiveness can be improved by forming a polymer network structure.
  • the crosslinking agent can be used in various ways that are commonly used in the art, preferably dicumyl peroxide (DCP, Dicumyl peroxide), dibenzoyl peroxide (Dibenzoyl peroxide), cyclohexanone peroxide (Cyclohexanone peroxide), t-Butyl peroxy isopropyl carbonate, t-Butyl peroxy laurylate, t-Butyl peroxy acetate, di-t -Butyldiperoxyphthalate (Di-t-Butylperoxy phthalate), t-butylperoxymaleic acid (t-Butyl peroxy maleic acid), t-butylcumyl peroxide (t-Butylcumyl peroxide), t-butyl hydroperoxide (t -Butyl hydroperoxide), 1,3-bis (t-butyl peroxyisopropyl) benzene (1,3-di- (t-Buty
  • the present invention comprises the steps of (1) adding and blending a low specific gravity hollow filler and a plasticizer to a substrate made of a polyolefin-based elastomer; and (2) obtaining a non-foaming low specific gravity polyolefin-based elastomer composition through the above blending.
  • step (1) the compounding of step (1) is preferably performed using a kneader in order to minimize damage to the low specific gravity hollow filler.
  • the compounding of step (1) may be carried out for 5 to 20 minutes in a temperature range of 80 ⁇ 200 °C. In this case, a uniformly mixed composition can be obtained without damaging the low specific gravity hollow filler.
  • the present invention can obtain a molded article by pressing the non-foaming low specific gravity polyolefin-based elastomer composition under high temperature conditions.
  • the present invention provides a molded article formed from any one of the compositions described above.
  • the present invention can provide a molded article that is light and exhibits excellent physical properties such as strength and viscosity because it can be reduced in weight without foaming. It has the advantage that it can be used as an outsole or a shoe skin.
  • the present invention includes the foamed masterbatch chip and the high heat resistant resin chip in a weight ratio of 10 to 40: 60 to 90, and the foamed masterbatch chip contains 5 to 15 parts by weight of a foaming agent and 15 to 15 parts by weight of a foaming agent based on 100 parts by weight of a polymer resin.
  • a solution to the above problems was sought by providing a foaming composition comprising 25 parts by weight.
  • the present invention can minimize the denaturation of the additive under high-temperature conditions, so that the foaming is performed stably, so that the foaming uniformity of the foam is stable. There is an effect that can provide a foam.
  • the foamed masterbatch chip of the present invention includes all of a polymer resin, a foaming agent and an additive. Accordingly, even under high-temperature conditions for processing a polymer resin having excellent heat resistance, the additives do not change, and as a result, the foaming occurs stably, so that the foaming uniformity of the foam can be stably expressed. At the same time, since it also contains additives, it is released after crosslinking is sufficiently performed, so that heat resistance can be excellently expressed.
  • the processing process for the high heat resistant resin chip can be omitted, thereby improving process efficiency.
  • thermoplastic polymer resin having excellent heat resistance may be used as the resin.
  • thermoplastic polymer resin is selected from the group consisting of ethylene vinyl acetate copolymer, low density polyethylene copolymer, styrene polyethylene polybutylene styrene copolymer, styrene butyrene butyrene styrene copolymer, styrene polyisoprene styrene copolymer, and thermoplastic polyurethane. It may be configured to include any one or more.
  • ethylene vinyl acetate copolymer (Ethylene Vinylacetate Copolymer, EVA), low density polyethylene copolymer (Low Density Polyethylene Copolymer, LDPE), olefin block copolymer (Olefin Block Copolymer) and isotactic polypropylene (Isotactic Polypropylene) may be configured to include any one or more selected from the group consisting of.
  • the foaming agent is a material that generates bubbles by generating a large amount of gas by being blended with a polymer resin to cause a reaction such as thermal decomposition on its own.
  • Boneamide (ADCA) type dinitrosopentamethylene tetramine (DPT) type. It may be at least one selected from the group consisting of toluene sulfonyl hydrazide (TSH)-based, inorganic and capsule-type foaming agents (Micropearl).
  • the blowing agent is azodicarbonamide (ADCA), 4,4'-oxydibenzenesulfonyl hydrazide (4,4'-Oxydibenzenesulfonyl hydrazide, OBSH), dinitroso Any one selected from the group consisting of pentamethylene tetramine (N,N'-Dinitrosopentamethylenetetramine, DPT), P-toluenesulfonylhydrazide (PToluenesulfonylhydrazide, TSH), P-toluenesulfonyl semicarbazide (PTSS) There may be more than one.
  • ADCA azodicarbonamide
  • OBSH 4,4'-oxydibenzenesulfonyl hydrazide
  • OBSH 4,4'-Oxydibenzenesulfonyl hydrazide
  • OBSH 4,4'-Oxydi
  • the foaming agent is included in an amount of 5 to 15 parts by weight based on 100 parts by weight of the polymer resin.
  • the foamed masterbatch chip of the present invention satisfies the above range, the desired foaming uniformity and foaming stability are excellent, and thus the effect of producing a foam of a uniform size and shape can be expressed.
  • it may be included in an amount of 7 to 13 parts by weight based on 100 parts by weight of the polymer resin.
  • the foaming agent is included in less than the above range or the foaming agent is included in excess of the above range, foaming uniformity and foaming stability are deteriorated, so that it is difficult to produce a desired foam.
  • any one or more selected from the group consisting of a crosslinking agent, a crosslinking activator, a heat stabilizer, an additive for preventing premature foaming, a metal oxide, stearic acid, and a reactive additive may be used. Can be used.
  • the additive is included in an amount of 15 to 25 parts by weight based on 100 parts by weight of the polymer resin.
  • the foamed masterbatch chip of the present invention has an effect that heat resistance can be sufficiently expressed because foaming can be performed after crosslinking is sufficiently made by additives only when the above range is satisfied.
  • it may be included in an amount of 15 to 20 parts by weight based on 100 parts by weight of the polymer resin. More preferably, it may be included in an amount of 16 to 18 parts by weight based on 100 parts by weight of the polymer resin.
  • the foamed masterbatch chip of the present invention contains additives within the above weight range, additives can not be denatured even under high-temperature conditions for processing heat-resistant polymer resins, so that a stable foam can be manufactured, and at the same time, crosslinking can be performed by the additives. After being sufficiently formed, foaming can be performed, so that the heat resistance of the polymer resin can be excellently expressed.
  • the foamed masterbatch chip of the present invention contains additives such as a crosslinking agent, a crosslinking activator, a heat stabilizer, an additive for preventing premature foaming, a metal oxide, stearic acid, and a reactive additive within the above-mentioned weight range without detracting from the physical properties to be obtained by the present invention. It can be optionally included within the scope.
  • the crosslinking agent serves to evenly improve various physical properties of the foamed masterbatch chip of the present invention.
  • a crosslinking agent commonly used in the art may be used, but preferably 2,5-bis(tertbutylperoxy)-2,5-dimethyl-3-hexene, ditertbutylperoxide, 2, 5-bis(tertbutylperoxy)-2,5-dimethyl-hexene, dibenzoyl peroxide, bis(tertbutylperoxyisopropyl)benzene, butyl 4,4-bis(tertbutylperoxy)valerate, 1 Any one or more selected from ,1-bis(tertbutylperoxy)3,3,5-trimethylchlorohexane, tertbutylperoxybenzoate, lauryl peroxide and dicumyl peroxide (DCP) may be used, and more Preferably, dicumyl peroxide (DCP) may be used.
  • DCP dicumyl
  • the crosslinking agent may be included in an amount of 5 to 15 parts by weight, more preferably 8 to 12 parts by weight, based on 100 parts by weight of the polymer resin.
  • the degree of crosslinking of the foam is low and the mechanical strength is lowered, as well as the loss of the foaming gas is increased, so that the foam cannot be formed. If the content of the crosslinking agent is greater than the above range Since the degree of crosslinking is high, there may be a problem that the foam cell bursts by suppressing the expansion.
  • the crosslinking activator may be added to prevent excessive decomposition of the polymer and maintain stability of the generated radicals, and those commonly used in the art may be used.
  • divinylbenzene, ethylene glycol dimethacrylate, triallyl cyanurate (TAC), diethylene glycol dimethacrylate, allyl methacrylate or trimethylolpropane trimethacrylate may be used.
  • the crosslinking aid may be included in an amount of 01 to 2 parts by weight based on 100 parts by weight of the thermoplastic polymer mixture.
  • the anti-foaming additive may be added to prevent premature foaming inside the injection machine, which may occur when a polymer having a high melting point is used. Those commonly used in the art may be used.
  • the metal oxide may be added as a crosslinking activator and reinforcing agent in order to control the crosslinking rate and promote decomposition of the foaming agent.
  • Any one commonly used in the art may be used, but preferably any one or more selected from the group consisting of zinc oxide, magnesium oxide, titanium oxide and calcium oxide. More preferably, it may be zinc oxide.
  • the metal oxide may be included in an amount of 05 to 6 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the polymer resin. If the metal oxide is included below the above range, there may be problems in that the crosslinking rate and the foaming rate are lowered. This can happen.
  • Stearic acid may be added as an internal mold release agent to improve storage stability and processability.
  • sreanic acid may be included in an amount of 05 to 6 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the polymer resin.
  • the heat stabilizer serves to prevent the mechanical properties of the polymer resin from being deteriorated during foaming.
  • the heat stabilizer is non-toxic, has stability at the processing and molding temperature, and has high compatibility with resins can be used.
  • the reactive additive may improve heat resistance by uniformly dispersing components such as a filler.
  • a filler may be uniformly dispersing components.
  • the reactive additive may be treated with a filler to improve the dispersibility of the filler to use a formulation capable of improving the thermal insulation and heat resistance of the present invention, but preferably a silane coupling agent, polyethylene glycol, polypropylene glycol, and itaconic acid. It may be any one or more selected from the group, and more preferably a silane coupling agent.
  • the additive may include 05 to 6 parts by weight of metal oxide, 05 to 6 parts by weight of stearic acid, and 5 to 15 parts by weight of a crosslinking agent.
  • the additive includes the materials within the above range, it is possible to improve the heat resistance of the foam, and at the same time, there is an effect that all other physical properties can be excellently expressed.
  • the foamed masterbatch chip of the present invention is blended with a high heat-resistant resin chip to mold a foam of a desired shape.
  • the 'high heat-resistance resin chip' refers to a chip-shaped resin made of only high-heat-resistance resin among polymer resins. That is, the foamed masterbatch chip of the present invention is formed independently and is used together with the high heat-resistant resin chip to form the foamed composition.
  • the independently formed foamed masterbatch chip is used together with the high heat-resistant resin chip, there is no need to process at a high heat-resistant temperature, so the denaturation of the additive can be prevented, and the additives are included together with the resin and foaming agent in an appropriate amount. Accordingly, foaming can be performed after crosslinking has occurred sufficiently. In addition, there is an effect that the molded foam can sufficiently express the excellent heat resistance of the polymer resin by forming the composition by separately using the high heat-resistance resin chip.
  • a composition is formed by independently preparing a high heat resistant resin chip and a foamed masterbatch chip as described above, and a foam molding process is performed using the composition
  • a commercially available resin chip can be used as the high heat resistant resin chip. , it is possible to omit the processing process for the high heat-resistance resin chip, so that the process efficiency can be significantly improved.
  • the foamed masterbatch chip suffices as long as it is easy to mix with the high heat-resistant resin chip commonly used in the technical field, and preferably has an average particle diameter of 80 to 120% compared to the average particle diameter of the high heat-resistant resin chip used in molding the foaming agent. can have More preferably, the average particle diameter of the foamed masterbatch chips may be 4 to 6 mm.
  • the polymer resin contained in the foamed masterbatch chip and the high heat-resistance resin contained in the high-heat-resistance resin chip may use the same polymer resin depending on the case, or those with good compatibility because they are easy to mix with each other may be used.
  • the high heat-resistance resin chip is made of a thermoplastic polymer resin with excellent heat resistance. This is because when the foamed masterbatch chip and the high heat resistant resin chip are used together to form a foam by the process described later, the foam tends to follow the heat resistance of the high heat resistant resin contained in the high heat resistant resin chip. Accordingly, the excellent heat resistance of the high heat resistant resin can be expressed in the foam, and as a result, a foam having excellent heat resistance can be molded through a simple process.
  • the high heat resistance resin chip may be a resin containing an olefin block copolymer.
  • the high heat resistance resin chip may be a resin containing an olefin block copolymer.
  • the foaming composition of the present invention may satisfy the following relation (1).
  • HDT p heat deflection temperature of the high heat resistant resin contained in the high heat resistant resin chip
  • HDT mb the heat deflection temperature of the polymer resin contained in the foamed masterbatch chip
  • heat deflection temperature is one of the thermal properties of a polymer, and means a temperature at which deformation occurs by an arbitrary amount under a constant load.
  • the heat deformation temperature of the high heat resistance resin contained in the high heat resistance resin chip is the same as or higher than that of the polymer resin contained in the master batch chip, the heat resistance of the molded foam is excellently expressed. .
  • the present invention comprises the steps of preparing a foamed masterbatch chip; forming a foamed composition by blending the foamed masterbatch chip with a high heat-resistant resin chip in a weight ratio of 10 to 40: 60 to 90; and processing the foaming composition to form a foam; the foamed masterbatch chip provides a foam molding method comprising 5 to 15 parts by weight of a foaming agent and 15 to 25 parts by weight of an additive based on 100 parts by weight of a polymer resin do.
  • the foam molding method of the present invention comprises the steps of preparing a foamed masterbatch chip (S10), and blending the foamed masterbatch chip and the high heat resistant resin chip in a weight ratio of 10 to 40: 60 to 90 to form a foamed composition Forming a (S20), and processing the foam composition to mold a foam (S30).
  • the step of preparing the foamed masterbatch chip (S10) includes the step of preparing the foamed masterbatch chip, which means a step of preparing the foamed masterbatch chip of the above-described components and contents.
  • the step of preparing the master batch chip (S10) comprises mixing 5 to 15 parts by weight of a foaming agent and 15 to 20 parts by weight of an additive with respect to 100 parts by weight of the polymer resin and then extruding the same. including can be performed.
  • the present invention can minimize the denaturation of the additive under high-temperature conditions, so that the foaming is performed stably, so that the foaming uniformity of the foam is stable. There is an effect that the foam can be molded.
  • the polymer resin, the foaming agent, and the additive may be sequentially mixed at the same time or may be added and mixed non-sequentially, but preferably, the additive is first added to the polymer resin, and then the foaming agent is added sequentially It can be carried out by mixing with As such, when the foaming agent is added after the additive is first added to the polymer resin, the foaming agent is prevented from reacting due to the heat generated during mixing, thereby reducing the occurrence of defective products.
  • step (S20) of blending the foamed masterbatch chip and the high heat resistant resin chip in a weight ratio of 10 to 40: 60 to 90 to form a foamed composition (S20) will be described.
  • the excellent heat resistance inherent in the polymer resin can be expressed by mixing the masterbatch chip and the high heat-resistant resin chip to form a foam, thereby stabilizing the heat resistance of the injection product.
  • the heat resistance of the foam can be expressed as excellently as the heat resistance of the high heat resistant resin. That is, it is possible to provide a foam having excellent foaming uniformity and heat resistance as the object of the present invention is only by using a large amount of high heat-resistance resin chips than the masterbatch chips.
  • the foamed masterbatch chip and the high heat resistant resin chip may be blended in a weight ratio of 15 to 30: 70 to 85. More preferably, the foamed masterbatch chip and the high heat resistant resin chip may be blended in a weight ratio of 18 to 25: 75 to 82.
  • the masterbatch chip is included in less than the above range, stable foaming may not occur and a problem may occur that a foam excellent in the desired foaming uniformity cannot be provided. There may be a problem that heat resistance is not sufficiently expressed.
  • the blending of the step (S20) of forming the foam composition is preferably performed through dry blending (Dry Blending).
  • the masterbatch chip and the high heat-resistant resin chip can be efficiently mixed to form a uniform composition.
  • the step (S30) of molding the foam by processing the foam composition is performed by injecting the foam from the foam composition formed in the step S20.
  • the molding of the foam may be performed through methods commonly used within the art.
  • the injection time may be 300 to 500 seconds. More preferably, it may be 320 to 460 seconds.
  • An ethylene octene copolymer (EOR) and a propylene-based elastomer (PBE) were mixed to form a polyolefin-based elastomer substrate, and 10 parts by weight of paraffinic oil and 5 parts by weight of glass bubbles were added with respect to 100 parts by weight of the polyolefin-based elastomer substrate. Then, the composition was prepared by mixing with a kneader at 120° C. for 10 minutes. The composition was pressed at 180° C. to form a molded body.
  • Example 1 (parts by weight)
  • Example 2 (parts by weight)
  • Example 3 (parts by weight)
  • Example 4 (parts by weight)
  • Example 5 (parts by weight) Comparative Example 1 (parts by weight) polyolefin elastomer Ethylene octene copolymer (EOR) 20 20 20 20 20 20 20 100 Proprene-Based Elastomer (PBE) 80 80 80 80 80 - paraffinic oil 10 10 10 10 10 10 10 - glass bubble 5 10 15 20 25 -
  • Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Specific gravity (g/cc) 0.831 0.795 0.757 0.728 0.749 0.861 Hardness (@22°C) (Type A) 57 60 64 67 71 56 Elongation (%) >900 >900 >900 >900 >900 >900 >900 >900
  • Polymer resins, foaming agents and additives according to Tables 3 to 6 were mixed using a kneader and then extruded to form foamed masterbatch (M/B) chips.
  • the kneader temperature was set to 90° C.
  • the foaming agent was secondarily added.
  • the masterbatch chip and the high heat-resistance resin chip were dry-blended in a weight ratio according to Tables 3 and 4 below to form a foaming composition.
  • a foam was molded by injection from the foam composition at a mold temperature of 180° C. for 5 minutes.
  • Example 6 The same procedure as in Example 6 was carried out, except that the foaming composition was formed by mixing all of the polymer resin, the foaming agent and the additive according to the following Tables 7 and 8 at once.
  • Example 6 Example 7 Example 8 Example 9 Example 10
  • Example 11 Example 12 Foam Masterbatch chip polymer resin isotactic polypropylene (Vistamaxx 6202) isotactic polypropylene (Vistamaxx 6202 isotactic polypropylene (Vistamaxx 6202 isotactic polypropylene (Vistamaxx 6202 isotactic polypropylene (Vistamaxx 6202 isotactic polypropylene (Vistamaxx 6202 isotactic polypropylene (Vistamaxx 6202 blowing agent Azodicarbonamide (AC 3000) azodicarbonamide (AC 3000) azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (
  • Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Foamed Masterbatch Chips polymer resin isotactic polypropylene (Vistamaxx 6202) isotactic polypropylene (Vistamaxx 6202) isotactic polypropylene (Vistamaxx 6202, Vistamax 3980FL) isotactic polypropylene (Vistamaxx 6202, Vistamax 3980FL) isotactic polypropylene (Vistamaxx 6202, Vistamax 3980FL) isotactic polypropylene (Vistamaxx 6202, Vistamax 3980FL) blowing agent azodicarbonamide (AC 3000) azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) Azodicarbonamide (AC 3000) metal oxide zinc oxide (ZnO) zinc oxide (ZnO) zinc oxide (
  • Example 6 (parts by weight)
  • Example 7 (parts by weight)
  • Example 8 (parts by weight)
  • Example 9 (parts by weight)
  • Example 10 (parts by weight)
  • Example 11 (parts by weight)
  • Example 12 (parts by weight)
  • Foamed Masterbatch Chips polymer resin 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Example 13 (parts by weight)
  • Example 14 (parts by weight)
  • Example 15 (parts by weight)
  • Example 16 (parts by weight)
  • Example 17 (parts by weight)
  • Example 18 (parts by weight)
  • Foamed Masterbatch Chips polymer resin 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Comparative Example 2 Comparative Example 3 Foamed Masterbatch Chips polymer resin isotactic polypropylene (Vistamaxx 6202) isotactic polypropylene (Vistamaxx 6202) blowing agent Azodicarbonamide (AC 3000) azodicarbonamide (AC 3000) metal oxide zinc oxide (ZnO) zinc oxide (ZnO) stearic acid St/A St/A crosslinking agent dicumyl peroxide (DCP) dicumyl peroxide (DCP) High heat-resistance resin chip Olefin block copolymer (Infuse 9807) Olefin block copolymer (Infuse 9807)
  • Comparative Example 2 parts by weight
  • Comparative Example 3 parts by weight
  • Foamed Masterbatch Chips polymer resin 100 100 blowing agent 12.5 12.5 metal oxide 5 5 stearic acid 2.5 2.5 crosslinking agent 10
  • the measurement was performed using a test piece prepared in the form of a cylinder having a diameter of 30 ⁇ 0.05 mm and a thickness of about 10 mm.
  • the specimen was placed between parallel metal plates, a spacer corresponding to 50% of the thickness of the specimen was inserted, and the specimen was compressed and left in an air circulation oven maintained at 50 ⁇ 0.1° C. for 6 hours. Then, the test piece was taken out from the compression device, aged at room temperature for 30 minutes, and then the thickness was measured.
  • the compression set (Cs) was calculated by the following formula.
  • t 0 initial thickness of the test piece
  • t f thickness when cooled after testing
  • t s thickness of spacer bar
  • the elasticity of the foam was measured by a ball drop method using a test piece having a thickness of 10 mm or more.
  • a specimen having a size of 70 ⁇ 70 (mm 2 ) of the foam prepared in Examples and Comparative Examples was immersed in water heated to a high temperature and taken out after a certain period of time to measure the size of the specimen.
  • the measured values are shown in Table 9 below.
  • Example 6 Example 7
  • Example 8 Example 9
  • Example 10 Example 11
  • Example 12 Foaming ratio (%) 144 - - - - - - - Hardness (Type C, 22.2°C) 38 - - - - - - Density (g/cc) 0.255 - - - - - - -
  • Tensile strength (kg/cm 2 ) 14.1 - - - - - - - - -
  • Tear strength kg/cm
  • 9.4 - - - - - - - - Elongation (%) 399.8 Permanent compression reduction rate (%)
  • Elasticity (%, 22.2°C) 60 Torque Minimum (ML, dNm) 0.117 0.102 0.123 0.128 0.104 0.069 0.174 Torque maximum value (MH, dNm) 0.714 0.193 0.871 0.915 0.660 0.174 1.542 Torque change (dNm) 0.597 0.091
  • Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Foaming ratio (%) - - 154 151 151 151 Hardness (Type C, 22.2°C) - - 50 48 52 50 Density (g/cc) - - 0.219 0.227 0.234 0.229 Tensile strength (kg/cm 2 ) - - 19.5 18.4 17.4 18.1 Tear strength (kg/cm) - - 11.9 11.6 10.1 11.5 Elongation (%) - - 482.7 406.5 291.8 348.9 Permanent compression reduction rate (%) - - 66 51 36 44 Elasticity (%, 22.2°C) - - 56 56 60 60 60 Torque Minimum (ML, dNm) 0.197 0.191 - - - - Torque maximum value (MH, dNm) 1.784 1.661 - - - - Torque change (dNm) 1.587 1.470 - - - - t 10 (min) 58" 53"
  • the foamed masterbatch chip contained 7.5 parts by weight of a foaming agent based on 100 parts by weight of the polymer resin; 17.5 parts by weight of the additive. In this case, it can be seen that physical properties such as expansion ratio, hardness, tensile strength, and tear strength are more excellent than in Example 6. In addition, it can be seen that a stable injection molding process is possible, and the appearance of the foam is also excellent.
  • Comparative Example 2 it can be seen that the hardness, tensile strength, tear strength, etc. are shown as low values, which is relatively poor.
  • Comparative Example 3 it can be seen that the hardness and strength are excellent, but the density is high and the lightness is poor.
  • FIG. 2 is an external image of a foam according to a preferred embodiment of the present invention.
  • FIG. 2A is an external image of the foam according to Example 1
  • FIG. 2B is an external image of the foam according to Example 11.
  • FIG. 2 It can be seen that both of FIGS. 2A and 2B are well formed without damage such as distortion or the like.
  • Examples 6 to 8 have better molding stability than Examples 9 to 14, and it can be seen that the appearance of the foam is excellent.
  • Example 6 horizontal line 70 70 67 64 vertical line 70 70 67 62 Comparative Example 2 horizontal line 70 59 51 52 vertical line 70 63 53 52
  • FIG. 12 it can be seen that when the foamed masterbatch chip of the present invention is mixed with the high heat-resistance resin chip to form a foam, there is an effect of improving heat resistance.
  • Figure 3 is an image comparing the appearance of the foam of Example 6 and Comparative Example 2.
  • Example 6 (a), (b), and (c) the length of the foam is maintained without a significant difference, whereas in Comparative Example 2, it can be seen that the horizontal and vertical lengths are greatly reduced. From this, it can be seen that the foam of the present invention has relatively excellent heat resistance.
  • Example 15 Example 16 Example 17
  • Example 18 (a) (b) (c) (a) (b) (c) (a) (b) (c) (a) (b) (c) (a) (b) (c) (a) (b) (c) (c) Injection time (sec) 360 390 420 360 390 420 360 390 420 Foaming ratio (%) 152 154 - 150 151 149 - 151 - 151 - - Hardness (Type C, 22.2°C) 50 50 - 49 48 49 - 52 - 50 - - Density (g/cc) 0.221 0.219 - 0.226 0.227 0.229 - 0.234 - 0.229 - - Tensile strength (kg/cm 2 ) 19.5 19.5 - 19.7 18.4 19.0 - 17.4 18.1 - - Tear strength (kg/cm) 12.0 11.9 - 13.6 11.6 12.5 - 10.1 - 11.5 - - Elong
  • Example 16 it can be seen that a relatively stable molding process is possible compared to Examples 15, 17, and 18, and the physical properties of the foam are also excellent.
  • the appearance of the foam is excellent when injected in 360 seconds.
  • the permanent compression ratio has a relatively low value, and thus the heat resistance is excellent.

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Abstract

La présente invention concerne une composition élastomère à base de polyoléfine, à faible densité, sans mousse, qui permet d'obtenir un produit léger sans opération d'expansion, de sorte que des contaminants tels que des gaz nocifs ne sont pas générés au cours d'une opération d'expansion, et il n'y a aucun risque de retrait, ce qui a pour effet d'assurer une excellente stabilité dimensionnelle. Une composition de moussage et un procédé de moulage d'un corps expansé l'utilisant selon la présente invention peuvent minimiser la dénaturation d'un additif dans des conditions de haute température, ce qui permet de mettre en œuvre l'expansion d'une manière stable, et elle aura ainsi pour effet consistant à stabiliser l'uniformité d'expansion du corps expansé. En outre, la présente invention donne un corps expansé qui est expansé après une réticulation suffisante et est donc susceptible de présenter d'une manière excellente la résistance souhaitée à la chaleur.
PCT/KR2020/014704 2020-05-13 2020-10-27 Composition, article moulé formé à partir de cette dernière et procédé de moulage l'utilisant WO2021230439A1 (fr)

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Citations (6)

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