WO2014073774A1 - Composition pour joint de réfrigérateur - Google Patents

Composition pour joint de réfrigérateur Download PDF

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Publication number
WO2014073774A1
WO2014073774A1 PCT/KR2013/006935 KR2013006935W WO2014073774A1 WO 2014073774 A1 WO2014073774 A1 WO 2014073774A1 KR 2013006935 W KR2013006935 W KR 2013006935W WO 2014073774 A1 WO2014073774 A1 WO 2014073774A1
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WO
WIPO (PCT)
Prior art keywords
composition
refrigerator
block copolymer
refrigerator gasket
gasket
Prior art date
Application number
PCT/KR2013/006935
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English (en)
Korean (ko)
Inventor
이성율
Original Assignee
화인케미칼 주식회사
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Publication of WO2014073774A1 publication Critical patent/WO2014073774A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • C09K3/1021—Polyurethanes or derivatives thereof
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
    • F25D23/00—General constructional features

Definitions

  • the technology disclosed herein relates to a composition for a refrigerator gasket.
  • the refrigerator gasket is profile extrusion of a composition including additives such as fillers and stabilizers in a soft vinyl chloride resin (PVC), and at this time, the rubber is mixed with a ferrite inside the gasket to extrude and magnetize. It is made by inserting the rubber strip of the made strip shape and heat-sealed to a predetermined length.
  • PVC soft vinyl chloride resin
  • the vinyl chloride resin may generate dioxin upon incineration, and the plasticizer used to process the vinyl chloride resin has a problem when used in a product having high contact potential with food as an environmental hormone component. Therefore, Korean Patent Publication No. 2003-0042229 and Japanese Laid-Open Patent Publication No. 2000-017142 have been trying to substitute other materials for the manufacture of refrigerator gaskets instead of vinyl chloride.
  • the melting point of the polymer substrate includes a olefin block copolymer having a melting point of at least 100 °C or more, and a thermoplastic polyurethane, wherein the melt index (190 °C, 5kg) of the polymer substrate is 0.01 to A composition for a refrigerator gasket, which is 50 g / 10 minutes, is provided.
  • a blend of an olefin block copolymer, and a thermoplastic polyurethane as a polymer substrate wherein the melt index of the polymer substrate (190 °C, 5kg) is 0.01 to 50g / 10 minutes, Refrigerator gaskets with Shore A hardness of 60 to 80 are provided.
  • composition for a refrigerator gasket may include a blend of an olefin block copolymer (OCC) and a thermoplastic polyurethane (TPU) as a polymer substrate.
  • OCC olefin block copolymer
  • TPU thermoplastic polyurethane
  • olefin block copolymer generally refers to a block copolymer of a polymer comprising ethylene or propylene and an ⁇ -olefin having two or more carbon atoms.
  • the ⁇ -olefin is an olefin having 2 or more carbon atoms having a double bond at the terminal.
  • ethylene or propylene makes up the major mole fraction of the total polymer, ie ethylene or propylene makes up about 50 mol% or more of the total polymer. More preferably, ethylene or propylene comprises at least about 60 mol%, at least about 70 mol%, or at least about 80 mol% and the substantial remainder of the total polymer is preferably an ⁇ -olefin having at least 3 carbon atoms One or more other comonomers.
  • compositions for ethylene / octene copolymers, preferred compositions have an ethylene content of at least about 80 mole percent of the total polymer, and an octene content of about 10 to about 15 mole percent, preferably about 15 to about 20 mole percent of the total polymer. It includes.
  • the olefin block copolymer (olefin block copolymer, OBC) is a multiblock copolymer. They are preferably end-to-end relative to polymers comprising two or more chemically distinct zones or segments (referred to as "blocks") joined in a linear manner, ie polymerized ethylene- or propylene-functional groups rather than pendant or grafted A polymer comprising chemically separated units which are terminally bound.
  • the olefin block copolymer means ethylene / ⁇ -olefin multiblock copolymer or propylene / ⁇ -olefin multiblock copolymer.
  • the olefin block copolymer comprises ethylene or propylene in the form of polymerized one or more copolymerizable ⁇ -olefin comonomers, and multiblock copolymer having a plurality of blocks or segments of two or more polymerized monomer units having different chemical or physical properties. It is characterized by a chain.
  • the content of olefins and ⁇ -olefins in the OBC is the same as described for the ORC.
  • the multiblock copolymer can be represented by the formula:
  • n is an integer of 1 or more, preferably more than 1, such as 2, 3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or more ;
  • A represents a hard block or segment;
  • B represents a soft block or segment.
  • a and B are connected in a linear fashion rather than in a branched or star fashion.
  • a "hard” segment refers to a block of polymerized units in which ethylene or propylene is present in an amount of at least 95% by weight in some embodiments and at least 98% by weight in other embodiments.
  • the comonomer content in the hard segments is in some embodiments no more than 5% by weight of the total weight of the hard segments, in other embodiments no more than 2% by weight.
  • the hard segments are all or substantially all composed of ethylene or propylene.
  • a “soft” segment is a polymerized unit having a comonomer content of at least 5% by weight of the total weight of the soft segment in some embodiments, at least 8%, at least 10%, or at least 15% by weight in various other embodiments. Means block.
  • the comonomer content in the soft segment may be at least 20 wt%, at least 25 wt%, at least 30 wt%, at least 35 wt%, at least 40 wt%, at least 45 wt%, 50 wt% in various other embodiments. Or 60 wt% or more.
  • the olefin block copolymer may have a density of 0.85 to 0.91 g / cc, or 0.86 to 0.88 g / cc.
  • the olefin block copolymer has a melt index (MI) as measured by ASTM D1238 (190 ° C., 2.16 kg) of 0.01 to 30 g / 10 minutes, or 0.01 to 20 g / 10 minutes, or 0.1 to 10 g / 10 minutes, or 0.1 to 5.0 g / 10 minutes, or 0.1 to 3.0 g / 10 minutes, or 0.1 to 1.0 g / 10 minutes, or 0.3 to 0.6 g / 10 minutes.
  • MI melt index
  • olefin block copolymer is Infuse of Dow Chemical.
  • the OBC used in the technology disclosed herein has a high melting point of at least 100 ° C. or higher, and thus release extrusion can be performed.
  • most of the OBCs capable of release extrusion are difficult to use in refrigerator gaskets due to their low elasticity. Therefore, it is necessary to blend other materials to satisfy the low hardness and viscosity of the molten resin required for release extrusion for use in refrigerator gaskets.
  • it is preferable that the airtightness of the gasket is maintained even after opening and closing operations of tens of thousands to several hundred thousand times. This requires considerable high elasticity.
  • the styrene block copolymer may be blended, but when blending more than a predetermined amount to give elasticity, the surface roughness may be severe and adhesion may be reduced when the refrigerator is mounted.
  • thermoplastic polyurethane TPU is blended with OBC to improve low hardness, high elasticity, high viscosity properties during extrusion, as well as melt adhesion and surface properties.
  • TPU is prepared by the reaction of organic diisocyanates, polymeric diols and chain extenders, and has a unique elasticity due to the phase separation between the hard and soft segments.
  • Any TPU known in the art may be used in the compositions disclosed herein.
  • the TPU may be one selected from the group consisting of ester TPU, ether TPU, lactone TPU, and butadiene TPU.
  • the formulation of the TPU used in the composition is not particularly limited as long as it is thermoplastic, and is substantially prepared from a bifunctional component, and contains a small amount of over two functional components (eg, chain extenders such as glycerin, trimethylolpropane). May be used.
  • Preferred TPUs are polymers made from mixtures comprising organic diisocyanates, at least one polymeric diol and at least one difunctional chain extender.
  • the diisocyanate which is a raw material of the TPU required for the present composition includes an aromatic, aliphatic and alicyclic diisocyanate and a combination of two or more of these compounds.
  • Polymeric diols that can be used include those conventionally used in the art in the preparation of TPU elastomers.
  • the polymeric diols are responsible for the formation of soft segments of the resulting polymer, preferably having a number average molecular weight of 200 to 10,000 g / mol, preferably 400 to 4,000 g / mol, more preferably 500 to 3,000 g / mol Is in range.
  • polymeric diols examples include polyether diols, polyester diols, hydroxy terminated polycarbonates, hydroxy terminated polybutadienes, hydroxy terminated polybutadiene-acrylonitrile copolymers, dialkyl siloxanes and alkylene jades Seeds and the like.
  • Chain extenders can be aliphatic, cycloaliphatic or aromatic and are exemplified by diols, diamines and amino alcohols.
  • the polyurethane has a density of at least 0.90 g / cc, preferably at least 0.95 g / cc, more preferably at least 1.00 g / cc. In another embodiment, the polyurethane has a density of 1.30 g / cc or less, preferably 1.25 g / cc or less, more preferably 1.20 g / cc or less. In another embodiment, the polyurethane has a density of 0.90 g / cc to 1.30 g / cc, preferably 0.95 g / cc to 1.25 g / cc, more preferably 1.00 g / cc to 1.20 g / cc.
  • the polyurethane has a melt index of at least 0.1 g / 10 minutes, preferably at least 0.5 g / 10 minutes, more preferably at least 1 g / 10 minutes (ASTM D-1238-04, 190 ° C., 8.7 measured by kg). In another embodiment, the polyurethane has a melt index of 100 g / 10 min or less, preferably 50 g / 10 min or less, more preferably 20 g / 10 min or less (ASTM D-1238-04, 190 ° C., Measured by 8.7 kg).
  • the polyurethane has a melt index of 0.1 g / 10 minutes to 100 g / 10 minutes, preferably 0.5 g / 10 minutes to 50 g / 10 minutes, more preferably 1 g / 10 minutes to 20 g / 10 min (as measured by ASTM D-1238-04, 190 ° C., 8.7 kg).
  • the content of TPU in the polymer substrate including OBC and TPU is 10% by weight or more, preferably 20% by weight or more, 75% by weight or less, preferably 70% by weight or less, more preferably Is preferably at most 60% by weight, even more preferably at most 50% by weight.
  • the TPU may be included in 10 to 75% by weight. If the TPU is less than 10% by weight, the surface smoothness of the extrudate may be insufficient, and if it is more than 75% by weight, the release extrudability may be poor due to the decrease in the melt viscosity.
  • Compatibilizers may be further included to increase the miscibility of the OBC and TPU.
  • suitable compatibilizers include amine modified SBBS (amine modified styrene-butadiene / butylene-styrene, ex: Tuftec MP-10 from Asahi Kasei) or maleic anhydride (MAH) modified EPDM.
  • a lubricant such as stearic acid, ethylene bis stearamide, or a mixture of silica (SiO 2 ) is used to further lower the MI of the mixture or to increase the viscosity.
  • Fillers such as, MgCO 3 , CaCO 3 , Talc, Al (OH) 3 , Mg (OH) 2, and the like.
  • the polymer substrate may further include an ethylene copolymer (eg, EVA, EEA, EMA, EBA, ENMMA, POE, etc.) or a thermoplastic rubber (eg, 12-PB, SBC, TPEE, etc.) in addition to OBC and TPU.
  • the polymer substrate may further include a styrene block copolymer (SBC) in addition to the OBC and the TPU.
  • SBC styrene block copolymer
  • the composition for a refrigerator gasket may include, for example, an ethylene-octene block copolymer and a styrene-ethylene-butylene-styrene block copolymer as a polymer substrate.
  • ORC olefin random copolymers
  • LDPE low density polyethylene
  • the MI (190 ° C., 5 kg) of the final mixed composition is 0.01 to 50.0 g / 10 minutes, preferably 1.0 to 30.0 g / 10 minutes, more preferably 1.0 to 15.0 g / 10 minutes, even more preferably 1.0 to 10.0 g / 10 min is preferred.
  • the MI (190 °C, 5kg) of the final mixed composition is less than 0.01g / 10 minutes extruded too high pressure on the extruder high risk of damage to the machine and the extrusion amount is so small that it takes too long time to produce the desired product If the MI (190 °C 5kg) is more than 50g / 10 minutes, the viscosity of the mixture exiting the die of the extruder is low, the product is warped, the desired shape can not be obtained.
  • the refrigerator gasket may be manufactured by release extrusion of the composition for a refrigerator gasket disclosed herein.
  • Mixing of the composition for a refrigerator gasket may be performed in a manner known to those skilled in the art.
  • a mixer such as a Banbury mixer or booth kneader may be used. It is also possible to use conventional single or twin screw extruders for extrusion.
  • Refrigerator gasket manufactured using the composition for a refrigerator gasket disclosed in the present disclosure has excellent extrusion workability, excellent elasticity, excellent corner adhesiveness, no surface stickiness, and excellent surface smoothness.
  • the polymer base comprises a blend of an olefin block copolymer and a thermoplastic polyurethane, wherein the polymer has a melt index (190 ° C., 5 kg) of from 0.01 to 50 g / 10 minutes and a Shore A hardness of 60 to An 80-person refrigerator gasket is provided.
  • the olefin block copolymer is preferably a melting point of 100 °C or more.
  • the olefin block copolymer may be ethylene or a copolymer of propylene and octene.
  • a rubber magnet may be included in the body of the refrigerator gasket.
  • the rubber magnet may be a strip made by extruding and magnetizing a mixture of magnetic powder and rubber.
  • the content of TPU in the polymer substrate is 10% by weight or more, preferably 20% by weight or more, 75% by weight or less, preferably 70% by weight or less, more preferably. Preferably at most 60% by weight, even more preferably at most 50% by weight.
  • ORC-1 Olefin Random Copolymer (Ethylene-Butene), Density: 0.875 g / cc, MI (190 ° C, 2.15 kg): 2.0
  • OBC-1 Olefin Block Copolymer (Ethylene-Octene), Density: 0.870 g / cc, MI (190 ° C, 2.15 kg): 3.0
  • EVA-1 Ethylene Vinylacetate (VA 26%), MI (190 ° C 2.15 kg): 2.5
  • SEBS-1 styrene ethylene butylene styrene (Styrene Ethylene Buthylene Styrene, Styrene 30%), MI (190 °C, 2.15 kg): 4.0
  • TPU-1 ester-based TPU (Ester based TPU, Dongsung Hichem Grade 5080A)
  • TPU-2 Ether based TPU (Dongsung Hichem Grade 6180A)
  • TPU-3 lactone-based TPU (Lactone based TPU, Dongsung Hichem Grade 4080A)
  • Extrusion workability After adjusting the cylinder temperature to 170 ° C. in an extruder in which a die of a gasket shape is combined with an extruder having a cylinder diameter of 100 mm and a L / D of 36: 1, extrude the mixtures of the comparative examples and the examples. Immediately after the extrudate comes out through the die, it passes through a chamber equipped with a freezer (set at a temperature of 100 °C and a pass time of 20 seconds) to obtain the desired shape and comprehensively judge the extrudeability.
  • a freezer set at a temperature of 100 °C and a pass time of 20 seconds
  • Corner adhesiveness Make the specimens 5mm thick and 100mm long, and contact the two specimens with both surfaces of the double-sided heater with a temperature of 250 °C to melt the surface, remove the heaters, and stick the specimens together for 1 second, 2 seconds, 3 A second, 4 second, and 5 second release was followed by grading the grades A, B, C, D, and E, depending on how quickly the adhesive was fixed.
  • the refrigerator gasket manufactured by releasing and extruding a composition for a refrigerator gasket using OBC and TPU as the polymer substrate at the same time has excellent compression workability, but has surface characteristics, shape retention, It has excellent corner adhesiveness and has very suitable properties as a gasket.
  • Comparative Example 5 generally exhibited excellent physical properties but lacked surface smoothness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Gasket Seals (AREA)

Abstract

L'invention concerne une composition pour un joint de réfrigérateur qui comprend un copolymère bloc d'oléfines dont le point de fusion est de 100 °C ou plus, et un mélange de polyuréthanne thermoplastique en tant que substrat polymère, l'indice de fusion du substrat polymère (190 °C, 5 kg) étant situé dans la plage comprise entre 0,01 et 50 g/10 min.
PCT/KR2013/006935 2012-11-06 2013-08-01 Composition pour joint de réfrigérateur WO2014073774A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2012-0124666 2012-11-06
KR1020120124666A KR101263701B1 (ko) 2012-11-06 2012-11-06 냉장고 가스켓용 조성물

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WO2014073774A1 true WO2014073774A1 (fr) 2014-05-15

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WO (1) WO2014073774A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109931744A (zh) * 2017-12-19 2019-06-25 Aqua株式会社 冰箱门封条
CN112477722A (zh) * 2020-12-02 2021-03-12 广东英得尔实业发展有限公司 一种tpu冰箱外壳
WO2022135516A1 (fr) * 2020-12-25 2022-06-30 广东美的白色家电技术创新中心有限公司 Matériau d'étanchéité et son procédé de préparation, et bande d'étanchéité

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KR101388194B1 (ko) * 2013-09-13 2014-04-23 화인케미칼 주식회사 냉장고 가스켓용 조성물
KR102243436B1 (ko) * 2016-11-17 2021-04-21 주식회사 엘지화학 에틸렌 비닐아세테이트 공중합체 및 이로부터 제조된 성형품
KR102244068B1 (ko) * 2016-11-17 2021-04-22 주식회사 엘지화학 에틸렌 비닐아세테이트 공중합체의 제조 방법

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KR20100132234A (ko) * 2009-06-09 2010-12-17 주식회사 엘지화학 내이행성이 뛰어난 냉장고 도어 가스켓용 염화비닐 수지 조성물
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109931744A (zh) * 2017-12-19 2019-06-25 Aqua株式会社 冰箱门封条
CN112477722A (zh) * 2020-12-02 2021-03-12 广东英得尔实业发展有限公司 一种tpu冰箱外壳
WO2022135516A1 (fr) * 2020-12-25 2022-06-30 广东美的白色家电技术创新中心有限公司 Matériau d'étanchéité et son procédé de préparation, et bande d'étanchéité

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