WO2002018482A2 - Mousse de resine polyolefinique extrudee - Google Patents

Mousse de resine polyolefinique extrudee Download PDF

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Publication number
WO2002018482A2
WO2002018482A2 PCT/JP2001/007310 JP0107310W WO0218482A2 WO 2002018482 A2 WO2002018482 A2 WO 2002018482A2 JP 0107310 W JP0107310 W JP 0107310W WO 0218482 A2 WO0218482 A2 WO 0218482A2
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WO
WIPO (PCT)
Prior art keywords
foam
weight
resin
parts
component
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Ceased
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PCT/JP2001/007310
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English (en)
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WO2002018482A3 (fr
WO2002018482A9 (fr
Inventor
Seiji Takahashi
Naochika Kogure
Takashi Kitahama
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JSP Corp
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JSP Corp
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Priority to AU2001280177A priority Critical patent/AU2001280177A1/en
Priority to US10/038,897 priority patent/US6541533B2/en
Publication of WO2002018482A2 publication Critical patent/WO2002018482A2/fr
Publication of WO2002018482A9 publication Critical patent/WO2002018482A9/fr
Publication of WO2002018482A3 publication Critical patent/WO2002018482A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/03—Extrusion of the foamable blend
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/04—Foams characterised by their properties characterised by the foam pores
    • C08J2205/05—Open cells, i.e. more than 50% of the pores are open
    • 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
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers

Definitions

  • This invention relates to extruded polyolefin resin foam used in cushion material, packaging material, sound absorbing material, water absorbing material, anti- vibration material, and various kinds of industrial filters, etc.
  • the open cell foams made of synthetic resins known to the prior art include urethane foams, foam rubber, and ethylene-vinyl acetate copolymer foams, etc. These foams, because they are flexible and exhibit good processability, have been used in such applications as cleaning sponges, shock absorbing materials, cushion materials, sound absorbing materials, and various industrial filters. Nevertheless, applications for these open " cell extruded foams have been limited due to their inferiority in terms of chemical resistance (acid resistance, alkali resistance, etc.) and weatherability. Furthermore, urethane foams and foam rubber are very difficult to recycle back to raw materials, while ethylene-vinyl acetate copolymer foams are problematic because of their large amount of foul odor during manufacture.
  • Polyolefin resins exhibit very outstanding chemical resistance and weatherability, as well as outstanding recyclability. Accordingly, the problems noted above can be overcome if the open cell extruded foam is made of a polyolefin resin.
  • open cell polyolefin resin foams Prior to develop open cell polyolefin resin foams.
  • Art is known, for example, for subjecting a closed cell polyolefin resin foam to pinhole processing to form open cell foam.
  • open cell polyolefin resin foams obtained by simply subjecting closed cell foams made from polyethylene resin or polypropylene resin base material to pinhole processing exhibit high permanent compression set, and do not have sufficient shock-absorbing properties to stand up under prolonged use.
  • a foam is disclosed wherein for 0 to 50 parts by weight of a polyolefin resin are used 100 to 50 parts by weight of a costly ionomer resin.
  • the extrusion pressure is high, wherefore heat generation at the die is severe, making it very difficult to obtain good open cell extruded foams exhibiting a high expansion ratio and high thickness.
  • the molten resin setting temperature (hereinafter called the foaming temperature) must be regulated within a narrow range during extrusion foaming in order to obtain the open cell extruded foam, making stable manufacture difficult.
  • a foam wherein for 100 parts by weight of a polyolefin resin, 60 to 150 parts by weight of an ionomer resin are used, but this is small rod-shaped foam having a cross-sectional area of 0.1 cm 2 or so which is used as core material in sealers used in window frames and the like, for example.
  • an open cell extruded foam is described wherein a mixture of two or three or more polyolefin resins having different melting points is used as the base resin. More specifically, in this patent application, an open cell extruded foam is described, the main component whereof is a mixed polymer configured by a component consisting of a polyolefin resin, and a component consisting either of one or two or more
  • polymers selected from a group made up of ethylene- ⁇ , or ⁇ unsaturated carboxylic acid copolymers (but excluding ionomers), olefin elastomers, styrene elastomers, and ethylene-vinyl acetate copolymers, or of such mixed polymer to which a heat reversible crosslinked polymer has been added.
  • the range of suitable foaming temperatures wherewith the open cell foam can be stably obtained is narrow, and, if the foaming temperature is higher than the suitable foaming temperatures, the foam contracts, making it difficult to obtain foam having the desired expansion ratio and thickness, whereas, if the foaming temperature is lower than the suitable foaming temperatures, the closed cell foaming ratio rises and the desired open cell foam is not obtained. If an attempt is made to obtain an open cell foam of high foaming expansion ratio, moreover, the cell wall thickness of the foam becomes thin, it becomes very difficult to retain the shape of the open cell foamed cell walls during extrusion foaming, and good foam is difficult to obtain.
  • extruded open cell foam of uniform physical product properties, with a high expansion ratio, and uniform cell diameter, particularly such extruded open cell foam that is thick.
  • the present invention is an extruded polyolefin resin open cell foam having an open cell foaming ratio of 50% or higher.
  • the base resin of the foam of the present invention has as its main component a mixed polymer consisting of 4.5 to 75 parts by weight of a component A consisting of an ethylene ionomer resin, 0.5 to 30 parts by weight of a component B consisting of a polyolefin resin
  • a melting point exceeding 120°C and 20 to 95 parts by weight of a component C consisting of one or two or more polymers selected from a group of ethylene-propylene rubbers , styrene elastomers , and polyethylene resins having
  • the component B consisting of the polyolefin resin
  • having a melting point exceeding 120°C should be one or two or more mixed resins selected from among polypropylene resin, linear low-density polyethylenes , and polyethylene resins having a density of 940 kg/m 3 or greater.
  • the polyethylene resin having a melting point of 120°C or lower in component C should be one or two or more mixed resins selected from among low-density polyethylenes,
  • An anti-shrinking agent can be added to the base resin, whereupon the amount added should be 0.1 to 15 parts by weight for 100 parts by weight of the basic resin.
  • the extruded open cell foam of the present invention should have a density of 15 to 200 kg/m 3 and thickness of 0.5 to 200 mm, which can be configured either as sheet-form foam or plank-form foam.
  • the shape is not limited to a flat shape, however, and rod-shaped foam can also be configured.
  • the form of the rod shapes may be either one with a hollow cross-section or solid cross-section, with a density of 15 to 100 kg/m 3 and an area of cross-section (perpendicular to direction of extrusion) of 0.7 cm 2 or greater being preferred.
  • the extruded polyolefin resin foam of the present invention is an extruded polyolefin resin open cell foam having an open cell foaming ratio of 50% or higher.
  • the base resin for this extruded open cell foam has as its main component a mixed polymer consisting of 4.5 to 75 parts by weight of a component A consisting of an ethylene ionomer resin, 0.5 to 30 parts by weight of a component B consisting of a polyolefin resin having a melting point
  • component C consisting of one or two or more polymers selected from a group of ethylene-propylene rubbers, styrene elastomers, and polyethylene resins having melting
  • a closed cell foam is formed at a resin extrusion temperature wherewith a foam is obtained, and the targeted foam cannot be obtained even by making the extrusion temperature higher in an effort to obtain open cell foam.
  • the component A exceeds 75 parts by weight, on the other hand, heat generation in the die becomes severe, and it is very difficult to obtain extruded open cell foam of high thickness and high expansion ratio.
  • component B When component B is less than 0.5 parts by weight , moreover, the shape retention effect in the cells configuring the foam becomes small and it becomes very difficult to obtain extruded open cell foam exhibiting a high expansion ratio and high wall thickness having uniform physical properties, and, particularly in a thick foam, cell uniformity is lost and giant cells are generated.
  • component B exceeds 30 parts by weight, on the other hand, foamability is impaired, and good extruded open cell foam cannot be obtained.
  • component C When component C is less than 20 parts by weight, there will be little quantity of component of low melt tension in the vicinity of the foaming temperature, making it very difficult to obtain extruded open cell foam.
  • component C exceeds 95 parts by weight, on the other hand, closed cell foam forms readily, and it becomes very difficult to obtain extruded open cell foam.
  • the extruded polyolefin resin foam of the present invention has an open cell foaming ratio of 50% or higher.
  • the open cell foaming ratio is less than 50%, certain effects manifest by the peculiar functions exhibited by the extruded open cell foam, such as restorability after repeated stress, cushioning properties, flexibility, sound absorption, water absorption, and gas permeability, are lessened, and it becomes difficult to deal with an open cell foam in terms of function and physical properties .
  • the open cell foaming ratio of the extruded open cell foam in the present invention moreover, is meant not just a value for a portion of the foam, but an average value for the foam overall.
  • the open cell foaming ratio should be 70% or higher and preferably 80% or higher. When the open cell foaming ratio is 70% or higher, the foam becomes extremely soft to the touch, and clearly differs from foam having an open cell foaming ratio below 70%.
  • the open cell foaming ratio in the present invention is measured as noted below, in accordance with ASTM D-2856- 70 (procedure C) .
  • the true volume Vx (cm 3 ) of the measurement specimen is found using an air pycnometer, the apparent volume Va (cm 3 ) of the measurement specimen is found from the outer dimensions thereof, and the open cell foaming ratio (%) is calculated by formula 1 below.
  • true volume Vx is meant the sum of the volume of the resin and the volume of the closed cell portion in the measurement specimen.
  • Open cell foaming ratio (%) ⁇ (Va -Vx)/(Va - W/p) ⁇ x 100 where W is the weight (g) of the measurement specimen, and
  • p is the density (g/cm 3 ) of the base resin configuring the foam.
  • the dimensions of the measurement specimen is 25 mm longitudinally, 25 mm laterally, and 40 mm in thickness.
  • the extruded foam of the present invention as described subsequently, can be configured in a sheet-form, plank-form, or rod-shaped form, in every which case samples are formed by cutting to the prescribed dimensions. In such cases, if a specimen having dimensions matching the dimensions of the measurement specimen described above cannot be obtained from one cutout sample, then multiple cutout samples are combined to prepare one measurement specimen. If, for example, one cutout sample were 25 mm longitudinally, 25 mm laterally, and 20 mm in thickness, then two cutout samples having these dimensions would be stacked together to prepare a measurement specimen measuring 25 mm longitudinally, 25 mm laterally, and 40 mm in thickness.
  • the main component in the base resin of the extruded open cell foam of the present invention is a mixed polymer configured of a component A consisting of an ethylene ionomer resin, a component B consisting of a polyolefin
  • resin having a melting point exceeding 120°C and a component C consisting of one or two or more polymers selected from a group of ethylene-propylene rubbers, styrene elastomers, and polyethylene resins having melting
  • the mixed polymer is the main component in the base resin is meant that the mixed polymer is contained in an amount that at least exceeds 50 wt.% of the base resin configuring the extruded open cell foam, but preferably 75 wt.% or more, and even more preferably 90 wt.% or more.
  • a conventionally known resin or rubber or the like can be mixed, within a range of up to but not including 50 wt.%, in the base resin of the extruded open cell foam of the present invention, among which those with which a polymer composition of a denatured polyolefin polymer such as an ethylene-maleic acid anhydride-ethyl acrylate terpolymer or ethylene- butene-1 copolymer and a hydroxyl group containing polymer such as hydroxyl group ended polybutadiene hydrogenation product, methacrylic acid 2-hydroxyethyl graft ethylene- butene-1 copolymer, or low molecular weight polyolefin polyol are mixed, wherewith the crosslinked structure is weakened by heating, having so-called heat reversible crosslinked structures, being particularly preferred because therewith compressive elasticity is enhanced, and outstanding extruded open cell foam exhibiting little permanent compress
  • ethylene ionomer resin configuring component A of the base resin in the present invention is meant a metal salt crosslinked compound of a copolymer between an
  • ethylene monomer and an ⁇ or ⁇ unsaturated carboxylic acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, or cinnamic acid, etc.
  • metal salts examples include alkali metal salts, alkali earth metal salts, typical metal salts, and transition metal salts.
  • Metal salt crosslinked compounds of these polymers form a type of crosslinked structure between molecules by the ionic bonding force of the metal ions, whereby physical properties like those of crosslinked molecules are exhibited at room temperature, but processability like that of a non-crosslinked polymer is exhibited at the high temperatures where extrusion molding is possible.
  • ethylene ionomer resins include ionomer resins wherein crosslinking is effected by metal ions between the molecules of such copolymers as ethylene-acrylic acid copolymer, ethylene- acrylic acid-methylacrylate copolymer, ethylene-acrylic a ⁇ id-ethylacrylate copolymer, ethylene-methacrylic acid- methylacrylate copolymer, ethylene-methacrylic acid- ethylacrylate copolymer, or ethylene-methacrylic acid copolymer, etc.
  • the ethylene ionomer resin limited to a single resin, but may be one wherein two or more ethylene ionomer resins have been mixed.
  • the component B comprising the polyolefin resin having
  • a melting point exceeding 120°C that configures the base resin in the present invention may be a polyethylene resin, polypropylene resin, or polybutene resin or the like.
  • polyethylene resin polyethylenes having a density of 940 kg/m 3 or greater, and linear low-density polyethylenes and the like may be cited.
  • polyolefin resin in component B of the resins noted above, either one type or a mixture of two or more types of polypropylene resin linear low-density polyethylene or polyethylene having a density of 940 kg/m 3 or greater is preferable.
  • the range of suitable foaming temperatures during extraction foaming is broadened and it becomes possible to stably manufacture good extruded open cell foam.
  • ethylene on the one hand, and an ⁇ -olefin having 3 to 12 carbons or the like, on the other, wherein the ethylene component is contained in an amount of 50 wt.% or more.
  • Specific examples thereof that may be cited include high- density polyethylenes, medium-density polyethylenes, linear low-density polyethylenes, ethylene-anhydrous maleic acid copolymers, ethylene-butene copolymers, ethylene-vinyl alcohols, and ethylene-glycidyl methacrylates , etc,
  • the polyethylene resin is not limited to a single resin but may be one wherein two or more types of polyethylene resin have been mixed.
  • the component B is meant a propylene homo-polymer or a copolymer between propylene, on the one hand, and another monomer component on the other, wherein the propylene component is contained in an amount that is 50 wt.%.or greater.
  • That copolymer may be a random copolymer, a block copolymer, or a graft copolymer.
  • Examples of the other monomer component configuring the copolymer that may be cited include ethylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3,4- dimethyl-1-butene, 1-pentene, and 3-methyl-1-hexene, etc.
  • the polypropylene resin is not limited to a single resin but may be one wherein two or more polypropylene resins have been mixed.
  • component B in the present invention not only may a polyethylene resin, polypropylene resin, or polybutene resin or the like be used singly, but a mixture of two or more types thereof may be used.
  • the component C configuring the base resin in the present invention is one or two or more types of polymer selected from among the group of ethylene-propylene rubbers, styrene elastomers, and polyethylene resins having a
  • the polyethylene resin having a melting point of 120° or lower configuring the component C is an ethylene homo- polymer or a copolymer between ethylene, on the one hand,
  • ethylene component is contained in an amount of 50 wt.% or greater.
  • Specific examples thereof that may be cited include low-density polyethylenes, medium-density polyethylenes, linear low-density polyethylenes, very low-density polyethylenes, ethylene- anhydrous maleic acid copolymers, ethylene-butene copolymers, ethylene-vinyl alcohols, ethylene-glycidyl
  • this polyethylene resin is not limited to a single resin, but use may be made of one wherein two or more types have been mixed.
  • these polyethylene resins one type or a mixed resin of two or more types selected from among the low-density polyethylenes,
  • ethylene- ⁇ or ⁇ unsaturated carboxylic acid copolymers but excluding ionomers
  • ethylene-vinyl acetate copolymers is particularly to be preferred.
  • acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and cinnamic acid together with alkyl esters and the like thereof may be cited, of which, from the perspective of general- purposefulness, acrylic acid, methacrylic acid, and alkyl esters thereof are to be preferred.
  • ethylene-acrylic acid copolymers More specifically, ethylene-acrylic acid copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene- methacrylic acid copolymers, ethylene-methyl methacrylate copolymers, and ethylene-ethyl methacrylate copolymers and
  • the content ratio for the ⁇ or ⁇ unsaturated carboxylic acid in the ethylene- ⁇ or ⁇ unsaturated carboxylic acid copolymer noted above should be 2 to 50 wt.%, with 10 to 40 wt.% being particularly to be preferred.
  • the vinyl acetate content prefers to be 5 to 50 wt.%. Because the difference in viscosity with the component A is appropriate, extruded open cell foam can be obtained with even greater stability in the extraction process.
  • the melting point of the polyolefin resin configuring the component B and of the polyethylene resin configuring the component C is made the temperature at the apex of a peak found from test pieces subjected to a certain heat treatment according to the heat flux DSC curve based on JIS K7121 (1987). When two or more peaks appear, the temperature at the apex of the main peak having the largest peak area is made the melting point .
  • the density of the polyethylene resin of the component B is found according to JIS K7112 (1980).
  • Citable examples for the styrene propylene rubber configuring the component C include ethylene-propylene copolymers and ethylene-propylene-diene copolymers.
  • Citable examples for the ethylene elastomer configuring the component C include styrene-butadiene- styrene block copolymers (SBS), styrene-isoprene-styrene block copolymers (SIS), styrene-ethylene copolymers, styrene-ethylene-propylene copolymers, SBS hydrogenation product, and SIS hydrogenation product, etc.
  • additives such as anti-shrinking agents, foam regulators, weather-resisting agents, UN radiation absorbers, UV radiation reflectors, infrared radiation absorbers, infrared radiation reflectors, flame retardants, lubricants, colorants, thermal stabilizers, anti-oxidants, crystallization nucleating agents, inorganic fillers, and rubbers, etc.
  • additives such as anti-shrinking agents, foam regulators, weather-resisting agents, UN radiation absorbers, UV radiation reflectors, infrared radiation absorbers, infrared radiation reflectors, flame retardants, lubricants, colorants, thermal stabilizers, anti-oxidants, crystallization nucleating agents, inorganic fillers, and rubbers, etc.
  • an anti-shrinking agent be added to 100 parts by weight of the base resin because thereby it is possible to obtain good foam, especially foam exhibiting a high expansion ratio and high thickness.
  • this anti-shrinking agent examples include esters of a fatty acid having 10 or more but preferably from 15 to 25 carbons and a polyvalent alcohol having 3 to 7 hydroxyl groups, fatty acid amines having 10 or more but preferably from 15 to 25 carbons, and fatty acid amides having 10 or more but preferably from 15 to 25 carbons, etc.
  • stearic acid, oleic acid, lauric acid, behenic acid, lignoceric acid, cerotic acid, heptaconic acid, montanic acid, melissic acid, and laccelic acid, etc. may be cited, while for the polyvalent alcohol having 3 to 7 hydroxyl groups, glycerin, diglycerin, triglycerin, erythritol, arabitol, xylitol, mannitol, sorbitol, and sorbitan may be cited.
  • the anti- shrinking agent moreover, a mixture of two or more anti- shrinking agents may also be used.
  • anti-shrinking agents include glyceryl monostearate, glyceryl monobehenate, glyceryl distearate, glyceryl tristearate, polyoxyethylene myristyl amine, polyoxyethylene palmitin amine, polyoxyethylene stearyl amine, lauric acid amide, myristic acid amide, palmitic acid amide, and stearic acid amide, etc.
  • foam regulator examples include fine powdered forms of such inorganic substances as talc, • silica, and clay, etc., and such carbonate or bicarbonate salts as alkali metal salts of polyvalent carboxylic acid such as sodium hydrogen tartrate, potassium hydrogen succinate, sodium citrate, potassium citrate, sodium bicarbonate, sodium carbonate, and sodium oxalate, etc., which prefer to be added in an amount of 0.01 to 10 parts by weight to 100 parts by weight of the base resin.
  • foaming agent used in the manufacture of the extruded open cell foam of the present invention either a physical foaming agent or a decomposing type foaming agent can be used, but the use of a physical foaming agent is preferred in order to obtain extruded open cell foam of high expansion ratio.
  • fatty hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane, normal hexane, isohexane, and cyclohexane, etc
  • chloro-hydrocarbons as methyl chloride and ethyl chloride
  • fluoro-hydrocarbons as 1, 1, 1,2-tetrafluoroethane and 1, 1-difluoroethane, etc
  • inorganic substances as carbon dioxide, nitrogen, and water, etc
  • azodicarbonamide and the like may be cited.
  • the foaming agents noted above can be used in mixtures of two or more, and a decomposing type foaming agent may be used together with a physical foaming agent and thus serve also to regulate the cell diameter.
  • the extruded open cell foam of the present invention prefers to have a density of 15 to 200 kg/m 3 and a thickness of 0.5 to 200 mm, configured either as sheet-form foam or plank-form foam.
  • this foam limited to a flat form, but may be configured as rod-shaped foam.
  • the form of the rod-shaped foam may be cross-sectionally hollow or cross-sectionally solid.
  • the sheet-form foam prefers to have a density of 15 to 200 kg/m 3 and better still 15 to 60 kg/m 3 , and a thickness of 0.5 mm or greater but less than 10 mm.
  • the width of the sheet-form foam prefers to be 45 cm or greater, and more preferably with 90 cm or greater, and with an upper limit for the width of 190 cm or so.
  • Sheet-form foam so configured exhibits outstanding flexibility and makes ideal packaging material. It is also possible to subject this foam to such processing as bag fabrication or thermoforming or the like, for use as bags, fruit trays, or other containers .
  • This foam can be used in a wide variety of applications including partitioning materials obtained by performing stamping processing or cutting processing on laminated sheet wherein materials exhibiting shape retention such as other polypropylene resin foam sheet or polystyrene resin foam sheet are integrally laminated, and packaging containers such as fruit packaging materials or precision instrument packaging containers exhibiting high shock-absorption obtained by thermoforming such laminated sheet .
  • the extruded open cell foam of the present invention is plank-form foam
  • the density prefers to be 15 to 100 kg/m 3 and the thickness 10 to 200 mm.
  • the width of the plank-form foam should be at least 8 cm, with 25 cm or greater being preferable, and with an upper limit on the width of 150 cm or so.
  • Plank-form foam so configured is ideal for shock absorbing pads, sound absorbing materials, and cushion materials and the like.
  • the plank-form foam of the present invention exhibits mild compressive strain (the deforming speed being slower than that of ordinary soft urethane), which property is an outstanding property deserving particular mention for applications such as cushion material.
  • This plank-form foam can be made into any desired shape, to suit the application, by stamping processing or cutting processing.
  • the density prefers to be 15 to 100 kg/m 3
  • the area of the cross-section perpendicular to the direction of extrusion prefers to be 0.7 cm 2 or greater and more preferably from 1 to 900 cm 2 .
  • the rod-shaped foam has a hollow cross-section, it is configured in a cylindrical shape, whereas when the rod- shaped foam has a solid cross-section, it is configured in a columnar shape.
  • the thickness and density of the extruded open cell foam are measured as described below. That is, for the thickness of the extruded open cell foam, the thickness of the foam is measured at ten points at equal intervals from one edge to the other edge in the width dimension, and the arithmetic mean of those ten points is taken.
  • the density of the extruded open cell foam the weight (g) of a test piece that is 5 cm longitudinally, 5 cm across, and the thickness of the foam is measured, the volume (cm 3 ) of the test piece is next found from the outer dimensions of the test piece, and the quotient obtained by dividing the weight (g) of the test piece by the volume thereof is converted to kg/m 3 units .
  • the extruded open cell foam of the present invention can be obtained by taking the base resin noted earlier, such additives as anti-shrinking agents or foaming regulators such as talc which are added as necessary, supplying those to an extruder, subjecting those materials to melting under heating and kneading, then supplying a foaming agent and forming a foaming molten resin mixture, then regulating the extrusion resin temperature, pressure inside the extrusion die, and discharge volume, etc. , and extruding the mixture from the die attached to the tip of the extruder into a low-pressure region and causing foaming.
  • additives as anti-shrinking agents or foaming regulators such as talc which are added as necessary
  • a known method can be adopted such as the method of dry-blending the mixture components, or the method of using a screw feeder of the like to introduce each of the mixture components from an extruder raw material supply port and mixing them together inside the extruder.
  • extruded open cell foam of various shapes can be manufactured, whether sheet-form foam, plank-form foam, or rod-shaped foam, etc. If a circular die is attached, for example, sheet-form foam can be obtained, whereas if a flat die is attached, plank-form foam can be obtained, and if a die having a hole matching the cross-sectional shape of the rod bodies is attached, rod-shaped foam can be obtained that is cylindrical or columnar or the like, but if a many- holed die is attached, cord-shaped foam or foam having a wide perpendicular cross-section at right angles to the direction of extrusion wherein multiple rod-shaped foam body side surfaces are fused together can be obtained, and if dies of different shape are attached then foam bodies having different cross-sectional shapes can be manufactured.
  • an apparatus may be installed wherewith the foaming molten resin mixture is accumulated between the extruder and the die or inside the die under conditions of high temperature and high pressure, and, after a prescribed volume has accumulated, that mixture is extruded from the die all at once using a movable ram.
  • an accumulator By installing an accumulator, the discharge speed can be increased dramatically, wherefore, even if the extruder is small, the foam of the present invention having high expansion ratio and high thickness can be obtained, especially foam that is plank-form or rod-shaped.
  • extruded open cell foam wherein the open cell foaming ratio is 50% or greater can be formed, as described above, by supplying the base resin and foaming agent and the like to an extruder, heating, melting, and kneading those materials to form a foaming molten resin mixture, and then adjusting the extrusion resin temperature to be within a suitable foaming temperature range. That is, the foaming molten resin mixture wherein the extrusion resin temperature has been adjusted to be within a suitable foaming temperature range exhibits visco-elasticity that resists the foaming power of the foaming agent, so that the mixture foams uniformly, and, at the stage where cell walls are formed, the component C consisting of the polyolefin resin having a melting point
  • the component B is also contained in the base resin, wherefore the molten viscosity enhancing effect due to the crystallization of the component B after foaming leads to an enhancement in the rigidity of the cells that configure the foam, that in turn results in reinforcing the cell shape retaining function of the component A, as a consequence whereof the suitable foaming temperature range wherein the extruded open cell foam is stably obtained is broadened.
  • the extrusion resin temperature prefers
  • extrusion resin temperature is below 100°C, the elastic force of the component A and the component C at the time of foaming will be too strong, whereupon it has possibility that extruded open cell foam having a high expansion ratio can not obtain it .
  • the open cell foaming ratio of the extruded open cell foam can be regulated by such methods as that of selecting the polymer in the component C in the base resin described earlier, that of adding a lubricant to the polymer of the component C, or that of adjusting the viscosity of the component C.
  • the open cell foaming ratio of the foam can be raised further by a secondary process such as one employing the method of subjecting the foam to a pin-hole process, piercing it with needles or the like, or one employing the method of destroying cell walls by expansion under heat, or by compression or the like.
  • a secondary process such as one employing the method of subjecting the foam to a pin-hole process, piercing it with needles or the like, or one employing the method of destroying cell walls by expansion under heat, or by compression or the like.
  • Ionomer Ethylene-methacrylic acid-acrylic-acid ester terpolymer metal salts cross-linked compound
  • HDPE High-density polyethylene
  • LLDPE Linear low-density polyethylene
  • PP Polypropylene homopolymer
  • LDPE Low-density polyethylene
  • VLDPE Linear very low-density polyethylene
  • the foaming temperature range is less than 5 kg/m 3 , and the variation in open cell foaming ratio across a temperature width of 3°C or more in the foaming temperature range is 5% or lower,
  • the average cell diameters given in the table are values arrived at by drawing a straight line crossing the entire thickness of the foam in the thickness dimension, based on photographs obtained from cross-sections perpendicular to the foam extrusion direction or width dimension, counting the number of cells intersecting that straight line, and dividing the foam thickness (mm) by the number of cells so obtained.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin B,” and 57 parts by weight of "resin H.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 3.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin B,” 28.5 parts by weight of "resin F,” and 28.5 parts by weight of "resin I.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 4.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 5.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 33.3 parts by weight of "resin A,” 16.7 parts by weight of "resin B,” 25 parts by weight of "resin F,” and 25 parts by weight of "resin I.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 6.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 40 parts by weight of "resin A,” 3 parts by weight of "resin B,” 28.5 parts by weight of “resin F,” and 28.5 parts by weight of "resin I”, and 8.7 parts by weight of isobutane were pressure-injected and kneaded into 100 parts by weight of the mixed resin inside the extruder.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 7.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A, " 5 parts by weight of "resin B,” 28.5 parts by weight of “resin F,” and 28.5 parts by weight of “resin I”, and 8.7 parts by weight of isobutane were pressure-injected and kneaded into 100 parts by weight of the mixed resin inside the extruder.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 8.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of “resin C,” 28.5 parts by weight of “resin F, “ and 28.5 parts by weight of “resin I”, and 8.7 parts by weight of isobutane were pressure-injected and kneaded into 100 parts by weight of the mixed resin inside the extruder.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 9.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin D,” 28.5 parts by weight of “resin F,” and 28.5 parts by weight of “resin I”, and 8.7 parts by weight of isobutane were pressure-injected and kneaded into 100 parts by weight of the mixed resin inside the extruder.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 10.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin E,” 28.5 parts by weight of “resin F,” and 28.5 parts by weight of “resin I”, and 8.7 parts by weight of isobutane were pressure-injected and kneaded into 100 parts by weight of the mixed resin inside the extruder.
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 11.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 29 parts by weight of "resin A, " 5 parts by weight of "resin B,” 37 parts by weight of "resin F,” and 29 parts by weight of "resin G.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 12.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin B,” 28.5 parts by weight of "resin F,” and 28.5 parts by weight of "resin J.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 13.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 38 parts by weight of "resin A,” 5 parts by weight of "resin B,” 28.5 parts by weight of "resin F,” and 28.5 parts by weight of "resin K.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 14.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 43 parts by weight of "resin A,” and 57 parts by weight of "resin G.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross- sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 15.
  • Embodiment 1 is recognized as exhibiting more outstanding manufacturing stability. Also, although the foam obtained in Comparative Example 1 is usable as a product, cell unevenness is observed very locally in the foam cross-section, wherefore the foam of Embodiment 1 exhibits more outstanding cell uniformity.
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 43 parts by weight of "resin A,” 28.5 parts by weight of "resin F,” and 28.5 parts by weight of "resin I.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 16.
  • Comparative Example 2 is a comparative example for Embodiment 3. With Comparative Example 2 , in a foaming
  • the foam obtained at a foaming temperature of 117°C or higher is the foam obtained at a foaming temperature of 117°C or higher.
  • Comparative Example 3 is a comparative example for Embodiment 7. With Comparative Example 3 , in a foaming
  • the foam obtained at a foaming temperature of 120°C or higher is the foam obtained at a foaming temperature of 120°C or higher.
  • Comparative Example 4 is a comparative example for Embodiment 11. With Comparative Example 4, in a foaming
  • Extruded plank-form extruded open cell foam was obtained with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 43 parts by weight of "resin A,” 28.5 parts by weight of "resin F,” and 28.5 parts by weight of "resin J.”
  • the density, open cell foaming ratio, average cell diameter, thickness, and width of the foam so obtained were measured, respectively, the foam cross-sectional cell uniformity and manufacturing stability were evaluated as noted above, and the results indicated, respectively, in Table 19.
  • Comparative Example 5 is a comparative example for Embodiment 12. With Comparative Example 5, in a foaming
  • the foam obtained at a foaming temperature of 119°C or higher the foam obtained at a foaming temperature of 119°C or higher.
  • Comparative Example 6 An attempt was made to obtain rod-shaped extruded open cell foam with the same conditions as in Embodiment 1 except in that 100 parts by weight of mixed resin were made by mixing 5 parts by weight of "resin B,” 67 parts by weight of "resin F,” and 28 parts by weight of "resin H,”
  • test pieces were made 50 mm longitudinally x 50 mm across x the thickness of the foam.
  • the test piece was subjected to 80,000 continuously repeated compressions to 50% of the thickness thereof, at a speed of 60 revolution/minute. Then the thickness of the test piece was measured, 30 minutes and 24 hours after the compression was released, respectively, and the percentage of defection set by repeated compressions was calculated therefrom.
  • the extruded polyolefin resin foam of the present invention exhibits a high expansion ratio, uniform cell diameter, and outstanding mechanical properties, and is well suited for use as cushion material, packaging material, sound absorbing material, water absorbing material, anti- vibration material, and various types of industrial filter.

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Abstract

Mousse extrudée épaisse qui est une résine polyoléfinique à cellules ouvertes, utilisée comme matière d'amortissement et d'emballage et analogue, et qui possède des propriétés physiques uniformes, un taux d'expansion élevé et un diamètre uniforme des cellules. La mousse extrudée à cellules ouvertes selon la présente invention présente un taux de moussage à cellules ouvertes de 50 % ou plus. La résine de base de cette mousse est constituée principalement d'un polymère mélangé constitué de 4,5 à 75 parties en poids d'un constituant A qui est une résine ionomère d'éthylène, de 0,5 à 30 parties en poids d'un constituant B qui est une résine polyoléfinique ayant un point de fusion supérieur à 120 °C, et de 20 à 95 % en poids d'un constituant C qui est composé d'un ou plusieurs polymères choisis dans un groupe comportant les caoutchoucs d'éthylène-propylène, les élastomères styrène, et les résines de polyéthylène ayant des points de fusion de 120 °C ou moins (le constituant A + le constituant B + le constituant C = 100 parties en poids). Divers types d'additifs tels que des agents anti-retrait peuvent être ajoutés à cette résine extrudée.
PCT/JP2001/007310 2000-08-29 2001-08-27 Mousse de resine polyolefinique extrudee Ceased WO2002018482A2 (fr)

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Cited By (8)

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WO2005021622A3 (fr) * 2003-08-25 2005-04-21 Dow Global Technologies Inc Mousse d'ecume durable de polymeres a olefines dispersees, procedes de fabrication de mousse et articles prepares a partir de cette mousse
WO2006036224A1 (fr) * 2004-09-24 2006-04-06 Kimberly-Clark Worldwide, Inc. Mousse thermoplastique a alveoles ouvertes, a faible densite, souple, elastique et absorbante
US7358282B2 (en) 2003-12-05 2008-04-15 Kimberly-Clark Worldwide, Inc. Low-density, open-cell, soft, flexible, thermoplastic, absorbent foam and method of making foam
US7361694B2 (en) 2004-02-27 2008-04-22 Dow Global Technologies Inc. Durable foam of olefin polymers, methods of making foam and articles prepared from same
US8158689B2 (en) 2005-12-22 2012-04-17 Kimberly-Clark Worldwide, Inc. Hybrid absorbent foam and articles containing it
US8357727B2 (en) 2004-02-27 2013-01-22 Dow Global Technologies Llc Durable foam of olefin polymers, methods of making foam and articles prepared from same
CN112194834A (zh) * 2020-09-30 2021-01-08 广德祥源新材科技有限公司 一种耐高温收缩的聚乙烯发泡片材及其制备方法
CN113845736A (zh) * 2021-09-18 2021-12-28 无锡会通轻质材料股份有限公司 一种tpv发泡料及高发泡倍率、高形状自由度的超轻质tpv发泡制品

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990014385A1 (fr) * 1989-05-16 1990-11-29 Toray Industries, Inc. Feuille continue en mousse reticulee par un faisceau d'electrons
DE59408978D1 (de) * 1993-07-28 2000-01-13 Alkor Gmbh Tiefziehfähige Folie, Verfahren zu deren Herstellung und Verwendung derselben

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7439276B2 (en) 2003-08-25 2008-10-21 Dow Global Technologies Inc. Froth and durable foam of dispersed olefin polymers, methods of making foam and articles prepared from same
EP2298832A1 (fr) * 2003-08-25 2011-03-23 Dow Global Technologies Inc. Mousse et mousse durable de polymères d'olefine dispersée, procédés de fabrication de mousse et articles préparés à partir de celles-ci
WO2005021622A3 (fr) * 2003-08-25 2005-04-21 Dow Global Technologies Inc Mousse d'ecume durable de polymeres a olefines dispersees, procedes de fabrication de mousse et articles prepares a partir de cette mousse
US7358282B2 (en) 2003-12-05 2008-04-15 Kimberly-Clark Worldwide, Inc. Low-density, open-cell, soft, flexible, thermoplastic, absorbent foam and method of making foam
US7456228B2 (en) 2004-02-27 2008-11-25 Dow Global Technologies Inc. Durable foam of olefin polymers, methods of making foam and articles prepared from same
US7361694B2 (en) 2004-02-27 2008-04-22 Dow Global Technologies Inc. Durable foam of olefin polymers, methods of making foam and articles prepared from same
US7812062B2 (en) 2004-02-27 2010-10-12 Dow Global Technologies, Inc. Durable foam of olefin polymers, methods of making foam and articles prepared from same
US8357727B2 (en) 2004-02-27 2013-01-22 Dow Global Technologies Llc Durable foam of olefin polymers, methods of making foam and articles prepared from same
US8686056B2 (en) 2004-02-27 2014-04-01 Dow Global Technologies Llc Durable foam of olefin polymers, methods of making foam and articles prepared from same
US7291382B2 (en) 2004-09-24 2007-11-06 Kimberly-Clark Worldwide, Inc. Low density flexible resilient absorbent open-cell thermoplastic foam
WO2006036224A1 (fr) * 2004-09-24 2006-04-06 Kimberly-Clark Worldwide, Inc. Mousse thermoplastique a alveoles ouvertes, a faible densite, souple, elastique et absorbante
US8158689B2 (en) 2005-12-22 2012-04-17 Kimberly-Clark Worldwide, Inc. Hybrid absorbent foam and articles containing it
CN112194834A (zh) * 2020-09-30 2021-01-08 广德祥源新材科技有限公司 一种耐高温收缩的聚乙烯发泡片材及其制备方法
CN112194834B (zh) * 2020-09-30 2023-04-28 广德祥源新材科技有限公司 一种耐高温收缩的聚乙烯发泡片材及其制备方法
CN113845736A (zh) * 2021-09-18 2021-12-28 无锡会通轻质材料股份有限公司 一种tpv发泡料及高发泡倍率、高形状自由度的超轻质tpv发泡制品

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