WO2016121142A1 - 発泡体 - Google Patents

発泡体 Download PDF

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Publication number
WO2016121142A1
WO2016121142A1 PCT/JP2015/065567 JP2015065567W WO2016121142A1 WO 2016121142 A1 WO2016121142 A1 WO 2016121142A1 JP 2015065567 W JP2015065567 W JP 2015065567W WO 2016121142 A1 WO2016121142 A1 WO 2016121142A1
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WO
WIPO (PCT)
Prior art keywords
mass
polypropylene resin
foam
paper
density polyethylene
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2015/065567
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English (en)
French (fr)
Inventor
敬通 松下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kankyokeieisogokenkyusho Co Inc
Original Assignee
Kankyokeieisogokenkyusho Co Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kankyokeieisogokenkyusho Co Inc filed Critical Kankyokeieisogokenkyusho Co Inc
Priority to KR1020167028217A priority Critical patent/KR101922648B1/ko
Priority to BR112016025074-5A priority patent/BR112016025074B1/pt
Priority to CA2944780A priority patent/CA2944780C/en
Priority to US15/300,927 priority patent/US10100177B2/en
Priority to EP15880036.7A priority patent/EP3305836B1/en
Priority to JP2016524613A priority patent/JP5985787B1/ja
Priority to PCT/JP2015/065567 priority patent/WO2016121142A1/ja
Publication of WO2016121142A1 publication Critical patent/WO2016121142A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/38—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation
    • B65D81/3813—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation rigid container being in the form of a box, tray or like container
    • B65D81/3823—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents with thermal insulation rigid container being in the form of a box, tray or like container formed of different materials, e.g. laminated or foam filling between walls
    • 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
    • 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
    • C08J9/12—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 physical blowing agent
    • C08J9/125—Water, e.g. hydrated salts
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    • 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
    • C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02—Cellulose; Modified cellulose
    • 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
    • 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—Polyethylene
    • 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
    • C08J2203/10—Water or water-releasing compounds
    • 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
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • 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
    • C08J2423/02—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
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/02—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
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • 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
    • C08J2453/00—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2453/02—Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • 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
    • C08J2497/00—Characterised by the use of lignin-containing materials
    • C08J2497/02—Lignocellulosic material, e.g. wood, straw or bagasse
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • 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

Definitions

  • the present invention relates to a foam suitably used as a heat insulating material for cold insulation of a cold insulation container.
  • a foam for example, a foam comprising 10 to 40% by weight of a paper powder component or a vegetable powder component, 25 to 40% by weight of a starch component as an auxiliary agent, and 35 to 50% by weight of a polypropylene component.
  • the body is known (see, for example, Patent Document 1).
  • the foam is made of government-made postcard paper or general wastepaper as the paper powder component, and can be combusted as general waste after use. Moreover, the said foam is supposed to be able to acquire the outstanding cold insulation effect with respect to this cold storage space by covering the inside six surfaces of cardboard boxes, such as a cardboard box, and making the inside into a cold insulation space.
  • Patent Document 1 may not be able to obtain a sufficient cooling effect, and a foam having an excellent cooling effect is desired.
  • an object of the present invention is to provide a foam having a further excellent cold insulation effect as a cold insulation heat insulating material for a cold insulation container.
  • the foam of the present invention comprises 50.0 to 70.0% by mass of paper pellets, which are a mixture of fine paper powder and hydrophilic polymer, and a foamable polypropylene resin and other polypropylene resins.
  • Polypropylene resin group consisting of 22.0 to 34.0% by mass, low density polyethylene resin 3.0 to 20.0% by mass, and compatibilizer of polypropylene resin and polyethylene resin 0.6 to 2.0% by mass
  • the paper pellets comprise 30.0 to 50.0% by mass of fine paper powder having a particle size of 30 to 200 ⁇ m and 50.0 to 70.0% by mass of a hydrophilic polymer.
  • the polypropylene resin group is characterized in that it comprises 5.0 to 11.0% by mass of expandable polypropylene resin and 17 to 23% by mass of other polypropylene resins.
  • the foam of the present invention includes the paper pellet, the propylene resin group, the low-density polyethylene resin, and a compatibilizer (hereinafter simply abbreviated as “compatibilizer”) of the polypropylene resin and the polyethylene resin.
  • a compatibilizer hereinafter simply abbreviated as “compatibilizer”
  • the paper fine powder can be mixed with the polypropylene resin group and the low-density polyethylene resin by mixing with the hydrophilic polymer to form paper pellets.
  • the polypropylene resin group and the low density polyethylene resin can be mixed uniformly by mixing in the presence of the compatibilizing agent.
  • the foam of the present invention is superior to the conventional foam by being foam-molded including the polypropylene resin group having the mass in the range and the low-density polyethylene resin having the mass in the range. A cold insulation effect can be obtained.
  • the foam of the present invention it is difficult to uniformly mix the paper fine powder with the polypropylene resin group and the low-density polyethylene resin when the particle size exceeds 200 ⁇ m. Moreover, it is technically difficult to make the particle size of the paper fine powder less than 30 ⁇ m.
  • the paper fine powder is less than 30.0% by mass relative to the total amount of the paper pellets, the amount of the polypropylene resin group and the low-density polyethylene resin cannot be sufficiently reduced, and the foam after use Can not be combusted as general waste. Further, if the paper fine powder is more than 50.0% by mass with respect to the total amount of the paper pellets, it is difficult to mix the paper fine powder with the polypropylene resin group and the low density polyethylene resin.
  • the hydrophilic polymer When the hydrophilic polymer is less than 50.0% by mass with respect to the total amount of the paper pellets, the ratio of paper becomes excessive when pelletized with the paper fine powder, and the pellets are divided into the polypropylene resin group and the pellets. It becomes an obstacle when mixing with low density polyethylene resin.
  • the hydrophilic polymer is more than 70.0% by mass with respect to the total amount of the paper pellets, and the amount of the hydrophilic polymer is excessive with respect to the paper fine powder having the mass within the above range. It becomes an obstacle when mixing with low density polyethylene resin.
  • the polypropylene resin group When the polypropylene resin group is less than 22.0% by mass, an excellent cooling effect cannot be obtained when mixed with the low-density polyethylene resin having the mass within the above range. Moreover, the polypropylene resin group cannot be mixed with the low-density polyethylene resin having a mass within the above range if it exceeds 34.0% by mass.
  • the polypropylene resin group is composed of 5.0 to 11.0% by mass of expandable polypropylene resin and 17 to 23% by mass of other polypropylene resins.
  • the expandable polypropylene resin is less than 5.0% by mass, it is difficult to obtain a foam. Further, even if the foamable polypropylene resin exceeds 11.0% by mass, no further effect can be obtained.
  • the foamable polypropylene resin is a polypropylene resin that has uniform and independent bubbles by having high melt tension and strain hardening.
  • the low density polyethylene resin is less than 3.0% by mass, an excellent cooling effect cannot be obtained when mixed with the polypropylene resin group having the mass within the above range. Moreover, the said low density polyethylene resin cannot be mixed with the said polypropylene resin group of the mass of the said range in more than 20.0 mass%.
  • the low-density polyethylene resin is defined in JIS K 6899-1: 2000, and the density is defined as polyethylene having a density of 0.910 or more and less than 0.930 in the former JIS K6748: 1995.
  • the compatibilizer is less than 0.6% by mass, the polypropylene resin group having the mass within the above range and the low-density polyethylene resin cannot be mixed. Further, even if the compatibilizing agent exceeds 2.0% by mass, no further effect can be obtained.
  • the foam of the present invention comprises, for example, a plurality of rod-like foams, and each of the plurality of rod-like foams has a skin layer without bubbles formed on the surface thereof, and a foam formed by coating the skin layer on the inside thereof. A surface layer, and the surfaces of the skin layer are closely bonded to each other.
  • the foam of the present invention can be formed into a plurality of rod-like foams to form a uniform foam layer with a predetermined length and a predetermined diameter. Moreover, the foam of this invention can obtain the outstanding mechanical strength, when the several rod-shaped foam is closely bonded between the surfaces of the said skin layer. Also, at this time, the rod-shaped foam is coated with a skin layer having no air bubbles, and has a foam layer inside thereof, so that an excellent heat insulating effect can be obtained. In addition, an excellent cooling effect can be obtained.
  • the paper pellet is 53.9 to 68.0% by mass
  • the polypropylene resin group is the expandable polypropylene resin 6.0 to 10.5% by mass
  • the other polypropylene resin It is preferably 17.9 to 22.0% by mass, and the total is 26.4 to 30.5% by mass
  • the low-density polyethylene resin is preferably 4.0 to 16.0% by mass.
  • the compatibilizing agent is preferably a hydrogenated styrene thermoplastic elastomer.
  • the hydrogenated styrene thermoplastic elastomer include hydrogenated styrene-ethylene-butylene-styrene block copolymers (for example, trade name: Tuftec H1602 manufactured by Asahi Kasei Chemicals Corporation).
  • the foam of the present invention has a pigment of 1.0 parts by mass or less relative to 100 parts by mass of the paper pellet, the polypropylene resin group, the low density polyethylene resin, and the compatibilizer. May be added, and the pigment can be colored to a desired color, for example, white.
  • the foam 1 of this embodiment has a plurality of rod-like bodies 2 extending in the axial direction.
  • the foam 1 of the present embodiment actually has dimensions of a width of 1 m, a length of 1 m, and a thickness of 30 mm, but FIG. 1 shows a part thereof enlarged.
  • each rod-like body 2 has a two-layer structure of a skin layer 3 and a foam layer 4, and a large number of bubbles 5 are present in the foam layer 4.
  • each rod-like body 2 is in a state in which the surface skin layers 3 are closely bonded to each other.
  • gap 6a is formed between each rod-shaped body 2, and it becomes the groove
  • the foam 1 of the present embodiment comprises 50.0 to 70.0% by mass of paper pellets, preferably 53.9 to 68.0% by mass, and 22.0 to 34.0% by mass of polypropylene resin group, preferably 26 0.4 to 30.5% by mass, low-density polyethylene resin 3.0 to 20.0% by mass, preferably 4.0 to 16.0% by mass, and a compatibilizer of polypropylene resin and polyethylene resin 0.6 It is obtained by mixing with 2.0% by mass and foam molding.
  • the paper pellet is a mixture of 30.0 to 50.0% by mass of fine paper powder having a particle size in the range of 30 to 200 ⁇ m and 50.0 to 70.0% by mass of a hydrophilic polymer.
  • the paper fine powder is mixed with the hydrophilic polymer in advance to form paper pellets.
  • the paper fine powder is obtained by roughly crushing, for example, about 2 mm square of damaged paper such as roll paper that has become industrial waste, and finely crushing the particle size to 30 to 200 ⁇ m using a vertical roller mill (not shown).
  • a vertical roller mill (not shown).
  • starch such as industrial starch can be used.
  • the polypropylene resin group comprises a foamable polypropylene resin of 5.0 to 11.0% by mass, preferably 6.0 to 10.5% by mass, and another polypropylene resin of 17 to 23% by mass, for example, 17.9 to 22%. It consists of 0% by mass.
  • the foam 1 may contain additives such as pigments, antioxidants and fungicides.
  • the pigment include a white pigment such as titanium dioxide, and the white pigment may be mixed with a polyethylene resin to form a master batch.
  • the additive such as the pigment can be contained in the paper pellet, for example.
  • An extruder 10 shown in FIG. 3 includes a hopper 11 for charging raw materials and a cylinder 13 having a biaxial screw 12 inside, and a die 14 having a plurality of small holes is provided at the downstream end of the cylinder 13. Yes.
  • the cylinder 13 is provided with a plurality of heaters 15 for heating the inside of the cylinder 13 in the axial direction of the cylinder 13.
  • a motor 16 that rotates the screw 14 is provided on the upstream side of the cylinder 13.
  • paper pellets 17, polypropylene resin group pellets 18, low-density polyethylene resin pellets 19 and a compatibilizer (not shown) as raw materials are charged into the extruder 10 from the hopper 11.
  • the supply amount of the raw material is adjusted by a raw material supply device (not shown), and is introduced into the hopper 11.
  • the compatibilizing agent may be blended in advance in either the polypropylene resin group pellet 18 or the low density polyethylene resin pellet 19 or may be added independently.
  • the raw material charged into the hopper 11 is supplied into the cylinder 13, heated by the heater 15 while being stirred by the two screws 12 in the cylinder 13, and melt mixed.
  • raw material paper pellets 17, polypropylene resin group pellets 18, and low density polyethylene resin pellets 19 are kneaded, and the paper fine powder, starch, polypropylene resin group, low density polyethylene resin, The solubilizer is mixed.
  • the raw material in the cylinder 13 is melted by being heated by the heater 15 and conveyed to the downstream side while being kneaded by the screw 12.
  • the molten mixture of paper fine powder, starch, polypropylene resin group, low density polyethylene resin, and compatibilizer is uniformly kneaded, and the paper fine powder is uniformly diffused throughout the mixture.
  • water is added to the melt-kneaded raw material by supplying water stored in the water tank 22 from the water supply channel 21 to the inside of the cylinder 13, and bubbles 5 are generated by vaporizing the added water.
  • the water can be added, for example, in the range of 2.0 to 10.0 parts by mass with respect to 100 parts by mass of the raw material.
  • the raw material melted and kneaded in the cylinder 13 is extruded to the outside through a die 14 composed of a plurality of small holes to form a plurality of rod-shaped foams 2.
  • the foam 5 is expanded and foamed due to expansion of the internal bubbles 5, and as a result, rod-like foaming occurs.
  • the skin layer 3 and the foam layer 4 are formed.
  • the raw materials forming the skin layer 3 are still in a molten state immediately after being extruded from the die 14, so that the adjacent rod-shaped foams 2 are The foam 1 is formed by tightly bonding through the skin layer 3.
  • a thickness adjusting roller 20 is provided on the downstream side of the die 14 of the extruder 10, and the thickness adjusting roller 20 is a foaming interval between the metal rollers disposed above and below and the roller passing between the rollers. The thickness of the foam 1 is adjusted by the elastic force pressed against the body 1.
  • the foam 1 is cooled while the thickness is made constant by the thickness adjusting roller 20, conveyed to the downstream side, and cut to a desired length.
  • Example 1 In Example 1, 68% by mass of paper pellets, 26.4% by mass of polypropylene resin group, 4.0% by mass of low-density polyethylene resin (trade name: L719, manufactured by Ube Maruzen Polyethylene Co., Ltd.) and a compatibilizer (Asahi Kasei) Chemicals Co., Ltd., trade name: Tuftec H1062) 0.8% by mass and white pigment (Toyocolor Co., Ltd., trade name: high concentration titanium oxide masterbatch TET 1TA538 WHT-FD) 0.8% by mass Then, using the extruder 10 shown in FIG. 3, 3.0% by mass of water was added to the total amount of the raw material and foamed to produce the foam 1 shown in FIG.
  • the paper pellet contains 22.0% by mass of paper fine powder having an average particle size of 100 ⁇ m and 46.0% by mass of industrial starch, based on the total amount of the raw materials.
  • the ratio of the fine paper powder to the total amount of the paper pellets is 32.4% by mass, and the ratio of the industrial starch is 67.6% by mass.
  • the said polypropylene resin group is 8.5 mass% of expandable polypropylene resins (made by Nippon Polypro Co., Ltd., brand name: New Former), and a normal polypropylene resin (made by Nippon Polypro Co., Ltd., products) with respect to the total amount of the above raw materials. Name: FY-6) 17.9% by mass.
  • the white pigment is composed of 70% by mass of titanium oxide and 30% by mass of low density polyethylene resin.
  • the foam 1 of this Example 1 had 22% by mass of the fine paper powder, 46% by mass of industrial starch, 26.4% by mass of the polypropylene resin group, and 4.0% by mass of the low-density polyethylene resin. And 0.8% by mass of a compatibilizing agent and 0.8% by mass of a white pigment.
  • Example 2 a cold insulating container in which the foam 1 obtained in Example 1 is disposed on the six inner surfaces of a corrugated cardboard box having an inner size of 170 mm ⁇ 149 mm ⁇ 144 mm is prepared, and 2 kg of dry ice is accommodated in the cold insulating container. Then, the change with time of the remaining weight of dry ice was measured. The results are shown in FIG.
  • Example 2 In Example 2, 56.1% by mass of paper pellets, 28.5% by mass of polypropylene resin group, 14.6% by mass of low-density polyethylene resin (trade name: Petrocene 221 manufactured by Tosoh Corporation), and a compatibilizing agent (Asahi Kasei Chemicals Co., Ltd., trade name: Tuftec H1062) 0.8% by mass as a raw material, and using the extruder 10 shown in FIG. The foam 1 shown in FIG. 1 was created by molding.
  • the paper pellet contains 18.2% by mass of fine paper powder having an average particle size of 100 ⁇ m and 37.9% by mass of industrial starch, based on the total amount of the raw materials.
  • the ratio of the paper fine powder to the total amount of the paper pellets is 32.3 mass%, and the ratio of the industrial starch is 67.7 mass%.
  • the said polypropylene resin group is 8.5 mass% of expandable polypropylene resins (made by Nippon Polypro Co., Ltd., brand name: New Former), and a normal polypropylene resin (made by Nippon Polypro Co., Ltd., products) with respect to the total amount of the above raw materials. Name: VS700) 20.0 mass%.
  • the foam 1 of this example had 18.2% by mass of the fine paper powder, 37.9% by mass of industrial starch, 28.5% by mass of the polypropylene resin group, and 14.6% of low-density polyethylene resin.
  • the composition contains 0.8% by mass of a compatibilizing agent and 0.8% by mass.
  • Example 2 a cold insulating container in which the foam 1 obtained in Example 2 is disposed on the inner six surfaces of a cardboard box having an inner size of 170 mm ⁇ 149 mm ⁇ 144 mm is prepared, and 2 kg of dry ice is accommodated in the cold insulating container. Then, when the change with time of the remaining weight of dry ice was measured, the same performance as the foam 1 of Example 1 could be obtained.
  • Example 3 In Example 3, 53.9% by mass of paper pellets, 30.5% by mass of the polypropylene resin group, 14.0% by mass of low-density polyethylene resin (trade name: L719, manufactured by Ube Maruzen Polyethylene Co., Ltd.), a compatibilizing agent (Asahi Kasei Chemicals Corporation, trade name: Tuftec H1062) 0.8% by mass and white pigment (Toyocolor Co., Ltd., trade name: high concentration titanium oxide masterbatch TET 1TA538 WHT-FD) 0.8% by mass
  • the foam 1 shown in FIG. 1 was created by using the extruder 10 shown in FIG. 3 and adding 3.0% by mass of water to the raw material to perform foam molding.
  • the paper pellets contain 17.5% by mass of paper fine powder having an average particle size of 100 ⁇ m and 36.4% by mass of industrial starch, based on the total amount of the raw materials.
  • the ratio of the fine paper powder to the total amount of the paper pellets is 32.4% by mass, and the ratio of the industrial starch is 67.6% by mass.
  • the said polypropylene resin group is 10.5 mass% of expandable polypropylene resins (Nippon Polypro company make, brand name: New Former) with respect to the whole quantity of the said raw material, and normal polypropylene resin (Nippon Polypro company make, goods). Name: FY-6) 20.0 mass%.
  • the foam 1 of Example 3 had 17.5% by mass of the paper fine powder, 36.4% by mass of industrial starch, 30.5% by mass of the polypropylene resin group, and 14.0% of low-density polyethylene resin. It contains 0.8% by mass of a compatibilizer and 0.8% by mass of a white pigment.
  • Example 3 a cold insulation container in which the foam 1 obtained in Example 3 is disposed on the inner six surfaces of a corrugated cardboard box having an inner dimension of 170 mm ⁇ 149 mm ⁇ 144 mm is prepared, and 2 kg of dry ice is accommodated in the cold insulation container. Then, when the change with time of the remaining weight of dry ice was measured, the same performance as the foam 1 of Example 1 could be obtained.
  • Example 4 In Example 4, 54.4% by mass of paper pellets, 28.0% by mass of a polypropylene resin group, 16.0% by mass of a low density polyethylene resin (trade name: L719, manufactured by Ube Maruzen Polyethylene Co., Ltd.), a compatibilizing agent (Asahi Kasei Chemicals Corporation, trade name: Tuftec H1062) 0.8% by mass and white pigment (Toyocolor Co., Ltd., trade name: high concentration titanium oxide masterbatch TET 1TA538 WHT-FD) 0.8% by mass
  • the foam 1 shown in FIG. 1 was created by using the extruder 10 shown in FIG. 3 and adding 3.0% by mass of water to the raw material to perform foam molding.
  • the paper pellet contains 17.6% by mass of fine paper powder having an average particle diameter of 100 ⁇ m and 36.8% by mass of industrial starch with respect to the total amount of the raw material.
  • the ratio of the fine paper powder to the total amount of the paper pellets is 32.4% by mass, and the ratio of the industrial starch is 67.6% by mass.
  • the polypropylene resin group is composed of 6.0% by mass of a foamable polypropylene resin (manufactured by Nippon Polypro Co., Ltd., trade name: New Former) and a normal polypropylene resin (manufactured by Nippon Polypro Co., Ltd. Name: FY-6) 22.0% by mass.
  • a foamable polypropylene resin manufactured by Nippon Polypro Co., Ltd., trade name: New Former
  • a normal polypropylene resin manufactured by Nippon Polypro Co., Ltd. Name: FY-6 22.0% by mass.
  • the fine paper powder 17.6% by mass, industrial starch 36.8% by mass, polypropylene resin group 28.0% by mass, and low density polyethylene resin 16.0%. It contains 0.8% by mass of a compatibilizer and 0.8% by mass of a white pigment.
  • Example 4 a cold insulation container in which the foam 1 obtained in Example 4 is disposed on the inner six surfaces of a corrugated cardboard box having an inner dimension of 170 mm ⁇ 149 mm ⁇ 144 mm is prepared, and 2 kg of dry ice is accommodated in the cold insulation container. Then, when the change with time of the remaining weight of dry ice was measured, the same performance as the foam 1 of Example 1 could be obtained.
  • water is appropriately supplied to 24% by weight of a paper powder component having a particle size of about 150 to 80 ⁇ m, 36% by weight of a starch component, and 40% by weight of a polypropylene resin component, and then kneaded thoroughly with a kneader and extruded. It is the one that was put into the machine and foamed. The results are shown in FIG.

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Abstract

　保冷容器の保冷用断熱材等として優れた保冷効果を備える発泡体を提供する。　発泡体１は、紙ペレット５０．０～７０．０質量％と、ポリプロピレン樹脂群２２．０～３４．０質量％と、低密度ポリエチレン樹脂３．０～２０．０質量％と、ポリプロピレン樹脂とポリエチレン樹脂との相溶化剤０．６～２．０質量％とを含む。紙ペレットは、３０～２００μｍの粒径を有する紙微粉体３０．０～５０．０質量％と、親水性高分子５０．０～７０．０質量％とを混合してなる。ポリプロピレン樹脂群は、発泡性ポリプロピレン樹脂５．０～１１．０質量％と、他のポリプロピレン樹脂１７～２３質量％とからなる。

Description

発泡体
　本発明は、保冷容器の保冷用断熱材等として好適に用いられる発泡体に関する。
　現在、保冷容器の保冷用断熱材等として、多くの種類の発泡体等が用いられている。このような発泡体として、例えば、１０～４０重量％の紙粉末成分又は植物性粉末成分と、補助剤として２５～４０重量％の澱粉成分と、３５～５０重量％のポリプロピレン成分とからなる発泡体が知られている（例えば、特許文献１参照）。
　前記発泡体は、前記紙粉末成分に官製葉書古紙又は一般古紙が用いられ、使用後は一般ゴミとして燃焼処理することができるとされている。また、前記発泡体は、ダンボール箱等の箱体内部六面を覆って内部を保冷空間とすることにより、該保冷空間に対して優れた保冷効果を得ることができるとされている。
特許第３３２３４８１号公報
　しかしながら、特許文献１記載の発泡体では、十分な保冷効果が得られないことがあり、さらに優れた保冷効果を備える発泡体が望まれる。
　本発明は、かかる事情に鑑み、保冷容器の保冷用断熱材等としてさらに優れた保冷効果を備える発泡体を提供することを目的とする。
　かかる目的を達成するために、本発明の発泡体は、紙微粉体と親水性高分子との混合物である紙ペレット５０．０～７０．０質量％と、発泡性ポリプロピレン樹脂と他のポリプロピレン樹脂とからなるポリプロピレン樹脂群２２．０～３４．０質量％と、低密度ポリエチレン樹脂３．０～２０．０質量％と、ポリプロピレン樹脂とポリエチレン樹脂との相溶化剤０．６～２．０質量％とを含む発泡体であって、前記紙ペレットは、３０～２００μｍの粒径を有する紙微粉体３０．０～５０．０質量％と、親水性高分子５０．０～７０．０質量％とを混合してなり、前記ポリプロピレン樹脂群は、発泡性ポリプロピレン樹脂５．０～１１．０質量％と、他のポリプロピレン樹脂１７～２３質量％とからなることを特徴とする。
　本発明の発泡体は、前記紙ペレットと、前記プロピレン樹脂群と、前記低密度ポリエチレン樹脂と、前記ポリプロピレン樹脂とポリエチレン樹脂との相溶化剤（以下、単に「相溶化剤」と略記する）とを原料とし、該原料を押出機のシリンダー内で溶融混練し、さらに水を添加して発泡成形することにより得ることができる。
　前記紙微粉末は、前記親水性高分子と混合して紙ペレットとすることにより、前記ポリプロピレン樹脂群、前記低密度ポリエチレン樹脂と混合することができる。また、前記ポリプロピレン樹脂群と、前記低密度ポリエチレン樹脂とは、前記相溶化剤の存在下に混合することにより均一に混合することができる。
　このとき、本発明の発泡体は、前記範囲の質量の前記ポリプロピレン樹脂群と、前記範囲の質量の前記低密度ポリエチレン樹脂とを含んで発泡成形されていることにより、従来の発泡体よりも優れた保冷効果を得ることができる。
　本発明の発泡体において、前記紙微粉体は、粒径が２００μｍ超であるときには、前記ポリプロピレン樹脂群及び前記低密度ポリエチレン樹脂と均一に混合することが難しくなる。また、前記紙微粉体の粒径を３０μｍ未満とすることは技術的に難しい。
　前記紙微粉体は、前記紙ペレットの全量に対して、３０．０質量％未満では、前記ポリプロピレン樹脂群及び前記低密度ポリエチレン樹脂の量を十分に低減することができず、使用後の発泡体を一般ゴミとして燃焼処理することができない。また、前記紙微粉体は、前記紙ペレットの全量に対して、５０．０質量％超では、前記ポリプロピレン樹脂群及び前記低密度ポリエチレン樹脂に混合すること自体が難しくなる。
　前記親水性高分子は、前記紙ペレットの全量に対して、５０．０質量％未満では、前記紙微粉末とペレット化した際に紙の割合が過多となり、前記ペレットを前記ポリプロピレン樹脂群及び前記低密度ポリエチレン樹脂に混合する際の障害となる。また、前記親水性高分子は、前記紙ペレットの全量に対して、７０．０質量％超では、前記範囲の質量の前記紙微粉末に対して過多となり、前記ペレットを前記ポリプロピレン樹脂群及び前記低密度ポリエチレン樹脂に混合する際の障害となる。
　前記ポリプロピレン樹脂群は、２２．０質量％未満では、前記範囲の質量の前記低密度ポリエチレン樹脂と混合したときに優れた保冷効果を得ることができない。また、前記ポリプロピレン樹脂群は、３４．０質量％超では、前記範囲の質量の前記低密度ポリエチレン樹脂と混合することができない。
　ここで、前記ポリプロピレン樹脂群は、発泡性ポリプロピレン樹脂５．０～１１．０質量％と、他のポリプロピレン樹脂１７～２３質量％とからなる。前記発泡性ポリプロピレン樹脂が５．０質量％未満であるときには、発泡体を得ることが難しい。また、前記発泡性ポリプロピレン樹脂は１１．０質量％超としても、それ以上の効果を得ることはできない。
　前記発泡性ポリプロピレン樹脂とは、高い溶融張力と歪み硬化性を持つことにより、均一で独立した気泡が形成されるポリプロピレン樹脂である。
　前記低密度ポリエチレン樹脂は、３．０質量％未満では、前記範囲の質量の前記ポリプロピレン樹脂群と混合したときに優れた保冷効果を得ることができない。また、前記低密度ポリエチレン樹脂は、２０．０質量％超では、前記範囲の質量の前記ポリプロピレン樹脂群と混合することができない。
　前記低密度ポリエチレン樹脂とは、ＪＩＳ　Ｋ　６８９９－１：２０００に定義されており、その密度は、旧ＪＩＳ　Ｋ６７４８：１９９５において０．９１０以上～０．９３０未満のポリエチレンと定義されている。
　前記相溶化剤は、０．６質量％未満では、前記範囲の質量の前記ポリプロピレン樹脂群と前記低密度ポリエチレン樹脂とを混合することができない。また、前記相溶化剤は、２．０質量％超としても、それ以上の効果を得ることはできない。
　本発明の発泡体は、例えば、複数の棒状発泡体からなり、該複数の棒状発泡体はそれぞれ表面に形成された気泡のない表皮層と、前記表皮層に被覆されその内部に形成された発泡層とを備え、該表皮層の表面同士が密着結合してなる。
　本発明の発泡体は、まず、複数の棒状発泡体とすることにより、所定の長さ及び所定の径において、均質な発泡層を形成することができる。また、本発明の発泡体は、複数の棒状発泡体が前記表皮層の表面同士で密着結合していることにより、優れた機械的強度を得ることができる。また、このとき、前記棒状発泡体は、表面が気泡のない表皮層で被覆され、その内部に発泡層を備えることにより、優れた断熱効果を得ることができ、この結果、従来の発泡体よりも優れた保冷効果を得ることができる。
　本発明の発泡体は、前記紙ペレットが５３．９～６８．０質量％であり、前記ポリプロピレン樹脂群が、前記発泡性ポリプロピレン樹脂６．０～１０．５質量％と、前記他のポリプロピレン樹脂１７．９～２２．０質量％とからなり、これらを合わせて２６．４～３０．５質量％であり、前記低密度ポリエチレン樹脂が４．０～１６．０質量％であることが好ましい。
　また、本発明の発泡体において、前記相溶化剤は、水添スチレン系熱可塑性エラストマーであることが好ましい。前記水添スチレン系熱可塑性エラストマーとしては、例えば、水添スチレン－エチレン－ブチレン－スチレンブロックコポリマー（例えば、旭化成ケミカルズ株式会社製、商品名：タフテックＨ１６０２）を挙げることができる。
　さらに、本発明の発泡体は、前記紙ペレットと前記ポリプロピレン樹脂群と前記低密度ポリエチレン樹脂と、前記相溶化剤とを合わせて１００質量部にしたものに対し、１．０質量部以下の顔料を添加してもよく、前記顔料により所望の色、例えば白色に着色することができる。
本発明の発泡体の一部を切り出した状態を示す説明図。 図１の一部を拡大して切断面の状態を示す模式図。 本発明の発泡体の製造方法を示す説明図。 本発明の発泡体の保冷効果を示すグラフ。
　次に、添付の図面を参照しながら本発明の実施の形態についてさらに詳しく説明する。
　本実施形態の発泡体１は、図１に示すように、軸方向に延びる棒状体２が複数結合している。本実施形態の発泡体１は、実際には幅が１ｍ、長さが１ｍ、厚さが３０ｍｍの寸法を備えているが、図１ではその一部を拡大して図示している。
　各棒状体２は、図１及び２に示すように、表皮層３と発泡層４の２層構造となっており、発泡層４には多数の気泡５が存在している。また、各棒状体２は、表面の表皮層３同士が密着結合した状態となっている。また、図１に示すように、各棒状体２の間には空隙６ａが形成されており、発泡体１の表面では溝６ｂとなっている。
　本実施形態の発泡体１は、紙ペレット５０．０～７０．０質量％、好ましくは５３．９～６８．０質量％と、ポリプロピレン樹脂群２２．０～３４．０質量％、好ましくは２６．４～３０．５質量％と、低密度ポリエチレン樹脂３．０～２０．０質量％、好ましくは４．０～１６．０質量％と、ポリプロピレン樹脂とポリエチレン樹脂との相溶化剤０．６～２．０質量％とを混合し、発泡成形することにより得られる。
　前記紙ペレットは、３０～２００μｍの範囲の粒径を有する紙微粉体３０．０～５０．０質量％と、親水性高分子５０．０～７０．０質量％との混合物である。前記紙微粉体は、予め前記親水性高分子と混合されることにより、紙ペレットとされている。
　このとき、前記紙微粉体は、例えば産業廃棄物となったロール紙等の損紙を約２ｍｍ角程度に粗粉砕し、図示しない竪型ローラミルを使用して粒径を３０～２００μｍに微粉砕したものを用いることができる。また、前記親水性高分子としては、工業用デンプン等のデンプンを用いることができる。
　前記ポリプロピレン樹脂群は、発泡性ポリプロピレン樹脂５．０～１１．０質量％、好ましくは６．０～１０．５質量％と、他のポリプロピレン樹脂１７～２３質量％、例えば１７．９～２２．０質量％とからなる。
　さらに、発泡体１は、顔料、酸化防止剤、防かび剤等の添加剤を含んでいてもよい。前記顔料としては、例えば、二酸化チタン等の白色顔料を挙げることができ、該白色顔料はポリエチレン樹脂と混合されてマスターバッチを形成していてもよい。前記顔料等の添加剤は、例えば、前記紙ペレットに含有させておくことができる。
　次に、図３を参照して、本実施形態の発泡体１の製造方法について説明する。
　図３に示す押出機１０は、原料を投入するホッパー１１と、内部に２軸のスクリュー１２を有するシリンダー１３とを備え、シリンダー１３の下流端に複数の小孔からなるダイ１４が設けられている。また、シリンダー１３には、シリンダー１３の内部を加熱するヒーター１５がシリンダー１３の軸方向に向けて複数設けられている。また、シリンダー１３の上流側には、スクリュー１４を回転させるモーター１６が設けられている。
　本実施形態では、まず、ホッパー１１から原料としての紙ペレット１７とポリプロピレン樹脂群ペレット１８と低密度ポリエチレン樹脂ペレット１９と相溶化剤（図示せず）とを押出機１０に投入する。前記原料は、図示しない原料供給装置により供給量が調節されて、ホッパー１１に投入される。
　ここで、前記相溶化剤は、ポリプロピレン樹脂群ペレット１８又は低密度ポリエチレン樹脂ペレット１９のいずれかに予め配合されていてもよく、独立に投入されてもよい。
　ホッパー１１に投入された原料は、シリンダー１３内に供給され、シリンダー１３内で２本のスクリュー１２によって撹拌されながらヒーター１５によって加熱され、溶融混合される。この状態で、原料である紙ペレット１７と、ポリプロピレン樹脂群ペレット１８と、低密度ポリエチレン樹脂ペレット１９とが混練され、紙微粉体と、デンプンと、ポリプロピレン樹脂群と、低密度ポリエチレン樹脂と、相溶化剤とが混合される。このとき、シリンダー１３内の原料は、ヒーター１５に加熱されることにより溶融され、スクリュー１２によって混練されながら、下流側に運搬される。この結果、紙微粉体と、デンプンと、ポリプロピレン樹脂群と、低密度ポリエチレン樹脂と、相溶化剤との溶融混合物が均一に混練され、紙微粉体が混合物全体に均一に拡散される。
　次に、水タンク２２内に貯留されている水を給水路２１からシリンダー１３内部に供給することにより溶融混練された原料に水を添加し、添加された水を気化させることにより気泡５を発生させる。前記水は、前記原料１００質量部に対し、例えば２．０～１０．０質量部の範囲で添加することができる。
　次に、シリンダー１３内で溶融混練された原料は、複数の小孔からなるダイ１４から外部に押し出され、複数の棒状発泡体２を形成する。前記原料の溶融混練物は、ダイ１４から押し出され大気圧下に開放されると、内部の気泡５が膨張することにより前記発泡性ポリプロピレン樹脂が伸張されて発泡すると考えられ、この結果、棒状発泡体２において、表皮層３と発泡層４が形成されると考えられる。
　そして、隣り合う棒状発泡体２の表皮層３同士が互いに接触すると、表皮層３を形成する原料はダイ１４から押し出された直後にはまだ溶融状態にあるため、隣接する棒状発泡体２同士が表皮層３を介して密着結合し、発泡体１が形成される。
　押出機１０のダイ１４から下流側には、調厚ローラー２０が設けられており、調厚ローラー２０は、上下に配置された金属製のローラーの間隔と、該ローラーがローラー間を通過する発泡体１に押圧される弾性力とにより、発泡体１の厚さを調節する。
　その後、発泡体１は、調厚ローラー２０で厚さが一定にされつつ冷却され、下流側に搬送されて、所望の長さに切断される。
　次に、本発明の実施例及び比較例を示す。
　〔実施例１〕
　実施例１では、紙ペレット６８質量％と、ポリプロピレン樹脂群２６．４質量％と、低密度ポリエチレン樹脂（宇部丸善ポリエチレン社製、商品名：Ｌ７１９）４．０質量％と、相溶化剤（旭化成ケミカルズ株式会社製、商品名：タフテックＨ１０６２）０．８質量％と、白色顔料（トーヨーカラー株式会社製、商品名：高濃度酸化チタンマスターバッチＴＥＴ　１ＴＡ５３８　ＷＨＴ－ＦＤ）０．８質量％とを原料とし、図３に示す押出機１０を用い、原料全量に対して３．０質量％の水を添加して発泡成形することにより、図１に示す発泡体１を作成した。
　前記紙ペレットは、前記原料の全量に対し、平均粒径１００μｍの紙微粉末２２．０質量％と、工業用デンプン４６．０質量％とを含んでいる。ここで、前記紙ペレットの全量に占める前記紙微粉末の割合は３２．４質量％であり、前記工業用デンプンの割合は６７．６質量％である。
　また、前記ポリプロピレン樹脂群は、前記原料の全量に対し、発泡性ポリプロピレン樹脂（日本ポリプロ社製、商品名：ニューフォーマー）８．５質量％と、通常のポリプロピレン樹脂（日本ポリプロ社製、商品名：ＦＹ－６）１７．９質量％とを含んでいる。
　また、前記白色顔料は、その全量の７０質量％の酸化チタンと、３０質量％の低密度ポリエチレン樹脂とからなる。
　この結果、本実施例１の発泡体１は、前記紙微粉末２２質量％と、工業用デンプン４６質量％と、ポリプロピレン樹脂群２６．４質量％と、低密度ポリエチレン樹脂４．０質量％と、相溶化剤０．８質量％と、白色顔料０．８質量％とを含むものとなっている。
　次に、本実施例１で得られた発泡体１を、内寸法１７０ｍｍ×１４９ｍｍ×１４４ｍｍのダンボール箱の内部六面に配設した保冷容器を作成し、該保冷容器内にドライアイス２ｋｇを収容して、ドライアイスの残重量の経時変化を測定した。結果を図４に示す。
　〔実施例２〕
　本実施例２では、紙ペレット５６．１質量％と、ポリプロピレン樹脂群２８．５質量％と、低密度ポリエチレン樹脂（東ソー社製、商品名：ペトロセン２２１）１４．６質量％と、相溶化剤（旭化成ケミカルズ株式会社製、商品名：タフテックＨ１０６２）０．８質量％とを原料とし、図３に示す押出機１０を用い、原料全量に対して３．０質量％の水を添加して発泡成形することにより、て図１に示す発泡体１を作成した。
　前記紙ペレットは、前記原料の全量に対し、平均粒径１００μｍの紙微粉末１８．２質量％と、工業用デンプン３７．９質量％とを含んでいる。ここで、前記紙ペレットの全量に占める前記紙微粉末の割合は３２．３質量％であり、前記工業用デンプンの割合は６７．７質量％である。
　また、前記ポリプロピレン樹脂群は、前記原料の全量に対し、発泡性ポリプロピレン樹脂（日本ポリプロ社製、商品名：ニューフォーマー）８．５質量％と、通常のポリプロピレン樹脂（日本ポリプロ社製、商品名：ＶＳ７００）２０．０質量％とを含んでいる。
　この結果、本実施例の発泡体１は、前記紙微粉末１８．２質量％と、工業用デンプン３７．９質量％と、ポリプロピレン樹脂群２８．５質量％と、低密度ポリエチレン樹脂１４．６質量％と、相溶化剤０．８質量％と含むものとなっている。
　次に、実施例２で得られた発泡体１を、内寸法１７０ｍｍ×１４９ｍｍ×１４４ｍｍのダンボール箱の内部六面に配設した保冷容器を作成し、該保冷容器内にドライアイス２ｋｇを収容して、ドライアイスの残重量の経時変化を測定したところ、実施例１の発泡体１と同様の性能を得ることができた。
　〔実施例３〕
　実施例３では、紙ペレット５３．９質量％と、ポリプロピレン樹脂群３０．５質量％と、低密度ポリエチレン樹脂（宇部丸善ポリエチレン社製、商品名：Ｌ７１９）１４．０質量％と、相溶化剤（旭化成ケミカルズ株式会社製、商品名：タフテックＨ１０６２）０．８質量％と、白色顔料（トーヨーカラー株式会社製、商品名：高濃度酸化チタンマスターバッチＴＥＴ　１ＴＡ５３８　ＷＨＴ－ＦＤ）０．８質量％とを原料とし、図３に示す押出機１０を用い、原料全量に対して３．０質量％の水を添加して発泡成形することにより、図１に示す発泡体１を作成した。
　前記紙ペレットは、前記原料の全量に対し、平均粒径１００μｍの紙微粉末１７．５質量％と、工業用デンプン３６．４質量％とを含んでいる。ここで、前記紙ペレットの全量に占める前記紙微粉末の割合は３２．４質量％であり、前記工業用デンプンの割合は６７．６質量％である。
　また、前記ポリプロピレン樹脂群は、前記原料の全量に対し、発泡性ポリプロピレン樹脂（日本ポリプロ社製、商品名：ニューフォーマー）１０．５質量％と、通常のポリプロピレン樹脂（日本ポリプロ社製、商品名：ＦＹ－６）２０．０質量％とを含んでいる。
　この結果、実施例３の発泡体１は、前記紙微粉末１７．５質量％と、工業用デンプン３６．４質量％と、ポリプロピレン樹脂群３０．５質量％と、低密度ポリエチレン樹脂１４．０質量％と、相溶化剤０．８質量％と、白色顔料０．８質量％とを含むものとなっている。
　次に、実施例３で得られた発泡体１を、内寸法１７０ｍｍ×１４９ｍｍ×１４４ｍｍのダンボール箱の内部六面に配設した保冷容器を作成し、該保冷容器内にドライアイス２ｋｇを収容して、ドライアイスの残重量の経時変化を測定したところ、実施例１の発泡体１と同様の性能を得ることができた。
　〔実施例４〕
　実施例４では、紙ペレット５４．４質量％と、ポリプロピレン樹脂群２８．０質量％と、低密度ポリエチレン樹脂（宇部丸善ポリエチレン社製、商品名：Ｌ７１９）１６．０質量％と、相溶化剤（旭化成ケミカルズ株式会社製、商品名：タフテックＨ１０６２）０．８質量％と、白色顔料（トーヨーカラー株式会社製、商品名：高濃度酸化チタンマスターバッチＴＥＴ　１ＴＡ５３８　ＷＨＴ－ＦＤ）０．８質量％とを原料とし、図３に示す押出機１０を用い、原料全量に対して３．０質量％の水を添加して発泡成形することにより、図１に示す発泡体１を作成した。
　前記紙ペレットは、前記原料の全量に対し、平均粒径１００μｍの紙微粉末１７．６質量％と、工業用デンプン３６．８質量％とを含んでいる。ここで、前記紙ペレットの全量に占める前記紙微粉末の割合は３２．４質量％であり、前記工業用デンプンの割合は６７．６質量％である。
　また、前記ポリプロピレン樹脂群は、前記原料の全量に対し、発泡性ポリプロピレン樹脂（日本ポリプロ社製、商品名：ニューフォーマー）６．０質量％と、通常のポリプロピレン樹脂（日本ポリプロ社製、商品名：ＦＹ－６）２２．０質量％とを含んでいる。
　この結果、実施例３の発泡体１は、前記紙微粉末１７．６質量％と、工業用デンプン３６．８質量％と、ポリプロピレン樹脂群２８．０質量％と、低密度ポリエチレン樹脂１６．０質量％と、相溶化剤０．８質量％と、白色顔料０．８質量％とを含むものとなっている。
　次に、実施例４で得られた発泡体１を、内寸法１７０ｍｍ×１４９ｍｍ×１４４ｍｍのダンボール箱の内部六面に配設した保冷容器を作成し、該保冷容器内にドライアイス２ｋｇを収容して、ドライアイスの残重量の経時変化を測定したところ、実施例１の発泡体１と同様の性能を得ることができた。
　〔比較例〕
　本比較例では、特許文献１の実施品とされる市販の発泡体を用いた以外は、発泡体の寸法等を実施例１と同一条件にして、ドライアイスの残重量の経時変化を測定した。
　特許文献１によれば、粒径が約１５０～８０μｍの紙粉末成分２４重量％と澱粉成分３６重量％、ポリプロピレン樹脂成分４０重量％に、水を適宜供給して混練機で良く混練し、押出機に投入して発泡させたものとなっている。結果を図４に示す。
　図４から、実施例１の発泡体１を用いた保冷容器では、測定開始から５２時間１５分後のドライアイスの残重量が０．３９ｋｇであったのに対し、比較例の市販の発泡体を用いた保冷容器では、０．１９ｋｇであった。従って、本実施例の保冷容器では、比較例の保冷容器に対して、２倍強のドライアイスが残存しており、本発明の発泡体１は優れた保冷性能を備えていることが明らかである。
　１…発泡体、　２…棒状体、　３…表皮層、　４…発泡層、　５…気泡、　６ａ…空隙、　６ｂ…溝。

Claims (5)

  1. 　紙微粉体と親水性高分子との混合物である紙ペレット５０．０～７０．０質量％と、
    　発泡性ポリプロピレン樹脂と他のポリプロピレン樹脂とからなるポリプロピレン樹脂群２２．０～３４．０質量％と、
    　低密度ポリエチレン樹脂３．０～２０．０質量％と、
    　ポリプロピレン樹脂とポリエチレン樹脂との相溶化剤０．６～２．０質量％とを含む発泡体であって、
    　前記紙ペレットは、３０～２００μｍの粒径を有する紙微粉体３０．０～５０．０質量％と、親水性高分子５０．０～７０．０質量％とを混合してなり、
    　前記ポリプロピレン樹脂群は、発泡性ポリプロピレン樹脂５．０～１１．０質量％と、他のポリプロピレン樹脂１７～２３質量％とからなることを特徴とする発泡体。
  2. 　請求項１記載の発泡体において、
    　前記紙ペレットが５３．９～６８．０質量％であり、
    　前記ポリプロピレン樹脂群が、前記発泡性ポリプロピレン樹脂６．０～１０．５質量％と、前記他のポリプロピレン樹脂１７．９～２２．０質量％とからなり、これらを合わせて２６．４～３０．５質量％であり、
    　前記低密度ポリエチレン樹脂が４．０～１６．０質量％であることを特徴とする発泡体。
  3. 　請求項１記載の発泡体において、前記相溶化剤は、水添スチレン系熱可塑性エラストマーであることを特徴とする発泡体。
  4. 　請求項３記載の発泡体において、前記水添スチレン系熱可塑性エラストマーは、水添スチレン－エチレン－ブチレン－スチレンブロックコポリマーであることを特徴とする発泡体。
  5. 　請求項１記載の発泡体において、前記紙ペレットと前記ポリプロピレン樹脂群と前記低密度ポリエチレン樹脂と、前記相溶化剤とを合わせて１００質量部にしたものに対し、１．０質量部以下の顔料を添加することを特徴とする発泡体。
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EP3305836B1 (en) 2020-07-08
KR101922648B1 (ko) 2018-11-27
CA2944780A1 (en) 2016-08-04
CA2944780C (en) 2019-04-23
KR20180004646A (ko) 2018-01-12
BR112016025074A2 (ja) 2018-07-10
EP3305836A1 (en) 2018-04-11
JP5985787B1 (ja) 2016-09-06
US20170015818A1 (en) 2017-01-19

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