WO2022074731A1 - Resin composition, film formed from resin composition, and method for producing film - Google Patents

Resin composition, film formed from resin composition, and method for producing film Download PDF

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Publication number
WO2022074731A1
WO2022074731A1 PCT/JP2020/037857 JP2020037857W WO2022074731A1 WO 2022074731 A1 WO2022074731 A1 WO 2022074731A1 JP 2020037857 W JP2020037857 W JP 2020037857W WO 2022074731 A1 WO2022074731 A1 WO 2022074731A1
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Prior art keywords
film
resin composition
mass
thermal conductivity
less
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PCT/JP2020/037857
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French (fr)
Japanese (ja)
Inventor
良博 堀籠
学 大崎
圭輔 山本
康弘 中川
晃 鈴野
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日本サニパック株式会社
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Priority to PCT/JP2020/037857 priority Critical patent/WO2022074731A1/en
Priority to JP2022524036A priority patent/JPWO2022074731A1/ja
Publication of WO2022074731A1 publication Critical patent/WO2022074731A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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

Definitions

  • the present invention relates to a resin composition, a film formed from the resin composition, and a method for producing the film.
  • it has good moldability when manufacturing films such as garbage bags and plastic shopping bags, and has weather resistance that makes it difficult for the film to undergo deterioration such as deformation, discoloration, and deterioration due to heat and light during actual use.
  • the resin composition having.
  • plastics can suppress the generation of carbon dioxide by implementing the so-called 3Rs (Reuse, Reuse, Recycle), but especially for disposable plastics packaging materials, Recycle (recycle). ) And Reuse (reduction of the amount of plastics used) are also important.
  • Patent Document 1 discloses that the manufacturing method has been devised to solve such a problem.
  • Patent Document 2 a calcium carbonate-containing dust bag in which the molecular weight distribution of the thermoplastic resin is limited in order to provide appropriate opacity while improving the kneadability at the time of molding so that the thickness of the dust bag becomes uniform.
  • a resin composition for use is disclosed (Patent Document 2, paragraph 0009-0010, etc.).
  • Patent Document 3 discloses a composition for an inorganic-filled polyethylene film having improved heat-sealing properties by adjusting the MFR (melt flow rate) of polyethylene and adopting heavy calcium carbonate surface-treated with a higher fatty acid. (Patent Document 3, paragraph 0003-0004, etc.).
  • the molded film has further reduced weather resistance, so that it is necessary to add an antioxidant or a weather resistant agent. For this reason, when the recycled product is a part or all of the raw material, there is a problem that the product cost increases if the deterioration of the physical properties is prevented.
  • the present invention has been made in view of the above circumstances, and has good moldability on a film even in a resin composition containing calcium carbonate and in a resin composition obtained by recycling the resin composition as a raw material.
  • Another object of the present invention is to provide a resin composition having weather resistance such that the film is less likely to be deformed, discolored, deteriorated or otherwise deteriorated by heat or light during actual use.
  • the resin composition of the present invention comprises a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m ⁇ K or less, and a black pigment having a thermal conductivity of 5 W / m ⁇ K or less.
  • the inorganic compound is characterized in that it is 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition.
  • the black pigment is preferably 0.5% by mass or more and 3% by mass or less with respect to the total amount of the resin composition.
  • the inorganic compound may contain any one or more of calcium carbonate, titanium dioxide, talc, and silicon dioxide.
  • the polyolefin is preferably polyethylene-based.
  • the film of the present invention is characterized by being molded by the above resin composition.
  • the film may be a garbage bag, a plastic shopping bag, a shopping bag, an agricultural material, an industrial material, or a distribution material.
  • the method for producing a film of the present invention comprises a component containing a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m ⁇ K or less, and a black pigment having a thermal conductivity of 5 W / m ⁇ K or less.
  • the step of cutting the heat-sealed tubular film or roll-shaped film, the inorganic compound is characterized in that it is 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition. do.
  • the step of molding into the tubular film may be inflation molding. Further, the step of forming the roll-shaped film may be T-die extrusion molding.
  • the film of the present invention formed by the resin composition has good moldability, and the film is in actual use. It has weather resistance that does not easily cause deterioration such as deformation, discoloration, and deterioration with respect to heat and light. Further, even when a recycled polyolefin is blended with the resin composition of the present invention, the film formed by the resin composition has good moldability, weather resistance and heat resistance. Therefore, it is not necessary to add additives such as antioxidants and weather resistant agents, and the product cost can be reduced. Further, according to the method for producing a film of the present invention, it is possible to produce a film having good moldability, weather resistance and heat resistance.
  • the resin composition of the present invention contains a polyolefin, an inorganic compound, and a black pigment.
  • the polyolefin of the present invention is a polymer obtained by polymerizing alkene, which is an unsaturated hydrocarbon having one double bond between CC, as a monomer.
  • alkene which is an unsaturated hydrocarbon having one double bond between CC
  • polyethylene type there are polyethylene type, polypropylene type and the like, and polyethylene type is preferable.
  • Polyethylene type is classified into low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and the like according to the density and the degree of linear / branching.
  • Low-density polyethylene is polyethylene with a density of 0.910 to 0.930, and ethylene as a monomer is randomly branched and polymerized. Due to its branched structure, it has a low melting point and is soft.
  • Linear low density polyethylene is polyethylene having a density of 0.910 to 0.925, and the monomer ethylene is more linear than low density polyethylene (LDPE) and more than high density polyethylene (HDPE). Is branched and polymerized.
  • the linear low density polyethylene (LLDPE) has about 10 to 30 short chain branches (SCBs) with respect to the ethylene monomer 1000.
  • SCBs short chain branches
  • the flexibility and heat resistance of linear low density polyethylene (LLDPE) lies between low density polyethylene (LDPE) and high density polyethylene (HDPE), but the chemical resistance and resistance to stress cracking are low density. Higher than polyethylene (LDPE) and high density polyethylene (HDPE).
  • High-density polyethylene is polyethylene having a density of 0.942 or more, and is obtained by linearly polymerizing ethylene as a monomer with almost no branching.
  • High-density polyethylene has about 1 to 5 short chain branches (SCBs) with respect to ethylene monomer 1000.
  • High-density polyethylene (HDPE) has high crystallinity, rigidity, impact resistance, and cold resistance, and is opaque even when film-molded.
  • monomers such as C4, C6 and C8 (butene, hexene, octene and alkenes having a branched structure thereof).
  • Polyethylene classified into three types as described above can be blended in a resin composition by mixing two or more types depending on the purpose.
  • a recycled product (recycled LL) of linear low-density polyethylene (LLDPE) or a recycled product (recycled HD) of high-density polyethylene (HDPE) can be used as a part or all of the polyolefin raw material.
  • Recycled LL is a re-pelletized linear low-density polyethylene film
  • recycled HD is a re-pelletized molded high-density polyethylene.
  • the inorganic compound of the present invention is blended for the purpose of reducing the amount of plastics used. Further, when the film formed by the resin composition is incinerated in an incinerator, the inorganic compound is blended so that the incinerator does not become too hot and a high maintenance cost is not incurred. It is desirable that the inorganic compound has a small thermal conductivity, more preferably 30 W / m ⁇ K or less, and further preferably 20 W / m ⁇ K or less, and 10 W / m ⁇ K or less.
  • the inorganic compound is preferably about 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition, although it depends on the thermal conductivity of the inorganic compound, 10% by mass or more and 40% by mass or less, and 10% by mass or more and 35. It is more preferably mass% or less.
  • the amount of the inorganic compound is less than 10% by mass with respect to the total amount of the resin composition, the effect of reducing the use of plastics is reduced, although it contributes to the improvement of heat resistance.
  • the amount of the inorganic compound exceeds 50% by mass with respect to the total amount of the resin composition, heat is easily conducted to the polyolefin, and the film is liable to undergo deterioration such as deformation, discoloration, and deterioration due to the heat and light of the sun during actual use. As a result, weather resistance and heat resistance are reduced.
  • the inorganic compound is not particularly limited as long as it is a compound within the above thermal conductivity range, and examples thereof include calcium carbonate, titanium dioxide, talc (Mg 3 Si 4 O 10 (OH) 2 ), silicon dioxide, and zirconium dioxide.
  • Inorganic compounds can also be blended in a masterbatch. In this case, the amount of the inorganic compound itself contained in the masterbatch is defined by the above mass%. In addition, the resin contained in the masterbatch is calculated as the blending amount of each type of resin.
  • the black pigment of the present invention is a black pigment and is used to color a film formed of a resin composition into black.
  • the black pigment one having a thermal conductivity of 5 W / m ⁇ K or less, preferably 3 W / m ⁇ K or less is selected.
  • the thermal conductivity of the black pigment exceeds 5 W / m ⁇ K, heat is easily conducted to the polyolefin, and the film is liable to undergo deterioration such as deformation, discoloration, and deterioration due to the heat and light of the sun during actual use.
  • the weather resistance is low.
  • the black pigment is preferably about 0.5% by mass or more and 3% by mass or less, and 0.8% by mass or more and 2.4% by mass or less, based on the thermal conductivity of the black pigment. Is more preferable.
  • the black pigment is less than 0.5% by mass with respect to the total amount of the resin composition, the black pigment is deteriorated, although it contributes to the improvement of heat resistance.
  • the black pigment exceeds 3% by mass based on the total amount of the resin composition, heat is easily conducted to the polyolefin, and the film is easily deformed, discolored, deteriorated or deteriorated by the heat and light of the sun during actual use. As a result, weather resistance and heat resistance are reduced.
  • the black pigment can also be blended in a masterbatch.
  • the amount of the black pigment itself contained in the masterbatch is defined by the above mass%.
  • the resin contained in the masterbatch is calculated as the blending amount of each type of resin.
  • a masterbatch of a black pigment and a masterbatch of an inorganic compound can be prepared separately and blended with the polyolefin, or one masterbatch containing both the black pigment and the inorganic compound can be prepared and blended with the polyolefin. You can also do it.
  • the black pigment is not particularly limited as long as it is a compound that can be colored black within the range of the above thermal conductivity, and examples thereof include carbon black, lamp black, vegetable black, bone black, and graphite.
  • the film of the present invention is molded and manufactured from the above resin composition.
  • a resin composition is obtained by blending a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m ⁇ K or less, and a black pigment having a thermal conductivity of 5 W / m ⁇ K or less.
  • the resin composition is formed into a tube-shaped or roll-shaped film, and the formed film is heat-sealed and cut.
  • Inorganic compounds and black pigments can also be blended in a masterbatch.
  • An inflation molding method is exemplified as a method for molding into a tubular film.
  • the inflation molding method is a method in which a mold having an annular lip is installed at the tip of the extruder, the resin composition is extruded into a tube shape, and compressed air is blown from the center of the mold through an air hole to continuously mold the resin composition.
  • a T-die extrusion molding method is exemplified.
  • the T-die extrusion molding method is a method in which a T-die (a mold having a linear lip) is installed at the tip of an extruder and a flat resin composition is extruded and molded.
  • the use of the film having the constitution of the present invention is not particularly limited, but includes garbage bags, plastic shopping bags, shopping bags, agricultural materials, industrial materials, distribution materials, etc., which are required to have moldability, weather resistance, heat resistance, etc. Illustrated.
  • the resin composition of the present invention may or may not contain additives used in ordinary film resins.
  • additives used in ordinary film resins include antioxidants and weather resistant agents.
  • Example 1- 78% by mass of linear low density polyethylene (LLDPE) (Suitomo Chemical Asia, model number FS153S), 20% by mass of calcium carbonate masterbatch (containing 80% CaCO 3 ) (GCR, model number GRANIC422), black A 2% by mass blend of a pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470), an inner diameter of 55 mm, and a screw (L / D28) extruder (manufactured by Placo). ) was added, and a tubular film was formed using a die diameter of 100 m ⁇ and a lip of 3 mm at an extrusion temperature of 170 ° C.
  • LLDPE linear low density polyethylene
  • the tubular film was heat-sealed to a length of 600 mm with a bag making machine (manufactured by Nozaki Kogyo) and cut into a bag shape.
  • the temperature of the heat seal was in the range of 160 ° C to 180 ° C.
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the calcium carbonate masterbatch GRANIC422 contains 80% CaCO 3 and 20% LLDPE using C8 (octene) as a monomer.
  • the black pigment masterbatch F31470 contains 40% carbon black, 50% LDPE and 10% calcium carbonate.
  • the obtained film was evaluated for (1) film formability, (2) color, (3) film strength, and (4) thermal deterioration.
  • the film molded from the resin composition of Example 1 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • Example 2- 78% by mass of high density polyethylene (HDPE) (Saudi Basic Industries Corporation, model number FJ009052), 20% by mass of calcium carbonate masterbatch (80% of Ca 2 CO 3 ) (GCR, model number GRANIC422), A masterbatch of black pigment (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) is blended in an amount of 2% by mass, a tubular film is formed in the same manner as in Example 1, and heat is formed. It was sealed and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • HDPE high density polyethylene
  • FJ009052 20% by mass of calcium carbonate masterbatch
  • GCR model number GRANIC422
  • a masterbatch of black pigment containing 40% carbon black and 10% calcium carbonate
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the film molded from the resin composition of Example 2 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • Recycled resins were prepared using films that did not become products in the film manufacturing process and films that were recovered after use in the market.
  • the recovered film was separated into HDPE-based and LLDPE-based, the film was crushed by washing or no washing, extruded into strands by an extruder, and cut into pellets.
  • an LLDPE-based recycled resin hereinafter referred to as “recycled LL” was used.
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the film molded from the resin composition of Example 3 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • HDPE-based recycled resin (hereinafter referred to as “recycled HD”) was used in Example 4. 78% by mass of HDPE-based recycled resin (recycled HD), 20% by mass of calcium carbonate masterbatch (containing 80% of Ca 2 CO 3 ) (GCR, model number GRANIC422), black pigment masterbatch (carbon black) (Contains 40% and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) is blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, cut and bag-shaped. And said. The obtained film was evaluated in the same manner as in Example 1.
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the film formed by the resin composition of Example 4 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • LLDPE Linear low density polyethylene
  • FS153S LLDPE-based recycled resin
  • Ca 2 CO 3 calcium carbonate masterbatch
  • GCR model number GRANIC422
  • black pigment masterbatch carbon black is 40%, calcium carbonate is contained at 10%
  • DI Co., Ltd., model number F31470 is blended by 2% by mass.
  • a tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 32% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the film formed by the resin composition of Example 5 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • High-density polyethylene (HDPE) (manufactured by Saudi Basic Industries Corporation, model number FJ009052) is 26% by mass, HDPE-based recycled resin (recycled HD) is 50% by mass, and titanium dioxide masterbatch (70% of TiO 2 is contained) ( 20% by mass of DIC Co., Ltd., model number L-11167MPT) and 4% by mass of black pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (DIC Co., Ltd., model number F31470).
  • a tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • the titanium dioxide masterbatch L-11167MPT contains 70% titanium dioxide and 30% LLDPE.
  • the thermal conductivity of titanium dioxide which is an inorganic compound in the film, is 10 W / m ⁇ K and the concentration is 14% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K and the concentration is 1. It was 0.6% by mass.
  • the film formed by the resin composition of Example 6 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • Example 7- 66% by mass of linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical Asia, model number FS153S), talc masterbatch (containing 70% of Mg 3 Si 4 O 10 (OH) 2 ) (manufactured by Takehara Chemical Industry Co., Ltd.) , Model No. 1270T) by 30% by mass, and black pigment masterbatch (containing 40% of carbon black and 10% of calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) by 4% by mass, in the same manner as in Example 1.
  • a tube-shaped film was formed, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • the talc masterbatch 1270T contains 70% talc and 30% LLDPE.
  • the thermal conductivity of talc which is an inorganic compound in the film, is 0.3 W / m ⁇ K and the concentration is 21% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K and the concentration is It was 1.6% by mass.
  • the film formed by the resin composition of Example 7 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • Example 8 50% by mass of the inorganic compound silicon dioxide (manufactured by Nittetsu Chemical & Materials Co., Ltd., model number HS-311) and 50% by mass of polyethylene powder (manufactured by Ube-Maruzen Polyethylene Co., Ltd., model number UM1805) are mixed, and 5 by super mixer. After mixing for a minute, it was extruded into strands by a twin-screw extruder and cut into pellets. This was designated as a silicon dioxide masterbatch.
  • HDPE high density polyethylene
  • FJ009052 50% by mass of HDPE-based recycled resin
  • silicon dioxide masterbatch 50% by weight of silicon dioxide masterbatch (containing 50% SiO 2 ).
  • a tube-shaped film was formed by blending 26% by mass and 6% by mass of a black pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) in the same manner as in Example 1. It was molded, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • the thermal conductivity of silicon dioxide, which is an inorganic compound in the film, is 1.4 W / m ⁇ K, the concentration is 13% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 2.4% by mass.
  • the film formed by the resin composition of Example 8 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • Example 9 Among the recycled resins described in Example 3, HDPE-based recycled resin (recycled HD) was used in Example 9. 85% by mass of HDPE-based recycled resin (recycled HD), 13% by mass of calcium carbonate masterbatch (containing 80% of CaCO 3 ) (GCR, model number GRANIC422), black pigment masterbatch (40% of carbon black) (Contains 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) was blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. .. The obtained film was evaluated in the same manner as in Example 1.
  • the thermal conductivity of calcium carbonate, which is an inorganic compound in the film is 1.0 W / m ⁇ K, the concentration is 10% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 0.8% by mass.
  • the film formed by the resin composition of Example 9 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • the thermal conductivity of aluminum which is an inorganic compound in the film, is 204 W / m ⁇ K and the concentration is 14% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K and the concentration is 0. It was 8% by mass.
  • the film formed by the resin composition of Comparative Example 1 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • HDPE high density polyethylene
  • FJ009052 65% by mass of calcium carbonate masterbatch (80% of CaCO 3 )
  • GCR model number GRANIC422
  • black pigment A masterbatch containing 40% carbon black and 10% calcium carbonate
  • the thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 52% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 1.6% by mass.
  • the film formed by the resin composition of Comparative Example 2 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • LLDPE resin 78% by mass of LLDPE resin (m-LLDPE) synthesized with a metallocene catalyst, 20% by mass of alumina masterbatch (containing 50% of Al 2 O 3 ), black pigment masterbatch (40% of carbon black, calcium carbonate) (Contains 10%) was blended in an amount of 2% by mass, a tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
  • alumina masterbatch containing 50% of Al 2 O 3
  • black pigment masterbatch 40% of carbon black, calcium carbonate
  • Alumina which is an inorganic compound in the film, has a thermal conductivity of 36 W / m ⁇ K and a concentration of 10% by mass
  • a black pigment carbon black
  • the film formed by the resin composition of Comparative Example 3 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • LLDPE Linear low density polyethylene
  • GCR model number GRANIC422
  • a masterbatch of black pigment containing 40% carbon black and 10% calcium carbonate is blended in an amount of 10% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. bottom. The obtained film was evaluated in the same manner as in Example 1.
  • the thermal conductivity of calcium carbonate which is an inorganic compound in the film, is 1.0 W / m ⁇ K, the concentration is 60% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m ⁇ K, concentration. Was 4.0% by mass.
  • the film formed by the resin composition of Comparative Example 4 was evaluated as (1) film formability ⁇ , (2) color ⁇ , (3) film strength ⁇ , and (4) thermal deterioration ⁇ .
  • a polyolefin an inorganic compound having a thermal conductivity of 10% by mass or more and 50% by mass or less and a thermal conductivity of 20 W / m ⁇ K or less, and a thermal conductivity of 5 W / m ⁇ K or less. It was found that the film formed by the resin composition containing the black pigment has good moldability, is less likely to decrease in strength or deteriorate due to heat, and is environmentally friendly.

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Abstract

Even in both a resin composition in which calcium carbonate is mixed, and a resin composition obtained by recycling said resin composition as a raw material, provided is a resin composition having: good moldability to a film; and weather resistance which is the property of being less likely to cause alterations, such as deformation, discoloration, and deterioration due to heat and light, when the film is actually used.　The resin composition is characterized by comprising: a polyolefin; an inorganic compound having a thermal conductivity of at most 20 W/m•K; and a black pigment having a thermal conductivity of at most 5 Wm/m•K.

Description

樹脂組成物、樹脂組成物により成形されたフィルム、及び、フィルムの製造方法A resin composition, a film formed from the resin composition, and a method for producing the film.
　本発明は、樹脂組成物、該樹脂組成物により成形されたフィルム、及び、該フィルムの製造方法に関する。特に、ゴミ袋やレジ袋等のフィルムを製造する際の成形性が良好であり、かつ、該フィルムが実使用時の熱や光に対し変形、変色、劣化等の変質を起こしにくい耐候性を有する、樹脂組成物に関する。 The present invention relates to a resin composition, a film formed from the resin composition, and a method for producing the film. In particular, it has good moldability when manufacturing films such as garbage bags and plastic shopping bags, and has weather resistance that makes it difficult for the film to undergo deterioration such as deformation, discoloration, and deterioration due to heat and light during actual use. With respect to the resin composition having.
　プラスチックス製の包装材料の分野においても、近年の地球温暖化に伴い、二酸化炭素の発生量の削減を強く求められてきている。プラスチックスは、いわゆる３Ｒ（Ｒｅｄｕｃｅ、Ｒｅｕｓｅ、Ｒｅｃｙｃｌｅ）を実施することにより、二酸化炭素の発生を抑制することができるとされているが、特に使い捨てのプラスチックス製の包装材料においては、Ｒｅｃｙｃｌｅ（リサイクル）とともにＲｅｄｕｃｅ（プラスチックスの使用量の低減）も重要となる。 In the field of packaging materials made of plastics, there is a strong demand for reduction of carbon dioxide generation due to global warming in recent years. It is said that plastics can suppress the generation of carbon dioxide by implementing the so-called 3Rs (Reuse, Reuse, Recycle), but especially for disposable plastics packaging materials, Recycle (recycle). ) And Reuse (reduction of the amount of plastics used) are also important.
　プラスチックス自体の使用量を減らすために、炭酸カルシウム等を大量に配合すると、機械的強度の低下を招き、また、ゴミ袋の表面が固くなりすぎて折り曲げ等に不便になるといった課題があった（特許文献１段落０００６参照）。特許文献１では製造方法を工夫し、かかる課題を解決したことを開示している。 If a large amount of calcium carbonate or the like is added in order to reduce the amount of plastics used, there is a problem that the mechanical strength is lowered and the surface of the garbage bag becomes too hard, which makes it inconvenient to bend. (Refer to paragraph 0006 of Patent Document 1). Patent Document 1 discloses that the manufacturing method has been devised to solve such a problem.
　また、特許文献２では、ゴミ袋の膜厚が均一となるように成形時の混練性を高めつつ、適度の不透明性を備えるため、熱可塑性樹脂の分子量分布を限定した、炭酸カルシウム含有ゴミ袋用樹脂組成物を開示している（特許文献２段落０００９－００１０等）。 Further, in Patent Document 2, a calcium carbonate-containing dust bag in which the molecular weight distribution of the thermoplastic resin is limited in order to provide appropriate opacity while improving the kneadability at the time of molding so that the thickness of the dust bag becomes uniform. A resin composition for use is disclosed (Patent Document 2, paragraph 0009-0010, etc.).
　さらに特許文献３では、ポリエチレンのＭＦＲ（メルトフローレート）を調整し、高級脂肪酸により表面処理された重質炭酸カルシウムを採用することにより、ヒートシール性を高めた無機質充填ポリエチレンフィルム用組成物を開示している（特許文献３段落０００３－０００４等）。 Further, Patent Document 3 discloses a composition for an inorganic-filled polyethylene film having improved heat-sealing properties by adjusting the MFR (melt flow rate) of polyethylene and adopting heavy calcium carbonate surface-treated with a higher fatty acid. (Patent Document 3, paragraph 0003-0004, etc.).
　上記のように、炭酸カルシウムを配合した樹脂組成物において、プラスチックスの使用量を低減すると同時に発生する製造時や製造直後の各種課題は、製造方法やその構成成分を工夫することにより解決されてきた。
　しかしながら、従来の炭酸カルシウム等を配合した樹脂組成物により成形されたフィルムが実際に使用される場合、炭酸カルシウム等の配合により、該フィルムは太陽の熱や光の照射により変形、変色、劣化等の物性低下、すなわち耐候性の低下が見られるという課題があった。
　また、従来の耐候性の低下したフィルムをリサイクルした場合、成形されたフィルムはさらに耐候性の低下が見られるため、酸化防止剤や耐候剤を添加する必要が生じた。このため、リサイクル品を原料の一部又は全部とした場合、物性の低下を防止すると製品コストが膨らむという課題も生じた。 As described above, in the resin composition containing calcium carbonate, various problems at the time of manufacturing and immediately after manufacturing that occur at the same time as reducing the amount of plastics used have been solved by devising the manufacturing method and its constituent components. rice field.
However, when a film formed by a conventional resin composition containing calcium carbonate or the like is actually used, the film is deformed, discolored, deteriorated, etc. due to the heat of the sun or irradiation with light due to the addition of calcium carbonate or the like. There was a problem that the physical properties of calcium carbonate were deteriorated, that is, the weather resistance was deteriorated.
In addition, when the conventional film having reduced weather resistance is recycled, the molded film has further reduced weather resistance, so that it is necessary to add an antioxidant or a weather resistant agent. For this reason, when the recycled product is a part or all of the raw material, there is a problem that the product cost increases if the deterioration of the physical properties is prevented.
特開２００２－１１４３０１号公報Japanese Unexamined Patent Publication No. 2002-114301 特開２０１８－２１１２１号公報Japanese Unexamined Patent Publication No. 2018-21121 特開平５－１７６３６号公報Japanese Unexamined Patent Publication No. 5-176636
　本発明は、上記事情を鑑みたものであり、炭酸カルシウムを配合した樹脂組成物においても、また、該樹脂組成物をリサイクルして原料とした樹脂組成物においても、フィルムへの成形性が良好であり、かつ、該フィルムが実使用時の熱や光に対し変形、変色、劣化等の変質を起こしにくい耐候性を有する、樹脂組成物を提供することを課題とする。 The present invention has been made in view of the above circumstances, and has good moldability on a film even in a resin composition containing calcium carbonate and in a resin composition obtained by recycling the resin composition as a raw material. Another object of the present invention is to provide a resin composition having weather resistance such that the film is less likely to be deformed, discolored, deteriorated or otherwise deteriorated by heat or light during actual use.
　上記課題を解決するために、本発明の樹脂組成物は、ポリオレフィンと、熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、熱伝導率が５Ｗ／ｍ・Ｋ以下である黒顔料と、を含み、前記無機化合物は前記樹脂組成物全量に対し１０質量％以上５０質量％以下であることを特徴とする。 In order to solve the above problems, the resin composition of the present invention comprises a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m · K or less, and a black pigment having a thermal conductivity of 5 W / m · K or less. , And the inorganic compound is characterized in that it is 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition.
　前記黒顔料は前記樹脂組成物全量に対し０．５質量％以上３質量％以下であることが好ましい。 The black pigment is preferably 0.5% by mass or more and 3% by mass or less with respect to the total amount of the resin composition.
　前記無機化合物は、炭酸カルシウム、二酸化チタン、タルク、二酸化ケイ素のいずれか１以上を含んでもよい。 The inorganic compound may contain any one or more of calcium carbonate, titanium dioxide, talc, and silicon dioxide.
　前記ポリオレフィンはポリエチレン系であることが好ましい。 The polyolefin is preferably polyethylene-based.
　本発明のフィルムは、上記樹脂組成物により成形されたことを特徴とする。 The film of the present invention is characterized by being molded by the above resin composition.
　前記フィルムは、ゴミ袋、レジ袋、買い物袋、農業用資材、工業用資材、流通用資材であってもよい。 The film may be a garbage bag, a plastic shopping bag, a shopping bag, an agricultural material, an industrial material, or a distribution material.
　本発明のフィルムの製造方法は、ポリオレフィンと、熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、熱伝導率が５Ｗ／ｍ・Ｋ以下である黒顔料と、を含む成分を配合して樹脂組成物を得るステップと、前記得られた樹脂組成物をチューブ状のフィルム又はロール状のフィルムに成形するステップと、前記成形されたチューブ状のフィルム又はロール状のフィルムをヒートシールするステップと、前記ヒートシールされたチューブ状のフィルム又はロール状のフィルムをカットするステップと、を含み、前記無機化合物は、樹脂組成物全量に対し１０質量％以上５０質量％以下であることを特徴とする。 The method for producing a film of the present invention comprises a component containing a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m · K or less, and a black pigment having a thermal conductivity of 5 W / m · K or less. The step of obtaining the resin composition, the step of molding the obtained resin composition into a tubular film or a roll-shaped film, and the step of heat-sealing the molded tubular film or the roll-shaped film. And the step of cutting the heat-sealed tubular film or roll-shaped film, the inorganic compound is characterized in that it is 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition. do.
　前記チューブ状のフィルムに成形するステップは、インフレーション成形であってもよい。また、前記ロール状のフィルムに成形するステップは、Ｔダイ押出成形であってもよい。 The step of molding into the tubular film may be inflation molding. Further, the step of forming the roll-shaped film may be T-die extrusion molding.
　本発明の樹脂組成物の無機化合物及び黒顔料の熱伝導率を特定することにより、該樹脂組成物により成形された本発明のフィルムは成形性が良好であり、かつ、該フィルムは実使用時の熱や光に対し変形、変色、劣化等の変質を起こしにくい耐候性を有する。
　また、本発明の樹脂組成物にリサイクル品のポリオレフィンを配合した場合においても、該樹脂組成物により成形されたフィルムは、成形性が良好であり、かつ、耐候性、耐熱性を有する。このため、酸化防止剤や耐候剤等の添加剤を追加しなくてもよく、製品コストを削減することができる。
　さらに、本発明のフィルムの製造方法によれば、成形性が良好で、かつ、耐候性、耐熱性を備えたフィルムを製造することができる。 By specifying the thermal conductivity of the inorganic compound and the black pigment of the resin composition of the present invention, the film of the present invention formed by the resin composition has good moldability, and the film is in actual use. It has weather resistance that does not easily cause deterioration such as deformation, discoloration, and deterioration with respect to heat and light.
Further, even when a recycled polyolefin is blended with the resin composition of the present invention, the film formed by the resin composition has good moldability, weather resistance and heat resistance. Therefore, it is not necessary to add additives such as antioxidants and weather resistant agents, and the product cost can be reduced.
Further, according to the method for producing a film of the present invention, it is possible to produce a film having good moldability, weather resistance and heat resistance.
　本発明の樹脂組成物は、ポリオレフィンと、無機化合物と、黒顔料を含む。 The resin composition of the present invention contains a polyolefin, an inorganic compound, and a black pigment.
　本発明のポリオレフィンは、Ｃ－Ｃ間に二重結合を１つ有する不飽和炭化水素であるアルケンをモノマーとし、重合させたポリマーである。アルケンの種類により、ポリエチレン系、ポリプロピレン系等があり、ポリエチレン系が好ましい。
　ポリエチレン系は密度と直鎖／分岐の程度により、低密度ポリエチレン（ＬＤＰＥ）、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）等に分類される。 The polyolefin of the present invention is a polymer obtained by polymerizing alkene, which is an unsaturated hydrocarbon having one double bond between CC, as a monomer. Depending on the type of alkene, there are polyethylene type, polypropylene type and the like, and polyethylene type is preferable.
Polyethylene type is classified into low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and the like according to the density and the degree of linear / branching.
　低密度ポリエチレン（ＬＤＰＥ）は、密度が０．９１０～０．９３０のポリエチレンであり、モノマーのエチレンがランダムに分岐して重合したものである。その分岐構造から、融点が低く柔らかい性質を有する。 Low-density polyethylene (LDPE) is polyethylene with a density of 0.910 to 0.930, and ethylene as a monomer is randomly branched and polymerized. Due to its branched structure, it has a low melting point and is soft.
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）は、密度が０．９１０～０．９２５のポリエチレンであり、モノマーのエチレンが、低密度ポリエチレン（ＬＤＰＥ）よりは直鎖状に、高密度ポリエチレン（ＨＤＰＥ）よりは分岐して重合したものである。直鎖状低密度ポリエチレン（ＬＬＤＰＥ）は、エチレンモノマー１０００に対し短鎖分岐（ＳＣＢ）数は１０～３０程度である。
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）の柔軟性、耐熱性は、低密度ポリエチレン（ＬＤＰＥ）と高密度ポリエチレン（ＨＤＰＥ）の中間に位置するが、耐薬品性やストレスクラッキングへの耐性は、低密度ポリエチレン（ＬＤＰＥ）や高密度ポリエチレン（ＨＤＰＥ）よりも高い。 Linear low density polyethylene (LLDPE) is polyethylene having a density of 0.910 to 0.925, and the monomer ethylene is more linear than low density polyethylene (LDPE) and more than high density polyethylene (HDPE). Is branched and polymerized. The linear low density polyethylene (LLDPE) has about 10 to 30 short chain branches (SCBs) with respect to the ethylene monomer 1000.
The flexibility and heat resistance of linear low density polyethylene (LLDPE) lies between low density polyethylene (LDPE) and high density polyethylene (HDPE), but the chemical resistance and resistance to stress cracking are low density. Higher than polyethylene (LDPE) and high density polyethylene (HDPE).
　高密度ポリエチレン（ＨＤＰＥ）は、密度が０．９４２以上のポリエチレンであり、モノマーのエチレンが分岐をほとんど持たずに直鎖状に重合したものである。高密度ポリエチレン（ＨＤＰＥ）は、エチレンモノマー１０００に対し短鎖分岐（ＳＣＢ）数は１～５程度である。
　高密度ポリエチレン（ＨＤＰＥ）は、結晶化度、剛性、耐衝撃性、耐寒性が高く、フィルム成形しても不透明である。なお、結晶化度を調整するために、Ｃ４、Ｃ６、Ｃ８等のモノマー（ブテン、ヘキセン、オクテンやそれらの分岐構造のアルケン）と共重合させることもできる。 High-density polyethylene (HDPE) is polyethylene having a density of 0.942 or more, and is obtained by linearly polymerizing ethylene as a monomer with almost no branching. High-density polyethylene (HDPE) has about 1 to 5 short chain branches (SCBs) with respect to ethylene monomer 1000.
High-density polyethylene (HDPE) has high crystallinity, rigidity, impact resistance, and cold resistance, and is opaque even when film-molded. In addition, in order to adjust the degree of crystallinity, it is also possible to copolymerize with monomers such as C4, C6 and C8 (butene, hexene, octene and alkenes having a branched structure thereof).
　上記のように３種類に分類されたポリエチレンは、目的により２種類以上を混合して樹脂組成物に配合することもできる。
　さらに、直鎖状低密度ポリエチレン（ＬＬＤＰＥ）のリサイクル品（リサイクルＬＬ）や、高密度ポリエチレン（ＨＤＰＥ）のリサイクル品（リサイクルＨＤ）をポリオレフィン原料の一部又は全部とすることもできる。なお、リサイクルＬＬは成形された直鎖状低密度ポリエチレンフィルムを再ペレット化したものであり、リサイクルＨＤは成形された高密度ポリエチレンを再ペレット化したものである。 Polyethylene classified into three types as described above can be blended in a resin composition by mixing two or more types depending on the purpose.
Further, a recycled product (recycled LL) of linear low-density polyethylene (LLDPE) or a recycled product (recycled HD) of high-density polyethylene (HDPE) can be used as a part or all of the polyolefin raw material. Recycled LL is a re-pelletized linear low-density polyethylene film, and recycled HD is a re-pelletized molded high-density polyethylene.
　本発明の無機化合物は、背景技術で述べたように、プラスチックスの使用量を減らすこと等を目的として配合される。また、樹脂組成物により成形されたフィルムを焼却炉で焼却したときに、焼却炉が高温になり過ぎて高額の保守管理費用がかからないように、該無機化合物は配合される。
　該無機化合物は、その熱伝導率が小さいことが望ましく、３０Ｗ／ｍ・Ｋ以下であることがより好ましく、２０Ｗ／ｍ・Ｋ以下、１０Ｗ／ｍ・Ｋ以下であることがさらに好ましい。無機化合物の熱伝導率が３０Ｗ／ｍ・Ｋを超えると、ポリオレフィンへ熱が伝導しやすくなり、フィルムが実使用時に太陽の熱や光に対し変形、変色、劣化等の変質を起こしやすくなり、耐候性が低くなるからである。 As described in the background art, the inorganic compound of the present invention is blended for the purpose of reducing the amount of plastics used. Further, when the film formed by the resin composition is incinerated in an incinerator, the inorganic compound is blended so that the incinerator does not become too hot and a high maintenance cost is not incurred.
It is desirable that the inorganic compound has a small thermal conductivity, more preferably 30 W / m · K or less, and further preferably 20 W / m · K or less, and 10 W / m · K or less. When the thermal conductivity of the inorganic compound exceeds 30 W / m · K, heat is easily conducted to the polyolefin, and the film is liable to undergo deterioration such as deformation, discoloration, and deterioration due to the heat and light of the sun during actual use. This is because the weather resistance is low.
　無機化合物は、無機化合物の持つ熱伝導率によるが、樹脂組成物全量に対し、概ね１０質量％以上５０質量％以下であることが好ましく、１０質量％以上４０質量％以下、１０質量％以上３５質量％以下であることがより好ましい。
　無機化合物が樹脂組成物全量に対し１０質量％未満の場合、耐熱性向上には寄与するものの、プラスチックスの使用を削減（Ｒｅｄｕｃｅ）する効果が少なくなる。一方、無機化合物が樹脂組成物全量に対し５０質量％を超えると、ポリオレフィンへ熱が伝導しやすくなり、フィルムが実使用時に太陽の熱や光に対し変形、変色、劣化等の変質を起こしやすくなり、耐候性、耐熱性が低下する。 The inorganic compound is preferably about 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition, although it depends on the thermal conductivity of the inorganic compound, 10% by mass or more and 40% by mass or less, and 10% by mass or more and 35. It is more preferably mass% or less.
When the amount of the inorganic compound is less than 10% by mass with respect to the total amount of the resin composition, the effect of reducing the use of plastics is reduced, although it contributes to the improvement of heat resistance. On the other hand, when the amount of the inorganic compound exceeds 50% by mass with respect to the total amount of the resin composition, heat is easily conducted to the polyolefin, and the film is liable to undergo deterioration such as deformation, discoloration, and deterioration due to the heat and light of the sun during actual use. As a result, weather resistance and heat resistance are reduced.
　無機化合物は、上記熱伝導率の範囲にある化合物であれば特に限定されないが、炭酸カルシウム、二酸化チタン、タルク（Ｍｇ3Ｓｉ4Ｏ10（ＯＨ）2）、二酸化ケイ素、二酸化ジルコニウム等が例示される。
　なお、無機化合物をマスターバッチで配合することもできる。この場合、マスターバッチに含まれる無機化合物のそのものの量が上記質量％で規定される。また、該マスターバッチに含まれる樹脂は、それぞれの種類の樹脂の配合量として計算される。 The inorganic compound is not particularly limited as long as it is a compound within the above thermal conductivity range, and examples thereof include calcium carbonate, titanium dioxide, talc (Mg 3 Si 4 O 10 (OH) 2 ), silicon dioxide, and zirconium dioxide. To.
Inorganic compounds can also be blended in a masterbatch. In this case, the amount of the inorganic compound itself contained in the masterbatch is defined by the above mass%. In addition, the resin contained in the masterbatch is calculated as the blending amount of each type of resin.
　本発明の黒顔料は、黒い顔料であり、樹脂組成物により成形されたフィルムを黒色に色付けするために用いられる。
　黒顔料は、その熱伝導率が５Ｗ／ｍ・Ｋ以下、好ましくは３Ｗ／ｍ・Ｋ以下であるものが選定される。黒顔料の熱伝導率が５Ｗ／ｍ・Ｋを超えると、ポリオレフィンへ熱が伝導しやすくなり、フィルムが実使用時に太陽の熱や光に対し変形、変色、劣化等の変質を起こしやすくなり、耐候性が低くなる。 The black pigment of the present invention is a black pigment and is used to color a film formed of a resin composition into black.
As the black pigment, one having a thermal conductivity of 5 W / m · K or less, preferably 3 W / m · K or less is selected. When the thermal conductivity of the black pigment exceeds 5 W / m · K, heat is easily conducted to the polyolefin, and the film is liable to undergo deterioration such as deformation, discoloration, and deterioration due to the heat and light of the sun during actual use. The weather resistance is low.
　黒顔料は、黒顔料の持つ熱伝導率によるが、樹脂組成物全量に対し、概ね０．５質量％以上３質量％以下であることが好ましく、０．８質量％以上２．４質量％以下であることがより好ましい。
　黒顔料が樹脂組成物全量に対し０．５質量％未満の場合、耐熱性向上には寄与するものの、黒色の着色性が低下する。一方、黒顔料が樹脂組成物全量に対し３質量％を超えると、ポリオレフィンへ熱が伝導しやすくなり、フィルムが実使用時に太陽の熱や光に対し変形、変色、劣化等の変質を起こしやすくなり、耐候性、耐熱性が低下する。
　なお、黒顔料をマスターバッチで配合することもできる。この場合、マスターバッチに含まれる黒顔料のそのものの量が上記質量％で規定される。また、該マスターバッチに含まれる樹脂は、それぞれの種類の樹脂の配合量として計算される。
　また、黒顔料のマスターバッチと無機化合物のマスターバッチを別々に用意してポリオレフィンに配合することもできるし、黒顔料と無機化合物の両方が含まれる１つのマスターバッチを用意してポリオレフィンに配合することもできる。 The black pigment is preferably about 0.5% by mass or more and 3% by mass or less, and 0.8% by mass or more and 2.4% by mass or less, based on the thermal conductivity of the black pigment. Is more preferable.
When the black pigment is less than 0.5% by mass with respect to the total amount of the resin composition, the black pigment is deteriorated, although it contributes to the improvement of heat resistance. On the other hand, when the black pigment exceeds 3% by mass based on the total amount of the resin composition, heat is easily conducted to the polyolefin, and the film is easily deformed, discolored, deteriorated or deteriorated by the heat and light of the sun during actual use. As a result, weather resistance and heat resistance are reduced.
The black pigment can also be blended in a masterbatch. In this case, the amount of the black pigment itself contained in the masterbatch is defined by the above mass%. In addition, the resin contained in the masterbatch is calculated as the blending amount of each type of resin.
Further, a masterbatch of a black pigment and a masterbatch of an inorganic compound can be prepared separately and blended with the polyolefin, or one masterbatch containing both the black pigment and the inorganic compound can be prepared and blended with the polyolefin. You can also do it.
　黒顔料は、上記熱伝導率の範囲にある黒色に色付けできる化合物であれば特に限定されないが、カーボンブラック、ランプブラック、ベジタブルブラック、ボーンブラック、グラファイトが例示される。 The black pigment is not particularly limited as long as it is a compound that can be colored black within the range of the above thermal conductivity, and examples thereof include carbon black, lamp black, vegetable black, bone black, and graphite.
　本発明のフィルムは、上記樹脂組成物により成形され、製造される。
　具体的には、ポリオレフィンと、熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、熱伝導率が５Ｗ／ｍ・Ｋ以下である黒顔料と、を配合して樹脂組成物を得て、該樹脂組成物をチューブ状又はロール状のフィルムに成形し、該成形されたフィルムをヒートシールし、カットすることにより製造される。
　無機化合物や黒顔料はマスターバッチで配合することもできる。 The film of the present invention is molded and manufactured from the above resin composition.
Specifically, a resin composition is obtained by blending a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m · K or less, and a black pigment having a thermal conductivity of 5 W / m · K or less. , The resin composition is formed into a tube-shaped or roll-shaped film, and the formed film is heat-sealed and cut.
Inorganic compounds and black pigments can also be blended in a masterbatch.
　チューブ状のフィルムに成形する方法としては、インフレーション成形法が例示される。インフレーション成形法は、押出機の先端に環状のリップを備える金型を設置し、チューブ状に樹脂組成物を押し出し、金型の中央から空気孔から圧縮空気を吹き込んで連続的に成形する方法である。
　ロール状のフィルムに成形する方法としては、Ｔダイ押出成形法が例示される。Ｔダイ押出成形法は、押出機の先端にＴダイ（直線状のリップを備える金型）を設置し、平たく樹脂組成物を押し出して成形する方法である。 An inflation molding method is exemplified as a method for molding into a tubular film. The inflation molding method is a method in which a mold having an annular lip is installed at the tip of the extruder, the resin composition is extruded into a tube shape, and compressed air is blown from the center of the mold through an air hole to continuously mold the resin composition. be.
As a method of forming into a roll-shaped film, a T-die extrusion molding method is exemplified. The T-die extrusion molding method is a method in which a T-die (a mold having a linear lip) is installed at the tip of an extruder and a flat resin composition is extruded and molded.
　本発明の構成を有するフィルムの用途は、特に限定されないが、成形性、耐候性、耐熱性等を求められるゴミ袋、レジ袋、買い物袋、農業用資材、工業用資材、流通用資材等が例示される。 The use of the film having the constitution of the present invention is not particularly limited, but includes garbage bags, plastic shopping bags, shopping bags, agricultural materials, industrial materials, distribution materials, etc., which are required to have moldability, weather resistance, heat resistance, etc. Illustrated.
　なお、本発明の樹脂組成物には、通常のフィルム用樹脂に用いられる添加剤を添加してもよいし、しなくてもよい。該添加剤として、酸化防止剤や耐候剤が例示される。 The resin composition of the present invention may or may not contain additives used in ordinary film resins. Examples of the additive include antioxidants and weather resistant agents.
　以下に本発明の実施例を具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
　実施例及び比較例について、表１にまとめた。 Examples of the present invention will be specifically described below, but the present invention is not limited to these examples.
Examples and comparative examples are summarized in Table 1.
－実施例１－
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）（Ｓｕｍｉｔｏｍｏ　Ｃｈｅｍｉｃａｌ　Ａｓｉａ製、型番ＦＳ１５３Ｓ）を７８質量％、炭酸カルシウムマスターバッチ（ＣａＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、内径５５ｍｍ、スクリュー（Ｌ／Ｄ２８）の押出機（プラコー社製）にブレンドされた樹脂組成物を投入し、ダイス径１００ｍφ、リップ３ｍｍを使用し、押出温度１７０℃、ブロー比約３．０にてチューブ状のフィルムを成形した。
　その後、製袋機（野崎工業製）で該チューブ状のフィルムを長さ６００ｍｍにヒートシールし、カットして袋状とした。ヒートシールの温度は、１６０℃～１８０℃の範囲であった。 -Example 1-
78% by mass of linear low density polyethylene (LLDPE) (Suitomo Chemical Asia, model number FS153S), 20% by mass of calcium carbonate masterbatch (containing 80% CaCO 3 ) (GCR, model number GRANIC422), black A 2% by mass blend of a pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470), an inner diameter of 55 mm, and a screw (L / D28) extruder (manufactured by Placo). ) Was added, and a tubular film was formed using a die diameter of 100 mφ and a lip of 3 mm at an extrusion temperature of 170 ° C. and a blow ratio of about 3.0.
Then, the tubular film was heat-sealed to a length of 600 mm with a bag making machine (manufactured by Nozaki Kogyo) and cut into a bag shape. The temperature of the heat seal was in the range of 160 ° C to 180 ° C.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は１６質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　炭酸カルシウムマスターバッチＧＲＡＮＩＣ４２２は、ＣａＣＯ3が８０％、Ｃ８（オクテン）をモノマーとするＬＬＤＰＥが２０％含まれる。黒顔料マスターバッチＦ３１４７０は、カーボンブラックが４０％、ＬＤＰＥが５０％、炭酸カルシウムが１０％含まれる。 The calcium carbonate masterbatch GRANIC422 contains 80% CaCO 3 and 20% LLDPE using C8 (octene) as a monomer. The black pigment masterbatch F31470 contains 40% carbon black, 50% LDPE and 10% calcium carbonate.
　得られたフィルムについて、（１）フィルムの成形性、（２）色目、（３）フィルムの強度、（４）熱劣化について評価を行った。 The obtained film was evaluated for (1) film formability, (2) color, (3) film strength, and (4) thermal deterioration.
（１）フィルムの成形性の評価
　フィルムをチューブ状に成形する際に、安定してフィルムが成形されるかを評価した。通常樹脂と同様に安定してフィルムが成形された場合を○、通常樹脂よりも不安定であるがフィルムが連続して成形できた場合を△、不安定で成形できなかった場合を×とした。 (1) Evaluation of Formability of Film When the film was formed into a tube shape, it was evaluated whether the film was stably formed. The case where the film was stably formed like the normal resin was marked with ○, the case where the film was more unstable than the normal resin but could be continuously molded was marked with Δ, and the case where the film was unstable and could not be molded was marked with ×. ..
（２）色目の評価
　成形されたフィルムを目視で確認し、黒もしくは黒に準ずる色であった場合を○、商品として黒色と認知されない色であった場合を×とした。 (2) Evaluation of color The molded film was visually confirmed, and the case where the color was black or similar to black was evaluated as ◯, and the case where the color was not recognized as black as a product was evaluated as x.
（３）フィルムの強度の評価
　成形されたフィルムを親指で突き刺して評価した。突き刺しの容易性から、突き刺した穴から破れが広がらず強度が高い場合を○、突き刺した穴から破れが広がる場合を△、容易に突き刺せ強度が低い場合を×とした。
　なお、上記親指による突き刺し評価は、現場において精密機械を用いずに簡単に強度を判断できる方法として、有用である。 (3) Evaluation of film strength The molded film was pierced with a thumb and evaluated. For ease of piercing, the case where the tear did not spread from the pierced hole and the strength was high was evaluated as ◯, the case where the tear spread from the pierced hole was evaluated as Δ, and the case where the piercing strength was low was evaluated as ×.
The thumb piercing evaluation is useful as a method for easily determining the strength in the field without using a precision machine.
（４）熱劣化の評価
　５００ｍｌの水入りペットボトルを３本、袋状のフィルムに入れ、太陽光が当たる屋外にて１か月吊るし、外観を観察して熱劣化を評価した。フィルム表面に変化がなかった場合を○、フィルム表面がややザラザラした場合を△、フィルム表面がザラザラする、もしくは、ピンホールが見られた場合は×とした。 (4) Evaluation of heat deterioration Three 500 ml PET bottles containing water were placed in a bag-shaped film and hung outdoors for one month in the sunlight, and the appearance was observed to evaluate the heat deterioration. The case where there was no change on the film surface was evaluated as ◯, the case where the film surface was slightly rough was evaluated as Δ, and the case where the film surface was rough or pinholes were observed was evaluated as ×.
　実施例１の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film molded from the resin composition of Example 1 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例２－
　高密度ポリエチレン（ＨＤＰＥ）（Ｓａｕｄｉ　Ｂａｓｉｃ　Ｉｎｄｕｓｔｒｉｅｓ　Ｃｏｒｐｏｒａｔｉｏｎ社製、型番ＦＪ００９５２）を７８質量％、炭酸カルシウムマスターバッチ（Ｃａ2ＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 2-
78% by mass of high density polyethylene (HDPE) (Saudi Basic Industries Corporation, model number FJ009052), 20% by mass of calcium carbonate masterbatch (80% of Ca 2 CO 3 ) (GCR, model number GRANIC422), A masterbatch of black pigment (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) is blended in an amount of 2% by mass, a tubular film is formed in the same manner as in Example 1, and heat is formed. It was sealed and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は１６質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　実施例２の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film molded from the resin composition of Example 2 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例３－
　フィルムの製造過程において製品にならなかったフィルムや、市場での使用後に回収されたフィルムを用い、リサイクル樹脂を用意した。
　回収されたフィルムは、ＨＤＰＥ系とＬＬＤＰＥ系に分別し、洗浄もしくは無洗浄にてフィルムを粉砕し、押出機でストランド状に押し出し、ペレット状に切断した。実施例３ではＬＬＤＰＥ系のリサイクル樹脂（以下、「リサイクルＬＬ」という。）を用いた。
　ＬＬＤＰＥ系のリサイクル樹脂（リサイクルＬＬ）を７８質量％、炭酸カルシウムマスターバッチ（ＣａＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 3-
Recycled resins were prepared using films that did not become products in the film manufacturing process and films that were recovered after use in the market.
The recovered film was separated into HDPE-based and LLDPE-based, the film was crushed by washing or no washing, extruded into strands by an extruder, and cut into pellets. In Example 3, an LLDPE-based recycled resin (hereinafter referred to as “recycled LL”) was used.
78% by mass of LLDPE-based recycled resin (recycled LL), 20% by mass of calcium carbonate masterbatch (containing 80% of CaCO 3 ) (GCR, model number GRANIC422), 40% of black pigment masterbatch (carbon black) (Contains 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) was blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. .. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は１６質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　実施例３の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film molded from the resin composition of Example 3 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例４－
　実施例３に記載したリサイクル樹脂のうち、実施例４ではＨＤＰＥ系のリサイクル樹脂（以下、「リサイクルＨＤ」という。）を用いた。
　ＨＤＰＥ系のリサイクル樹脂（リサイクルＨＤ）を７８質量％、炭酸カルシウムマスターバッチ（Ｃａ2ＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 4-
Among the recycled resins described in Example 3, HDPE-based recycled resin (hereinafter referred to as “recycled HD”) was used in Example 4.
78% by mass of HDPE-based recycled resin (recycled HD), 20% by mass of calcium carbonate masterbatch (containing 80% of Ca 2 CO 3 ) (GCR, model number GRANIC422), black pigment masterbatch (carbon black) (Contains 40% and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) is blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, cut and bag-shaped. And said. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は１６質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 16% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　実施例４の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 4 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例５－
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）（Ｓｕｍｉｔｏｍｏ　Ｃｈｅｍｉｃａｌ　Ａｓｉａ社製、型番ＦＳ１５３Ｓ）を８質量％、ＬＬＤＰＥ系のリサイクル樹脂（リサイクルＬＬ）を５０質量％、炭酸カルシウムマスターバッチ（Ｃａ2ＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を４０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 5-
Linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical Asia, model number FS153S) is 8% by mass, LLDPE-based recycled resin (recycled LL) is 50% by mass, and calcium carbonate masterbatch (Ca 2 CO 3 is 80%). (Included) (GCR, model number GRANIC422) is blended by 40% by mass, and black pigment masterbatch (carbon black is 40%, calcium carbonate is contained at 10%) (DIC Co., Ltd., model number F31470) is blended by 2% by mass. A tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は３２質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 32% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　実施例５の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 5 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例６－
　高密度ポリエチレン（ＨＤＰＥ）（Ｓａｕｄｉ　Ｂａｓｉｃ　Ｉｎｄｕｓｔｒｉｅｓ　Ｃｏｒｐｏｒａｔｉｏｎ社製、型番ＦＪ００９５２）を２６質量％、ＨＤＰＥ系のリサイクル樹脂（リサイクルＨＤ）を５０質量％、二酸化チタンマスターバッチ（ＴｉＯ2が７０％含まれる）（ＤＩＣ株式会社製、型番Ｌ－１１１６７ＭＰＴ）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を４質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。
　二酸化チタンマスターバッチＬ－１１１６７ＭＰＴは、二酸化チタンが７０％、ＬＬＤＰＥが３０％含まれる。 -Example 6-
High-density polyethylene (HDPE) (manufactured by Saudi Basic Industries Corporation, model number FJ009052) is 26% by mass, HDPE-based recycled resin (recycled HD) is 50% by mass, and titanium dioxide masterbatch (70% of TiO 2 is contained) ( 20% by mass of DIC Co., Ltd., model number L-11167MPT) and 4% by mass of black pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (DIC Co., Ltd., model number F31470). A tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
The titanium dioxide masterbatch L-11167MPT contains 70% titanium dioxide and 30% LLDPE.
　フィルム中の無機化合物である二酸化チタンの熱伝導率は１０Ｗ／ｍ・Ｋ、濃度は１４質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は１．６質量％であった。 The thermal conductivity of titanium dioxide, which is an inorganic compound in the film, is 10 W / m · K and the concentration is 14% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K and the concentration is 1. It was 0.6% by mass.
　実施例６の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 6 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例７－
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）（Ｓｕｍｉｔｏｍｏ　Ｃｈｅｍｉｃａｌ　Ａｓｉａ社製、型番ＦＳ１５３Ｓ）を６６質量％、タルクマスターバッチ（Ｍｇ3Ｓｉ4Ｏ10（ＯＨ）2が７０％含まれる）（竹原化学工業社製、型番１２７０Ｔ）を３０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を４質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。
　タルクマスターバッチ１２７０Ｔは、タルクが７０％、ＬＬＤＰＥが３０％含まれる。　 -Example 7-
66% by mass of linear low density polyethylene (LLDPE) (manufactured by Sumitomo Chemical Asia, model number FS153S), talc masterbatch (containing 70% of Mg 3 Si 4 O 10 (OH) 2 ) (manufactured by Takehara Chemical Industry Co., Ltd.) , Model No. 1270T) by 30% by mass, and black pigment masterbatch (containing 40% of carbon black and 10% of calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) by 4% by mass, in the same manner as in Example 1. A tube-shaped film was formed, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
The talc masterbatch 1270T contains 70% talc and 30% LLDPE.
　フィルム中の無機化合物であるタルクの熱伝導率は０．３Ｗ／ｍ・Ｋ、濃度は２１質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は１．６質量％であった。 The thermal conductivity of talc, which is an inorganic compound in the film, is 0.3 W / m · K and the concentration is 21% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K and the concentration is It was 1.6% by mass.
　実施例７の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 7 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例８－
　無機化合物の二酸化ケイ素（日鉄ケミカル＆マテリアル社製、型番ＨＳ－３１１）を５０質量％、及び、ポリエチレン粉末（宇部丸善ポリエチレン株式会社製、型番ＵＭ１８０５）を５０質量％配合し、スーパーミキサーで５分間混合後、２軸押出機によりストランド状に押し出し、ペレット状に切断した。これを二酸化ケイ素マスターバッチとした。
　高密度ポリエチレン（ＨＤＰＥ）（Ｓａｕｄｉ　Ｂａｓｉｃ　Ｉｎｄｕｓｔｒｉｅｓ　Ｃｏｒｐｏｒａｔｉｏｎ社製、型番ＦＪ００９５２）を１８質量％、ＨＤＰＥ系のリサイクル樹脂（リサイクルＨＤ）を５０質量％、二酸化ケイ素マスターバッチ（ＳｉＯ2が５０％含まれる）を２６質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を６質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 8-
50% by mass of the inorganic compound silicon dioxide (manufactured by Nittetsu Chemical & Materials Co., Ltd., model number HS-311) and 50% by mass of polyethylene powder (manufactured by Ube-Maruzen Polyethylene Co., Ltd., model number UM1805) are mixed, and 5 by super mixer. After mixing for a minute, it was extruded into strands by a twin-screw extruder and cut into pellets. This was designated as a silicon dioxide masterbatch.
18% by mass of high density polyethylene (HDPE) (manufactured by Saudi Basic Industries Corporation, model number FJ009052), 50% by mass of HDPE-based recycled resin (recycled HD), and 50% by weight of silicon dioxide masterbatch (containing 50% SiO 2 ). A tube-shaped film was formed by blending 26% by mass and 6% by mass of a black pigment masterbatch (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) in the same manner as in Example 1. It was molded, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である二酸化ケイ素の熱伝導率は１．４Ｗ／ｍ・Ｋ、濃度は１３質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は２．４質量％であった。 The thermal conductivity of silicon dioxide, which is an inorganic compound in the film, is 1.4 W / m · K, the concentration is 13% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 2.4% by mass.
　実施例８の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 8 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－実施例９－
　実施例３に記載したリサイクル樹脂のうち、実施例９ではＨＤＰＥ系のリサイクル樹脂（リサイクルＨＤ）を用いた。
　ＨＤＰＥ系のリサイクル樹脂（リサイクルＨＤ）を８５質量％、炭酸カルシウムマスターバッチ（ＣａＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を１３質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Example 9-
Among the recycled resins described in Example 3, HDPE-based recycled resin (recycled HD) was used in Example 9.
85% by mass of HDPE-based recycled resin (recycled HD), 13% by mass of calcium carbonate masterbatch (containing 80% of CaCO 3 ) (GCR, model number GRANIC422), black pigment masterbatch (40% of carbon black) (Contains 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) was blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. .. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は１０質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 10% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 0.8% by mass.
　実施例９の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度○、（４）熱劣化○と評価された。 The film formed by the resin composition of Example 9 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ○, and (4) thermal deterioration ○.
－比較例１－
　ＬＬＤＰＥ系のリサイクル樹脂（リサイクルＬＬ）を７８質量％、アルミニウムマスターバッチ（Ａｌが７０％含まれる）（東洋アルミニウム社製、型番ＮＭＥ００５）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Comparative example 1-
78% by mass of LLDPE-based recycled resin (recycled LL), 20% by mass of aluminum masterbatch (containing 70% of Al) (manufactured by Toyo Aluminum Co., Ltd., model number NME005), black pigment masterbatch (40% of carbon black, (Containing 10% of calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) was blended in an amount of 2% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物であるアルミニウムの熱伝導率は２０４Ｗ／ｍ・Ｋ、濃度は１４質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 The thermal conductivity of aluminum, which is an inorganic compound in the film, is 204 W / m · K and the concentration is 14% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K and the concentration is 0. It was 8% by mass.
　比較例１の樹脂組成物により成形したフィルムは、（１）フィルムの成形性×、（２）色目×、（３）フィルムの強度△、（４）熱劣化×と評価された。 The film formed by the resin composition of Comparative Example 1 was evaluated as (1) film formability ×, (2) color ×, (3) film strength Δ, and (4) thermal deterioration ×.
－比較例２－
　高密度ポリエチレン（ＨＤＰＥ）（Ｓａｕｄｉ　Ｂａｓｉｃ　Ｉｎｄｕｓｔｒｉｅｓ　Ｃｏｒｐｏｒａｔｉｏｎ社製、型番ＦＪ００９５２）を３１質量％、炭酸カルシウムマスターバッチ（ＣａＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を６５質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）（ＤＩＣ株式会社製、型番Ｆ３１４７０）を４質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Comparative example 2-
31% by mass of high density polyethylene (HDPE) (Saudi Basic Industries Corporation, model number FJ009052), 65% by mass of calcium carbonate masterbatch (80% of CaCO 3 ) (GCR, model number GRANIC422), black pigment A masterbatch (containing 40% carbon black and 10% calcium carbonate) (manufactured by DIC Co., Ltd., model number F31470) is blended in an amount of 4% by mass, a tubular film is formed and heat-sealed in the same manner as in Example 1. , Cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は５２質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は１．６質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 52% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 1.6% by mass.
　比較例２の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目×、（３）フィルムの強度×、（４）熱劣化×と評価された。 The film formed by the resin composition of Comparative Example 2 was evaluated as (1) film formability ○, (2) color ×, (3) film strength ×, and (4) thermal deterioration ×.
－比較例３－
　無機化合物のアルミナ（昭和電工株式会社製、型番ＣＢ－Ｐ０２）を５０質量％、及び、ポリエチレン粉末（宇部丸善ポリエチレン株式会社製、型番ＵＭ１８０５）を５０質量％配合し、スーパーミキサーで５分間混合後、２軸押出機によりストランド状に押し出し、ペレット状に切断した。これをアルミナマスターバッチとした。
　メタロセン触媒で合成したＬＬＤＰＥ樹脂（ｍ－ＬＬＤＰＥ）を７８質量％、アルミナマスターバッチ（Ａｌ2Ｏ3が５０％含まれる）を２０質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）を２質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Comparative example 3-
50% by mass of the inorganic compound alumina (Showa Denko KK, model number CB-P02) and 50% by mass of polyethylene powder (Ube-Maruzen Polyethylene Co., Ltd., model number UM1805) are mixed and mixed with a super mixer for 5 minutes. It was extruded into strands by a twin-screw extruder and cut into pellets. This was used as an alumina masterbatch.
78% by mass of LLDPE resin (m-LLDPE) synthesized with a metallocene catalyst, 20% by mass of alumina masterbatch (containing 50% of Al 2 O 3 ), black pigment masterbatch (40% of carbon black, calcium carbonate) (Contains 10%) was blended in an amount of 2% by mass, a tubular film was formed in the same manner as in Example 1, heat-sealed, and cut into a bag shape. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物であるアルミナの熱伝導率は３６Ｗ／ｍ・Ｋ、濃度は１０質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は０．８質量％であった。 Alumina, which is an inorganic compound in the film, has a thermal conductivity of 36 W / m · K and a concentration of 10% by mass, and a black pigment (carbon black) has a thermal conductivity of 2.2 W / m · K and a concentration of 0. It was 8% by mass.
　比較例３の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目×、（３）フィルムの強度○、（４）熱劣化×と評価された。 The film formed by the resin composition of Comparative Example 3 was evaluated as (1) film formability ○, (2) color ×, (3) film strength ○, and (4) thermal deterioration ×.
－比較例４－
　直鎖状低密度ポリエチレン（ＬＬＤＰＥ）（Ｓｕｍｉｔｏｍｏ　Ｃｈｅｍｉｃａｌ　Ａｓｉａ社製、型番ＦＳ１５３Ｓ）を１５質量％、炭酸カルシウムマスターバッチ（ＣａＣＯ3が８０％含まれる）（ＧＣＲ社製、型番ＧＲＡＮＩＣ４２２）を７５質量％、黒顔料マスターバッチ（カーボンブラックが４０％、炭酸カルシウムが１０％含まれる）を１０質量％ブレンドし、実施例１と同様にチューブ状のフィルムを成形し、ヒートシールし、カットして袋状とした。得られたフィルムについて、実施例１と同様な評価を行った。 -Comparative example 4-
Linear low density polyethylene (LLDPE) (Suitomo Chemical Asia, model number FS153S) is 15% by mass, calcium carbonate masterbatch (80% of CaCO 3 is contained) (GCR, model number GRANIC422) is 75% by mass, A masterbatch of black pigment (containing 40% carbon black and 10% calcium carbonate) is blended in an amount of 10% by mass to form a tubular film in the same manner as in Example 1, heat-sealed, and cut into a bag shape. bottom. The obtained film was evaluated in the same manner as in Example 1.
　フィルム中の無機化合物である炭酸カルシウムの熱伝導率は１．０Ｗ／ｍ・Ｋ、濃度は６０質量％であり、黒顔料（カーボンブラック）の熱伝導率は２．２Ｗ／ｍ・Ｋ、濃度は４．０質量％であった。 The thermal conductivity of calcium carbonate, which is an inorganic compound in the film, is 1.0 W / m · K, the concentration is 60% by mass, and the thermal conductivity of the black pigment (carbon black) is 2.2 W / m · K, concentration. Was 4.0% by mass.
　比較例４の樹脂組成物により成形したフィルムは、（１）フィルムの成形性○、（２）色目○、（３）フィルムの強度×、（４）熱劣化×と評価された。 The film formed by the resin composition of Comparative Example 4 was evaluated as (1) film formability ○, (2) color ○, (3) film strength ×, and (4) thermal deterioration ×.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以上の実施例及び比較例から、ポリオレフィンと、１０質量％以上５０質量％以下であり熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、熱伝導率が５Ｗ／ｍ・Ｋ以下である黒顔料を含む樹脂組成物により成形されたフィルムは、成形性が良好であり、熱による強度の低下や劣化が少ない、環境に優しいものであることが分かった。 From the above Examples and Comparative Examples, a polyolefin, an inorganic compound having a thermal conductivity of 10% by mass or more and 50% by mass or less and a thermal conductivity of 20 W / m · K or less, and a thermal conductivity of 5 W / m · K or less. It was found that the film formed by the resin composition containing the black pigment has good moldability, is less likely to decrease in strength or deteriorate due to heat, and is environmentally friendly.

Claims (9)

  1. 　樹脂組成物であって、
    　ポリオレフィンと、
    　熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、
    　熱伝導率が５Ｗｍ／ｍ・Ｋ以下である黒顔料と、
    を含み、
    　前記無機化合物は前記樹脂組成物全量に対し１０質量％以上５０質量％以下である、樹脂組成物。     It is a resin composition
    With polyolefin
    Inorganic compounds with thermal conductivity of 20 W / m · K or less,
    Black pigments with a thermal conductivity of 5 Wm / m · K or less,
    Including
    The resin composition in which the inorganic compound is 10% by mass or more and 50% by mass or less with respect to the total amount of the resin composition.
  2. 　前記黒顔料は前記樹脂組成物全量に対し０．５質量％以上３質量％以下である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the black pigment is 0.5% by mass or more and 3% by mass or less with respect to the total amount of the resin composition.
  3. 　前記無機化合物は、炭酸カルシウム、二酸化チタン、タルク、二酸化ケイ素のいずれか１以上を含む、請求項１又は２に記載の樹脂組成物。 The resin composition according to claim 1 or 2, wherein the inorganic compound contains any one or more of calcium carbonate, titanium dioxide, talc, and silicon dioxide.
  4. 　前記ポリオレフィンはポリエチレン系である、請求項１～３いずれか一項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 3, wherein the polyolefin is polyethylene-based.
  5. 　請求項１～４いずれか一項に記載の樹脂組成物により成形された、フィルム。 A film formed by the resin composition according to any one of claims 1 to 4.
  6. 　前記フィルムは、ゴミ袋、レジ袋、買い物袋、農業用資材、工業用資材、流通用資材である、請求項５に記載のフィルム。 The film according to claim 5, wherein the film is a garbage bag, a plastic shopping bag, a shopping bag, an agricultural material, an industrial material, and a distribution material.
  7. 　フィルムの製造方法であって、
    　ポリオレフィンと、熱伝導率が２０Ｗ／ｍ・Ｋ以下である無機化合物と、熱伝導率が５Ｗ／ｍ・Ｋ以下である黒顔料と、を含む成分を配合して樹脂組成物を得るステップと、
    　前記得られた樹脂組成物をチューブ状のフィルム又はロール状のフィルムに成形するステップと、
    　前記成形されたチューブ状のフィルム又はロール状のフィルムをヒートシールするステップと、
    　前記ヒートシールされたチューブ状のフィルム又はロール状のフィルムをカットするステップと、を含み、
    　前記無機化合物は、樹脂組成物全量に対し１０質量％以上５０質量％以下である、フィルムの製造方法。     It ’s a film manufacturing method.
    A step of blending a component containing a polyolefin, an inorganic compound having a thermal conductivity of 20 W / m · K or less, and a black pigment having a thermal conductivity of 5 W / m · K or less to obtain a resin composition.
    The step of molding the obtained resin composition into a tube-shaped film or a roll-shaped film, and
    The step of heat-sealing the molded tubular film or roll-shaped film,
    Including the step of cutting the heat-sealed tubular film or roll-shaped film.
    A method for producing a film, wherein the inorganic compound is 10% by mass or more and 50% by mass or less based on the total amount of the resin composition.
  8. 　前記チューブ状のフィルムに成形するステップは、インフレーション成形である、請求項７に記載のフィルムの製造方法。 The film manufacturing method according to claim 7, wherein the step of molding into the tubular film is inflation molding.
  9. 　前記ロール状のフィルムに成形するステップは、Ｔダイ押出成形である、請求項７に記載のフィルム製造方法。 The film manufacturing method according to claim 7, wherein the step of molding into the roll-shaped film is T-die extrusion molding.
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Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143640A (en) * 1984-08-07 1986-03-03 Karupu Kogyo Kk Resin composition
JPS62275748A (en) * 1985-06-05 1987-11-30 出光石油化学株式会社 Resin laminate
JPH02276763A (en) * 1989-11-13 1990-11-13 Taiyo Plant Kk Folding device for plastic sheet
JPH05125203A (en) * 1991-11-01 1993-05-21 Agency Of Ind Science & Technol Method of bonding polyolefin-based synthetic resin molding
JPH0648903A (en) * 1992-07-08 1994-02-22 Azetsukusu:Kk Synthetic resin composition
JPH0657053A (en) * 1992-08-11 1994-03-01 Mitsui Petrochem Ind Ltd Light screening film
JPH0753792A (en) * 1993-08-17 1995-02-28 Mitsubishi Chem Corp Polyethylene resin composition for packaging bag and production of packaging bag therefrom
JPH09221568A (en) * 1996-02-14 1997-08-26 Maruzen Petrochem Co Ltd Photodegradable green mulching film
JPH1017723A (en) * 1996-07-01 1998-01-20 Calp Corp Polyolefin composite resin composition of good slidtng properties
JP2001162743A (en) * 1999-09-29 2001-06-19 Sumitomo Bakelite Co Ltd Surface-conductive polyolefin sheet
JP2004269058A (en) * 2004-04-12 2004-09-30 Sumitomo Chem Co Ltd Bag comprising thermoplastic resin film
JP2007211195A (en) * 2006-02-13 2007-08-23 Kaneka Corp Resin composition
JP2011006707A (en) * 1998-12-09 2011-01-13 Kureha Corp Synthetic resin composition
JP2018021121A (en) * 2016-08-03 2018-02-08 プロパテント株式会社 Resin composition for garbage bag, garbage bag, and method for producing garbage bag

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5342862A (en) * 1990-03-13 1994-08-30 Biolan Corporation Process for controlling the photodegradation of mulch film
JP3244906B2 (en) * 1993-12-29 2002-01-07 日本石油化学株式会社 Polyolefin garbage bag
JP3244907B2 (en) * 1993-12-29 2002-01-07 日本石油化学株式会社 Easy incineration trash bag
JPH07206005A (en) * 1993-12-29 1995-08-08 Nippon Petrochem Co Ltd Garbage bag
JPH07196818A (en) * 1993-12-29 1995-08-01 Nippon Petrochem Co Ltd Garbage bag excellent in feeling
JP3030026B1 (en) * 1999-06-23 2000-04-10 株式会社クルー Synthetic resin composition, synthetic resin film comprising the resin composition, method for producing the same, and bag comprising the film
JP2001341801A (en) * 2000-05-31 2001-12-11 Shikoku Kako Kk Refuse bag with functional window
US7811597B2 (en) * 2004-09-24 2010-10-12 Jad Corporation Of America Garbage bag or container
JP2007100048A (en) * 2005-10-07 2007-04-19 Masamitsu Nagahama Low-density polyethylene resin product, manufacturing method of low-density polyethylene resin product and use of particulate
US9896574B2 (en) * 2013-04-10 2018-02-20 Dow Global Technologies Llc Films with improved dart impact resistance
US20140308496A1 (en) * 2013-04-10 2014-10-16 Dow Global Technologies Llc Multilayer films with improved opacity and strength
CN111057368A (en) * 2019-12-31 2020-04-24 王晖 Infrared light reflection nylon 6 plastic material and preparation method thereof

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6143640A (en) * 1984-08-07 1986-03-03 Karupu Kogyo Kk Resin composition
JPS62275748A (en) * 1985-06-05 1987-11-30 出光石油化学株式会社 Resin laminate
JPH02276763A (en) * 1989-11-13 1990-11-13 Taiyo Plant Kk Folding device for plastic sheet
JPH05125203A (en) * 1991-11-01 1993-05-21 Agency Of Ind Science & Technol Method of bonding polyolefin-based synthetic resin molding
JPH0648903A (en) * 1992-07-08 1994-02-22 Azetsukusu:Kk Synthetic resin composition
JPH0657053A (en) * 1992-08-11 1994-03-01 Mitsui Petrochem Ind Ltd Light screening film
JPH0753792A (en) * 1993-08-17 1995-02-28 Mitsubishi Chem Corp Polyethylene resin composition for packaging bag and production of packaging bag therefrom
JPH09221568A (en) * 1996-02-14 1997-08-26 Maruzen Petrochem Co Ltd Photodegradable green mulching film
JPH1017723A (en) * 1996-07-01 1998-01-20 Calp Corp Polyolefin composite resin composition of good slidtng properties
JP2011006707A (en) * 1998-12-09 2011-01-13 Kureha Corp Synthetic resin composition
JP2001162743A (en) * 1999-09-29 2001-06-19 Sumitomo Bakelite Co Ltd Surface-conductive polyolefin sheet
JP2004269058A (en) * 2004-04-12 2004-09-30 Sumitomo Chem Co Ltd Bag comprising thermoplastic resin film
JP2007211195A (en) * 2006-02-13 2007-08-23 Kaneka Corp Resin composition
JP2018021121A (en) * 2016-08-03 2018-02-08 プロパテント株式会社 Resin composition for garbage bag, garbage bag, and method for producing garbage bag

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