WO2005087864A1 - 無機系造核剤含有樹脂組成物、その成形品及びその製造方法 - Google Patents
無機系造核剤含有樹脂組成物、その成形品及びその製造方法 Download PDFInfo
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- WO2005087864A1 WO2005087864A1 PCT/JP2005/004374 JP2005004374W WO2005087864A1 WO 2005087864 A1 WO2005087864 A1 WO 2005087864A1 JP 2005004374 W JP2005004374 W JP 2005004374W WO 2005087864 A1 WO2005087864 A1 WO 2005087864A1
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
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- C08K3/34—Silicon-containing compounds
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/704—Crystalline
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/72—Density
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C08L23/0853—Vinylacetate
- C08L23/0861—Saponified vinylacetate
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- 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
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
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- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Definitions
- the present invention relates to a resin composition containing an inorganic nucleating agent, a molded article thereof, and a method for producing the same.
- the present invention has a high elastic modulus in a high temperature region above room temperature, has excellent impact resistance in a low temperature region below the freezing point, and has a level at which odor can withstand food applications, and minimizes an increase in specific gravity.
- a propylene resin composition which utilizes an inorganic filler such as talc, which is relatively close to the composition of the present invention, as a rigidity improving material and also uses an ethylene-a-one-year-old olefin copolymer rubber.
- Patent Documents 1-4 A propylene resin composition is disclosed which utilizes an inorganic filler such as talc, which is relatively close to the composition of the present invention, as a rigidity improving material and also uses an ethylene-a-one-year-old olefin copolymer rubber.
- composite reinforced polypropylene consisting of about 20-30% by mass of ethylene propylene rubber (EPR) and about 10% by mass of talc based on meta-impact block polypropylene (B-PP) is widely used for automobiles. Is known (Non-Patent Document 1, etc.).
- EBR ethylene butene rubber
- C4-C20 ethylene a one-year-old olefin
- Talc is known to act as a crystal nucleating agent for crystalline thermoplastic resins. There are few proposals to add trace amounts to a polypropylene-based system.
- Patent Document 8 it is added only for the purpose of maintaining transparency in order to reduce post-shrinkage of the interior material of automobiles and to ensure internal visibility (Patent Document 8 and the like).
- Patent Document 9 a crystal nucleating agent to polypropylene
- B-PP block polypropylene
- Patent Document 10 a crystallization nucleating agent and talc are used to improve the rigidity and low-temperature impact strength of block polypropylene (B-PP). It is also effective to mix them together (Patent Document 10, etc.).
- the aim of the present invention to achieve a thinner molded article and a higher weight reduction rate by improving the elastic modulus of the polypropylene while maintaining the impact resistance of the polypropylene at a certain level or higher is the above composition. Is not suitable.
- ethylene- ⁇ -olefin copolymers disclosed herein are only those having a density region corresponding to linear low-density polyethylene.
- the ethylene ⁇ -olefin olefin copolymer used in the present invention has a density range corresponding to an elastomer, is essentially different from the above composition, and has a low-temperature impact resistance as the object of the present invention.
- the use amount of talc disclosed as an embodiment and used as a filler is 5% by weight and 10% by weight, which is different from the use amount range of the present invention, and is used as a filler. Philosophical ideas are different.
- an inorganic substance such as talc is used in a smaller specific usage range. It is mainly expected to have a nucleation effect of the polypropylene crystal, and can avoid disadvantages such as generation of odor and bad appearance when used as a filler because of a small amount used.
- Containers for retort foods and the like are required to have heat resistance, rigidity, low-temperature impact resistance, low odor, light weight, and the like.
- Patent Documents 19 to 23, etc. In the case of containers and the like, since easy opening is required at the same time as maintaining heat resistance, an invention has been made to impart a function of easily peeling off a layer sealing a lid material (Patent Documents 19 to 23, etc.) ).
- Patent Documents 19 to 21 and the like if a resin layer is provided to provide a peeling function, heat resistance and rigidity may be sacrificed in some cases.
- Patent Documents 22 to 23, etc. In order to solve this problem, it has been proposed to use polyolefin having high heat resistance (Patent Documents 22 to 23, etc.), but the rigidity of the polypropylene resin layer is insufficient and the rigidity as a whole is reduced. There is.
- control of the molecular structure such as enhancing the stereoregularity of polypropylene, control of the higher order structure such as biaxial stretching, and the incorporation of a crystal nucleating agent are also carried out.
- Patent Document 1 Japanese Patent Application Laid-Open No. 6-263960
- Patent Document 2 Patent No. 2839840
- Patent Document 3 JP-A-10-273569
- Patent Document 4 JP 2003-183460
- Patent Document 5 Patent No. 3115766
- Patent Document 6 JP-A-11-1599
- Patent Document 7 JP-A-11-209532
- Patent Document 8 JP-A-6-287364
- Patent Document 9 JP-A-9-194652
- Patent Document 10 Patent No. 1782354
- Patent Document 11 Japanese Patent Laid-Open No. 10? No. 120849
- Patent Document 12 Patent No. 3506538
- Patent Document 13 Patent No. 3472933
- Patent Document 14 JP-A-11 293059
- Patent Document 15 JP-A-11-240986
- Patent Document 16 JP-A-11 29661
- Patent Document 17 JP-A-8-156201
- Patent Document 18 JP-A-2000-336218
- Patent Document 19 Japanese Patent Publication No. 7-2409
- Patent Document 20 Patent No. 2965825
- Patent document 21 JP-A-6-71824
- Patent Document 22 Patent No. 3124206
- Patent Document 23 JP-A-10-291561
- Non-patent Document 1 Nomura et al., Collection of Polymer Papers, Vol. 50, No. 2, 81 (1993)
- the phosphorus-containing organic nucleating agent which is generally considered to have a low odor level, generates a strong odor in the system of the present invention. Disclosure of the invention
- the present invention has a high elastic modulus in a high temperature range of room temperature or higher, has excellent impact resistance in a low temperature range of freezing point or lower, and has a level at which an odor can endure food use.
- the present invention provides an inorganic nucleating agent-containing resin composition in which the composition is minimized, a multilayer structure using the composition in at least one layer, a container and a molded product obtained by thermoforming the same, and a method for producing the same. It is a subject.
- the present inventors have found that a resin composition containing a combination of a propylene homopolymer or a propylene-based block copolymer, an ethylene alpha-olefin copolymer rubber and an inorganic nucleating agent, has a rigidity and a rigidity.
- the inventors have found that the impact resistance balance is improved, the specific gravity is low, the odor is low, and the above problem can be solved, and the present invention has been completed.
- the present invention provides:
- component (a) is a propylene homopolymer
- a multilayer structure having a total thickness of 200 m or more, wherein at least one layer of the multilayer structure has an inorganic nucleating agent-containing resin composition (A) according to any one of the above items 17 to 17.
- the thickness of the resin composition layer is 50% or more of the total thickness
- a multilayer structure having a total thickness of 200 m or more, wherein at least one layer of the multilayer structure has an inorganic nucleating agent-containing resin composition (A) according to any one of the above items 17 to 17. And the thickness of the resin composition layer is 50% or more of the total thickness, and a propylene-based resin or a surface layer composed of the propylene-based resin composition (B); Resin composition or resin (C) containing a combination of resin-based resin less than 80% by mass and thermoplastic resin other than propylene-based resin at 20% by mass or more, and the thickness is 0.1-10% of the total thickness
- a multilayer structure comprising a release functional layer, wherein the peel strength of a surface layer portion including the surface layer is at least 1.0-10 N ZlOmm width.
- the resin composition containing an inorganic nucleating agent containing a combination of a propylene homopolymer or a propylene block copolymer, an ethylene olefin copolymer rubber and an inorganic nucleating agent according to the present invention has a rigidity and It has excellent impact resistance balance, low specific gravity, no odor and low cost.
- the impact resistance in the low temperature range where problems such as odor generation are eliminated is maintained at a certain level or more, the elastic modulus in the high temperature range above normal temperature is improved, and finally the weight of the molded product is improved. Since the reduction can be achieved, it is possible to obtain not only the cost reduction of the production of the molded product but also the effect that the volume reduction can be achieved when the molded product fulfills a predetermined role and is discarded.
- FIG. 1 is a cross-sectional view of an example of the multilayer structure of the present invention.
- FIG. 2 is a top view (a) and a cross-sectional view (b) of an example of the multilayer structure in the container of the present invention.
- FIG. 3 is a conceptual diagram showing the relationship among the S value, the impact strength at -5 ° C falling weight (Y axis), and the elastic modulus at 80 ° C (X axis).
- FIG. 4 shows the effect of talc content with an average particle size of 4.9 m on the weight reduction rate of molded articles (see Examples 13-15 and Comparative Examples 18-20 in Table 5).
- FIG. 5 shows the effect of talc content with an average particle size of 1.0 m on the weight reduction rate of molded articles (see Examples 27-29 and Comparative Examples 24-26 in Table 6).
- a propylene homopolymer or a propylene homopolymer having an isotactic pentad fraction of a propylene chain portion of 0.90 or more is used as the component (a).
- a block copolymer is used as the component (a).
- propylene-based block copolymer examples include, for example, a propylene-based block composed of a propylene homopolymer and an ethylene-propylene random copolymer having a relatively large ethylene unit content and a copolymer part having a high strength.
- Crystalline propylene ethylene a copolymer of ⁇ -olefin such as butene 1 or a copolymer thereof, or a copolymer of ⁇ -olefin such as butene 1 in the propylene-based block copolymer.
- the propylene-based block copolymer and the propylene homopolymer preferably have an isotactic pentad fractional power of 0.95 or more from the viewpoint of rigidity and heat resistance.
- the isotactic pentad fraction is defined as a method disclosed by A. Zambelli et al. In Macromolecules, 6, 925 (1973), that is, a propylene polymer molecular chain measured using 13 C-NMR. It is the fraction of the isotactic chain in pentad units in the middle, in other words, the propylene monomer unit at the center of the chain in which five propylene monomer units are consecutively meso-bonded.
- the isotactic pentad fraction is measured as the area fraction of the mmmm peak in all the absorption peaks in the methyl carbon region of the 13 C-NMR spectrum.
- the propylene homopolymer is subjected to “C NMR measurement as it is, and the propylene-based block copolymer is dissolved in heated xylene and then dissolved in insoluble components when returned to room temperature. was measured for 13 C-NMR.
- Such a highly stereoregular propylene homopolymer and propylene-based block copolymer can be produced, for example, using a Ziegler-Natta type catalyst or the like.
- melt flow rate MFR temperature: 230 ° C., load: 21.2N
- a melt flow rate in the range of 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min can be used.
- the ethylene-a-olefin copolymer rubber of the component (b) may be ethylene, having 3 to 20 carbon atoms. Examples thereof include those obtained by random copolymerizing ⁇ -olefin or the ⁇ -olefin and a gen-based monomer.
- Examples of the ⁇ -olefin having 3 to 20 carbon atoms include propylene, butene 1, hexene 1, otaten 1, nonene-1, decene 1, undene 1, dodecene 1, and the like.
- it is an ⁇ -olefin having 4 to 12 carbon atoms.
- the diene monomer examples include conjugated diene compounds such as butadiene and isoprene, 1,4-hexadiene, 1,6-tactadene, cyclopentadiene, 5-ethylidene-2 norbornene, and isopropylidene-2 norbornene.
- the ethylene ⁇ - olefin copolymer rubber includes ethylene propylene copolymer rubber (EPR), ethylene propylene copolymer rubber (EPDM), and ethylene butene-1 copolymer rubber (EBR).
- ethylene-1 hexene 1 copolymer rubber ethylene octene-1 copolymer rubber (EOR), ethylene-decene-1 copolymer rubber, ethylene-dodecene 1 copolymer rubber, and the like.
- thermoplastic elastomers These all belong to the thermoplastic elastomers.
- the inorganic nucleating agent of the component (d) dramatically increases the generation rate of crystal nuclei during the crystallization process of polypropylene.
- talc my strength, carbon black, silica, dolomite powder, silicate , Quartz powder, diatomaceous earth, alumina and the like.
- the inorganic nucleating agent can be directly dry-blended with the resin material, but the viewpoint of the dispersibility of the inorganic nucleating agent in the resin is based on the fact that the resin such as polypropylene is filled in advance at a high concentration. It is preferable to use a thing (master batch)! / ,.
- a masterbatch containing 5-80% by mass as the concentration of the inorganic nucleating agent can be used, but is not limited to this.
- the method of producing the master batch may be a known method such as a continuous method using a single-screw or twin-screw kneading extruder, or a batch method using a Banbury mixer, a Henschel mixer, or the like. A method can be used.
- the inorganic nucleating agent may be used without any treatment, but for the purpose of improving interfacial adhesion and dispersibility, generally known various silane coupling agents, titanium coupling agents, higher fatty acids, etc. And those obtained by treating the surface with a higher fatty acid ester, a higher fatty acid amide, a higher fatty acid salt or another surfactant.
- the particle size of the inorganic nucleating agent is not particularly limited, but the finer the particle, the greater the effect as a nucleating agent.
- fine powder having an average particle size of usually 15 m or less, preferably 7 m or less, is used.
- the smallest particle size among commercially available talc is: Lm.
- the average particle size of talc is preferably as small as possible, as long as it is uniformly dispersed during the master batch production stage and the final molded article stage, as well as the rigidity and impact resistance Norance surface force.
- Talc is an inorganic powder obtained by finely pulverizing talc and containing hydrous magnesium silicate [Mg Si O (O
- Equivalent particle diameter D means sedimentation method (using centrifugal sedimentation type
- the value of the integral distribution curve of the sieving method measured by suspending in a dispersion medium such as alcohol is generally 2 to 5 times higher than the value obtained by the 50% equivalent particle diameter D50).
- the average particle size is within the above range, the effect as a nucleating agent can be sufficiently obtained even with a relatively small amount of blending while ensuring uniform dispersibility in the resin composition (A) containing an inorganic nucleating agent. Since it can be exerted, the rigidity is improved, the thickness of the composition can be reduced, and the impact resistance can be reduced little by being uniformly dispersed in the resin composition.
- the inorganic nucleating agent containing ⁇ composition (A) of the present invention there are two aspects, the first aspect, the (a) the propylene block copolymer 100- 70 mass 0/0, ( b) Ethylene ⁇ -olefin copolymer rubber 0 to 10% by mass, (c) high density polyethylene 0 to 20% by mass, and the total amount of the above components (a), (b) and (c) 100
- the composition contains a combination of 0.4 to 3.0 parts by mass of the inorganic nucleating agent with respect to parts by mass.
- the preferable content ratio is 99 to 75% by mass of the propylene-based block copolymer, 0 to 5% by mass of the ethylene ⁇ -olefin copolymer rubber, 112 to 20% by mass of the high-density polyethylene, and the total amount 100 parts by weight of ⁇ components, inorganic nucleating agent is 0.5 4-3.
- the propylene block copolymer in the range of 0 part by weight, more preferably, is 95- 82 mass 0 / 0, ethylene ⁇ - old Refuin copolymer rubber 0 3 mass 0/0, with respect to high-density polyethylene 5-15 wt% and the total amount of 100 parts by weight of ⁇ components, no machine-based nucleating agent 0
- the range is 4 to 3.0 parts by mass.
- the density of the ethylene olefin copolymer rubber is preferably 840 to 900 kgZm 3 , Is Mashiku is in the range of 850- 890kgZm 3.
- the density of the high-density polyethylene is 935 kgZm 3 or more, preferably 945 kgZm 3 or more.
- the preferred content is propylene homopolymer 98 one 68 mass 0/0, ethylene ⁇ - Orefin copolymer rubber 1 one 12 mass 0/0, a high density polyethylene having 1 one 20 mass % and the total amount of 100 parts by weight of ⁇ components, inorganic nucleating agent 0.5 4-3. in the range of 0 part by weight, more preferably propylene homopolymer 93- 7 5 mass 0 / 0, ethylene ⁇ - Orefin copolymer rubber 2-10 wt 0/0, the total amount 100 parts by weight of high-density polyethylene 5-15 wt% and their ⁇ components, inorganic nucleating agent 0.4 one 3 0 parts by mass.
- the density of the ethylene olefin copolymer rubber is preferably 840 to 900 kgZm 3 , Is Mashiku is in the range of 850- 890kgZm 3.
- the density of the high-density polyethylene ethylene is 935 kg / m 3 or more, preferably 945 kgZm 3 or more.
- the resin composition (A) containing an inorganic nucleating agent used in the present invention As a method for producing the resin composition (A) containing an inorganic nucleating agent used in the present invention, all the components can be blended and kneaded at once.
- an inorganic nucleating agent such as talc was prepared in advance as a master batch having a higher concentration than the content of the resin composition (A) of the present invention, using a polyolefin such as polypropylene or polyethylene as a base material.
- the composition of the resin composition (A) of the present invention can also be obtained by supplying a raw material obtained by dry blending with an appropriate amount of other components to a hopper of a molding machine and extruding the raw material. .
- the fine talc powder used as the inorganic nucleating agent has a fine average particle size of 15 m or less.
- the compounding amount may be relatively small. Therefore, it is possible to suppress an increase in specific gravity and to improve rigidity and the like without causing a decrease in impact resistance. . Further, when the amount of the talc is within the above range, generation of an unusual odor is suppressed.
- nucleating agent examples include sorbitol derivatives such as dibenzylidene sorbitol and dimethylbenzylidene sorbitol, which are typical examples of organic nucleating agents, and sodium 2,2-methylenebis (4,6-di-butylbutyl) phosphate.
- sorbitol derivatives such as dibenzylidene sorbitol and dimethylbenzylidene sorbitol
- sodium 2,2-methylenebis (4,6-di-butylbutyl) phosphate sodium 2,2-methylenebis (4,6-di-butylbutyl) phosphate.
- Low-density polyethylene obtained using a Ziegler-Natta catalyst or a meta-mouth catalyst or a polyethylene resin obtained by a high-pressure method, such as polyethylene or an ethylene copolymer.
- SBR Styrene-butadiene rubber
- SEBS hydrogenated product
- the resin composition containing an inorganic nucleating agent (A) of the present invention is obtained by dry blending a predetermined component at a predetermined ratio, and then forming a single-screw extruder, a twin-screw extruder, a Bannory mixer, a Henschel mixer, and the like.
- a single-screw extruder such as extrusion, injection, blow, etc.
- a Bannory mixer a Henschel mixer, and the like.
- the melt molding method generally applied to thermoplastic resin such as extrusion, injection, blow, etc., through the steps of plasticization, melting and mixing, it is formed into various molded products through the melt mixing process such as Obtainable.
- the commonly used additives such as antioxidants, lubricating agents, and antistatic agents may be added to the inorganic nucleating agent-containing resin composition (A) of the present invention, if necessary. be able to.
- coloring agents can be further added.
- the extrusion method various extruded products such as a single-layer or multi-layer film or sheet can be obtained by using a T-die, a circular die, or the like, in addition to pellets and irregularly extruded products.
- the melt flow rate MFR of the propylene homopolymer or the propylene block copolymer (component (a)) (temperature 230 ° C)
- the load 21.2N) is preferably in the range of 0.01 to 20 gZlO, more preferably in the range of 0.1 to 5 gZlO.
- the melt flow rate of polypropylene is a force of about 3 to 100 gZlO, preferably about 5 to 50 gZlO, which is suitable for thin-walled molded products, and Because higher elastic modulus can be obtained, it is easy to make it thinner, Higher weight reduction rates can also be achieved.
- the MFR (temperature: 190 ° C, load: 21.2N) of the ethylene- ⁇ -olefin copolymer homopolymer rubber (b) is preferably in the range of 0.01 to 20gZlO. It is preferably in the range of 0.1 to 11 OgZ for 10 minutes.
- the ethylene a-olefin copolymer rubber is uniformly dispersed in the inorganic nucleating agent-containing resin composition (A), so that a composition and a molded article having excellent moldability and impact resistance can be obtained. can get.
- the multilayer structure according to the present invention has at least one layer composed of the inorganic nucleating agent-containing resin composition (A), and the inorganic nucleating agent-containing resin composition.
- the thickness of the layer made of the object (A) is 50% or more of the total thickness.
- a surface layer made of a propylene-based resin or a propylene-based resin composition (B), and a propylene-based resin 80% by mass adjacent to the surface layer.
- the peel strength of the surface layer including the surface layer can be set to 1.0-lONZlOmm width.
- the layer composed of the resin composition or the resin (C) functions to peel off the surface layer.
- This peeling mode may be a shift of the cohesive failure of the upper or lower interface comprising the above (C) or the above resin material itself which also becomes the above (C) force.
- propylene-based resin in the propylene-based resin or the propylene-based resin composition (B) examples include the propylene homopolymer, propylene described in the inorganic nucleating agent-containing resin composition (A).
- Block copolymers or random copolymers of propylene with other ⁇ -olefins specifically, propylene ethylene random copolymer, propylene butene 1 random copolymer, propylene ethylene butene 1 random copolymer Coalescence and the like.
- thermoplastic resin such as propylene resin and other olefin resin A product
- thermoplastic resin such as propylene resin and other olefin resin A product
- the propylene-based polymer in the resin composition or resin (C) having a peeling function is the same as the propylene-based resin exemplified in the above description (B). Can be mentioned.
- thermoplastic resin other than the propylene-based polymer examples include, for example, a-olefins such as ethylene, butene 1, 3-methylbutene 1, 3-methylpentene 1, and 4-methylpentene 1, and cyclic olefins such as norbornene alone. Examples thereof include polymers and copolymers thereof.
- Representative examples include high-, medium-, and low-density polyethylene, linear low-density polyethylene, ultra-high-molecular-weight polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, ethylene-norbornene copolymer, Examples thereof include an ethylene / tetracyclododecene copolymer, polybutene 1, and poly-4-methylpentene 1.
- thermoplastic resins may be used alone or in combination of two or more.
- the propylene polymer and the thermoplastic resin other than the propylene polymer are mixed in an amount of less than 80% by mass and less than 20% by mass, respectively.
- the peeling function of the surface layer portion can be sufficiently exhibited by interfacial peeling or cohesive peeling of the composition or the resin itself.
- the preferable content ratio is 0 to 75% by mass of the propylene polymer and 25 to 100% by mass of the thermoplastic resin other than the propylene polymer.
- the thickness is 200 ⁇ m or more, and more preferably 400 to 2000 / zm force! / ⁇ .
- the thickness of the layer composed of the resin composition (A) containing the inorganic nucleating agent is at least 50% (100 ⁇ m) of the total thickness (thickness of the multilayer structure), and more preferably at least 70%. .
- the thickness is 50% or more, the mechanical properties such as heat resistance, rigidity, and impact resistance of the multilayer structure can be maintained at a certain level or more.
- the thickness of the release functional layer is about 0.1 to 10% of the total thickness (thickness of the multilayer structure), and more preferably 0.3 to 7%.
- the thickness of the release functional layer can be uniform and stabilized, and when the thickness is 10% or less, a thermoplastic material other than the propylene polymer used for the release functional layer can be used. Even when the heat resistance and rigidity of the resin are inferior to those of the propylene resin, a certain level can be maintained as a whole of the multilayer structure.
- the peel strength of the multilayer structure is about 1.0-lONZlOmm width, and more preferably 1.5-5NZlOmm width.
- the peel strength is the peel strength of the surface layer portion, and means the cohesive peel strength of the peelable functional layer itself or the interfacial peel strength between the peelable functional layer and an adjacent layer.
- the peel strength is less than lONZlOmm width
- the resistance when trying to open the lid material becomes appropriate, and 1.0N / 10 If the width is not less than mm, the above resistance is appropriate, and the lid is not peeled off due to an impact in a physical distribution process or the like before the lid is artificially or intentionally opened, so that it can be put to practical use.
- the multilayer structure of the present invention may be provided with a layer having another material strength for the purpose of improving oxygen gas barrier property and reducing deformation.
- the layer made of another material examples include a resin layer such as ethylene butyl alcohol copolymer (EV OH), polyvinylidene chloride (PVDC), nylon, and polyethylene terephthalate, an aluminum vapor-deposited layer, aluminum foil, aluminum, Iron, copper, etc., which have excellent gas barrier properties.
- a resin layer such as ethylene butyl alcohol copolymer (EV OH), polyvinylidene chloride (PVDC), nylon, and polyethylene terephthalate, an aluminum vapor-deposited layer, aluminum foil, aluminum, Iron, copper, etc., which have excellent gas barrier properties.
- EVOH as the content of ethylene unit of 20-60 mole 0/0 is preferably used.
- EVOH contains 0.1 to 5000 ppm by mass of at least one antioxidant substance, which is also selected from vitamin E, vitamin C, flavonoid and carotenoid, with respect to the fat.
- a multi-layered structure having a further reduced odor level by blending an antioxidant substance; and A container can be obtained.
- a Shiridani biylidene-monoshidani butyl copolymer and a Shiridani biylidene-methacrylic acid copolymer are preferably used.
- the layer made of these other materials may be only one layer or two or more layers.
- it may be a composite material with metal, paper and the like.
- a propylene-based resin such as homopolypropylene, propylene-ethylene random copolymer, propylene-ethylene butene random copolymer, propylene-ethylene block copolymer, etc.
- a resin composition based on these can be used.
- the multilayer structure of the present invention comprises the above-mentioned resin composition containing an inorganic nucleating agent (A), a propylene resin or a propylene resin composition (B), a resin composition or a resin (C). ) And an oxygen gas barrier property improving material or the like, and can be formed by extrusion, lamination, or a combination thereof.
- the purpose of the present invention is not impaired in the resin composition containing an inorganic nucleating agent (A), the propylene resin or the propylene resin composition (B), and the resin composition or the resin (C). ⁇
- an inorganic nucleating agent (A) the propylene resin or the propylene resin composition (B), and the resin composition or the resin (C).
- antioxidants ultraviolet absorbers, lubricants, pigments, antistatic agents, copper damage inhibitors, flame retardants, neutralizers, foaming agents, plasticizers, nucleating agents, bubble inhibitors
- An additive such as a crosslinking agent can be appropriately blended.
- the multilayer structure according to the present invention can be formed as a co-extruded multilayer molded product by, for example, a co-extrusion method using a plurality of extruders and extruding a material constituting each layer by a multilayer die force.
- the adhesive resin layer may be made of a copolymer of ethylene- (meth) acrylate such as maleic anhydride-modified polypropylene, polyethylene, ethylene (meth) methyl acrylate copolymer, ethylene (meth) ethyl acrylate copolymer. Polymer, ethylene-vinyl acetate copolymer, Examples include an ethylene-styrene copolymer.
- the multilayer structure of the present invention is formed by lamination, for example, a method such as extrusion lamination, hot melt lamination, dry lamination, or wet lamination can be used as the lamination.
- the co-extruded multilayer sheet is recovered in a layer composed of a resin composition containing an inorganic nucleating agent (A).
- FIG. 1 is a cross-sectional view showing an example of the configuration of the multilayer structure of the present invention.
- the multilayer structure 10 is formed on both surfaces of an oxygen gas barrier layer 1 via adhesive resin layers 2a and 2b, respectively.
- the inorganic nucleating agent-containing resin composition layers 3a and 3b are provided, and the release functional layer 4 and the surface layer 5 are sequentially laminated on the inorganic nucleating agent-containing resin composition layer 3a. It has a structured structure.
- the container having multi-layer structure strength of the present invention is obtained by thermoforming using the above-mentioned multi-layer structure by vacuum forming, air-pressure forming, vacuum-pressure forming, press forming or the like, or each of the above resins.
- the composition it can be obtained by molding using a molding method generally used for thermoplastic resins such as injection molding such as injection molding and injection blow molding, and extrusion molding such as extruded film 'sheet molding and blow molding. Can be.
- the container of the present invention is particularly useful as a container for retort foods such as cooked rice, a container for medical equipment and a container for precision parts for industry.
- a sheet-shaped extruded product is cut out to about 20 x 50 mm, a total of 10 g is placed in a 300 ml vial, heated at 90 ° C for 60 minutes, and then subjected to a sensory test by three panelists according to the 6-level evaluation method shown in Table 1. Was performed.
- the impact resistance and the elastic modulus of the polypropylene-based composition are in a trade-off relationship between a decrease in the elastic modulus and an increase in the impact resistance.
- the S value is an index obtained by quantifying the degree of deviation from the relationship. Therefore, the higher the force is above Equation 1 and the further away from Equation 1, the larger the S value, and the better the impact resistance and elastic modulus! / And the deviation.
- FIG. 3 is a conceptual diagram showing the relationship among the S value, -5 ° C falling weight impact strength (Y axis), and 80 ° C elastic modulus (X axis). ⁇ Thinning rate>
- Thinning rate (TRR) (E / E) 1 3 -l (Equation 3)
- E is the elastic modulus of the resin composition
- E is the elastic modulus of the reference polypropylene (the value of Comparative Example 13).
- Equation 3 The greater the value of the thinning ratio in Equation 3, the greater the possibility of maintaining the rigidity of the entire molded product even if the thickness of the molded product is reduced.
- the weight of a molded article is determined by the thickness of the molded article and the specific gravity of the material in the case of the same shape.
- the weight reduction rate (WRR) can be calculated as follows, taking into account the above-mentioned thinning rate and the rate of increase of the specific gravity with respect to the reference material.
- ⁇ is the specific gravity of the resin composition
- ⁇ is the specific gravity of the reference polypropylene (the value of Comparative Example 13 is 0.
- PP polypropylene
- the above sealed container was immersed in a water tank heated to 80 ° C for 30 minutes, and then a 20 mm square rubber seal was attached to the lid, and the inside of the container was evacuated by a vacuum pump with a syringe inserted. The pressure when the shape of the sample collapsed was measured.
- the extruded sheet having the above-mentioned resin composition strength was obtained by supplying the raw material previously dry-blended at a predetermined ratio to a hopper of an extruder and performing extrusion molding.
- B—PP block polypropylene; density 910 kgZm 3 , MFRO. 5 gZlO content (230 ° C), isotactic pentad fraction 0.94 [made by Idemitsu Petrochemical Co., Ltd., trade name “E—154G” ]
- H—PP highly stereoregular homopolypropylene; density 910 kgZm 3 , MFRO. 5 gZlO content (230 ° C), isotactic pentad fraction 0.97 [manufactured by Idemitsu Petrochemical Co., Ltd .; , E100GVJ]
- HDPE1 high density polyethylene; density 956kgZm 3, MFRO. (190 ° C) (Idemitsu Petrochemical Co., Ltd., trade name ⁇ Idemitsu Polyeti 548B '')
- EOR Ethylene otaten 1 copolymer (otaten 1 content 25 mass%); density 870 MFR5gZlO content (190 ° C) [manufactured by Dupont Dow Company, trade name “Engage8200”]
- Talc average particle size 4.9 m (trade name “TP-A25F”, manufactured by Fuji Talc)
- the talc used was a master batch having a concentration of 60% by mass prepared in advance.
- R-PP random polypropylene (manufactured by Idemitsu Petrochemicals Co., Ltd., trade name: “R720”) was used as the base material of this masterbatch, and 1.3 parts by mass of calcium stearate and 100 parts by mass of Preventive agent (Cilbas @ Charity Chemical Co., Ltd., Irganox 1010) Add 0.3 parts by mass and use a twin-screw kneader (CTM Co., Ltd., HTM-38) V, pellet master batch Got.
- the raw materials (PP: polypropylene, EZa R: ethylene a-olefin copolymer rubber (elastomer), talc, HDPE2: high-density polyethylene) that have the resin (RC) composition shown in Table 3 are used.
- PP polypropylene
- EZa R ethylene a-olefin copolymer rubber (elastomer), talc, HDPE2: high-density polyethylene
- RC resin composition shown in Table 3
- EC ethylene-vinyl alcohol copolymer
- AD adhesive resin
- the extruded sheet having the above-mentioned resin composition strength was obtained by supplying a dry-blended material at a predetermined ratio in advance to a hopper of an extruder and extruding the same.
- Adhesive resin maleic anhydride-modified PP (polypropylene); density 900 kgZm 3 , MFR2.8 gZlO content (190 ° C) [Mitsui Chemicals, Admar QF550]
- EVOH Ethylene Bulle alcohol copolymer; density 1180kgZm 3, MFR2 0g ZlO min (190 ° C) [manufactured by Kuraray Co., Ltd., J102B]
- Example 6 On one surface of the multilayer structure of Example 6, a multilayer structure having a structure in which a release functional layer and a surface layer were sequentially provided (see FIG. 1) was molded by a co-extrusion method, and further subjected to thermoforming by a vacuum / pressure method. A container having an inner diameter of 120 mm and a depth of 40 mm (see FIG. 2; multilayer structure is omitted) was prepared.
- R-PP with a thickness of 80 m was used as the surface layer.
- Example 9 A release function layer, have use a blend of HDPE2ZLDPE (80/20 by weight 0/0), and the layer thickness and 10 m.
- Example 10 Using a blend of H—PPZLDPE (50Z50% by mass) as the release functional layer And the layer thickness was 20 ⁇ m.
- Example 11 A release functional layer having the same composition as in Example 9 was used, and the layer thickness was set to 40 ⁇ m.
- Example 14 The multilayer structure of Example 8 was used instead of the multilayer structure of Example 6,
- a container was produced in the same manner as in Example 9.
- the thickness ratio (%) of the release functional layer indicates the percentage of the thickness of the release functional layer to the total thickness of the multilayer sheet used for the container.
- Comparative Example 11 The thickness of the release functional layer in Example 9 was set to 100 m.
- Comparative Example 12 In Example 11, the thickness of the release functional layer was 150 ⁇ m.
- HDPE2 high-density polyethylene; density 951 kgZm 3 , MFRO. 87 gZlO (trade name “Idemitsu Polyech 440M” manufactured by Idemitsu Petrochemical Co., Ltd.)
- LDPE high-pressure low-density polyethylene; density 920 kg / m 3 , MFR 6.7 gZlO content (190 ° C), Tml07 ° C (manufactured by Nippon Polyethylene Corporation, trade name “HE-30”)
- R-PP random polypropylene; density 910kgZm 3 , MFR1.3gZlO content (230 ° C), melting point 146 ° C [manufactured by Idemitsu Petrochemical Co., Ltd., trade name “Idemitsu Polypro E233GVJ”
- ADK STAB M701 phosphorus-containing organic nucleating agent
- NA11 master patch 5 mass% NA11 master patch
- ADK STAB M701 [phosphorus-containing organic nucleating agent]
- Example 13 23 Comparative Example 13-21 Using a raw material having the resin composition shown in Table 5, an extruded sheet having a thickness of 700 m was produced in the same manner as in Example 1 using a 30 ⁇ single screw extruder.
- talc indicates the number of parts by mass when the total weight of the resin is 100 parts by mass.
- the extruded sheet having the above-mentioned resin composition strength was obtained by supplying the raw material previously dry-blended at a predetermined ratio to a hopper of an extruder and performing extrusion molding.
- H—PP1 High stereoregular homopolypropylene; density 910 kg Zm 3 , MFRO. 5 g / 10 min (230 ° C), isotactic pentad fraction 0.97 [Idemitsu Petrochemical Co., Ltd. Polypro, E200GVJ]
- H PP2: highly stereoregular homopolypropylene; density 910 kg Zm 3 , MFR 1.6 g / 10 min (230 ° C), isotactic pentad fraction 0.97 [Idemitsu Petrochemical Co., Ltd., trade name “Idemitsu” Polypro, E200GVJ]
- H—PP3 High stereoregular homopolypropylene; density 910 kgZm 3 , MFR9. Og / 10 min (230 ° C), isotactic pentad fraction 0.97 [Idemitsu Petrochemical Co., Ltd., trade name “Idemitsu” Polypro, Y900GV ”)
- H—PP4 High stereoregular homopolypropylene; density 910 kgZm 3 , MFR18 gZlO content (230 ° C), isotactic pentad fraction 0.97 [Idemitsu Petrochemical Co., Ltd. ]
- EOR Ethylene otaten 1 copolymer (otaten 1 content 25 mass%); density 870 MFR5gZlO content (190 ° C) [manufactured by Dupont Dow Company, trade name “Engage8200”]
- 6.HDPE1 High density positive ethylene; density 956kgZm 3 , MFRO. (190 ° C) (Idemitsu Petrochemical Co., Ltd., trade name ⁇ Idemitsu Polyeti 548B '')
- B—PP block polypropylene; density 910 kgZm 3 , MFRO. 5 gZlO content (230 ° C), isotactic pentad fraction 0.94 [manufactured by Idemitsu Petrochemical Co., Ltd., trade name “E—154G” ]
- LH-PP1 Low stereoregular homopolypropylene; density 910 kgZm 3 , MFRO. 5 g / l 0 min (230 ° C), isotactic pentad fraction 0.93 [manufactured by Idemitsu Petrochemical Co., Ltd. Idemitsu Polypro, E105GM '') 9.
- Talc average particle size: 4.9 m [Fuji Talc Co., Ltd., trade name "TP-A25F"]
- talc the same master batch as in Examples 14 to 60 having a concentration of 60% by mass was prepared in advance. Was used.
- Figure 4 shows the effect of talc content with an average particle size of 4.9 ⁇ m on the weight reduction of molded articles (see Examples 13-15 and Comparative Examples 18-20 in Table 5). Examples 24 to 29, Comparative Examples 22 to 25
- talc indicates parts by mass with respect to 100 parts by mass of the resin.
- the extruded sheet having the above-mentioned resin composition power was obtained by supplying the above-mentioned raw material which had been dry-blended at a predetermined ratio to a hopper of an extruder.
- H—PP1 High stereoregular homopolypropylene; density 910 kg Zm 3 , MFRO. 5 g / 10 min (230 ° C), isotactic pentad fraction 0.97 [Idemitsu Petrochemical Co., Ltd. Polypro, E200GVJ]
- EOR1 Ethylene otaten 1 copolymer; density 857 kgZm 3 , MFR5gZlO content (190 ° C) (Dupont Dow Co., trade name “Engage8842”)
- EOR2 ethylene Otaten 1 copolymer; density 870kgZm 3, MFR5gZlO component (19 0 ° C) [Du Pont Dow Co., Ltd., trade name "Engage8200"]
- EOR3 Ethylene otatin 1 copolymer; density 885 kgZm 3 , MFR5gZlO content (190 ° C) [DuPont Dow, trade name “Engage8003”]
- EOR4 Ethylene otaten 1 copolymer; density 902 kgZm 3 , MFR5gZlO content (190 ° C) (Dupont Dow Co., trade name “Engage8450”)
- EOR5 Ethylene otaten 1 copolymer; density 910 kgZm 3 , MFR5gZlO content (190 ° C) [manufactured by DuPont Dow, trade name “Engage8445”]
- EBR1 Ethylene butene 1 copolymer; density 870kgZm 3 , MFR5. OgZlO content (190 ° C) [Dupont Dow Co., trade name “ENR7447”]
- Talc average particle size 4.9 m (trade name “TP—A25F”, manufactured by Fuji Talc)
- talc a master batch having the same concentration as in Example 14 and having a concentration of 60% by mass was used in advance.
- Talc average particle diameter 1.0 m [Product name: SG-2000, manufactured by Nippon Talc Co., Ltd.]
- Talc was prepared from a 20% by mass master using the same base material and additive formulation as in Examples 1-4. A batch prepared in advance was used.
- Figure 5 shows the effect of talc content with an average particle size of 1.0 ⁇ m on the weight reduction of molded articles (see Examples 27-29 and Comparative Examples 24-26 in Table 6).
- ADVANTAGE OF THE INVENTION According to the present invention, it has a high elastic modulus in a high temperature region above room temperature, has excellent impact resistance in a low temperature region below freezing point, and has a level at which odor can endure food applications, and minimizes an increase in specific gravity.
- Suppressed resin composition containing inorganic nucleating agent, multilayer structure having reduced weight by using the composition, resulting in reduced weight, container obtained by thermoforming, injection molded product, and extruded product Can be obtained at low manufacturing cost.
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Abstract
Description
Claims
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US10/592,479 US20070197712A1 (en) | 2004-03-11 | 2005-03-11 | Resin composition containing inorganic nucleating agent, molding thereof and process for producing the same |
KR1020067018460A KR101169617B1 (ko) | 2004-03-11 | 2005-03-11 | 무기계 조핵제 함유 수지 조성물, 그 성형품 및 그 제조방법 |
JP2006511016A JP4916307B2 (ja) | 2004-03-11 | 2005-03-11 | 多層構造体及び熱成形して得られる容器 |
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WO2011148912A1 (ja) * | 2010-05-28 | 2011-12-01 | 出光ユニテック株式会社 | 多層シート、熱成形容器、および、易開封性包装体 |
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US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
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CN102905897A (zh) * | 2010-05-28 | 2013-01-30 | 出光统一科技株式会社 | 多层片、热成形容器以及易开封包装体 |
KR101848944B1 (ko) | 2010-05-28 | 2018-04-13 | 이데미쓰 유니테크 가부시키가이샤 | 다층 시트, 열성형 용기, 및 개봉 용이성 포장체 |
CN102905897B (zh) * | 2010-05-28 | 2015-01-21 | 出光统一科技株式会社 | 多层片、热成形容器以及易开封包装体 |
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WO2014157400A1 (ja) * | 2013-03-28 | 2014-10-02 | 出光ユニテック株式会社 | シート、容器本体、包装容器、該シートの製造方法および該容器本体の製造方法 |
JP2016065179A (ja) * | 2014-09-26 | 2016-04-28 | 共栄産業株式会社 | 樹脂シート、樹脂及び容器 |
JP2017165865A (ja) * | 2016-03-16 | 2017-09-21 | 株式会社アイセロ | 熱可塑型接着フィルム |
US10710349B2 (en) | 2016-03-16 | 2020-07-14 | Aicello Corporation | Thermoplastic adhesive film, bonding method and bonded body |
JP2019014822A (ja) * | 2017-07-07 | 2019-01-31 | 日立化成株式会社 | 真空成形用樹脂シート |
JP2022524402A (ja) * | 2019-03-15 | 2022-05-02 | 金発科技股▲ふん▼有限公司 | ポリプロピレン組成物及びその製造方法 |
JP2022072704A (ja) * | 2020-10-30 | 2022-05-17 | 株式会社吉野工業所 | 射出成形容器 |
JP7496758B2 (ja) | 2020-10-30 | 2024-06-07 | 株式会社吉野工業所 | 射出成形容器 |
CN114031847A (zh) * | 2021-11-12 | 2022-02-11 | 天津金发新材料有限公司 | 一种良外观、高平整度高填充改性聚丙烯复合材料及其制备方法和应用 |
CN114031847B (zh) * | 2021-11-12 | 2023-05-09 | 天津金发新材料有限公司 | 一种良外观、高平整度高填充改性聚丙烯复合材料及其制备方法和应用 |
Also Published As
Publication number | Publication date |
---|---|
JP4916307B2 (ja) | 2012-04-11 |
JPWO2005087864A1 (ja) | 2008-01-24 |
KR101169617B1 (ko) | 2012-07-30 |
US20070197712A1 (en) | 2007-08-23 |
JP2011174088A (ja) | 2011-09-08 |
KR20070015382A (ko) | 2007-02-02 |
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