CN102757599A - Polypropylene resin compound and film formed therewith - Google Patents

Polypropylene resin compound and film formed therewith Download PDF

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Publication number
CN102757599A
CN102757599A CN2012101220550A CN201210122055A CN102757599A CN 102757599 A CN102757599 A CN 102757599A CN 2012101220550 A CN2012101220550 A CN 2012101220550A CN 201210122055 A CN201210122055 A CN 201210122055A CN 102757599 A CN102757599 A CN 102757599A
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composition
film
quality
propylene
polypropylene resin
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CN102757599B (en
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堀英明
龟尾幸司
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority claimed from JP2012039771A external-priority patent/JP5895590B2/en
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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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention is aimed at providing a film with high opaqueness, smoothness and excellent appearance and further providing a polypropylene resin compound for manufacture of the film. The invention discloses the polypropylene resin compound formed through fusion and mixing of the compounds of polyethylene (component (B)) with the density being greater than 0.900g/cm<3> and lower than 0.970g/cm<3> and the melt flow rate measured at the temperature of 190 DEG C and the load of 2.16 kg being 0.5-3g/10 minutes and a master batch (component (C)) obtained through infiltration of 1-30 mass percentage of organic peroxides in powdery polyolefin, and the film comprising layers formed by polypropylene resin compound.

Description

Polypropylene resin composite reaches by its film that forms
Technical field
The polypropylene resin composite of the film of the present invention relates to provide that opacity is high, slipperiness and outward appearance are excellent and by its film that forms.
Background technology
Acrylic resin is extensively utilized in fields such as packing, container, household appliances, trolley part.
In used for packing foods, medical, industrial, agricultural is used etc. film or sheet material, if according to purposes, there be the film or the sheet material of the demanding transparency (low haze valus), then also there be film or the sheet material that requires high opacity (high haze value) on the contrary.
As opaque film; For example in patent documentation 1, put down in writing at the following film of the laminated of single face at least of the biaxially oriented film that is made up of crystalline polypropylene and the translucent biaxial stretch-formed laminate film that obtains, the compsn that said film will be made up of crystalline polypropylene, Vilaterm, organo-peroxide uniaxial extension at least forms.
In addition; Put down in writing a kind of heat sealability delustring biaxial stretch-formed polypropylene film in the patent documentation 2; It is characterized in that; To be the high density polyethylene(HDPE) that new LDPE (film grade) and the MFR under 190 ℃ below 1g/10 minute are 0.01～0.3g/10 minute with respect to propylene copolymer, at the MFR under 190 ℃, organo-peroxide, the phenol that is added with specified amount be that the mixture layer of an alkali metal salt of inhibitor and lipid acid is laminated on the single face at least of PP SHEET FOR OPP TAPE.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication sho 56-38341 communique
Patent documentation 2: japanese kokai publication hei 5-329992 communique
Summary of the invention
Invent problem to be solved
Yet the opacity of the film of record is insufficient in the above-mentioned patent documentation 1.In addition, in the method for in patent documentation 2, putting down in writing, owing to use high density polyethylene(HDPE) and the new LDPE (film grade) of very low MFR, so problems such as worry flakes.
Problem to be solved by this invention is, opacity height, slipperiness and the excellent film of outward appearance is provided, and then provides as the useful polypropylene resin composite of the material of such film.
The scheme that is used to deal with problems
The present invention relates to a kind of polypropylene resin composite, it is characterized in that, it is the polypropylene resin composite that the mixture melting mixing of the composition (A), composition (B) and the composition (C) that comprise following definition is obtained,
Composition (A): the homopolymer of propylene or constitute and co-monomer content is that propylene below the 20 quality % is that random copolymers (wherein, the total mass of establishing propylene and be random copolymers is 100 quality %) is a Vestolen PP 7052 by propylene and the comonomer more than a kind,
Composition (B): density is 0.900g/cm 3More than and be lower than 0.970g/cm 3, the melt flow rate(MFR) under 190 ℃, 2.16kg load, measured is 0.5～3g/10 minute Vilaterm,
Composition (C): the organo-peroxide of 1～30 quality % that in powdery polyolefin, infiltrates and the masterbatch (master batch) (wherein, the total amount that is provided with machine superoxide and powdery polyolefin is 100 quality %) that obtains,
Said mixture is following mixture: when the total amount that is set as branch (A) and composition (B) is 100 quality %; The content of composition (A) is 65～95 quality %; The content of composition (B) is 5～35 quality %; And, contain the said organo-peroxide of 0.005～0.5 mass parts with respect to total 100 mass parts of composition (A) and composition (B).
In addition, the present invention relates to have the film more than 1 layer that forms by said polypropylene resin composite.
The effect of invention
Through the present invention, can obtain the excellent film of opacity height, slipperiness and outward appearance.
Embodiment
Below, embodiment of the present invention is elaborated.
Polypropylene resin composite of the present invention is the polypropylene resin composite that the mixture melting mixing of the composition (A), composition (B) and the composition (C) that comprise following definition is obtained,
Composition (A): the homopolymer of propylene or constitute and co-monomer content is that propylene below the 20 quality % is that random copolymers (wherein, the total mass of establishing propylene and be random copolymers is 100 quality %) is a Vestolen PP 7052 by propylene and the comonomer more than a kind,
Composition (B): density is 0.900g/cm 3More than and be lower than 0.970g/cm 3, the melt flow rate(MFR) under 190 ℃, 2.16kg load, measured is 0.5～3g/10 minute Vilaterm,
Composition (C): the organo-peroxide of 1～30 quality % that in powdery polyolefin, infiltrates and the masterbatch (wherein, the total amount that is provided with machine superoxide and powdery polyolefin is 100 quality %) that obtains,
Said mixture is following mixture: when the total amount that is set as branch (A) and composition (B) is 100 quality %; The content of composition (A) is 65～95 quality %; The content of composition (B) is 5～35 quality %; And, contain the said organo-peroxide of 0.005～0.5 mass parts with respect to total 100 mass parts of composition (A) and composition (B).
From the viewpoint of the processibility of said composition, the melt flow rate(MFR) of under 230 ℃, 2.16kg load, measuring of polypropylene resin composite of the present invention (below, note by abridging and be " MFR ".) be preferably 0.1～100g/10 minute, more preferably 0.1～50g/10 minute, further be preferably 0.1～10g/10 minute.The MFR of said composition can through change the composition (A) and the molecular weight of composition (B), the addition of composition (C) is regulated.
Polypropylene resin composite of the present invention extrude ratio of expansion (below, abbreviate " SR " as.) be preferably 1.00～1.25, more preferably 1.01～1.20.Here, the SR of so-called polypropylene resin composite is the diameter D of the polypropylene resin composite extruded from capillary die and the ratio (D/d) of the inner diameter d of this capillary die.Said SR measures under the rated load of 230 ℃ test temperature, 2.16kg according to JIS K7199.
Content about composition contained in the said mixture (A) and composition (B); When the quality that is set as the total of branch (A) and composition (B) is 100 quality %; The content of composition (A) is that the content of 65～95 quality %, composition (B) is 5～35 quality %; The content of preferred component (A) is that the content of 65～90 quality %, composition (B) is 10～35 quality %, and more preferably the content of composition (A) is that the content of 65～80 quality %, composition (B) is 20～35 quality %.
If the content of the composition (A) in the mixture is less than 65 quality %, the system film property deterioration of the compsn that then this mixture melting mixing is obtained is perhaps by often producing flake on the film of said composition manufacturing.
With respect to total 100 mass parts of composition (A) and composition (B), the content of contained organo-peroxide from composition (C) is 0.005～0.5 mass parts in the said mixture, is preferably 0.005～0.3 mass parts, more preferably 0.01～0.1 mass parts.Be less than 0.005 mass parts if contain the content of the organo-peroxide in composition (A), (B) and the mixture (C); Then by the opacity of the film of the compsn manufacturing that this mixture melting mixing is obtained become insufficient (in other words; The haze value of this film does not fully rise); If more than 0.5 mass parts, the then system film property deterioration of said compsn sometimes.In addition, when directly adding to organo-peroxide in composition (A) and the composition (B), organo-peroxide can't fully disperse, and often produces flake on the resulting film.Through using organo-peroxide is infiltrated up to the masterbatch that obtains in the powdery polyolefin, thereby processing property and security raising when cooperating organo-peroxide can make organo-peroxide homodisperse easily, can reduce the flake of resulting film.
Composition (A) is preferably crystalline polypropylene, more preferably isotatic polypropylene.Here, so-called " crystalline polypropylene " is meant the Vestolen PP 7052 that in the temperature-rise period of differential scanning calorimetric analysis method (DSC), in the temperature field more than 140 ℃, has peak (fusion enthalpy).As Vestolen PP 7052 is that the homopolymer of propylene or the propylene that is made up of propylene and the comonomer more than a kind are random copolymers, as comonomer, for example can enumerate out ethene, the terminal olefin of carbonatoms more than 4 etc.As said random copolymers, for example can enumerate out random copolymers, and the random copolymers of propylene and ethene and the terminal olefin of carbonatoms more than 4 of random copolymers, propylene and the terminal olefin of carbonatoms more than 4 of propylene and ethene.As the terminal olefin of carbonatoms more than 4 that constitutes said random copolymers, for example can enumerate out 1-butylene, 4-methyl-1-pentene, 1-octene, 1-hexene etc., be preferably 1-butylene.
Composition (A) is when being random copolymers for propylene; Inflexible viewpoint from the molding that forms by polypropylene resin composite; When if the total mass of this multipolymer is 100 quality %; The amount of contained comonomer is below the 20 quality % in this multipolymer, is preferably below the 15 quality %, more preferably below the 10 quality %.
From the inflexible viewpoint of the molding that formed by polypropylene resin composite, the fusing point of composition (A) is preferably more than 120 ℃, more preferably more than 125 ℃, is preferably in addition below 166 ℃.
From the viewpoint of the extrusion characteristics of polypropylene resin composite, the MFR of the composition of under 230 ℃, 2.16kg load, measuring according to JIS-K7210 (A) is preferably 0.1～10g/10 minute, more preferably 1～10g/10 minute.
Composition (A) can be made through known polymerization method through using known polymerizing catalyst.
As known polymerizing catalyst, for example can enumerate out the catalyzer system that constitutes by the solid catalyst component that contains magnesium, titanium and halogen, organo-aluminium compound and giving of using the as required catalyzer system that electronics property compound grade in an imperial examination 3 compositions constitute, by the compound and the alkylaluminoxane of the IV of the periodictable with cyclopentadienyl rings group 4 transition metal and form the compound of ionic complex compound by the transistion metal compound of the IV of the periodictable with cyclopentadienyl rings family, with its reaction and catalyzer system that organo-aluminium compound constitutes etc., for example be that the catalyzer of record in japanese kokai publication sho 61-218606 communique, japanese kokai publication sho 61-287904 communique, japanese kokai publication hei 1-319508 communique, the japanese kokai publication hei 7-216017 communique etc. is preferably by the solid catalyst component that contains magnesium, titanium and halogen, organo-aluminium compound and the catalyzer system that constitutes for electronics property compound.
As known polymerization method; For example can enumerate and send as an envoy to, preferably can enumerate out gaseous polymerization, or carry out the liquid phase-gaseous polymerization etc. for example of the method more than 2 kinds in the said polymerization continuously with the slurry polymerization process of unreactive hydrocarbons solvent or solvent polymerization method, based on solvent-free liquid polymerization, gaseous polymerization etc.
As composition (B), for example can enumerate out density is 0.900g/cm 3More than and be lower than 0.945g/cm 3Vilaterm promptly so-called " new LDPE (film grade) ", density be 0.945g/cm 3More than and be lower than 0.970g/cm 3Vilaterm promptly so-called " high density polyethylene(HDPE) " etc.When cooperating density to be lower than 0.900g/cm 3Vilaterm when replacing composition (B), the mist degree of film is not high enough sometimes.
As composition (B), use density to be 0.900g/cm 3More than and be lower than 0.945g/cm 3Vilaterm the time, as said Vilaterm, though can enumerate out the high-pressure process new LDPE (film grade) of making through tubular process or tremie method (bessel method), the multipolymer that also can be ethene and terminal olefin is a straight chain shape new LDPE (film grade).As constituting said poly terminal olefin, can enumerate out 1-butylene, 1-hexene, 1-octene etc., preferred 1-hexene.
The fusing point of composition (B) is preferably more than 100 ℃ and is lower than 140 ℃, more preferably more than 110 ℃ and be lower than 140 ℃.From the stable on heating viewpoint of polypropylene resin composite, the fusing point of composition (B) is preferably more than 100 ℃.
The MFR of the composition of under 190 ℃, 2.16kg load, measuring according to JIS-K7210 (B) is 0.5～3g/10 minute, is preferably 0.5～2g/10 minute.If the MFR of composition (B) was less than 0.5g/10 minute, then it becomes the reason that the flake in the resulting film takes place sometimes, if greater than 3g/10 minute, then the opacity of resulting film can not fully improve sometimes.
As the organo-peroxide that is used for prepared composition (C), can enumerate out more than 10 ℃ and be lower than under 30 ℃ the temperature for the solid material and more than 10 ℃ and be lower than under 120 ℃ the temperature and be the material of liquid.Be also included within more than 10 ℃ and be lower than under 30 ℃ the temperature material that becomes liquid for solid but through heating dissolving in the TR below 120 ℃.As the organo-peroxide that is used for prepared composition (C), can the organo-peroxide more than a kind or 2 kinds be mixed and use.
In addition, as be used for prepared composition (C) more than 10 ℃ and be lower than and be the solid organo-peroxide under 30 ℃ the temperature, but illustration goes out powdery or granulous material.The not special restriction of its particle diameter; From the convenience handled, the inhomogeneity viewpoint of distribution of organo-peroxide the composition (C); Be generally 100～2000 μ m (perhaps can pass through 9 purpose sieves); Be preferably 100～1000 μ m (perhaps can pass through 16 purpose sieves), more preferably 100～500 μ m (perhaps can pass through 32 purpose sieves).Here, the particle diameter of representing with the μ m of unit be meant transverse axis get particle diameter, the longitudinal axis get weight percent in the percentile particle diameter integral distribution curve of accumulating weight of particle reach 50% particle diameter (below, be designated as D 50).
As the organo-peroxide that is used for prepared composition (C), for example can enumerate and appear oxidation of alkyl class, peroxo-diacyl class, peroxyesters, peroxycarbonates class etc.As the peroxo-alkyls, for example can enumerate out dicumyl peroxide, ditertiary butyl peroxide, di-t-butyl cumyl peroxide, 2,5-dimethyl--2,5-two (tert-butyl hydroperoxide) hexane, 2; 5-dimethyl--2,5-two (tert-butyl hydroperoxide)-3-hexin, tertiary butyl cumyl peroxide, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene, 3 of 3-; 6,9-triethyl-3,6; 9-trimethylammonium-1,4,7-three peroxide nonanes etc.
As peroxo-diacyl class, for example can enumerate out Lucidol, lauroyl peroxide, decanoyl peroxide etc.As peroxyesters; For example can enumerate out 1,1,3; 3-tetramethyl butyl new decanoate ester peroxide, α-cumyl new decanoate ester peroxide, tert-butyl hydroperoxide neodecanoic acid ester, the new heptanoate of tert-butyl hydroperoxide, t-butylperoxy pivarate, uncle's hexyl peroxo-pivalate, 1; 1,3,3-tetramethyl butyl peroxo--2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, tert-butyl hydroperoxide-2-ethylhexanoate, tert-butyl hydroperoxide isobutyrate, di-tert-butyl peroxide six hydrogen terephthalate, t-amyl peroxy 3; 5; 5-tri-methyl hexanoic acid ester, tert-butyl hydroperoxide 3,5,5 Trimethylhexanoic acid ester, tert-butyl hydroperoxide acetic ester, tert butyl peroxy benzoate, dibutyl peroxo-trimethyladipic acid ester etc.
As the peroxycarbonates class, for example can enumerate out two-3-methoxyl group butyl peroxyization, two carbonic ethers, two (2-ethylhexyl) peroxy dicarbonate, di-isopropyl peroxycarbonates, tert-butyl hydroperoxide sec.-propyl carbonic ether, two (4-tert-butylcyclohexyl) peroxy dicarbonate, two hexadecyl peroxy dicarbonates, myristyl peroxy dicarbonate etc.
The organo-peroxide that is used for prepared composition (C) is preferably the peroxo-alkyls, and more preferably 2,5-dimethyl--2,5-two (tert-butyl hydroperoxide) hexane, 1; Two (tert-butyl hydroperoxide sec.-propyl) benzene or 3,6 of 3-, 9-triethyl-3,6; 9-trimethylammonium-1,4,7-three peroxide nonanes.
Composition (C) is that organo-peroxide is infiltrated up in the powdery polyolefin and the powder of preparation, in this specification sheets, this powder is called " masterbatch ".Through using said masterbatch, thereby the processing property raising of the organo-peroxide when making polypropylene resin composite can obtain providing the polypropylene resin composite of the few film of flake.The content of the organo-peroxide in the composition (C) is 1～30 quality %, and (total amount that wherein, is provided with machine superoxide and powdery polyolefin is 100 quality % to be preferably 3～20 quality %.)。
Reach 50% particle diameter (D as quality percentage in the particle diameter integral distribution curve of the powdery polyolefin that obtains through laser diffraction formula particle size distribution measuring method 50), the viewpoint of the dispersiveness of the organo-peroxide during from the manufacturing polypropylene resin composite is preferably 200 μ m～700 μ m.
The powdery polyolefin that is used for prepared composition (C) is alfon a mode; In alternate manner, for having from the structural unit of propylene and be selected from propylene copolymer, in other other mode, be their mixture by at least a kind of structural unit in the group of forming from the structural unit of ethene and from the structural unit of the terminal olefin of carbonatoms 4～10.In addition, in following explanation, sometimes " from the structural unit of ethene " and " from the structural unit of the terminal olefin of carbonatoms 4～10 " always is designated as " from the structural unit of comonomer.
Said powdery polyolefin is preferably to have 80～100 quality % and (wherein, establishes from the structural unit of propylene with from the 100 quality % that add up to of the structural unit of comonomer from the polyolefine of the structural unit of comonomer from the structural unit of propylene and 0～20 quality %.)。
About in the propylene copolymer as said powdery polyolefin contained from propylene structural unit and from the content of the structural unit of comonomer; Preferably be 80～99.9 quality %, be 0.1～20 quality % from the content of the structural unit of comonomer from the content of the structural unit of propylene; More preferably be 85～99.9 quality %, be 0.1～15 quality % from the content of the structural unit of comonomer from the content of the structural unit of propylene; Further preferably be 90～99 quality %, be 1～10 quality % from the content of the structural unit of comonomer from the content of the structural unit of propylene; Especially preferably be 90～97 quality %, be that 3～10 quality % (wherein, establish from the content of the structural unit of propylene with from the 100 quality % that add up to of the content of the structural unit of comonomer from the content of the structural unit of comonomer from the content of the structural unit of propylene.)。
As the terminal olefin of carbonatoms contained in the said propylene copolymer 4～10, can enumerate out 1-butylene, 1-amylene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene etc., be preferably 1-butylene, 1-hexene or 1-octene.
As said propylene copolymer, can enumerate out the random copolymers etc. of terminal olefin of random copolymers, propylene and ethene and carbonatoms 4～10 of the terminal olefin of propylene-ethylene random copolymers, propylene and carbonatoms 4～10.As the random copolymers of the terminal olefin of propylene and carbonatoms 4～10, can enumerate out propylene-1-butylene random copolymers, propylene-1-hexene random copolymers, propylene-1-octene random copolymers, propylene-1-decene random copolymers etc.As the random copolymers of the terminal olefin of propylene and ethene and carbonatoms 4～10, can enumerate out propylene-ethylene-butene-1 copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, propylene-ethylene-1-decene multipolymer etc.The powdery polyolefin of composition (C) usefulness can be the mixture of these propylene copolymers, also can be the mixture of alfon and propylene copolymer.
Said powdery polyolefin is preferably propylene-ethylene random copolymers particle, propylene-1-butylene random copolymers particle or propylene-ethylene-1-butylene random copolymers particle; The ethylene-propylene random copolymer particle that more preferably has 90～97 quality % from the structural unit of ethene from the structural unit of propylene and 3～10 quality %; Have propylene-1-butylene random copolymers particle of 90～97 quality %, or have ethylene-propylene-1-butylene random copolymers particle of the structural unit from propylene, 1～10 quality % of 80～98 quality % from the structural unit of 1-butylene from the structural unit of ethene and 1～10 quality % from the structural unit of 1-butylene from the structural unit of propylene and 3～10 quality %; The ethylene-propylene random copolymer particle that further preferably has the structural unit from propylene, 3～7 quality % of 93～97 quality % from the structural unit of ethene; Have propylene-1-butylene random copolymers particle of 93～97 quality %, or have ethylene-propylene-1-butylene random copolymers particle of the structural unit from propylene, 1～5 quality % of 85～98 quality % from the structural unit of 1-butylene from the structural unit of ethene and 1～10 quality % from the structural unit of 1-butylene from the structural unit of propylene and 3～7 quality %.
Said powdery polyolefin is preferably the multipolymer of propylene and other alkene and shows the particle of crystalline multipolymer.The crystalline degree of multipolymer can through 20 ℃ of contained in this multipolymer xylene soluble down partly the amount of (below, be designated as CXS) represent.The CXS of multipolymer is many, representes that amorphous portion is many in this multipolymer, and the crystallinity of this multipolymer is low, and the CXS of multipolymer is few, representes that amorphous portion is few in this multipolymer, and the crystallinity of this multipolymer is high.
It is above and be lower than 20 quality % that the content of the CXS of said powdery polyolefin is preferably 0.5 quality %, and more preferably 0.5 quality % is above and be lower than 10 quality %, and it is above and be lower than 5 quality % further to be preferably 1 quality %.
The fusing point of said powdery polyolefin is preferably more than 120 ℃ and is lower than 160 ℃.
Here, fusing point is meant the peak temperature of the maximum peak in the fusion endothermic curve of measuring through differential scanning calorimetric analysis method (DSC).The fusing point of said powdery polyolefin and the content of said CXS likewise are the indexs of crystalline degree that is used for the powdery polyolefin of composition (C).
From the rerum natura of resulting film and the viewpoint of the generation that suppresses the flake this film; The MFR of the said powdery polyolefin of under 230 ℃ of temperature, load 2.16kg, measuring is preferably 1～50g/10 minute; More preferably 1～30g/10 minute, further be preferably 2～20g/10 minute.
From the rerum natura of resulting film and the viewpoint of the generation that suppresses the flake this film; The limiting viscosity of the said powdery polyolefin of in 135 ℃ tetraline, measuring ([η]) is preferably more than the 1dl/g and is lower than 3dl/g; More preferably 1.3dl/g is above and be lower than 3dl/g, further is preferably the above and 2.5dl/g of 1.5dl/g.
The apparent bulk density of said powdery polyolefin is preferably 0.20g/cm 3More than and be lower than 0.45g/cm 3
Said powdery polyolefin is preferably the set of the particle of size distribution in specified range.Its size distribution is tried to achieve through laser diffraction formula particle size distribution measuring method (the not drying process of working medium).The laser diffraction formula particle size distribution measuring method of dry type is meant uses laser diffraction formula particle size distribution analyzer (for example the HELOS&RODOS of Sympatec manufactured (trade(brand)name) etc.) not use solvent to measure the method for size distribution.
It is above and be lower than 20 quality % that the content that the particle diameter of said powdery polyolefin is lower than the particle of 100 μ m is preferably 1 quality %; It is above and be lower than 80 quality % that the content that particle diameter is lower than the particle of 300 μ m is preferably 5 quality %, and the content that particle diameter is lower than the particle of 1000 μ m is preferably more than the 80 quality %.Quality percentage reaches 50% particle diameter (D in the particle diameter integral distribution curve of said powdery polyolefin 50) to be preferably 100 μ m above and be lower than 700 μ m, in the particle diameter integral distribution curve quality percentage reach 99% particle diameter (below, be designated as D 99) to be preferably 500 μ m above and be lower than 2000 μ m.
Size distribution about said powdery polyolefin; The content that the viewpoint of the homogeneity of the concentration of the organo-peroxide in the high-contentization of the organo-peroxide from composition (C), the composition (C) and the processing property of composition (C), preferable particle size are lower than the particle of 100 μ m is that 1 quality % is above and to be lower than content that 10 quality %, particle diameter are lower than the particle of 300 μ m be that 10 quality % are above and to be lower than the content that 70 quality %, particle diameter are lower than the particle of 1000 μ m be that 80 quality % are above, D 50Be that 200 μ m are above and be lower than 700 μ m, D 99Be that 700 μ m are above and be lower than 2000 μ m, more preferably to be lower than the content of the particle of 100 μ m be that 1 quality % is above and to be lower than content that 5 quality %, particle diameter are lower than the particle of 300 μ m be that 10 quality % are above and to be lower than the content that 50 quality %, particle are lower than the particle of 1000 μ m be that 80 quality % are above, D to particle diameter 50Be that 300 μ m are above and be lower than 700 μ m, D 99Be that 900 μ m are above and be lower than 2000 μ m.
As said powdery polyolefin, but illustration goes out: use known polymerizing catalyst, use alkene as monomer, through the polyolefin particles of known polymerization method manufacturing; To pulverize the particle that obtains through the polyolefine of known polymerization method manufacturing; To under its temperature more than fusing point, carry out melting mixing through the polyolefine of known polymerization method manufacturing, follow cooling curing, the particle that resulting cured article pulverizing is obtained etc.
Make said polyolefin particles or polyolefinic polymerizing catalyst as being used to, but illustration goes out: Ziegler-type catalyst system; Ziegler-natta catalyst system; By the compound of periodictable IV group 4 transition metal and the catalyzer system that alkylaluminoxane constitutes with cyclopentadienyl rings; Form the compound of ionic complex compound and catalyzer system that organo-aluminium compound constitutes by the compound of the IV of the periodictable with cyclopentadienyl rings group 4 transition metal, with its reaction; And load has the catalyzer system that the compound of the periodictable IV group 4 transition metal of cyclopentadienyl rings, the compound that forms ionic complex compound and the such catalyst component of organo-aluminium compound form on the inorganic particulate of silica and clay mineral that kind.These catalyzer for example tie up in japanese kokai publication sho 61-218606 communique, japanese kokai publication hei 5-194685 communique, japanese kokai publication hei 7-216017 communique, japanese kokai publication hei 9-316147 communique, japanese kokai publication hei 10-212319 communique, TOHKEMY 2004-182981 communique, the TOHKEMY 2004-067850 communique on the books.Polymerizing catalyst also can be the pre-polymerized catalyst that in the presence of above-mentioned catalyzer system, the monomer prepolymerization is prepared.
As polyolefin particles or polyolefinic method of manufacture, can routine be illustrated under the polymerization temperature and carry out the polymeric mass polymerization as medium with aqueous alkene; In the such unreactive hydrocarbons solvent of propane, butane, Trimethylmethane, pentane, hexane, heptane and octane, carry out polymeric solution polymerization process or slurry polymerization process; And with the monomer of gaseous phase as medium, in this medium with the gaseous polymerization of the monomer polymerization of gaseous phase.These polymerization methods carry out with intermittent type, continous way or their combination.These polymerization methods also can be through using the polymerization reaction trough more than 2 that connects, and the composition of adjustment polymkeric substance and the continuous multi-stage formula of characteristic are carried out in each polymerization reaction trough.From the viewpoint of industrialness and economy, the gaseous polymerization of preferred continous way or carry out the body-gaseous polymerization of mass polymerization and gaseous polymerization continuously.The such condition of polymerization temperature in these polymerization methods, polymerization pressure, monomer concentration, catalyzer input amount and polymerization time can suitably change according to the powdery polyolefin that is used for composition (C), decision.In order to remove such by product and the residual solvent of ultra-low molecular weight oligomers in this polymkeric substance, polyolefin particles or polyolefine also can be dry under than the low temperature of its melting temperature (Tm).
When the powdery polyolefin that is used for prepared composition (C) is that polyolefine is carried out melting mixing under the temperature more than the fusing point; Then carry out cooling curing; Resulting cured article is pulverized and during the particle that obtains; As its melting mixing method, can enumerate and send as an envoy to melt extruding the such known melting mixing device of machine or Banbury, under the temperature more than the polyolefinic fusing point with the method for this polyolefine melting mixing.When said polyolefine was propene polymer, the temperature during melting mixing was preferably more than 180 ℃, more preferably 180～300 ℃, further was preferably 180～250 ℃.
As known melting mixing device,, illustration rotates CMP (registered trademark), the FCM (registered trademark) of Kobe Steel, Ltd (strain) manufacturing or the incorgruous rotation forcing machine of twin screw of NCM (registered trademark) or LCM (registered trademark) that kind that forcing machine and JSW's (strain) make in the same way but going out the such twin screw of KZW (registered trademark) of the single screw extrusion machine of SZW (registered trademark) that kind of etc.ing of SE (registered trademark) that toshiba machine (strain) makes, FS (registered trademark) that (strain) pond shellfish is made, TECHNOVEL manufactured, ZSK (registered trademark) that Coperion Werner Pfleiderer makes, TEM (registered trademark) that toshiba machine (strain) is made, TEX (registered trademark) that JSW's (strain) makes, TECHNOVEL manufactured.
The shape of the cured article that obtains as the polyolefine melting mixing is carried out cooling curing again, but the particle that illustration goes out strand, sheet material, flat board and becomes suitable length to form the strand severing.
The powdery polyolefin that is used for prepared composition (C) is for the oxidative degradation in suppressing to store and stabilization also can contain known additives such as neutralizing agent, inhibitor.The cooperation of additive also can be through utilizing mixing tank etc. known blending means such as the method that mixes, melting mixing method carry out.With respect to said powdery polyolefin 100 mass parts, its use level when cooperating said additive is generally 0.001～0.5 mass parts, is preferably 0.01～0.2 mass parts.
As said powdery polyolefin; Use is pulverized polyolefine and the particle that obtains or polyolefine is carried out melting mixing then carry out cooling curing under the temperature more than the fusing point; Resulting cured article is pulverized and during the particle that obtains, can be used known shredding unit in the manufacturing of this particle.
As known shredding unit, but illustration exit spiral type mill, turbo-mill, needle mill, hammer mill, JET mill, jet-stream wind kibbler (single track jet mill, Jet-O-Mill), strand grinding machine (Cutter Mill), rotation strand grinding machine (Rotary Cutter Mill), ball mill, ball mill, roller mill, star formula mill (Star Mill), jaw crusher (Jaw Crusher mill), impeller shredder, vibration mill, impact grinder etc.
Preferred breaking method can be enumerated the freezing and pulverizing method of sening as an envoy to and pulverizing with liquid nitrogen as being used to obtain having the powdery polyolefin of target grain size distribution.
The freezing and pulverizing method is under the temperature more than the fusing point, to carry out melting mixing, then carry out cooling curing with the particle of under liquid nitrogen (approximately-196 ℃) atmosphere, polyolefine being pulverized and obtaining or with polyolefine; Resulting cured article is thus pulverized and after the particle that obtains is cooled to its temperature below brittleness temperature the method for using kibblers such as turbo-mill, needle mill, hammer mill, Linrex Mill (リ Application レ Star Network ス ミ Le), impeller shredder, spiral mill to pulverize.
In addition, distribute, can make the particle that the polyolefine pulverizing is obtained pass through strainer in order to reach target grain size.As said strainer, can use the strainer of known specification.
As known strainer, can enumerate out braided metal silk screen, curling wire cloth, welding base metal silk screen, cleaner, spiral metal silk screen, laminated metal strainer, metal sintering strainer etc.As the braided metal silk screen, but illustration goes out the braided metal silk screen of plain weave, the braided metal silk screen of twill weave, the braided metal silk screen of crowfoot satin, the flat folded braided metal silk screen of (plain dutch weave), the oblique folded braided metal silk screen of knitting (twilled dutch weave) etc. knitted.The material of strainer can be metal system or resinous any one, be preferably stainless steel.Polyolefinic sized particles can be passed through 1 strainer; Also can pass through many strainers of eclipsed; In addition; Can pass through strainer with 1 stage, also can divide 2 stages above in addition, can also the combination of filters of different size (material, shape, size of mesh etc.) be used through strainer.The size of mesh of strainer distributes and suitably decision according to target grain size.
The inhomogeneity viewpoint of the concentration of the organo-peroxide in the high-contentization of the organo-peroxide from composition (C), the composition (C); And then; In order to obtain providing the powdery polyolefin of the excellent composition (C) of the property handled; The size of mesh of strainer is preferably 100～3000 μ m, and more preferably 300～2000 μ m further are preferably 300～1500 μ m.The size of mesh of strainer is the value that defines with the method for the utilizing JIS-B8356 particle diameter (μ m) through the maximum granulated glass sphere of filter media.
The powdery polyolefin that is used for prepared composition (C) is when pulverizing the particle that obtains with polyolefine; From containing organo-peroxide with high density; And the viewpoint of making the excellent composition (C) of the property handled is effectively set out, and is preferably the polyolefin particles that satisfies specific size distribution.
The powdery polyolefin that is used for prepared composition (C) is when pulverizing the particle that obtains with polyolefine, with the polyolefinic D before pulverizing 50The size of expression is preferably 700～5000 μ m, and more preferably 700～3000 μ m further are preferably 700～1500 μ m.
In addition; The powdery polyolefin that is used for prepared composition (C) is for to carry out melting mixing with polyolefine under the temperature more than the fusing point; Then carry out cooling curing, and resulting cured article is pulverized and during the particle that obtains, the size of this cured article of representing with the length of the longest part is generally 1～50mm; Be preferably 2～10mm, more preferably 2～5mm.In addition, the productivity of the particle that obtains from this cured article is pulverized, the viewpoint of production stability, the preferred diameter of the shape of this cured article is the particulate state of 2～5mm.
As the method at the powdery polyolefin infiltration organo-peroxide that is used for composition (C), preferred limit uses known mixer mixing powdery polyolefin limit to add the method for organo-peroxide.As known mixing tank, but illustration goes out tumbler mixer, Henschel mixer, super mixing machine etc.
Among the present invention, also can add additive in mutually at the said mixture that contains said composition (A), composition (B) and composition (C).As additive, for example can enumerate out inhibitor, UV light absorber, static inhibitor, lubricant, nucleator, antifogging agent, antiblocking agent etc.
The use level of said various additives is 0.01～0.5 mass parts with respect to total 100 mass parts of composition (A) and composition (B) preferably.
As lubricant; Can use the lubricant used as resin and known hydrocarbon system compound, fatty acid series compound, higher alcohols based compound, fatty acid acyl amine compound, fatty ester based compound, metallic soap based compound etc. especially preferably use fatty acid acyl amine compound or metallic soap based compound.
As the hydrocarbon system compound, for example can enumerate out whiteruss, solid paraffin, synthetic polyethylene waxes etc.As the fatty acid series compound, for example can enumerate out tetradecanoic acid, palmitinic acid, Triple Pressed Stearic Acid, eicosanoic acid 、 docosoic, Lignoceric acid, oleic acid, erucic acid, Selacholeic acid, linolic acid, linolenic acid, arachidonic acid etc.As the higher alcohols based compound, for example can enumerate out VLTN 6 、 behenyl alcohol, oleyl alcohol, lauryl alcohol etc.As the fatty acid acyl amine compound; Can enumerate out unsaturated fatty acid amide based compound or unsaturated fatty acids acid amides based compound; Particularly; Can enumerate out tetradecanoic acid acid amides, palmitic amide, stearylamide, eicosanoic acid acid amides 、 behenamide, Lignoceric acid acid amides, amine hydroxybenzene, erucicamide, Selacholeic acid acid amides, linolic acid acid amides, linolenamide, arachidonic acid acid amides, the two stearylamides of ethylene, methylene bis stearylamide, ethylene bis stearamide, the two hydroxyl stearylamides of ethylene, the two sad acid amides of ethylene, the two capric acid acidamides of ethylene etc.; Preferably can enumerate out amine hydroxybenzene, behenamide, erucicamide, further be preferably erucicamide.As the fatty ester based compound, can enumerate out Triple Pressed Stearic Acid stearyl ester, glyceryl monostearate, hardened castor oil etc.As the metallic soap based compound; Can enumerate out lithium stearate, Magnesium Stearate, calcium stearate, barium stearate, Zinic stearas, calcium laurate, barium laurate, zinc laurate, zinc octoate, ricinolic acid calcium, ricinolic acid barium, zinc ricinate 、 Shan Yu base zn phosphate, stearyl zn phosphate etc., preferred Magnesium Stearate or calcium stearate.
Film of the present invention is to have the film more than 1 layer that is formed by above-mentioned polypropylene resin composite, and said composition system film is obtained.
From the viewpoint of rigidity with the transparency, it is above and be lower than 100 μ m that the thickness of film of the present invention is preferably 5 μ m, and more preferably 10 μ m are above and be lower than 80 μ m, and it is above and be lower than 70 μ m further to be preferably 10 μ m.
As method by polypropylene resin composite system film of the present invention; For example except employing is generally used for making the method with the form system film of single thin film such as T modulus method, blow moulding, rolling process of resin film, can enumerate out method with at least 1 layer form system film of multilayer film.
Film of the present invention can be a single thin film, also can be comprise at least 1 layer by polypropylene resin composite of the present invention form the layer multilayer film.In addition, film of the present invention can be a non-stretched film, also can be this non-stretched film is stretched and the oriented film of manufacturing along single shaft direction or biaxially oriented.Be preferably non-stretched film.
Multilayer film are by polypropylene resin composite of the present invention layer that forms and the film that other layer constituted, and as other layer, for example can enumerate out the layer that is formed by alfon; By propylene and following propylene is the layer that random copolymers or segmented copolymer constitute, and propylene is that random copolymers or segmented copolymer are served as reasons and be selected from the comonomer formation more than a kind in ethene and the terminal olefin of carbonatoms 4 or more; Or the layer of the mixture of the copolymer elastomer of ethylene series resin, ethene and terminal olefins such as these acrylic polymer Vilaterm or polybutylenes etc.; The Vestolen PP 7052 biaxially oriented film; Do not stretch or oriented nylon film; Stretching polyethylene terephthalate film etc.
As the method for manufacture of multilayer film, for example can enumerate out coextrusion processing method, extruding layer platen press, lamination methods, dry lamination method etc.
Embodiment
Below, through embodiment and comparative example the present invention is described in more detail.The measuring method of the rerum natura that adopts in embodiment and the comparative example is shown below.
(1) melt flow rate(MFR) (MFR, unit: g/10 minute)
The MFR of macromolecular material measures according to JIS K7210.
Polyacrylic MFR measures under 230 ℃, 2.16k g load.
Poly MFR measures under 190 ℃, 2.16k g load.
The MFR that contains Vestolen PP 7052 and Vilaterm and Vestolen PP 7052 and be the compsn of staple measures under 230 ℃, 2.16kg load.
(2) extrude ratio of expansion (SR)
The ratio of expansion of extruding of macromolecular material is measured under the rated load of 230 ℃ test temperature, 2.16kg according to JIS K7199.
(3) (the unit: quality %) of the co-monomer content in the Vestolen PP 7052
Co-monomer content in the Vestolen PP 7052 utilizes polymer to analyze the method for record in the 616th page of handbook (nineteen ninety-five, the distribution of Kinokuniya bookstore), measures through infrared measure and obtains.
(4) xylene soluble under 20 ℃ in the Vestolen PP 7052 becomes component (CXS, unit: quality %)
After being dissolved into the polyacrylic sample of 1g in the 100ml boiling xylene fully, be cooled to 20 ℃, 20 ℃ of held 4 hours.Then, resulting mixture filtered be divided into precipitate and solution, will filtrate dry solidification and 70 ℃ of dryings down under reduced pressure obtain residue.Measure the quality of gained residue, calculate ratio, obtain the solvable one-tenth component (CXS) of 20 ℃ of YLENE by it with respect to the quality of institute's dissolved said sample.
(5) fusing point (Tm, unit: ℃)
Use differential scanning calorimeter (Perkin Elmer Co., Ltd. makes DSC), about 10mg coupons is kept under 220 ℃ being cooled to 150 ℃ with 300 ℃/minute speed after 5 minutes under nitrogen atmosphere.This coupons after keeping 1 minute under 150 ℃, is cooled to 50 ℃ with 5 ℃/minute speed.
Then, with this coupons 50 ℃ down keep 1 minute after, heat up with 5 ℃/minute speed, measure the fusion endothermic curve, with the peak temperature of the maximum peak of resulting fusion endothermic curve as Tm (fusing point).
In addition, using this tester is 156.6 ℃ with the Tm of the indium (In) of the determination of heating rate of 5 ℃/minute cooling rate and 5 ℃/minute.
(6) poly density (unit: g/cm 3)
Poly density is measured according to the A method (water displace method) of JIS K7112.
(7) mist degree (unit: %) of film
Mist degree (unit: %) measure as the index of transparency of film according to JIS K7136.
(8) the coefficientoffriction s of film, μ k
Frictional coefficient (μ s, μ k) as the index of the slipperiness of film is measured according to JIS K7125.Here, μ s, μ k are respectively static friction coefficient, kinetic friction coefficient.Frictional coefficient is low more, and then slipperiness is more excellent.
(9) appearance of films
As the index of appearance of films quality, the number of the flake that the per unit area of employing film exists.Use is arranged on the film shortcoming proofing unit MujiKen of (strain) NIRECO manufactured in the film-making machine, measures every 1m of film 2The number of the flake that the diameter 100 μ m that exist in the area are above.The FE of record is meant flake in table 1 and the table 2.The specification of proofing unit is described below.
Photographic camera: one dimension CCD, 8192 pixels
Scanning speed: the most about 0.06msec/ line (160MHz)
Resolving power: 50 μ m/ pixels
Employed Vestolen PP 7052 (A)
(Al): the crystallinity propylene-ethylene random copolymer of propylene content=96.0 quality %, ethylene content=4.0 quality %, MFR=6.2g/10 minute, fusing point=142 ℃, CXS content=2.9 quality %
(A2): the crystallinity propylene-ethylene random copolymer of propylene content=94.4 quality %, ethylene content=5.6 quality %, MFR=1.4g/10 minute, fusing point=133 ℃, CXS content=5.0 quality %
(A3): the alfon of MFR=7.8g/10 minute, fusing point=165 ℃, CXS content=0.8 quality %
(A4): the alfon of MFR=0.5g/10 minute, fusing point=165 ℃, CXS content=0.4 quality %
(A5): the crystallinity propylene/ethylene/butene random copolymers of propylene content=90.7 quality %, ethylene content=2.5 quality %, butene content=6.8 quality %, MFR=3.5g/10 minute, fusing point=132 ℃, CXS content=2.5 quality %
Employed Vilaterm (B)
(B1): Keiyo Polyethylene Co., high density polyethylene(HDPE) E3100 (density=0.952g/cm that Ltd. makes 3, MFR=1.0g/10 minute)
(B2): straight chain shape new LDPE (film grade) Sumikasen (registered trademark) α CS8051 (ethene/1-hexene copolymer, density=0.940g/cm that Sumitomo Chemical Co makes 3, MFR=2.2g/10 minute, fusing point=127 ℃)
(B3): straight chain shape new LDPE (film grade) Sumikasen (registered trademark) E FV102 (ethene/1-hexene copolymer, density=0.926g/cm that Sumitomo Chemical Co makes 3, MFR=0.73g/10 minute, fusing point=125 ℃)
(B4): new LDPE (film grade) Sumikasen (registered trademark) F218-0 (density=0.919g/cm that Sumitomo Chemical Co makes 3, MFR=1.0g/10 minute, fusing point=109 ℃)
(B5): straight chain shape new LDPE (film grade) Sumikasen (registered trademark) (registered trademark) E FV103 (ethene/1-hexene copolymer, density=0.905g/cm that Sumitomo Chemical Co makes 3, MFR=1.0g/10 minute, fusing point=113 ℃)
(B6): Keiyo Polyethylene Co., high density polyethylene(HDPE) G2500 (density=0.961g/cm that Ltd. makes 3, MFR=5.4g/10 minute)
(B7): Keiyo Polyethylene Co., high density polyethylene(HDPE) G1900 (density=0.955g/cm that Ltd. makes 3, MFR=16g/10 minute)
(B8): Prime Polymer Co., high density polyethylene(HDPE) HI-ZEX (registered trademark) 7000F (density=0.950g/cm that Ltd. makes 3, MFR=0.05g/10 minute)
(B9): straight chain shape new LDPE (film grade) Sumikasen (registered trademark) E FV401 (ethene/1-hexene copolymer, density=0.905g/cm that Sumitomo Chemical Co makes 3, MFR=3.8g/10 minute, fusing point=113 ℃)
(B10): ultra-low density polyethylene TAFMER (registered trademark) A0550S (ethylene/butylene copolymers, density=0.860g/cm that Mitsui Chemicals, Inc makes 3, MFR=0.6g/10 minute, fusing point＜50 ℃)
Employed infiltration has the masterbatch (C) of organo-peroxide
(C1): after the crystallinity propylene/ethylene/butene random copolymers of propylene content=93.3 quality %, ethylene content=2.2 quality %, butene content=4.5 quality %, MFR=7.0g/10 minutes, fusing point=140 ℃, CXS content=1.7 quality % fully cooled off with liquid nitrogen; This multipolymer imported continuously carry out pulverization process in the impeller shredder; Make resulting crushed material carry out classification, thereby obtain particle diameter D through strainer 50The powdery polyolefin of=400 μ m for this powder, makes PERHEXA (registered trademark) 25B (NOF Corp's system, chemical name: 2,5-dimethyl--2,5-two (tert-butyl hydroperoxide) hexane) of its 8 quality % that infiltrate and the polyolefin masterbatch that obtains.
[embodiment 1]
With respect to Vestolen PP 7052 (A1) 80 quality %, Vilaterm (B1) 20 quality %, (A1) and total metering 100 mass parts (B1); Adding infiltration has masterbatch (C1) 0.31 mass parts, calcium stearate (Common medicine Co., Ltd's system) 0.05 mass parts, inhibitor (Irganox (registered trademark) 1010 (Ciba Specialty Chemicals Inc. system)) 0.05 mass parts, inhibitor (Irganox (registered trademark) 1076 (Ciba Specialty Chemicals Inc. system)) 0.01 mass parts of organo-peroxide; After mixing 3 minutes with Henschel mixer, under 220 ℃, carry out melting mixing and obtain particle.The MFR of resulting granules is 12g/10 minute, and SR is 1.06.
[the system film of film]
In the forcing machine of the 50mm φ that possesses the T mould, the particle that obtains before at 240 ℃ of following melting mixings of temperature, is extruded from said T mould.With the resin temperature adjustment to 40 of extruding ℃, be put on the cooling roller with 18m/ minute speed rotation and transmit, thereby cooling curing obtains the film of thickness 30 μ m.The rerum natura of resulting film is shown in Table 1.Resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 2]
Among the embodiment 1, the use level that the use level of Vestolen PP 7052 (A1) is changed to 70 quality %, Vilaterm (B1) changes to 30 quality %, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 8.8g/10 minute, and SR is 1.18, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 3]
Among the embodiment 1, the use level that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A2), masterbatch (C1) changes to 0.45 mass parts, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 6.4g/10 minute, and SR is 1.10, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 4]
Among the embodiment 1, Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A3), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 15g/10 minute, and SR is 1.08, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 5]
Among the embodiment 1, Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 7.0g/10 minute, and SR is 1.10, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 6]
Among the embodiment 1, the quantitative change that Vilaterm (B1) is changed to Vilaterm (B2), masterbatch (C1) is 0.28 mass parts more, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 9.8g/10 minute, and SR is 1.06, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 7]
Among the embodiment 1, the quantitative change that Vilaterm (B1) is changed to Vilaterm (B3), masterbatch (C1) is 0.45 mass parts more, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 17g/10 minute, and SR is 1.11, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 8]
Among the embodiment 1, with Vilaterm (B1) change to Vilaterm (B3), its use level is set at 30 quality %, the use level of masterbatch (C1) changes to 0.45 mass parts, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 11g/10 minute, and SR is 1.27, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 9]
Among the embodiment 1, Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A3), Vilaterm (B1) is changed to Vilaterm (B3), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 17g/10 minute, and SR is 1.10, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 10]
Among the embodiment 1, the quantitative change that Vilaterm (B1) is changed to Vilaterm (B4), masterbatch (C1) is 0.28 mass parts more, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 16g/10 minute, and SR is 1.29, and resulting film is the film that mist degree is high, slipperiness is excellent.
[embodiment 11]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), masterbatch (C1) is 0.80 mass parts more, adds erucicamide 0.05 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 7.0g/10 minute, and SR is 1.10, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 12]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), masterbatch (C1) is 0.80 mass parts more, adds erucicamide 0.1 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 8.0g/10 minute, and SR is 1.09, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 13]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), masterbatch (C1) is 0.80 mass parts more, adds amine hydroxybenzene 0.1 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 7.5g/10 minute, and SR is 1.08, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 14]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), masterbatch (C1) is 0.80 mass parts more, adds behenamide 0.1 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 8.2g/10 minute, and SR is 1.08, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 15]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A2), masterbatch (C1) is 0.80 mass parts more, adds erucicamide 0.1 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 10.7g/10 minute, and SR is 1.08, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 16]
Among the embodiment 1, the quantitative change that Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A5), masterbatch (C1) is 0.80 mass parts more, adds erucicamide 0.1 mass parts as the fatty acid acyl amine compound, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 15.4g/10 minute, and SR is 1.05, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[embodiment 17]
Among the embodiment 1; Vestolen PP 7052 (A1) is changed to more 0.80 mass parts of quantitative change that Vestolen PP 7052 (A5), Vilaterm (B1) change to Vilaterm (B5), masterbatch (C1); Interpolation is as erucicamide 0.1 mass parts of fatty acid acyl amine compound; Make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 7.7g/10 minute, and SR is 1.05, and resulting film is the film that mist degree is high, slipperiness is excellent, flake is few.
[comparative example 1]
Among the embodiment 1, the use level that the use level that the use level of Vestolen PP 7052 (A1) is changed to 60 quality %, Vilaterm (B1) changes to 40 quality %, masterbatch (C1) changes to 0.45 mass parts, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 7.0g/10 minute, and SR is 1.24, and resulting film has a lot of holes.
[comparative example 2]
Among the embodiment 1, the use level of masterbatch (C1) is changed to 0.04 mass parts, make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 6.5g/10 minute, and SR is 1.22, and the mist degree of resulting film is not high enough.
[comparative example 3]
Among the embodiment 1, Vilaterm (B1) is changed to Vilaterm (B6), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 18g/10 minute, and SR is 1.15, and the mist degree of resulting film is not high enough.
[comparative example 4]
Among the embodiment 1, Vilaterm (B1) is changed to Vilaterm (B7), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 20g/10 minute, and SR is 2.29, and resulting film is that mist degree is low, flake is many, the film of appearance poor.
[comparative example 5]
Among the embodiment 1, the use level that Vilaterm (B1) is changed to Vilaterm (B8), masterbatch (C1) changes to 0.35 mass parts, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 15g/10 minute, and SR is 1.14.Resulting film is that the number through the detected flake of defect detector is many and produce the film of a lot of very large flakes, appearance poor.
[comparative example 6]
Among the embodiment 1, the use level of Vestolen PP 7052 (A1) is changed to 100 quality %, make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 29g/10 minute, and SR is 1.00, and resulting film is that mist degree is low, the film of slipperiness difference.
[comparative example 7]
After the particle that obtains in the comparative example 6 80 quality %, Vilaterm (B1) 20 quality % are carried out the particle blend with tumbler mixer, make film, obtain film according to embodiment 1.Resulting film is the film that mist degree is not high enough, flake is many.
[comparative example 8]
Among the embodiment 1, the use level that Vilaterm (B1) is changed to Vilaterm (B3), masterbatch (C1) changes to 0.04 mass parts, makes particle according to embodiment 1 in addition, obtains film.The MFR of resulting granules is 6.2g/10 minute, and SR is 1.29, and the mist degree of resulting film is not high enough.
[comparative example 9]
Among the embodiment 1, Vilaterm (B1) is changed to Vilaterm (B9), make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 15g/10 minute, and SR is 1.84, and resulting film is that mist degree is low, the film of slipperiness difference.
[comparative example 10]
Among the embodiment 1, Vilaterm (B1) is changed to the use level that Vilaterm (B3), its use level change to 40 quality %, masterbatch (C1) change to 0.45 mass parts, make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 6.0g/10 minute, and SR is 1.43, though resulting film mist degree is high, flake is many, has a lot of holes on the film.
[comparative example 11]
Among the embodiment 1; Vestolen PP 7052 (A1) is changed to more 0.80 mass parts of quantitative change that Vestolen PP 7052 (A4), Vilaterm (B1) change to Vilaterm (B10), masterbatch (C1); Interpolation is as erucicamide 0.1 mass parts of fatty acid acyl amine compound; Make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 15g/10 minute, and SR is 1.84, and resulting film is that mist degree is low, the film of slipperiness difference.
[comparative example 12]
Among the embodiment 1, Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4), do not use masterbatch (C1) and interpolation PERHEXA (registered trademark) 25B (NOF Corp's system) 0.064 mass parts, make particle according to embodiment 1 in addition, obtain film.The MFR of resulting granules is 3.3g/10 minute, and SR is 1.53, and resulting film is that mist degree is low, flake is very many, the film of appearance poor.
[comparative example 13]
Among the embodiment 1; Vestolen PP 7052 (A1) is changed to Vestolen PP 7052 (A4); Do not use masterbatch (C1) and add PERHEXA (registered trademark) 25B (NOF Corp's system) 0.080 mass parts; Interpolation is made particle according to embodiment 1 in addition as erucicamide 0.1 mass parts of fatty acid acyl amine compound, obtains film.The MFR of resulting granules is 6.9g/10 minute, and SR is 1.16, and resulting film is that mist degree is low, flake is very many, the film of appearance poor.
[table 1]
Figure BDA0000156526330000241
[table 2]
Figure BDA0000156526330000251
Utilizability on the industry
Polypropylene resin composite of the present invention can be used in food with, industrial, agricultural is used etc. sheet material or film.If use this compsn to make film,, also can obtain surperficial asperitiesization, mist degree is high, slipperiness is excellent, flake the is such few film of apparent defective even do not use the such inorganics of antiblocking agent.

Claims (7)

1. a polypropylene resin composite is characterized in that, it is the polypropylene resin composite that the mixture melting mixing of the composition (A), composition (B) and the composition (C) that comprise following definition is obtained,
Composition (A): the homopolymer of propylene or constitute and co-monomer content is that propylene below the 20 quality % is that random copolymers is a Vestolen PP 7052 by propylene and the comonomer more than a kind, wherein, the total mass of establishing propylene and be random copolymers is 100 quality %,
Composition (B): density is 0.900g/cm 3More than and be lower than 0.970g/cm 3, the melt flow rate(MFR) under 190 ℃, 2.16kg load, measured is 0.5～3g/10 minute Vilaterm,
Composition (C): the organo-peroxide of 1～30 quality % that in powdery polyolefin, infiltrates and the masterbatch that obtains, wherein, the total amount that is provided with machine superoxide and powdery polyolefin is 100 quality %,
Said mixture is following mixture:
When the total amount that is set as branch (A) and composition (B) is 100 quality %; The content of composition (A) is 65～95 quality %; The content of composition (B) is 5～35 quality %, and with respect to total 100 mass parts of composition (A) and composition (B), contains the said organo-peroxide of 0.005～0.5 mass parts.
2. polypropylene resin composite according to claim 1 is characterized in that, composition (B) is that density is 0.900g/cm 3More than and be lower than 0.945g/cm 3Vilaterm.
3. polypropylene resin composite according to claim 1 is characterized in that, composition (B) is that density is 0.945g/cm 3More than and be lower than 0.970g/cm 3Vilaterm.
4. according to each described polypropylene resin composite in the claim 1～3, it is characterized in that composition (A) is that the melt flow rate(MFR) under 230 ℃, 2.16kg load, measured is 0.1～10g/10 minute a Vestolen PP 7052.
5. according to each described polypropylene resin composite in the claim 1～4, it is characterized in that with respect to total 100 mass parts of composition (A) and composition (B), said mixture further contains the fatty acid acyl amine compound of 0.01～0.5 mass parts.
6. film, its have by each described polypropylene resin composite in the claim 1～5 form more than 1 layer.
7. film according to claim 6, it is a non-stretched film.
CN201210122055.0A 2011-04-28 2012-04-24 Polypropylene resin composite and the film formed by it Active CN102757599B (en)

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