CN1425041A - Propylene polymer composition, film thereof, and multilayered laminate - Google Patents
Propylene polymer composition, film thereof, and multilayered laminate Download PDFInfo
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- CN1425041A CN1425041A CN00818615A CN00818615A CN1425041A CN 1425041 A CN1425041 A CN 1425041A CN 00818615 A CN00818615 A CN 00818615A CN 00818615 A CN00818615 A CN 00818615A CN 1425041 A CN1425041 A CN 1425041A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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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- 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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Abstract
The invention provides a resin composition, film thereof, and multilayered laminate, suitable as food packaging materials and medical packaging materials. The resin composition is a propylene polymer composition which (1) when examined with a differential scanning calorimeter, gives a crystallization temperature curve which has a primary crystallization peak temperature (TCP1) of 105 to 110 DEG C. and a secondary crystallization peak temperature (TCP2) of 65 to 85 DEG C. and in which the proportion of the area of the secondary crystallization peak (TCA2) to that of the primary crystallization peak (TCA1), AR, is 4.0% or lower, (2) has a 25 DEG C. xylene-soluble content (XI) of 10 to 30 wt.%, and (3) satisfies the relationship TCP2</=-1.05XI+104; and a multilayered laminate comprising at least three layers composed of (A) two outer layers made of a propylene alpha -olefin block copolymer comprising (a1) 70 to 95 wt.% at least one polypropylene block and (a2) 30 to 5 wt.% of at least one elastomer block which is a copolymer of propylene and an alpha -olefin having 2 to 12 (excluding 3) carbon atoms and (C) an intermediate layer made of the propylene polymer composition.
Description
Technical field
The present invention relates to a kind of special prolylene polymer composition.More specifically, the present invention relates to a kind of propylene-alpha-olefin block copolymer composition, and the film of making by it that is applicable to packaging material for food and drug packages material, wherein the reduction of the heat-seal strength that will cause owing to thermal sterilization such as retort sterilization is limited to lower level, said composition has good low temperature impact strength, and has good radiation resistance.
In addition, the invention still further relates to a kind of laminated multi-layer thing that contains propylene-alpha-olefin block copolymer composition and special prolylene polymer composition.More specifically, the present invention relates to a kind of packaging material for food and drug packages material of being applicable to, and the especially suitable laminated multi-layer thing of making the heat sealing layer in the wrapping material, wherein the reduction of the heat seal strength that will cause owing to thermal sterilization such as retort sterilization is limited to lower level, this laminate has good low temperature impact strength and good anti-bleaching property, and this laminate can provide good production efficiency, produces gum shape thing in moulding process hardly.
Background technology
Usually, polypropylene screen since its for example cost is low, heat-resisting, chemicals-resistant and be easy to characteristic such as heat-sealing, and be used as various packaging materials for food and various drug packages material.
In the food product pack field, multilayer film is used as the wrapping material that boiling packing bag food is used, wherein the saponification resultant of aluminium foil, polyvinylidene dichloride or ethylene-vinyl acetate copolymer resin is used as the gas-barrier resin, they are used in combination with polyamide resin layer, polyester resin layer etc., and polypropylene is laminated on them as hot sealing layer.This external drug packages field, polypropylene also can be used in the hot sealing layer.
In the packing of food, after the content filling and packaging bag, carry out thermal sterilization, as scalding or retort sterilization, under normal temperature or low temperature, to preserve content.
In can be used as the polypropylene based material of hot sealing layer, the problem of homopolymer polypropylene is that its shock resistance is relatively poor and be not suitable for preserving at low temperatures.And, even shock resistance is better than polyacrylic ethylene-propylene random copolymer, it does not have gratifying shock strength at low temperatures yet, and the problem that it exists is, adhere to each other mutually or be out of shape by its film of thermal sterilization, and form orange peel line (irregular on the film surface).
Therefore, the polypropylene screen that packing bag is used as cooking food, such film was once proposed, they are by carrying out blend with thermoplastic elastomer component and propylene-based block copolymer or ethylene-propylene random copolymer, and be that film makes (for example referring to the open for the second time flat 6-86109 of (kokoku) No. of, Japanese patent application with blend molding; The open for the first time flat 7-26037 of (kokai) No. of Japanese patent application; The open for the first time flat 7-166024 of (kokai) No. of Japanese patent application; The open for the first time flat 8-302110 of (kokai) No. of Japanese patent application; And the open for the first time flat 10-152596 of (kokai) No. of Japanese patent application).
On the other hand, usually will be through electron beam irradiation sterilization or ionizing rays sterilization, as using the gamma-rays disinfectant drug packages material of cobalt 60, the problem of existence is, because said process, it has reduced low temperature impact strength after ionizing rays sterilization etc.
Known after ionizing rays, the heat-sealing stripping strength of wrapping body reduces few.The heat-sealing stripping strength is measured under low-speed conditions usually, and wherein peeling rate is 100～500mm/ minute.Yet when real wrapping body fell, it was with 1000mm/ minute or higher speed whereabouts, and therefore the problem that exists is that even the heat-sealing stripping strength after ionizing rays is fine, heat seal lands also can be broken.
As anti-this whereabouts disruptive test index, the film shock strength is arranged, its mensuration is to impact heat seal lands by the pendulum with the impact head with trilateral Pyramid, and thinks that the film shock strength is high more, actual whereabouts disruptive possibility is more little.
The film shock strength is disclosed in " Seihin Kagaku KenkyujoHoukoku (report of Industrial Products Research Institute) " No.79 of Matsumoto etc., pp.11-15 (1977).
In addition, the open for the first time flat 10-265622 of (kokai) No. of Japanese patent application discloses the sealing membrane that a kind of boiling is used, and it contains the mixture of propylene-based block copolymer and polypropylene flexible resin(a).
Yet, above-mentioned by thermoplastic elastomer component and propylene-based block copolymer or ethylene-propylene random copolymer are carried out blend, and with the prepared film of blend molding (for example referring to, the open for the second time flat 6-86109 of (kokoku) No. of Japanese patent application; The open for the first time flat 7-26037 of (kokai) No. of Japanese patent application; The open for the first time flat 7-166024 of (kokai) No. of Japanese patent application; The open for the first time flat 8-302110 of (kokai) No. of Japanese patent application; And the open for the first time flat 10-152596 of (kokai) No. of Japanese patent application) problem that exists is, compares with the heat seal strength before the thermal sterilization, and the heat seal strength after thermal sterilization such as retort sterilization has reduced, and forms the orange peel line on film.In addition, according to the research that the inventor did, contain the sealing membrane (the open for the first time flat 10-265622 of (kokai) No. of Japanese patent application) that the boiling of the mixture of propylene-based block copolymer and polypropylene flexible resin(a) is used, can not be satisfactory, this is because the effect that prevents the orange peel line after the retort sterilization process is not enough.
Summary of the invention
An object of the present invention is to provide a kind of resin combination and film thereof that is applicable to packaging material for food and drug packages material, wherein because the reduction of the heat seal strength that thermal sterilization such as retort sterilization cause is limited to lower level, said composition and film thereof have good low temperature impact strength and good radiation resistance, and it can prevent the orange peel line effectively.
Another object of the present invention provides a kind of laminated multi-layer thing that is applicable to packaging material for food and drug packages material, wherein because the reduction of the heat seal strength that thermal sterilization such as retort sterilization cause is limited to lower level, this laminate has good low temperature impact strength and good anti-bleaching property, and it provides good production efficiency, produces gum shape thing hardly.
Through deep research, the inventor has now found that as a result, above-mentioned purpose can be by a kind of resin combination that contains special propylene-alpha-olefin segmented copolymer, and contain above-mentioned resin combination as the laminated multi-layer thing middle layer, that make with the multilayer film form and realize, and be found to be the basis with this and finished the present invention.
That is to say, the invention provides following prolylene polymer composition and laminated multi-layer thing.
I. prolylene polymer composition:
(1) for the Tc curve by determine with dsc method, the primary crystallization peak temperature (T of said composition
CP1) be 105～110 ℃, the second Tc (T
CP2) be 65～85 ℃, the second peak crystallization area (T
CA2) and primary crystallization peak area (T
CA1) ratio (AR) be 4.0% or lower,
(2) said composition is 10～30 weight % in the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene, and
(3) said composition is at the second Tc (T
CP2) and the passes between the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene fasten and satisfy following formula:
T
CP2≤-1.05XI+104。
II. prolylene polymer composition, said composition contains:
(A) the propylene-alpha-olefin block copolymer composition of 60～95 weight %, said composition contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(B) the flexible propylene-alpha-olefin block copolymer composition of 40～5 weight %, said composition contains:
(b1) the propylene block of 30～60 weight % and
(b2) elastomeric blocks of 70～40 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin.
III. one kind contains following at least trilaminar laminated multi-layer thing:
(A) contain two skins of propylene-alpha-olefin block copolymer composition, described copolymer compositions contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(C) middle layer that contains according to the prolylene polymer composition of above-mentioned I.
Description of drawings
What Fig. 1 showed is the example of the isotropic substance nuclear magnetic resonance of carbon spectrogram of propylene-ethylene copolymers.
Fig. 2 shows is name to the carbon that distributes based on the polyolefine medium chain.
Fig. 3 shows is a kind of example of the DSC crystallization curve according to prolylene polymer composition of the present invention.
The best mode that carries out an invention
A. prolylene polymer composition and film thereof
According to a kind of prolylene polymer composition of the present invention:
(1) for the Tc curve of measuring by dsc (below be called " DSC "), the primary crystallization peak temperature (T of said composition
CP1) be 105～110 ℃, the second Tc (T
CP2) be 65～85 ℃, the second peak crystallization area (T
CA2) and primary crystallization peak area (T
CA1) ratio (AR) be 4.0% or lower,
(2) said composition is 10～30 weight % in the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene, and
(3) said composition is at the second Tc (T
CP2) and the passes between the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene fasten and satisfy following formula:
T
CP2≤-1.05XI+104。
Above-mentioned Tc curve can obtain according to JIS K7122, and JIS K7122 is the method for a kind of thermal distortion with heat energy form quantification, and wherein thermal distortion is caused when using DSC with constant speed the temperature of sample to be reduced.Particularly, (preferred about 3～5mg) sample melted 5 minutes makes temperature be reduced to-30 ℃ with 20 ℃/minute speed afterwards, can obtain the Tc curve by make about 2～5mg under 230 ℃.
The T that so records
CP1Be preferably 105.5～109 ℃, more preferably 106～108 ℃.T
CP2Be preferably 66～83 ℃, more preferably 68～83 ℃.The second peak crystallization area (below be called " T
CA2") with the primary crystallization peak area (below be called " T
CA1") ratio (AR) be preferably 3.8% or lower, more preferably 3.5% or lower.
T
CP1Must be in 105～110 ℃ scope.If T
CP1Be lower than 105 ℃, then because crystallization velocity is slower than the curing speed in slow and the moulding process, and make the processability variation, it is irregular to occur flowing in moulded products, and the heat seal strength variation after the thermal sterilization.On the other hand, T
CP1It also is not preferred surpassing 110 ℃, because the heat seal strength variation after radiation resistance, flexible, cold resistant and the thermal sterilization.
T
CP2Must be in 65～85 ℃ scope.If T
CP2Be lower than 65 ℃, then hardness and thermotolerance variation.On the other hand, if T
CP2Surpass 85 ℃, then the heat seal strength variation after radiation resistance, cold resistant and the thermal sterilization.
T
CA2With T
CA1Ratio (AR) be necessary for 4.0% or lower.Surpass 4.0% as if AR, then the heat seal strength variation after radiation resistance, cold resistant and the thermal sterilization.The lower limit of AR is not limited especially.Yet AR is preferably 0.1% or higher.
The amount of dissolving part in 25 ℃ of following dimethylbenzene (below be called " XI ") (2) is expressed as, 130 ℃ down with the sample dissolution of about 1 weight % in dimethylbenzene, then solution is cooled to after 25 ℃ the ratio of the dissolving part that records.For resin combination of the present invention, XI is 10～30 weight %, preferred 15～29 weight %, more preferably 20～27 weight %.If XI is less than 10 weight %, then shock-resistance and radiation resistance variation.On the other hand, it also is not preferred that XI surpasses 30 weight %, because thermotolerance and hardness variation.
In addition, above-mentioned T
CP2And the relation between the XI must satisfy following formula: T
CP2≤-1.05XI+104.The condition that does not satisfy this formula is not preferred, because sealing intensity reduces greatly after the thermal sterilization.T
CP2And the relation between the XI is preferably T
CP2≤-1.18XI+106, more preferably T
CP2≤-1.31XI+108.
An example that meets the prolylene polymer composition of above-mentioned condition is so a kind of prolylene polymer composition, and said composition contains:
(A) the propylene-alpha-olefin block copolymer composition of 60～95 weight % (following be called sometimes " component (A) "), said composition contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(B) the flexible propylene-alpha-olefin block copolymer composition of 40～5 weight % (following be called sometimes " component (B) "), said composition contains:
(b1) the propylene block of 30～60 weight % and
(b2) elastomeric blocks of 70～40 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin.
And for satisfying above-mentioned condition, the limiting viscosity of preferred aforesaid propylene-'alpha '-olefin block copolymers composition (A) is 3.5～6.0dl/g.
An example of the polypropylene block (a1) in the said components (A) is a kind of C of alfon or propylene and 5 weight % or less amount
2～C
12(remove C
3Outside) random copolymers of alpha-olefin.The ratio of the alpha-olefin of copolymerization is preferably less than 4.5 weight %, more preferably less than 4.0 weight %.It is not preferred that the ratio of the alpha-olefin of copolymerization surpasses 5 weight %, because hardness and thermotolerance reduce, and the increase of the amount of low crystallising part, this makes film adhere to mutually.
An example of elastomeric blocks (a2) is propylene and C
2～C
12(remove C
3Outside) copolymer elastomer of alpha-olefin, wherein the ratio of the alpha-olefin of copolymerization is 5～40 weight %, preferred 10～35 weight %, more preferably 15～30 weight %.
In component (A), the ratio of the component of copolymerization (a2) is 5～30 weight %, preferred 10～28 weight %, more preferably 15～25 weight %.It is not preferred that the ratio of the component of copolymerization (a2) is lower than 5 weight %, because the heat seal strength after the retort sterilization process reduces, and shock-resistance and cold resistant variation.On the other hand, it also is not preferred that the ratio of the component of copolymerization (a2) surpasses 30 weight %, because a problem that exists is that the result of thermal sterilization such as digestion process is the thermotolerance variation, and film adheres to mutually.
The limiting viscosity of component of the present invention (A) is preferably 3.8～6.0dl/g.The limiting viscosity of using among the present invention is to be dissolved in solution in the perhydronaphthalene, the value that records with regard to 25 ℃ of parts that are insoluble to dimethylbenzene under 135 ℃.Limiting viscosity is in thermostatic chamber, measures with Ubbelohde capillary viscosimeter, Ostwald-Fenske capillary viscosimeter etc.According to the Huggins viscosity equation, unlimited by being extrapolated to then by these viscosity datas, obtain limiting viscosity.Concrete example is disclosed in Elliott etc., J.App.Poly.Sci., Vol.14, p2947-2963 (1970); Billmeyer is by Moritaka Tajima translation, " Koubunshi Kagaku Kyoukasho (textbook of polymer science) ", Tokyo Denki University Press (1989); And minute oru Imoto andTatsuya Imoto, " Koubunshi Kagaku no Kiso (polymer chemistry basis) ", Japanization association (1996).
Limiting viscosity according to component of the present invention (A) is preferably 3.8～5.5dl/g, more preferably 4.0～5.0dl/g.If limiting viscosity less than 3.5dl/g, prevents that then the effect of orange peel line is very little.On the other hand, it also is not preferred that limiting viscosity surpasses 6.0dl/g, because tend to form gel, flake or gum shape thing, these will disfeature.
Melt flow rate (MFR) (MFR according to component of the present invention (A); , under 230 ℃, under the load of 21.18N (2.16kgf), measure according to JIS K7210) not limited especially and depend on forming method.For example, the suitable MFR that is used for the component (A) of T-die head moulding process is 0.5～5g/10 minute, preferred 0.8～4g/10 minute, and more preferably 1.0～3g/10 minute.It is not preferred that the MFR of component (A) is lower than 0.5g/10 minute, because tend to occur gum shape thing in moulding process, this has reduced production efficiency.On the other hand, it also is not preferred that the MFR of component (A) surpasses 5g/10 minute, because the consistency variation of component (A) and component (B), so the reduction of the heat seal strength of gained film after the retort sterilization process will become big.And, when component (A) is used for two of laminated multi-layer thing as described below when outer, it is not preferred that the MFR of component (A) surpasses 5g/10 minute, because the deterioration of impact resistance of gained laminated multi-layer thing, and the consistency variation in component (A) and middle layer, so the reduction of the heat seal strength of gained laminated multi-layer thing after the retort sterilization process will become big.
An example of the component (b1) in the component (B) is propylene and another kind of C
12Or the multipolymer of following alpha-olefin, wherein the ratio of the alpha-olefin of the copolymerization of non-propylene is 8.0 weight % or higher, preferred 9.0 weight % or higher, more preferably 10 weight % or higher.It is not preferred that the ratio of the alpha-olefin of the copolymerization of non-propylene is lower than 8.0 weight %, because hardness and thermotolerance reduce, perhaps the reduction of the heat seal strength of anti-thermal sterilization becomes big.
An example of component (b2) is propylene and a kind of C
2～C
12(remove C
3Outside) the copolymer elastomer of alpha-olefin, wherein the ratio of the alpha-olefin of copolymerization is 30～80 weight %, preferred 35～75 weight %, more preferably 38～72 weight %.If the ratio of the alpha-olefin of copolymerization is less than 30 weight %, then shock-resistance and cold resistant variation.On the other hand, it also is not preferred that the ratio of the alpha-olefin of copolymerization surpasses 80 weight %, because will diminish thermotolerance.
In component (B), the ratio of copolymerization component (b2) is 40～70 weight %, preferred 45～69 weight %, more preferably 50～68 weight %.The ratio of copolymerization component (b2) is not preferred less than 40 weight %, because the reduction of the heat seal strength after shock-resistance, cold resistant and the thermal sterilization will become big.On the other hand, it also is not preferred that the ratio of copolymerization component (b2) surpasses 70 weight % because hardness and the performance that is suitable for boiling, as the mutual adherent inhibition of film with variation.
In prolylene polymer composition of the present invention, the ratio of component (B) is 5～40 weight %, preferred 8～35 weight %, more preferably 10～30 weight %, if the ratio of component (B) is lower than 5 weight %, then heat seal strength after the thermal sterilization and radiation resistance are with variation.On the other hand, it also is not preferred that the ratio of component (B) surpasses 40 weight %, because thermotolerance, hardness and chemical-resistant variation.
The specific examples of above-mentioned alpha-olefin is ethene, 1-butylene, 3-methyl-1-butene, 3-Methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-amylene, vinyl pentamethylene and vinyl cyclohexane.Can use these alpha-olefins of a kind of single type, perhaps mix and use these alpha-olefins of two or more types.
When using blending method, the component (B) with superperformance preferably has following characteristics (a) and (b).
That is, (a) 25 ℃ of parts that are insoluble to dimethylbenzene are 25～65 weight %, (b) for the part that is dissolved in dimethylbenzene under 25 ℃, (i) according to two active sites (two-site) model, average propylene content (F
P) be 20～80 moles of %, (ii) according to two active site models, at a main multipolymer (P who takes place to generate on the active site of propylene polymerization
H) in propylene content (P
P) be 65～90 moles of %, and (iii) P
HRatio (P in multipolymer
F1) be 0.60～0.90.
The ratio of insoluble part (a) is the ratio of sedimentary insoluble part when measuring above-mentioned " being dissolved in the ratio of the part in the dimethylbenzene " in the dimethylbenzene.For component of the present invention (B), the ratio of insoluble part is 25～65 weight % in the dimethylbenzene, preferred 30～60 weight %.
Be dissolved in part (b) in the dimethylbenzene for above-mentioned XI, and the characteristic that preferably obtains according to two active site models is in above-mentioned scope.
Particularly, with 25 ℃ be dissolved in the ortho-xylene components dissolved be heated to 120 ℃ 1,2, in the solvent mixture of 4-trichlorobenzene/deuterium for benzene, make that the concentration of polymkeric substance is 10 weight %.This solution is placed the glass test tube of 10mm diameter, and carry out the isotropic substance nuclear magnetic resonance of carbon (
13C-NMR) test.
Shown propylene-ethylene copolymers among Fig. 1
13An example of C-NMR spectrogram.In this spectrogram, because the difference in distribute at chain (mode of ethene and propylene arrangement) has reflected 10 peaks with (1)～(10) expression.
The name of chain is disclosed in Carman, C.J.et al; Macromolecules, Vol.10, pp.536-544 (1977) has listed its title among Fig. 2.By the mechanism of supposition copolymerization, can explain these chains with the form of equation with reaction probability P.When total peak intensity is set at 1, can add up by Bernoulli as parameter with P, obtain the relative intensity at each peak, (1)～(10) by probability equation.
That is to say that suppose " p " expression propylene, " e " represents ethene, has 3 kinds of chains can demonstrate peak corresponding to S α α (1): [pppp], [pppe] and [eppe].Explain each of these chains with reaction probability P with the form of equation, then these equations are added up.As for remaining peak (2)～(10), also use the same method and set up equation.Obtain P by the optimum value that finds the result that can make these 10 equations to approach the actual peak intensity that records most.
Be applied in the supposition of these reaction mechanisms, be used for two active site models of the present invention, be disclosed in H.J.Cheng; Journal of Applied Polymer Science, Vol.35, pp.1639-1650 (1988).For using catalyzer to make this model of propylene and ethylene copolymerization, by supposition at the multipolymer (P that mainly carries out generating on the active site of propylene polymerization
H) propylene content (P
P), and the propylene content of the multipolymer that mainly carries out generating on the active site of vinyl polymerization (P '
P), and use P in the multipolymer
HRatio (P
F1) as parameter, promptly obtain the probability equation shown in the table 1.
Above-mentioned for guaranteeing
13The relative intensity of C-NMR spectrum and the probability equation shown in the table 1 are agreed, and can find three parameter P
P, P '
PAnd P
F1Optimum value.
By following equation, calculate the partly average propylene content (F in (i) of the component that is dissolved in dimethylbenzene (B) described in the present invention with three above-mentioned parameters
P).
F
P=P
P* P
F1+ P '
P* (1-P
F1) (% mole)
The F that obtains by above-mentioned equation
PBe 20～80 moles of %, preferred 30～70 moles of %.
P in the above-mentioned parameter
P(ii) be preferably 60～90 moles of %, more preferably 65～85 moles of %.
In addition, P
F1(iii) be preferably 0.60～0.90, more preferably 0.68～0.82.
Obtain the slurry process of example for carrying out in the presence of liquefaction alpha-olefin solvent of the polymerization process of component (B) among the present invention, the alpha-olefin solvent that liquefies for example is a propylene, perhaps inert solvent such as hexane, heptane and kerosene, and the gaseous polymerization of not using solvent.Be aggregated in room temperature to 130 ℃, preferred 50～90 ℃, and at 19.6～490MPa (2-50kgf/cm
2) pressure under carry out.As for the reactor in the polymerization process, those reactors that can use the present technique field to be used always aptly; For example can use any agitator tank reactor, fluidized-bed reactor and recirculation reactor according to any continuous processing, semi-continuous process or interrupter method.
Particularly, component (B) can obtain with known multistep polymerization method.That is, in the first step reactor, after polypropylene and/or the propylene-alpha-olefin copolymers, carry out method by the second stage reactor propylene copolymerization and alpha-olefin, these for example are disclosed in Japanese unexamined patent application and disclose the flat 4-224809 of No., flat 3-977447, flat 4-36912 for the first time, flat 4-96907, flat 3-174410, flat 2-170803, flat 2-170802, flat 3-205439, flat 4-153203, flat 5-93024, flat 4-261423.
Commercially available product preferred embodiment is " CATALLOY " (trade(brand)name) of being produced by Montell Polyolefins, " P.E.R. " (trade(brand)name) by Tokuyama Corporation production, " NEWCON " (trade(brand)name) by Chisso Corporation production, with by IdemitsuPetrochemical Co., " TPO " (trade(brand)name) that Ltd. produces.
According to two active site models, in above-mentioned component (A), the part that is dissolved in dimethylbenzene under 25 ℃ has (i) according to its average propylene content of two active site models (F
P) be 30～70 moles of %, preferred 35～68 moles of %, more preferably 38～65 moles of %; (ii) according in the two active site models at the multipolymer (P that mainly carries out generating on the active site of propylene polymerization
H) in, propylene content (P
P) be 60～90 moles of %, preferred 63～85 moles of %, more preferably 65～83 moles of %; (iii) P
HRatio (P in multipolymer
F1) be by weight 0.30～0.70, preferred 0.35～0.65, more preferably 0.38～0.60.
Be explanation the present invention, " thermal sterilization " is meant and kills the method for microorganism that causes the septic major cause of food.The temperature range of thermal sterilization depends on target microorganism, but thermal sterilization carries out in 60～135 ℃ temperature range usually.In these thermal sterilization methods, utilizing temperature is the thermal sterilization method that the heat of 100 ℃ or higher hot steam or hot water is carried out, and is called retort sterilization, and it can not destroy under the content taste prerequisite, carries out the short time under high temperature.
Wherein use the sterilization method of ionizing rays in addition.In the type of these ionizing rayss, hertzian wave, radar wave and infrared-ray generate the heat that is used for sterilizing process.On the other hand, the ionizing rays of ultraviolet ray, X ray, gamma-radiation etc. does not produce heat, but the molecule of material is excited and ionization by radiation, and they make the material sterilization.
Usually, in the sterilization that utilizes ionizing rays, use cobalt 60 or caesium 137 to carry out the method for radiotreatment as source of radiation.Usually use this method to prevent potato sprout, perhaps the apparatus to medicine equipment such as injection needle tube and instillation usefulness carries out disinfection.The dosage of ionizing rays is generally 20～50KGy.
The detailed introduction of thermal sterilization for example is disclosed in Isao SHIBAZAKI, " shokuhin SakkinKogaku (Foods Sterilization Engineering) ", Korin Zensho, 24 (1981.3.14 publication), and Ushio SHIMIZU and Norio YOKOYAMA, " RetorutoShokuhin no Riron to Jissai (theory and practice of cooking food) ", SaiwaiShobo (1981.1.15 publication).
For polymer composition of the present invention, usually (for example can add other additive that can be used for thermoplastic resin, antioxidant, weather stablizer, static inhibitor, lubricant, anti-hard caking agent, antifogging agent, dyestuff, pigment, oil, wax and filler) and other thermoplastic resin, the amount of adding should not damaged purpose of the present invention.
The example of these additives is: as having of antioxidant, 2,5-dibutyl quinhydrones, 2,6-di-t-butyl p-Cresol, 4,4 '-sulfo-two (6-tert.-butyl phenol), 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 3-(3 ', 5 '-di-t-butyl-1 '-hydroxy phenyl) propionic acid stearyl and 4,4 '-sulfo-two (6-butylphenol); As having of UV light absorber, 2-cyano-3,3-diphenyl ethyl acrylate, 2-(2 '-hydroxy-5-methyl base phenyl) benzotriazole and 2-hydroxyl-4-octyloxy benzophenone; As having of softening agent, dimethyl phthalate, diethyl phthalate, wax, whiteruss and phosphoric acid ester; As having of static inhibitor, oleic acid, polyoxyethylene and the carbowax of Stearinsaeure pentaerythritol ester, single palmitinic acid sorbitan ester, sulphating; As having of lubricant, ethylene bis stearamide and butyl stearate; As having of tinting material, carbon black, phthalein mountain valley with clumps of trees and bamboo dyestuff, quinacridone, indoline, azo class pigment, titanium oxide and red iron oxide etc.; Glass fibre, asbestos, mica, wollastonite, Calucium Silicate powder, pure aluminium silicate and lime carbonate are arranged as filler.In addition for the present invention, can also be blended into many other polymer blends, the degree of interpolation should not hinder effect of the present invention and effect.
Each component blended method of polymer composition of the present invention is not limited especially, can use any known method.The example of this method is for wherein mixing each component with mixing tank, with forcing machine etc. mixture carried out process for granulating then, above-mentioned mixer instance as for mixing roll, Banbury mixing machine, Henschel mixing machine, roll the machine of mixing and ribbon blender.Or, in mixing process, mix with component (A) with (B), and directly be sent to and make film in the forming machine by dry method.
MFR according to polymer composition of the present invention is not limited especially, and depends on forming method.For example, the suitable MFR that is used for the polymer composition of T-die head moulding process is 0.5～30g/10 minute, preferred 0.8～25g/10 minute, and more preferably 1.0～20g/10 minute.
The thickness of gained film is generally 20～180 μ m.Thickness is not preferred less than 20 μ m, because heat seal strength will suffer damage.On the other hand, it also is not preferred that thickness surpasses 180 μ m, because heat-sealing will be not easy to carry out and the transparency will suffer damage.Thickness is preferably 30～170 μ m, more preferably 40～160 μ m.
Can use known extruding-method laminated into type and forming machine that polymer composition of the present invention is made moulded products.In addition, can also be used in combination with other material according to polymer composition of the present invention, these materials are the gas-barrier layer for being made by aluminium foil for example, with metallic vapor precipitation film thereon, with the film of silicon oxide steam precipitation on it, permalon, the saponification resultant of vinyl-vinyl acetate copolymer etc., and with laminated polyamide resin layer of known dry method machine laminated into type and polycarbonate resin.
B. laminated multi-layer thing
Two the outer field propylene-alpha-olefin block copolymer compositions (A) that are used for laminated multi-layer thing of the present invention are same types, are that the A part of " prolylene polymer composition and film thereof " is described as title in front.Therefore, for the component (a1) in the component (A) of laminated multi-layer thing and (a2), its type, consumption and be identical to the reason that they make qualification are as the A part is described in front.
In laminated multi-layer thing of the present invention, the propene polymer of prolylene polymer composition (following be called sometimes " component (C) ") for as described in A part in front, obtaining.
With the above-mentioned propylene-alpha-olefin block copolymer composition of selecting under the identical condition of two outer field components (A) in the component (C) that is used in.Propylene-alpha-olefin block copolymer composition in component (C) and the component (A) can be identical or different type, but preferably they are same types.In addition, with be used in two outer field components (A) in, for the identical condition of the alpha-olefin of a component of copolymer elastomer block component (a2) under, be chosen in the component (C) that forms the middle layer, be the alpha-olefin of a component of the copolymer elastomer block (a2) of component (A).These alpha-olefins can identical or different type, but preferably they are same types.
According to laminated multi-layer thing of the present invention is to contain at least 3 layers laminate, is made up of the skin of two said components (A) and the internal layer of a component (C) for described 3 layers.The thickness ratio of suitable layer (A) and layer (C), promptly layer (A)/layer (B)/layer (C) is (0.5～2.0)/(6.0～9.0)/(0.5～2.0), preferably (0.6～1.7)/(6.6～8.8)/(0.6～1.7), more preferably (0.8～1.5)/(7.0～8.4)/(0.8～1.5).If the thickness of layer (A) then produces die orifice gum shape thing than less than 0.5, and thermotolerance reduces.On the other hand, the thickness of layer (A) also is not preferred than surpassing 2.0, because the reduction of anti-bleaching property, shock-resistance and heat seal strength becomes big after the retort sterilization process.
For example be under the situation of film, the total thickness of laminated multi-layer thing of the present invention is generally 20～180 μ m.Thickness is not preferred less than 20 μ m, because heat seal strength is damaged.On the other hand, it also is not preferred that thickness surpasses 180 μ m, because heat-sealing will be not easy to carry out and the transparency will suffer damage.Thickness is preferably 30～170 μ m, more preferably 40～160 μ m.
The implication of " thermal sterilization " partly used at laminated multi-layer thing of the present invention is described with the A part to be identical.
Each layer for laminated multi-layer thing of the present invention, (for example can add other additive that is generally used for thermoplastic resin, antioxidant, weather stablizer, static inhibitor, lubricant, anti-hard caking agent, antifogging agent, dyestuff, pigment, oil, wax and filler) and other thermoplastic resin, the amount of adding should not damaged purpose of the present invention.The example of these additives is at described those additives of A part.
Can obtain laminated multi-layer thing of the present invention by making each above-mentioned component carry out known extruding-method laminated into type and using known forming machine.In addition, laminated multi-layer thing of the present invention can use with other material in addition, these materials are the gas-barrier layer for being made by aluminium foil for example, with metallic vapor precipitation film thereon, with the film of silicon oxide steam precipitation on it, permalon, the saponification resultant of vinyl-vinyl acetate copolymer etc., and with laminated polyamide resin layer of known dry method machine laminated into type and polycarbonate resin.
Embodiment
The invention will be further described below with reference to embodiment.The following testing method of explanation earlier.
(1) is dissolved in dimethylbenzene and the mensuration that is insoluble to the dimethylbenzene part
Under 130 ℃ with polymer dissolution in ortho-xylene, the concentration that makes polymkeric substance is about 1 weight %, solution is cooled to 25 ℃ then.Sedimentary part is thought the insoluble part of dimethylbenzene, and the precipitation part is not thought the xylene soluble part, and obtains this two-part part by weight.Xylene soluble partly is used for following
13In the test of C-NMR spectrum.
(2)
13The test of C-NMR spectrum
Testing apparatus: by the JNM-GSX400 of JEOL LTD manufacturing.
Test mode: proton-decoupled method.
Pulse width: 8.0 μ s.
Pulse repetition time: 5.0 μ s.
Multiple cumulative frequency: 20000 times.
Solvent: 1,2,4-trichlorobenzene and deuterium are for the mixture (75/25 volume %) of benzene.
Interior mark: hexamethyldisiloxane.
Sample concentration: 300mg/3.0ml solvent.
Probe temperature: 120 ℃.
(3) T that carries out with Differential Scanning Calorimeter (DSC)
CP1, T
CP2With the mensuration of area than (AR)
Equipment: by 7 serial DSC of Perkin-Elmer Co. manufacturing.
Example weight: about 3～5mg.
Measuring method: sample is heated to 230 ℃ by 0 ℃, holding temperature 5 minutes, and reduce to 0 ℃ with 20 ℃/minute speed, obtain the Tc curve.By the Tc curve that so obtains, determine area T
CP1, area T
CP2With these areas than (AR).
(4) mensuration of limiting viscosity
With the Ubbelohde capillary viscosimeter is solvent with the perhydronaphthalene, measures limiting viscosity down at 135 ℃.
(5) processability
Begin until produce gum shape thing at the die head exit place with moulding, forming droplet and adhere on the film time of being experienced is benchmark, gives the processability divided rank with one of following 4 grades.
◎: 10 hours or longer
Zero: 7 hour or longer, but less than 10 hours
△: 2 hours or longer, but less than 7 hours
*: less than 2 hours
(6) sealing intensity
Cut the rectangular of next wide 15mm from film, use Orientec Co., the tensile testing machine (model RTA-100) that Ltd. makes is measured 180 ° of stripping strengths with 300mm/ minute draw speed.
(7) shock strength of film and heat-sealing shock strength
Described according to ASTM D781, with Toyo Seiki Seisaku-Sho, the film impact test instrument that Ltd. makes is 23 ℃ and-5 ℃ shock strength and the heat-sealing shock strengths of measuring film down.
(8) evaluation of orange peel line
The commodity pressure pad food (by AjinomotoCo., Inc. produces for " Chinjaorousu ", trade(brand)name) of in pouch, packing into.After the retort sterilization process, by the orange peel line (irregular phenomenon) that visual inspection produces on the surface of pouch, the appearance divided rank of giving the orange peel line with following 5 grades:
1: do not observe the appearance of orange peel line.
2: observe some unconspicuous orange peel lines.
3: observe the unconspicuous orange peel line in certain zone, but pouch can use still.
4: observe tangible orange peel line on the whole surface of pouch, pouch can not use.
5: observe serious irregular orange peel line on the whole surface of pouch, pouch can not use.
9) anti-bleaching property
With Tester Sangyo Co., the Gelbo Flex tester that Ltd. makes repeatedly carries out bending 50 times to sample, this tester has the cylinder of a diameter 90mm, and stroke is 178mm, and twist angle is 440 °, the distortion stroke is 89mm, and linear stroke is 63.5mm, and reciprocating speed is 40 times/minute.Give anti-bleaching property divided rank with one of following 4 grades.
◎: do not observe the part that bleaches.
Zero: observe some parts that bleach.
△: observe the big part that bleaches, film can not use.
*: observe a large amount of bleaching, film can not use.
The following describes employed material.
As component (A), use following material:
BPP-1: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 20 weight %, and the insoluble part of dimethylbenzene is 85.69 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 44.1 moles of %, 74.9 moles of % and 0.33, limiting viscosity is 3.8dl/g, and MFR is 23g/10 minute.
BPP-2: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 15 weight %, and the insoluble part of dimethylbenzene is 90.2 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 45.2 moles of %, 78.2 moles of % and 0.36, limiting viscosity is 4.2dl/g, and MFR is 5.8g/10 minute.
BPP-3: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 19 weight %, and the insoluble part of dimethylbenzene is 86.1 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 50.6 moles of %, 76.8 moles of % and 0.41, limiting viscosity is 5.2dl/g, and MFR is 2.5g/10 minute.
BPP-4: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 25 weight %, and the insoluble part of dimethylbenzene is 80.2 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 48.2 moles of %, 77.2 moles of % and 0.38, limiting viscosity is 4.7dl/g, and MFR is 3.4g/10 minute.
In order to compare, use following material.
BPP-a: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 20 weight %, and the insoluble part of dimethylbenzene is 85.8 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 44.2 moles of %, 75.3 moles of % and 0.35, limiting viscosity is 2.8dl/g, and MFR is 2.5g/10 minute.
BPP-b: propylene-alpha-olefin block copolymer composition, its limiting viscosity are 3.3dl/g, and MFR is 7.0g/10 minute (trade(brand)name " HC021 ", by Grand Polymer Co., Ltd. produces).
PP-1: alfon, its MFR are 7.2g/10 minute.
PP-2: ethylene-propylene random copolymer, its ethylene content are 4.6 weight %, and MFR is 6.8g/10 minute.
As component (B), use following material:
BPP-5: propylene-alpha-olefin block copolymer composition, its elastomeric blocks content are 65 weight %, and the insoluble part of dimethylbenzene is 34.8 weight %, the F of xylene soluble part
P, P
PAnd P
F1Be respectively 66.5 moles of %, 76.1 moles of % and 0.37, MFR is 0.8g/10 minute (" CATALLOYKS353P " produced by Motell Polyolefins).
In order to compare, use following material.
BPP-A: ethylene-butene copolymer, its 1-butylene content is 15 weight %, and MFR is 1.4g/10 minute (190 ℃, load is 21.18N (2.16kgf)) (trade(brand)name " TAFMER A1085 ", by MitsuiPetrochemical Industries, Ltd. produces).
BPP-B: ethylene-propylene copolymer, its ethylene content is 75 weight %, and MFR is 1.8g/10 minute (190 ℃, load is 21.18N (2.16kgf)) (trade(brand)name " TAFMER P0480 ", by MitsuiPetrochemical Industries, Ltd. produces).
PE-1: straight-chain low density polyethylene, its MFR are 15.8g/10 minute.
Notice that BPP-b, BPP-A and BPP-B can not analyze according to two active site models.
The preparation of prolylene polymer composition pellet
With rolling each combining form that the machine that mixes mixes the amount of Table 2 component (A) and (B) down, use Kobe Steel Co. then, the parallel dual-screw kneader (" KTX37 ") of Ltd. manufacturing carries out granulation to said mixture under 190～210 ℃.(A～S) is according to the Tc curve determination primary crystallization peak temperature T that obtains with DSC for the pellet of each gained
CP1) and the second Tc T
CP2), and measure its xylene soluble ratio partly.The results are shown in Table 2.
In addition, the DSC crystallization curve that has shown pellet A among Fig. 3.
Embodiment 1～10 and Comparative Examples 1～8
By each pellet A～R, use Yoshii Tekko, it is the film of 80 μ m that the T-die head shaper (diameter is 40mm φ, and die width is 250mm) that K.K. makes is produced thickness, wherein die head temperature is 250 ℃.
By doing laminating, the polyester film that with thickness is 12 μ m is in the same place with above-mentioned each film lamination that obtains, and with Tester Sangyo Co., the heat sealing machine that Ltd. makes makes laminate seal for 1 second, temperature is 160 or 170 ℃, and pressure is 19.6MPa (2kgf/cm
2).
Use Hisaka Works, " RCS-40T " that Ltd. makes carried out boiling 30 minutes to heat-sealing film under 121 ℃.Be determined at before the digestion process and heat seal strength afterwards and heat-sealing shock strength.
In addition, with the γ line of 25KGy heat-sealing film is carried out radiation, measure or estimate before digestion process and heat seal strength afterwards, heat-sealing shock strength and orange peel line with cobalt 60.
Listed above-mentioned result in the table 2,3 and 4.
Embodiment 11～16 and Comparative Examples 9～15
With Toshiba Machine Co., Ltd. make, the forcing machine diameter be 115 and 65mm φ, die width be that 3400mm, die lip gap are the T-die head shaper of the charging head dummy of 0.8mm, preparation thickness is the film of 70 μ m, the layer structure of this film listed in table 5, and the middle layer according to one of pellet A～D, the K～N of table 5 and S is arranged.The thickness ratio in suitably adjustment sheet surface layer as shown in table 5 and middle layer.
By doing laminating, be that the polyester film of 12 μ m is in the same place with above-mentioned each film lamination that obtains with thickness, with Tester Sangyo Co., the heat sealing machine that Ltd. makes makes laminate seal for 1 second, and temperature is 160 or 170 ℃, and pressure is 19.6MPa (2kgf/cm
2).
Use Hisaka Works, " RCS-40T " that Ltd. makes carried out boiling 30 minutes to the film as above-mentioned heat-sealing under 121 ℃.Be determined at before the digestion process and afterwards heat seal strength and anti-bleaching property.The results are shown in Table 6.
Table 1
| Signal | The probability equation of two active site models |
| ①Sαα ②Sαγ ③Sαδ ④Tδδ ⑤Sγγ+Tβδ ⑥Sγδ ? ⑦Sδδ ? ⑧Tββ ⑨Sβδ ⑩Sββ | P P 2×P f1+P’ P 2×(1-P f1) (-2P P 3+2P P 2)×P f1+(-2P’ P 3+2P’ P 2)×(1-P f1) (2P P 3-4P P 2+2P P)×P f1+(2P’ P 3-4P’ P 2+2P’ P)×(1-P f1) (P P 3-2P P 2+P P)×P f1+(P’ P 3-2P’ P 2+P’ P)×(1-P f1) (P P 4-4P P 3+3P P 2)×P f1+(P’ P 4-4P’ P 3+3P’ P 2)×(1-P f1) (-2P P 4+6P P 3-6P P 2+2P P)×P f1+(-2P’ P 4+6P’ P 3-6P’ P 2+2P’ P) ×(1-P f1) (P P 4-5P P 3+9P P 2-7P P+2)×P f1+(P’ P 4-5P’ P 3+9P’ P 2-7P’ P+2) ×(1-P f1) P P 3×P f1+P’ P 3×(1-P f1) (2P P 3-4P P 2+2P P)×P f1+(2P’ P 3-4P’ P 2+2P’ P)×(1-P P1) (-P P 3+P P 2×P f1+(-P’ P 3+P’ P 2)×(1-P f1) |
Table 2
| The prolylene polymer composition type | Component (A) | Component (B) | ?????T CP1????(℃) | ?????T CP2?????(C) | ????AR ????(％) | Xylene soluble part (wt%) | ||
| Type | ??wt％ | Type | ??wt％ | |||||
| Particle A particle B particle C particle D particle E particle F particle G particle H particle I particle J | ??BPP-1 ??BPP-1 ??BPP-1 ??BPP-1 ??BPP-2 ??BPP-2 ??BPP-3 ??BPP-3 ??BPP-4 ??BPP-4 | ????94 ????90 ????80 ????75 ????90 ????80 ????95 ????90 ????80 ????85 | ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 | ????6 ????10 ????20 ????25 ????10 ????20 ????5 ????10 ????20 ????15 | ????108.6 ????108.6 ????107.3 ????107.1 ????107.5 ????107.2 ????108.5 ????108.4 ????107.9 ????107.6 | ????82.3 ????79.6 ????69.3 ????64.8 ????71.4 ????70.9 ????82.1 ????79.5 ????80.8 ????80.5 | ????2.4 ????2.7 ????3.1 ????3.5 ????3.2 ????3.6 ????2.6 ????2.9 ????3.2 ????3.2 | ????18.7 ????20.8 ????25.2 ????28.7 ????18.4 ????24.9 ????17.8 ????18.1 ????22.5 ????19.6 |
| Particle K particle L particle M particle N particle O particle P particle Q particle R particle S | ??BPP-1 ??BPP-1 ??BPP-1 ??BPP-1 ??BPP-a ??BPP-a ??BPP-b ??BPP-b ??BPP-1 | ????94 ????90 ????80 ????75 ????90 ????80 ????90 ????80 ????85 | ????BPP-A ????BPP-A ????BPP-A ????BPP-B ????BPP-5 ????BPP-5 ????BPP-5 ????BPP-5 ?????PE-1 | ????6 ????10 ????20 ????25 ????10 ????20 ????10 ????20 ????15 | ????107.3 ????105.3 ????105.3 ????105.1 ????104.8 ????104.5 ????104.1 ????103.8 ????108.6 | ????86.3 ????82.3 ????79.6 ????76.7 ?????- ?????- ????65.2 ?????- ????98.9 | ????2.5 ????2.4 ????3.4 ????3.6 ?????- ?????- ????0.5 ?????- ????6.2 | ????21.3 ????24.4 ????32.6 ????36.8 ????24.8 ????33.1 ????24.2 ????31.5 ????28.3 |
Table 3
| Embodiment and Comparative Examples sequence number | Pellet | The boiling resistance energy | ||||||
| Before the digestion process | After the digestion process | |||||||
| Shock strength (Ncm/mm) | Heat seal strength (N/15mm is wide) | -5 ℃ of film shock strengths (Ncm) | Heat seal strength degree (N/15mm is wide) | |||||
| ??23℃ | ??-5℃ | ????160℃ | ????170℃ | ??160℃ | ????170℃ | |||
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 | Pellet A pellet B pellet C pellet D pellet E pellet F pellet G pellet H pellet I pellet J | ??2883 ??3119 ??3727 ??4168 ??3442 ??3874 ??3089 ??3560 ??3864 ??2717 | ??1589 ??1628 ??1863 ??1871 ??1746 ??1932 ??1726 ??1824 ??2108 ??1941 | ????59.8 ????60.8 ????58.8 ????59.8 ????63.7 ????66.7 ????62.8 ????66.7 ??＞78.5 ????75.5 | ????60.8 ????61.8 ????60.8 ????61.8 ????66.7 ????70.6 ????66.7 ????72.6 ??＞78.5 ??＞78.5 | ????53.0 ????60.8 ????57.9 ????60.8 ????63.7 ????66.7 ????56.9 ????64.7 ????96.1 ????80.4 | ??48.1 ??54.9 ??56.9 ??57.9 ??57.9 ??60.8 ??53.0 ??61.8 ??73.5 ??70.6 | ????53.9 ????55.9 ????54.9 ????55.9 ????59.8 ????62.8 ????60.8 ????63.7 ??＞78.5 ??＞78.5 |
| Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4 Comparative Examples 5 Comparative Examples 6 Comparative Examples 7 Comparative Examples 8 | Pellet K pellet L pellet M pellet N pellet O pellet P pellet Q pellet R | ??3060 ??2913 ??3413 ??3550 ??1814 ??1942 ??2658 ??2883 | ??1333 ??1304 ??1569 ??1687 ???765 ???853 ??1098 ??1216 | ????54.9 ????53.0 ????53.0 ????50.0 ????37.3 ????42.1 ????47.1 ????50.0 | ????54.9 ????51.0 ????49.0 ????48.1 ????43.1 ????47.1 ????51.0 ????53.0 | ????30.4 ????37.3 ????47.1 ????44.1 ????30.4 ????35.3 ????42.1 ????46.1 | ??38.2 ??26.5 ??23.5 ??21.6 ??17.7 ??14.7 ??37.3 ??41.2 | ????43.1 ????29.4 ????22.6 ????23.5 ????23.5 ????18.6 ????38.2 ????44.1 |
Table 4
| Embodiment and Comparative Examples sequence number | Radiation resistance | The orange peel line is estimated | |||||
| Before the gamma-radiation radiation | After the gamma-radiation radiation | ||||||
| Film shock strength (Ncm) | Shock strength (Ncm) | Film shock strength (Ncm) | |||||
| ??23℃ | ??-5℃ | ????23℃ | ????-5℃ | ????23℃ | ????-5℃ | ||
| Embodiment 1 | ??220 | ??171 | ????2138 | ????1236 | ????90 | ????81.3 | ????3 |
| Embodiment 2 | ??233 | ??179 | ????2206 | ????1285 | ????94 | ????85 | ????2 |
| Embodiment 3 | ??246 | ??189 | ????2265 | ????1353 | ????100 | ????90 | ????1 |
| Embodiment 4 | ??253 | ??194 | ????2471 | ????1442 | ????117 | ????104 | ????1 |
| Embodiment 5 | ??246 | ??187 | ????2334 | ????1393 | ????103 | ????93 | ????1 |
| Embodiment 6 | ??259 | ??199 | ????2422 | ????1481 | ????112 | ????110 | ????1 |
| Embodiment 7 | ??236 | ??181 | ????2334 | ????1324 | ????96 | ????89 | ????1 |
| Embodiment 8 | ??257 | ??193 | ????2403 | ????1471 | ????110 | ????99 | ????1 |
| Embodiment 9 | ??322 | ??246 | ????2765 | ????1971 | ????237 | ????211 | ????1 |
| Embodiment 10 | ??289 | ??233 | ????2599 | ????1834 | ????220 | ????190 | ????1 |
| Comparative Examples 1 | ??126 | ??90 | ????2226 | ????843 | ????76 | ????25 | ????4 |
| Comparative Examples 2 | ??138 | ??99 | ????2363 | ????961 | ????96 | ????31 | ????5 |
| Comparative Examples 3 | ??160 | ??133 | ????2442 | ????1059 | ????103 | ????37 | ????5 |
| Comparative Examples 4 | ??178 | ??138 | ????2560 | ????1128 | ????114 | ????44 | ????5 |
| Comparative Examples 5 | ??116 | ??84 | ????1687 | ????353 | ????67 | ????15 | ????3 |
| Comparative Examples 6 | ??136 | ??92 | ????1883 | ????667 | ????72 | ????21 | ????5 |
| Comparative Examples 7 | ??162 | ??96 | ????2167 | ????892 | ????83 | ????33 | ????4 |
| Comparative Examples 8 | ??173 | ??112 | ????2383 | ????1040 | ????89 | ????44 | ????5 |
Table 5
| The top layer | The middle layer | The top layer | ||||
| Type | Thickness (μ m) | Type | Thickness (μ m) | Type | Thickness (μ m) | |
| Embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 | ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 | ????7 ????7 ????7 ????7 ????10 ????14 | Pellet A pellet B pellet C pellet D pellet D pellet D | ????56 ????56 ????56 ????56 ????50 ????42 | ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 | ????7 ????7 ????7 ????7 ????7 ????14 |
| Ratio 10 Comparative Examples 11 Comparative Examples 12 Comparative Examples 13 Comparative Examples 14 Comparative Examples 15 during Comparative Examples 9 | ????PP-1 ????PP-2 ?????- ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 | ????7 ????7 ????- ????7 ????7 ????7 ????7 | Pellet B pellet C pellet K pellet L pellet M pellet N pellet S | ????56 ????50 ????70 ????56 ????56 ????56 ????56 | ????PP-1 ????PP-2 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 ????BPP-1 | ????7 ????7 ????- ????7 ????7 ????7 ????7 |
Table 6
| Processability | Before the digestion process | Behind the digestion process | ||||||
| Shock strength (kgfcm/mm) | Heat seal strength (kgf/15mm is wide) | Heat seal strength (kgf/15mm is wide) | Anti-bleaching property | |||||
| ???23℃ | ???-5℃ | ????160℃ | ????170℃ | ????160℃ | ????170℃ | |||
| Embodiment 11 | ???◎ | ???295 | ????168 | ????6.2 | ????6.3 | ????5.2 | ????5.8 | ????○ |
| Embodiment 12 | ???◎ | ???304 | ????175 | ????6.3 | ????6.4 | ????5.8 | ????6.2 | ????◎ |
| Embodiment 13 | ???◎ | ???318 | ????195 | ????6.3 | ????6.5 | ????5.9 | ????6.3 | ????◎ |
| Embodiment 14 | ???◎ | ???325 | ????202 | ????6.2 | ????6.4 | ????6.2 | ????6.2 | ????◎ |
| Embodiment 15 | ???◎ | ???283 | ????163 | ????6.5 | ????6.6 | ????6.3 | ????6.3 | ????◎ |
| Embodiment 16 | ???◎ | ???272 | ????158 | ????6.8 | ????6.9 | ????6.5 | ????6.5 | ????○ |
| Comparative Examples 9 | ???○ | ???195 | ????65 | ????6.1 | ????6.5 | ????3.8 | ????4.2 | ????○ |
| Comparative Examples 10 | ???○ | ???226 | ????98 | ????6.2 | ????6.4 | ????4.2 | ????4.5 | ????△ |
| Comparative Examples 11 | ???× | ???233 | ????106 | ????4.5 | ????4.9 | ????3.6 | ????3.8 | ????× |
| Comparative Examples 12 | ???△ | ???241 | ????115 | ????4.6 | ????4.8 | ????3.3 | ????3.5 | ????△ |
| Comparative Examples 13 | ???△ | ???248 | ????123 | ????4.5 | ????4.6 | ????2.7 | ????3.0 | ????△ |
| Comparative Examples 14 | ???△ | ???259 | ????132 | ????4.3 | ????4.5 | ????2.6 | ????2.8 | ????△ |
| Comparative Examples 15 | ???△ | ???208 | ????85 | ????4.5 | ????4.8 | ????2.8 | ????3.1 | ????× |
Industrial applicibility
Be applicable to packaging material according to prolylene polymer composition of the present invention, such as the hot sealing layer of packaging material for food and drug packages material, because because the reduction of the heat seal strength that causes of heating disinfection is very little, and its low temperature impact strength and radiation resistance are good.
According to suitable packaging material for food and the drug packages material done of laminated multi-layer thing of the present invention, because because the reduction of the heat seal strength that heating disinfection causes is very little, low temperature impact strength and anti-bleaching property are good, and produce hardly gum shape thing, and this is so that have good production efficiency.
Claims (8)
1. prolylene polymer composition:
(1) for the Tc curve by determine with dsc method, the primary crystallization peak temperature (T of said composition
CP1) be 105～110 ℃, the second Tc (T
CP2) be 65～85 ℃, the second peak crystallization area (T
CA2) and primary crystallization peak area (T
CA1) ratio (AR) be 4.0% or lower,
(2) said composition is 10～30 weight % in the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene, and
(3) said composition is at the second Tc (T
CP2) and the passes between the amount (XI) of 25 ℃ of dissolving parts in dimethylbenzene fasten and satisfy following formula:
T
CP2≤-1.05XI+104。
2. prolylene polymer composition, said composition contains:
(A) the propylene-alpha-olefin block copolymer composition of 60～95 weight %, said composition contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(B) the flexible propylene-alpha-olefin block copolymer composition of 40～5 weight %, said composition contains:
(b1) the propylene block of 30～60 weight % and
(b2) elastomeric blocks of 70～40 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin.
3. the prolylene polymer composition of claim 2, wherein the limiting viscosity of propylene-alpha-olefin block copolymer composition (A) is 3.5～6.0dl/g.
4. the prolylene polymer composition of claim 2, wherein flexible propylene-alpha-olefin block copolymer composition (B) have following characteristics (a) and (b):
(a) 25 ℃ of parts that are insoluble to dimethylbenzene be 25～65 weight % and
(b) for the part that is dissolved in dimethylbenzene under 25 ℃, (i) according to two active site models, average propylene content (F
P) be 20～80 moles of %, (ii) advance, at a main multipolymer (P who takes place to generate on the active site of propylene polymerization according to two active site models
H) in propylene content (P
P) be 65～90 moles of %, and (iii) P
HRatio (P in multipolymer
F1) be 0.60～0.90.
5. by processing the film that obtains as each described propylene resin composition of claim 1～4.
6. one kind contains following at least trilaminar laminated multi-layer thing:
(A) contain two skins of propylene-alpha-olefin block copolymer composition, described copolymer compositions contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(C) middle layer that contains the prolylene polymer composition of right requirement 1.
7. the laminated multi-layer thing of claim 6, wherein prolylene polymer composition (C) contains:
(A) the propylene-alpha-olefin block copolymer composition of 60～95 weight %, said composition contains:
(a1) the polypropylene block of 70～95 weight % and
(a2) elastomeric blocks of 30～5 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin, and
(B) the flexible propylene-alpha-olefin block copolymer composition of 40～5 weight %, said composition contains:
(b1) the propylene block of 30～60 weight % and
(b2) elastomeric blocks of 70～40 weight %, this elastomeric blocks are propylene and a kind of C
2～C
12(remove C
3Outside) the multipolymer of alpha-olefin.
8. the laminated multi-layer thing of claim 7, wherein flexible propylene-alpha-olefin block copolymer composition (B) have following characteristics (a) and (b):
(a) 25 ℃ of parts that are insoluble to dimethylbenzene be 25～65 weight % and
(b) for the part that is dissolved in dimethylbenzene under 25 ℃, (i) according to two active site models, average propylene content (F
P) be 20～80 moles of %, (ii) according to two active site models, at a main multipolymer (P who takes place to generate on the active site of propylene polymerization
H) in propylene content (P
P) be 65～90 moles of %, and (iii) P
HRatio (P in multipolymer
F1) be 0.60～0.90.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21720/00 | 2000-01-26 | ||
| JP21720/2000 | 2000-01-26 | ||
| JP2000021720A JP2000297197A (en) | 1999-02-08 | 2000-01-26 | Propylene based polymer composition and its film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1425041A true CN1425041A (en) | 2003-06-18 |
| CN1289599C CN1289599C (en) | 2006-12-13 |
Family
ID=18548094
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008186154A Expired - Fee Related CN1289599C (en) | 2000-01-26 | 2000-08-04 | Propylene polymer composition, film thereof, and multilayered laminate |
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| Country | Link |
|---|---|
| KR (1) | KR100494076B1 (en) |
| CN (1) | CN1289599C (en) |
| MY (1) | MY136845A (en) |
| WO (1) | WO2001055258A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITTO20120829A1 (en) | 2012-09-25 | 2014-03-26 | Torino Politecnico | METHOD AND SYSTEM FOR GENERATING CHANNEL CODES, IN PARTICULAR FOR A FRAME-HEADER |
| KR102124702B1 (en) * | 2018-11-14 | 2020-06-19 | 한화토탈 주식회사 | Polypropylene resin composition with excellent stress-whitening resistance, process for preparing the same, and article molded therefrom |
| KR102209154B1 (en) * | 2019-12-24 | 2021-01-29 | 한화토탈 주식회사 | Polypropylene Resin Composition with Excellent Stress-whitening Resistance, Process for Preparing the Same, and Article Molded Therefrom |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10265622A (en) * | 1997-03-27 | 1998-10-06 | Sekisui Chem Co Ltd | Sealant film for retort |
| JP4177911B2 (en) * | 1998-02-06 | 2008-11-05 | 日本ポリプロ株式会社 | Polypropylene resin composition |
| JP3934238B2 (en) * | 1998-03-03 | 2007-06-20 | 日本ポリプロ株式会社 | Laminated bags for food packaging |
-
2000
- 2000-08-03 MY MYPI20003542A patent/MY136845A/en unknown
- 2000-08-04 CN CNB008186154A patent/CN1289599C/en not_active Expired - Fee Related
- 2000-08-04 WO PCT/JP2000/005244 patent/WO2001055258A1/en active IP Right Grant
- 2000-08-04 KR KR10-2002-7009457A patent/KR100494076B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| MY136845A (en) | 2008-11-28 |
| KR100494076B1 (en) | 2005-06-10 |
| KR20020077893A (en) | 2002-10-14 |
| WO2001055258A1 (en) | 2001-08-02 |
| CN1289599C (en) | 2006-12-13 |
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