CN1868723A - Transparent polypropylene-family resin slice, manufacturing method thereof, and shaped pruduct - Google Patents
Transparent polypropylene-family resin slice, manufacturing method thereof, and shaped pruduct Download PDFInfo
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- CN1868723A CN1868723A CNA2006100751576A CN200610075157A CN1868723A CN 1868723 A CN1868723 A CN 1868723A CN A2006100751576 A CNA2006100751576 A CN A2006100751576A CN 200610075157 A CN200610075157 A CN 200610075157A CN 1868723 A CN1868723 A CN 1868723A
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- thin slice
- transparent polypropylene
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- 238000004519 manufacturing process Methods 0.000 title claims description 35
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- 239000004743 Polypropylene Substances 0.000 claims abstract description 122
- 239000004711 α-olefin Substances 0.000 claims abstract description 67
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims description 60
- 229920005673 polypropylene based resin Polymers 0.000 claims description 38
- 241000276489 Merlangius merlangus Species 0.000 claims description 25
- 239000000498 cooling water Substances 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 17
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- 238000001125 extrusion Methods 0.000 claims description 13
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- 230000000694 effects Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 7
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- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract 2
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- 230000008018 melting Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/002—Panels; Plates; Sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/04—Homopolymers or copolymers of ethene
- C08J2423/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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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
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
Abstract
This invention provides a transparent polypropylene resin flake, with upstanding transparency and outstanding physical properties, such as cold resistance, heat resistance and rigidity, comprising: melt and squeeze the resin mixture of 70-97%(mass ratio) polypropylene resin(a) with 85-99% uni-rate pentad and 0.1-30g/10min melting flow rate(MFR) and 30-3%(mass ratio) metal cyclopentadienyl ethane-alpha-olefin copolymer(b) produced with metal cyclopentadienyl catalyst, and with 8880-925kg/m<SUP>3</SUP> density and 1-30g/10min MFR to be flake, and then cool the flake immediately.
Description
Technical field
The present invention relates to the manufacture method, transparent polypropylene resinoid thin slice of the also excellent transparent polypropylene resinoid thin slice of various rerum naturas such as not only transparent outstanding but also cold-resistant impact and rigidity and the formed products that constitutes by this transparent polypropylene resinoid thin slice and practically very effective method and the temperature determination methods that prevents the formed products whiting that constitutes by transparent polypropylene resinoid thin slice.
Background technology
In the past, for example as the transparent sheet that is used to form various containers etc., polyvinyl chloride thin slice and thin polystyrene sheet have been extensive use of, but owing in recent years the consciousness of environmental problem etc. is improved day by day, the use of these resins is restricted, and requires to develop the new transparent sheet that can replace it thereupon.
In this case, at present to instead the exploitation of the transparent polypropylene resinoid thin slice of the material of transparent sheet in the past is also very active.
But, polypropylene is owing to be crystalline resin, so be difficult to obtain enough transparencys, and, when using transparent polypropylene resinoid thin slice to form various containers etc., with regard to regard to the transparent polypropylene resinoid thin slice of substrate sheet, except the transparency, also require also have excellent performance aspect other various rerum naturas according to its purposes.
For example, when when the food containers, in order to prevent to break when the freezing circulation of food etc., requirement has cold-resistant impact (in the impact strength of low-temperature region).In addition, in snacks shop (convenience store) etc., heat under the situation that the back need be overlapping with a plurality of containers when being incubated with warmer with micro-wave oven, for fear of because of the container deformation content attached on the lid or the problem of leaking, also need to guarantee hear resistance and rigidity, and then, whiting when also requiring to prevent to heat.
As mentioned above, want transparent polypropylene resinoid thin slice is supplied not only will guarantee the transparency in practicality that resistance to impact (cold-resistant impact), hear resistance, rigidity etc. also must be fully.
For the transparency of improving transparent polypropylene resinoid thin slice and resistance to impact etc., for example, in patent documentation 1, disclose the polypropylene-based resin that will in homo-polypropylene (HPP), be mixed with ethene-1-Butylene copolymer and melt extruded the back obtains thin slice by chilling method, in patent documentation 2, the method that is mixed with low density ethylene-1-Butylene copolymer and makes the polypropylene-based resin composition of nuclear agent in homo-polypropylene (HPP) of using is disclosed.
In addition, in patent documentation 3, disclose the homo-polypropylene (HPP) that has mixed straight chain shape low density polyethylene (LDPE) (L-LDPE) as the method for carrying out chilling after melt extruding under the situation of polypropylene-based resin, in patent documentation 4, disclose to use and be mixed with the polyacrylic polypropylene resin composite of low-crystalline and carry out chilling, heat-treating methods, in patent documentation 5, disclose and used mix polyethylene resinoid and the method for making the formed polyolefin resin of nuclear agent in polypropylene-based resin.
In addition, as the transparency of improving transparent polypropylene resinoid thin slice and the method for rigidity, in patent documentation 6, disclose in polyacrylic raw material and to have added the method for making nuclear agent and aliphatic or alicyclic ring same clan Petropols etc. and obtaining thin slice.
[patent documentation 1] special fair 6-81698 communique
[patent documentation 2] special fair 6-81796 communique
[patent documentation 3] spy opens flat 9-29818 communique
[patent documentation 4] spy opens the 2003-170485 communique
[patent documentation 5] spy opens the 2000-72938 communique
[patent documentation 6] spy opens clear 58-25341 communique
But, with regard to disclosed method among the patent documentation 1-3 among the above-mentioned technology,, can follow the decline of thin slice rigidity though be expected to improve resistance to impact, also can cause bad influence sometimes simultaneously to the transparency.In addition, when forming thin slice, can adhesion resin-like attachment (so-called " メ ヤ ニ ") on die lip etc., thereby can not produce continuously, the problem that causes manufacture view can produce problems such as appearance poor simultaneously because of gel when recycling thin slice, practical aspect exists not enough.
In addition, with regard to disclosed method in the patent documentation 4,5, can not improve the transparency and cold-resistant impact fully, and with regard to disclosed method in the patent documentation 6, the problem that existing resistance to impact descends also has the new problem that pollutes because of separating out of additive.
As mentioned above, transparent polypropylene thin slice in the past can not meet the demands when supplying in practicality as transparent sheet fully, in addition, even aspect transparent, also be still waiting further improvement.
Summary of the invention
The present invention In view of the foregoing proposes, purpose provides when having the good transparency and is also having manufacture method, the transparent polypropylene resinoid thin slice of the transparent polypropylene resinoid thin slice of excellent properties and the formed products that is made of this transparent polypropylene resinoid thin slice concurrently aspect the various rerum naturas such as cold-resistant impact, rigidity, in addition, also provide when with this transparent polypropylene resinoid thin slice very effective method and the temperature determination methods that prevents the formed products whiting that constitutes by transparent polypropylene resinoid thin slice in the practicality in practicality the time.
The manufacture method of transparent polypropylene resinoid thin slice of the present invention, it is to contain at least: isotactic pentad (ペ Application Star De) branch rate be 85-99%, molten flow velocity degree (MFR) for 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-925kg/m
3, molten flow velocity degree (MFR) melt extrudes for laminar for the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality %, afterwards by (1) at chill roll be wound onto between the endless conveyor of at least two rollers and carry out planar crimping, perhaps (2) make it by cooling water flows through below 40 ℃ slit being arranged and/or by in the cooling water below 40 ℃, thereby cooling melt extrudes method for laminar above-mentioned resin combination rapidly.
By this method, can obtain significantly to have improved transparent the time at the transparent polypropylene resinoid thin slice that also has sufficient performance aspect the various rerum naturas such as resistance to impact (cold-resistant impact), hear resistance, rigidity, in addition, produce メ ヤ ニ when also having suppressed manufacturing, and continuous production might as well.
In addition, the manufacture method of transparent polypropylene resinoid thin slice of the present invention can not contain the method for making the nuclear agent for above-mentioned polypropylene-based resin (a).
If this method is then made the nuclear agent by managing that energetically it is not contained, can keep the formability of the transparent polypropylene resinoid thin slice that obtained well, can avoid realizing that the situation that the transparency, resistance to impact clearly descend takes place simultaneously.
In addition, transparent polypropylene resinoid thin slice of the present invention can constitute as follows: by to contain isotactic pentad branch rate at least be 85-99%, molten flow velocity degree (MFR) for 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree (MFR) be that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, the tensile elasticity rate of extrusion molding direction (MD direction) is more than the 800MPa, total turbidity H satisfied following formula (1) when sheet thickness was t (mm).
H≤130t
2-63t+20……(1)
By this formation, can form and have the good transparency and at the transparent polypropylene resinoid thin slice that also has excellent performance aspect the various rerum naturas such as cold-resistant impact, hear resistance, rigidity concurrently, when especially being defined in tensile elasticity rate in the specific scope with total turbidity, can provide the rigidity and the transparency excellent more transparent polypropylene resinoid thin slice.
In addition, the impact strength (Du Pont impact strength) of transparent polypropylene resinoid thin slice of the present invention under 0 ℃ reached more than the 0.1J.
If this formation then can form the excellent more transparent polypropylene resinoid thin slice of cold-resistant impact, be suitable as the packaging material that use applicable to the various containers of low temperature environments such as low temperature circulation, keeping in order to be configured as most.
In addition, in the transparent polypropylene resinoid thin slice of the present invention, the fusing point that can make above-mentioned class of metallocenes ethene-alpha-olefin copolymer (b) is more than 105 ℃.
If this formation does not produce whiting yet in the time of then can managing to make it be heated to about 100 ℃ temperature.
In addition, in the transparent polypropylene resinoid thin slice of the present invention, can make the fusing point of above-mentioned class of metallocenes ethene-alpha-olefin copolymer (b) be lower than 100 ℃.
If this formation, then can be after being heated to about 100 ℃ temperature, by judging whether to keep the whiting state or returning to transparently, with the naked eye judge the decline situation of temperature after heating and the heating state of content at an easy rate.
In addition, the hot forming product of the present invention that are made of aforesaid transparent polypropylene resinoid thin slice are owing to more can keep the good transparency, rigidity, gloss than the hot forming product that are made of in the past transparent polypropylene resinoid thin slice, so be suitable as for example lid stock, the especially lid stock of micro-wave oven heating usefulness container.
In addition, formed products of the present invention has following feature: be made of transparent polypropylene resinoid thin slice, above-mentioned resin flake is formed by the resin combination that contains polypropylene-based resin and class of metallocenes ethene-alpha-olefin copolymer at least, also has following characteristic, promptly this formed products whitens under the temperature before and after the above-mentioned class of metallocenes ethene-alpha-olefin copolymer fusing point, and the surface temperature that shows formed products is under on the specified temp still being.
Wherein, so-called " temperature before and after the class of metallocenes ethene-alpha-olefin copolymer fusing point " and " surface temperature of formed products is in specific temperature " typically refer to respect to the fusing point of class of metallocenes ethene-alpha-olefin copolymer and are (fusing point-7) ℃～(fusing point+5) ℃, preferred (fusing point-5) ℃～fusing point.
According to this structure, the surface temperature of formed products is suitably adjusted when being heated by consideration, so that the fusing point of class of metallocenes ethene-alpha-olefin copolymer reaches the temperature of the temperature front and back that produce whiting in the formed products, be to be in transparent state or whiting according to formed products thus, the surface temperature that embodies formed products on specified temp still beneath, thereby can with the naked eye judge the cooling situation of formed products at an easy rate, the function that can give the lid temperature sensor.
This formed products of the present invention can be shaped by foregoing transparent polypropylene resinoid thin slice, in addition, because above-mentioned characteristic has invertibity, is used well so can be used as the temperature sensor when heating with micro-wave oven.
In addition, the method of the formed products whiting that prevents to be made of transparent polypropylene resinoid thin slice of the present invention is following method: be to reach temperature M[℃ arbitrarily by the surface temperature that the formed products that transparent polypropylene resinoid thin slice constitutes is heated to above-mentioned formed products] degree the time, can prevent the method for above-mentioned formed products whiting, wherein utilize used fusing point for (M+3) [℃] the foregoing transparent polypropylene resinoid thin slice of above class of metallocenes ethene-alpha-olefin copolymer (b), be configured as above-mentioned formed products.
By this method, even the surface temperature of formed products is heated to be the temperature of any setting, also can prevent the formed products whiting, in addition, realize this formed products of the present invention that prevents formed products whiting method, by preventing that surface temperature is heated to temperature M[℃ arbitrarily] the transparent polypropylene resinoid thin slice of time whiting constitutes, will use fusing point for (M+3) [℃] more than the foregoing transparent polypropylene resinoid thin slice of class of metallocenes ethene-alpha-olefin copolymer (b) form.
In addition, the temperature determination methods of the formed products that is made of transparent polypropylene resinoid thin slice of the present invention is as follows: in order with the naked eye to judge the surface temperature (N ℃ arbitrarily) of the heated formed products that is made of transparent polypropylene resinoid thin slice, utilization used fusing point as N to (N+3) [℃] the above-mentioned transparent polypropylene resinoid thin slice of class of metallocenes ethene-alpha-olefin copolymer (b), be configured as above-mentioned formed products.
By this method, whether the surface temperature that can with the naked eye judge formed products at an easy rate is below the temperature of setting arbitrarily, in addition, realize the formed products of the present invention of the temperature determination methods of this formed products, constitute by the transparent polypropylene resinoid thin slice of the surface temperature that can with the naked eye judge formed products (N ℃ arbitrarily), will use fusing point as N to (N+3) [℃] the above-mentioned transparent polypropylene resinoid thin slice of class of metallocenes ethene-alpha-olefin copolymer (b) form.
The invention effect
As mentioned above, according to the present invention, can provide to compare and significantly improve transparent transparent polypropylene resinoid thin slice with polypropylene-based resin thin slice in the past, in addition, can form and not only have the transparency but also at the transparent sheet that also has excellent properties aspect the various rerum naturas such as cold-resistant impact, hear resistance, rigidity concurrently.
Description of drawings
Fig. 1 is the schematic diagram of an example of manufacturing installation in first embodiment of expression transparent polypropylene resinoid thin slice of the present invention.
Fig. 2 is the schematic diagram of an example of manufacturing installation in second embodiment of expression transparent polypropylene resinoid thin slice of the present invention.
Fig. 3 is the enlarged drawing of the manufacturing installation major part shown in Fig. 2.
Among the figure,
2 thin slices
The laminar resin combination of 2a
10 T moulds
The 21-24 chill roll
25 endless conveyors
26 cooling water injection nozzles
27 tanks
30 small-sized tanks
The 30a slit
35 large-scale tanks
The specific embodiment
Below, the preferred embodiment of the present invention is described.
[first embodiment]
At first, first embodiment to the manufacture method of transparent polypropylene resinoid thin slice of the present invention describes, simultaneously to transparent polypropylene resinoid thin slice of the present invention and formed products and prevent that the method for the formed products whiting that is made of transparent polypropylene resinoid thin slice and the preferred implementation of temperature determination methods from describing.
In addition, Fig. 1 is the schematic diagram of an example of the manufacturing installation of the expression manufacturing that is applicable to transparent polypropylene resinoid thin slice in the present embodiment.
In the present embodiment, use the resin combination of forming by following polypropylene-based resin (a) and class of metallocenes ethene-alpha-olefin copolymer (b) to make transparent polypropylene resinoid thin slice.
[polypropylene-based resin (a)]
As polypropylene-based resin (a), use isotactic pentad to divide the high crystalline polypropylene-based resin of rate as 0.85-0.99, preferred 0.88-0.99.
If isotactic pentad divides rate in above-mentioned scope, then can form the thin slice of crystallinity excellence, tensile properties and resistance to impact excellence, simultaneously might as well with the balance of the transparency.On the other hand, if isotactic pentad divides rate not enough above-mentioned scope, then tensile elasticity rate etc. can descend sometimes, in addition, if isotactic pentad branch rate surpasses above-mentioned scope, then because inner turbidity variation in the chilling operation sometimes, be difficult to as transparent polypropylene resinoid thin slice, so not preferred.
Wherein, so-called isotactic pentad branch rate is meant with A.Zambelli etc. and is published in big molecule (Macromolecules), the method in 6,925 (1973), promptly uses isotactic branch rate in the pentad unit in the polypropylene molecular chain that the method for 13C-NMR measures.In other words, isotactic pentad branch rate is meant that 5 propylene monomer units are by the branch rate of meso in conjunction with the propylene monomer units at the chain center that is formed by connecting continuously.
Wherein, about the ownership at peak, according to big molecule (Macromolecules), the methods of 8,687 (1975) records are record in addition.
Specifically, measure isotactic pentad unit and divide rate as the intensity at the mmmm peak in the hypersorption peak, methyl carbon zone of 13C-NMR spectrum.
The molten flow velocity degree (MFR) of the polypropylene-based resin that uses in the present embodiment (a) is 0.1-30g/10 minute, but preferred 2-10g/10 minute, more preferably 2-5g/10 minute.If the not enough above-mentioned scope of MFR flows bad when then thin slice is shaped sometimes and causes varied in thickness, in addition,, then melt the tension force deficiency if MFR surpasses above-mentioned scope, viscosity and easily producing when being shaped hangs (draw down), and perhaps extrusion molding is bad.
In addition, the molten flow velocity degree (MFR) of polypropylene-based resin (a) can be used according to the method for JIS K7210 and measure.
In addition, the content of polypropylene-based resin (a) is the 70-97 quality % of resin combination integral body in the present embodiment.
If contain the above-mentioned scope of quantity not sufficient, then hear resistance, rigidity are not enough sometimes, in addition, if content surpasses above-mentioned scope, then sometimes the transparency, resistance to impact improve deficient change, so not preferred.
In addition,, in fact preferably use the homopolymers of propylene, but also can be the copolymer with other olefinic monomer below the 4 quality % as polypropylene-based resin (a).
[class of metallocenes ethene-alpha-olefin copolymer (b)]
The ethene-alpha-olefin copolymer that class of metallocenes ethene-alpha-olefin copolymer (b) is to use metalloscene catalyst to make.This class of metallocenes ethene-alpha-olefin copolymer (b) is principal component with ethene, simultaneously preferred carbon number 3-18, the more preferably alpha-olefin of carbon number 4-12, preferred especially carbon number 6-10 of using, more specifically, can be propylene, butene-1, amylene-1, hexene-1, octene-1, heptene-2,4-methyl-amylene-1,4-methyl-hexene-1,4,4-dimethyl pentene-1 grade uses known class of metallocenes catalyst to make as comonomer.
The class of metallocenes catalyst contains following (A)-(E) usually, metalloscene catalyst composition (A), Organoaluminoxy compound catalyst composition and/or ionic compound catalyst component (B), the finely particulate monomer (C) that adds as required, organo-aluminum compound catalyst component (D), the ionization ionic compound catalyst component (E) be made up of the periodic table IVB family excessive metallic compound with at least one dentate with cyclopentadienyi skeleton.
In addition, as (being total to) polymerization that uses the class of metallocenes catalyst, can enumerate vapor phase method, slurry process, high-pressure ion polymerization, solwution method etc.
In addition, the class of metallocenes ethene-alpha-olefin copolymer has the molecular weight distribution of obtaining with GPC method (GelPermeation Chromatography) (Mw/Mn) and is the narrow distribution characteristics of 1.5-4.0.
The density of the class of metallocenes ethene-alpha-olefin copolymer (b) that uses in the present embodiment is 880-925kg/m
3, preferred 900-920kg/m
3
If density in above-mentioned scope, then flexibility and good crystallinity, on the other hand, if the not enough above-mentioned scope of density, then low sometimes crystallised component is easily separated out, in addition, if density surpasses above-mentioned scope, the resistance to impact deficiency of thin slice sometimes then.
In addition, the density of class of metallocenes ethene-alpha-olefin copolymer (b) can be measured according to JIS K7112 (23 ℃).
The molten flow velocity degree (MFR) of the class of metallocenes ethene-alpha-olefin copolymer (b) that uses in the present embodiment in addition, is 1-30g/10 minute.
If the not enough above-mentioned scope of MFR flows bad when then thin slice is shaped sometimes and causes varied in thickness, in addition,, easily hang when then viscosity and thin slice are shaped if MFR surpasses above-mentioned scope, perhaps shape stability is not enough.
In addition, the MFR of class of metallocenes ethene-alpha-olefin copolymer (b) can use according to the method for JISK7210 and measure.
In addition, the content of class of metallocenes ethene-alpha-olefin copolymer (b) is the 30-3 quality % of resin combination integral body in the present embodiment, preferred 20-3 quality %.
If contain the above-mentioned scope of quantity not sufficient, so the then transparency, the improving a little less than the effect of resistance to impact sometimes be not preferred.In addition, if content surpasses above-mentioned scope, then hear resistance, rigidity can descend sometimes, so not preferred.
In the present embodiment, use resin combination manufacturing transparent polypropylene resinoid thin slice as mentioned above, the polypropylene-based resin (a) that constitutes above-mentioned transparent polypropylene resinoid thin slice does not preferably contain makes the nuclear agent.
Make the nuclear agent and have the effect of quickening crystallization speed, on the other hand, when being shaped through the fusing heating, crystallization always is to the shape that forms regulation sometimes, thereby makes fixed in shapeization, might bring bad influence to the formability in the thin slice shaping.Therefore, do not make the nuclear agent, can keep the formability of the transparent polypropylene resinoid thin slice that obtains well by not containing in the polypropylene-based resin (a) as material resin.
In addition, polypropylene is contained make when examining agent, can generate a plurality of small spherolites, improve the transparency of thin slice, but owing to there is the trend of its clarity difference, there is a plurality of spherolites that easily crack when being subjected to impacting and the interface of spherolite simultaneously, thereby has the resistance to impact downward trend.
Manufacture method according to the transparent polypropylene class thin slice of present embodiment, even do not make the transparency that the nuclear agent also can be guaranteed thin slice high-levelly owing to do not use, so make the nuclear agent by managing that energetically it is not contained, the phenomenon that can avoid not reaching the transparency, resistance to impact decline clearly takes place.
In addition, in the present embodiment in the resin combination that constitutes transparent polypropylene resinoid thin slice, except as the above-mentioned raw materials resin that must composition, what also can add known thin slice shaping usefulness such as the ethene that contains below the 10 quality % or the random polypropylene of the alpha-olefin of carbon number 4 or more in the scope that does not hinder the present embodiment effect contains other olefin copolymer, the antistatic additive as known thin slice shaping usefulness additive, lubricant, ultra-violet absorber, light stabilizer, colouring agent etc.
The transparent polypropylene class thin slice of present embodiment for example can be made with manufacturing installation 1 as shown in fig. 1, during manufacturing, at least the resin combination that contains above-mentioned specific polypropylene-based resin (a) 70-97 quality % and specific class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % is melt extruded for laminar, its chilling.
In addition, above-mentioned resin combination with raw material can according to sheet, Powdered, graininess etc. arbitrarily form supply with.
In addition, the manufacturing installation shown in Fig. 11 has first chill roll 21, second chill roll 22, the 3rd chill roll 23, the 4th chill roll 24, endless conveyor 25, cooling water injection nozzle 26, tank 27, suction roll 28 and stripper roll 29.
On the surface of first chill roll 21, be coated with nitrile-butadiene rubber (NBR) elastomeric material 21a.The hardness of this elastomeric material 21a (use according to the method for JIS K 6301A and measure) is preferably below 80 degree, thickness is preferably about 10mm.
In addition, the rotating shaft of at least one roller is connected with not shown rotary drive mechanism in the first, the 3rd, the 4th chill roll 21,23,24.
This second chill roll 22 is configured to together press from both sides the laminar resin combination 2a that melt extrudes toward by T mould 10 across the metal system endless conveyor 25 that is made of stainless steel etc. and first chill roll 21.
The surface that contacts with the laminar resin combination 2a that melt extrudes by T mould 10 in one endless conveyor 25 be preferably formed for surface roughness (Rmax) be the following minute surfaces of 1.0 μ m, and rotation freely is wrapped in the first, the 3rd, the 4th chill roll 21, on 23,24.
At this moment, the 3rd, the 4th chill roll 23,24 can be metal system roller, by adorning not shown cooling bodies such as water-cooled in the portion within it, can manage to regulate the temperature of endless conveyor 25.
In addition, cooling water injection nozzle 26 is arranged on the following side of second chill roll 22, thus, cooling water can be injected in the back side of endless conveyor 25.So,, endless conveyor 25 can be cooled off rapidly, also can will be become planar laminar resin combination 2a to cool off rapidly simultaneously by first, second chill roll 21,22 crimping by spraying cooling water by cooling water injection nozzle 26.
In addition, stripper roll 29 also can be provided with according to the mode that laminar resin combination 2a (thin slice 2) is crimped on the 3rd chill roll 23 sides, the spacing setting but preferably such as shown and the 3rd chill roll 23 is separated by manages to make the laminar resin combination 2a of its not crimping (thin slice 2).
By the manufacturing installation of formation like this, can make transparent polypropylene resinoid thin slice as described below.
At first, in order to ensure directly contact with laminar resin combination 2a and with the surface temperature of second chill roll 22 of its cooling and endless conveyor 25 be more than the dew point, below 50 ℃, preferred below 30 ℃, in advance each chill roll 22,23,24 is carried out temperature control.
Wherein, the surface temperature of second chill roll 22 and endless conveyor 25 is dew point when following, exists in the possibility that the surface produces dewfall and is difficult to evenly make film.On the other hand, if surface temperature is higher than 50 ℃, the transparency of the thin slice 2 that then might obtain descends, and α is brilliant simultaneously becomes many, is difficult to carry out hot forming.
Then, laminar resin combination 2a is melt extruded, sandwiched between the endless conveyor 25 and second chill roll 22 on first chill roll 21 by the T mould 22 of extruder.Under this state, carry out chilling when being planar with first, second chill roll 21,22 crimping with laminar resin combination 2a.
At this moment, the lip-deep elastomeric material 21a that covers first chill roll 21 is compressed and carries out strain, the part of strains takes place at elastomeric material 32 in laminar resin combination 2a, promptly corresponding with the center angle θ 1 of first chill roll 21 circular arc portion is planar by first, second chill roll 21,22 crimping.
In addition, Ci Shi surface pressing is preferably 0.1-20MPa.
Then, be sandwiched in the laminar resin combination 2a between second chill roll 22 and the endless conveyor 25, corresponding to second chill roll 22 circular arc portion of lower half roughly, implemented planar crimping by second chill roll 22 and endless conveyor 25, spray cooling water by cooling water injection nozzle 26 to endless conveyor 25 back sides one side simultaneously, carry out chilling further.
In addition, the surface pressing of this moment is preferably 0.01-0.5MPa, and the temperature of cooling water is preferably 0-30 ℃.In addition, injected cooling water is reclaimed by tank 27, and the water of Hui Shouing is discharged by outlet 29A simultaneously.
As mentioned above, carry out planar crimping and cooling between second chill roll 22 and the endless conveyor 25 for laminar resin combination 2a after, driving fit in the laminar resin combination 2a of endless conveyor 25 along with endless conveyor 25 rotations are moved on the 3rd chill roll 23.Then, the laminar resin combination 2a of being stripped from roller 29 guiding corresponding to the 3rd chill roll 23 haply the circular arc portion of half cycle by chilling.
In addition, remove to suction roll 28 absorptions that the 3rd chill roll 23 moves the way by being arranged on attached to the water at endless conveyor 25 back sides from second chill roll 22.
The laminar resin combination 2a that cools off on the 3rd chill roll 23, the thin slice 2 that promptly laminar resin combination 2a chilling is formed are peeled off from endless conveyor 17 under the effect of stripper roll 29, are batched by not shown takers-in speed according to the rules.
Can be by the transparent polypropylene resinoid thin slice in the above operation manufacturing present embodiment, at this moment, as constituent material, can obtain not only have the good transparency but also by resin combination that will be above-mentioned specific polypropylene-based resin (a) and specific class of metallocenes ethene-alpha-olefin copolymer (b) ratio are according to the rules mixed at the transparent polypropylene resinoid thin slice that has excellent properties aspect the various rerum naturas such as impact, hear resistance, rigidity that resist cold concurrently.In addition, produce メ ヤ ニ in the time of also can suppressing to make, continuous production might as well.
In the present embodiment, the tensile elasticity rate of the thin slice extrusion molding direction (MD direction) of the transparent polypropylene resinoid thin slice of Zhi Zaoing is more than the 800MPa, to be preferably more than the 1000MPa like this.
If the not enough 800MPa of the tensile elasticity rate of the extrusion molding direction of thin slice (MD direction) then can not obtain enough rigidity, thereby owing to the not enough purposes that has limited formed products of rigidity.Promptly, if the combined amount of class of metallocenes ethene-alpha-olefin copolymer (b) is many, the trend that then has the rigidity deficiency that causes thus, the hear resistance of thin slice worsens, thereby for example might being difficult to use in, micro-wave oven heats with purposes such as food containers, but the tensile elasticity rate of the extrusion molding direction of thin slice (MD direction) is defined as 800MPa when above, can avoids this unfavorable condition effectively.
In addition, when making the transparent polypropylene resinoid thin slice in the present embodiment, can be by suitable adjustment its create conditions and the total turbidity H when making sheet thickness be t (mm) such as material composition satisfies following formula (1).
H≤130t
2-63t+20……(1)
Wherein, the turbidity value of thin slice is subjected to the thickness effect of thin slice bigger, and the thin slice that the thickness of being made up of the good raw material of the transparency is thicker is also poorer than the thin slice of the thinner thickness of being made up of the raw material of transparency difference owing to its thickness can be evaluated as the transparency sometimes.Therefore, want to estimate the true transparency of thin slice, need not be subjected to the index about sheet thickness, but whether the transparency of thin slice is good when being scaled same thickness in order to estimate, make transverse axis for various polypropylene-based resin thin slices and represent that thickness t, the longitudinal axis represent to have obtained above-mentioned formula (1) by the recurrence mode after the curve of total turbidity H.
Therefore, for example, even the transparency is evaluated as good thin thin slice, if do not satisfy above-mentioned formula (1), then mean for its thin thickness, be the thin slice of transparency difference, in addition, even the transparency is evaluated as poor thicker thin slice,, then in fact mean it is the good thin slice of the transparency if satisfy above-mentioned formula (1).
In the present embodiment, if will make the transparent polypropylene resinoid thin slice that satisfies above-mentioned formula (1), be criterion for example, suitably adjust creating conditions in the above-mentioned manufacture method, material composition etc. and get final product according to (A)～(B) as follows.
(A) by slowing down the speed that laminar resin combination 2a is extruded by T mould 10, perhaps reduce the temperature of chill roll 22, endless conveyor 25, manage to make thin slice 2 fully to cool off, can improve the transparency of the thin slice 2 of final acquisition.
(B) by in the scope that allows at the thickness of the thin slice 2 that will obtain, increase is with the pressure of the planar crimping of laminar resin combination 2a, perhaps improve the minute surface degree of chill roll 22, endless conveyor 25, improve the minute surface degree of the final thin slice 2 that obtains, can improve the transparency of the thin slice 2 of final acquisition thus.
(C) by adjust cooperating, the density contrast of polypropylene-based resin when reducing to form thin slice (a) and class of metallocenes ethene-alpha-olefin copolymer (b) can improve the transparency of the thin slice 2 of final acquisition.
In addition, the impact strength of transparent polypropylene resinoid thin slice under 0 ℃ in the present embodiment is preferably more than the 0.1J.
Thus, can form outstanding transparent polypropylene resinoid thin slice according to cold-resistant impact.Therefore, for example, if the transparent polypropylene resinoid thin slice that uses present embodiment then is suitable as most the container (packaging material) of low temperature environments such as being suitable for low temperature circulation, keeping as the material that is used for the formed food container.
The transparent polypropylene resinoid thin slice of aforesaid present embodiment can mainly be used as hot forming product thin slice, but wherein, also is applicable to especially as the purposes of hot forming product with the thin slice requirement transparency, for example, and the lid of food containers etc.
Can consider suitably settings such as formability as this hot forming product with the thickness of the transparent polypropylene resinoid thin slice of the present embodiment of thin slice, be preferably 0.15-1mm, more preferably 0.2-0.6mm.
Below, by enumerating present embodiment transparent polypropylene resinoid thin slice is used for the example of micro-wave oven heating with the food containers lid, its practical purposes is described.
In recent years, the sale form that the food nursed one's health is sold with micro-wave oven heating back is widely used in the snacks shop etc., and the surface temperature of lid is generally about 100 ℃ of the boiling point of water when wherein heating with micro-wave oven.Polypropylene-based resin thin slice with regard in the past will produce whiting if be exposed under this high temperature, thereby causes lid to fog, thereby can not with the naked eye determine the content state.
If thisly be not resolved, then no matter how outstanding the transparency under the normal temperature environment is, all is equivalent to the user is forced in the inconvenience on using.
In the transparent polypropylene resinoid thin slice of present embodiment, can eliminate above-mentioned whiting by suitably adjusting fusing point as the class of metallocenes ethene-alpha-olefin copolymer (b) of necessary composition.
That is,, can eliminate the above-mentioned bad phenomenon that is used for the micro-wave oven heating usefulness lid, particularly for foodstuff containers period of the day from 11 p.m. to 1 a.m effectively by the fusing point of class of metallocenes ethene-alpha-olefin copolymer (b) is defined as more than 105 ℃.
In addition, when heating with micro-wave oven, often with the empty-handed container that from micro-wave oven, takes out heating, but this moment, if container still keeps high temperature, the user will undertake the danger of burn.For fear of this danger, if by the cooling situation of container as can be known just of quick glance only, then will be very convenient aspect practical.
For example, if lid whiting when being designed to the surface temperature of lid and being more than 90-100 ℃, revert to transparent when being cooled to its following temperature, thereby make the user can with the naked eye confirm the state of content, then the user can judge the cooling situation of container and the heating state of content thus, and then has avoided burn dangerous.
In the transparent polypropylene resinoid thin slice of present embodiment, this performance can be by being defined as 100 ℃ to the fusing point of class of metallocenes ethene-alpha-olefin copolymer (b) with the realization of getting off.
The very effective performance in this practical aspect is to wait the following opinion that obtains by wholwe-hearted research to realize according to the present inventor.
That is, if the temperature of lid rises near the temperature of fusing point of the class of metallocenes ethene-alpha-olefin copolymer (b) that is scattered in the resin combination, then class of metallocenes ethene-alpha-olefin copolymer (b) will melt.At this moment, the luxuriant class ethene-alpha-olefin copolymer of molten metal (b) and another must composition be the refringence of polypropylene-based resin (a), greater than with fusing before the refringence of class of metallocenes ethene-alpha-olefin copolymer (b), its as a result lid can whiten.On the other hand, if the temperature step-down of lid then because the luxuriant class ethene-alpha-olefin copolymer of molten metal (b) solidifies, so diminish with the refringence of polypropylene-based resin (a), transfers to transparent.
As mentioned above, form the lid of micro-wave oven heating by the transparent polypropylene resinoid thin slice that uses present embodiment with food containers, and the suitable fusing point of adjusting as the class of metallocenes ethene-alpha-olefin copolymer (b) of material resin, can be in transparent state or whiting according to lid, the surface temperature of confirming lid is under still being on the specified temp, can with the naked eye judge the cooling situation of container at an easy rate, thus the performance of giving the lid temperature sensor.Be specially, the surface temperature of lid (formed products) during the consideration heating, managing to make the fusing point of class of metallocenes ethene-alpha-olefin copolymer (b) is the temperature that produces temperature (being about 90-100 ℃ in the above-mentioned example) front and back of whitening in the formed products.
In addition, for example the content in being collected in container is under the situation of oil-based liquid thing, the temperature of the lid after just having heated with micro-wave oven may rise to for example 110-120 ℃ sometimes, perhaps may only rise to 80-90 ℃ sometimes, even but be in this situation, also can give aforesaid function.
Promptly, fusing point beguine by making the class of metallocenes ethene-alpha-olefin copolymer (b) that mixes as material resin according to content set just heat after the surface temperature of lid also high, for example high more than 33 ℃, preferred high more than 5 ℃, can prevent the whiting that produces because of heating.That is,, preferably the fusing point of class of metallocenes ethene-alpha-olefin copolymer (b) is defined as more than (M+3) ℃, more than preferred (M+5) ℃ if will when the surface temperature that container is heated to lid is M ℃, prevent lid whiting.
In addition, also identical when judging the cooling situation of container, if will with the naked eye judge the surface temperature of lid, be specially, if will judge whether the surface temperature of lid is temperature N ℃ arbitrarily, preferably the fusing point of class of metallocenes ethene-alpha-olefin copolymer (b) is adjusted into N～(N+3) ℃, thus, if lid whiting, then the user can judge at an easy rate that the surface temperature of lid is more than N ℃, in addition, transparent if lid reverts to, then the user can judge at an easy rate that the surface temperature of lid is lower than N ℃.
In addition, above-mentioned M, the value of N can be set arbitrarily, and the fusing point of aforesaid class of metallocenes ethene-alpha-olefin copolymer (b) is generally about 85-120 ℃, above-mentioned M, the value of N can be set in about 80-115 ℃ scope.
[second embodiment]
Below, second embodiment of transparent polypropylene class method of producing sheet of the present invention is described.
In addition, Fig. 2 is the schematic diagram that is applicable to an example of the manufacturing installation of making transparent polypropylene class thin slice in the expression present embodiment.
In the first above-mentioned embodiment, freely be wrapped in the first, the 3rd, the 4th chill roll 21 by second chill roll 22 and rotation, 23, endless conveyor 25 on 24 etc., cooled off the laminar resin combination 2a that melt extrudes by T mould 10 rapidly, but in the present embodiment, the mechanism that laminar resin combination 2a is carried out chilling is different with first embodiment.
Promptly, in the present embodiment, laminar resin combination 2a is carried out the mechanism of chilling, in the building mortion 1 that is shown in Fig. 2, be oppositely arranged and clamp first roller 31 of laminar resin combination 2a and second roller 32 by the large-scale tank 35 of filling cooling water, in large-scale tank 35, near the 4th roller 34 that is provided with also by the 3rd roller 33 of large-scale tank 35 bottom surfaces, large-scale tank 35 peripheries than these rollers 31,32 and small-sized tank 30 formations that are provided with at large-scale tank 35 upsides in the conveyance direction downstream side of laminar resin combination 2a.
In addition, in small-sized tank 30 bottom surface substantial middle parts, as shown in Figure 3, be formed with slit 30a according to its size in position corresponding to T mould 10 openings.
The interval of slit 30a is 1-20mm at the entrance side of slit 30a, preferred 3-10mm.On the other hand, thicker than laminar resin combination 20 at least at the outlet side of slit 30a, more than 0.5mm, more than the preferred 1.0mm.The normally thick about 1-10mm of this slit 30a, be about the wall shape of 30-70mm.In addition, the distance of 10 of slit 30a and T moulds is generally about 30-250mm.
In addition, though not shown, the cooling water that is used to cool off the laminar resin combination 20a that melt extrudes is supplied in the small-sized tank 30 by small-sized tank 30 outsides continuously by pump etc., to keep water level.
By this chilling mechanism, the laminar resin combination 20a that is melt extruded by the T mould 10 that is arranged on extruder 11 tops can be passed through slit 30a to dirty with the cooling water of constantly supplying with to small-sized tank 30, then, along with roller 31,32,33 rotation is introduced in the large-scale tank 35.Then, sandwiched first roller 31 and second roller 32 between on one side, send into the 3rd roller 33 on one side, lead outside the large-scale tank 35 by the 4th roller 34, batch by not shown takers-in speed according to the rules.
The laminar resin combination 2a that is melt extruded by T mould 10 by chilling, forms thin slice 2 during by small-sized tank 30 and large-scale tank 35.At this moment, the cooling water that is supplied to small-sized tank 30 is below 40 ℃ with the cooling water that fills up large-scale tank 35, and is preferred below 30 ℃, more preferably below 25 ℃.If cooling water surpasses 40 ℃, then the transparency of the thin slice 2 of Huo Deing might be not enough.
By this chilling mechanism, in the time of will carrying out chilling by the laminar resin combination 2a that T mould 10 melt extrudes, owing to directly carry out water-cooled with cooling water, do not carry out cooling curing so can in laminar resin combination 2a, not produce under the situation of distortion etc., form thin slice 2.
In addition, in the present embodiment, can suitably omit small-sized tank 30, will directly import in the large-scale tank 35, make it by in the cooling water that fills up large-scale tank 35 by the laminar resin combination 2a that T mould 10 melt extrudes, make laminar resin combination 2a carry out chilling, perhaps omit large-scale tank 35,, make the slit 30a of laminar resin combination 2a by small-sized tank 30 along with cooling water, make laminar resin combination 2a carry out chilling, also can change enforcement.
In the present embodiment, different with above-mentioned first embodiment is above characteristics, and other the structure and first embodiment are roughly the same, so omit detailed explanation.
Embodiment
Below, enumerate specific embodiment, the present invention is described in further detail.
[embodiment 1,2, comparative example 1,2]
Make before the transparent polypropylene resinoid thin slice resin combination that preparation forms the mixing as shown in table 1 of following material resin.
In addition, the value shown in the table 1 is quality %.
[table 1]
| | Embodiment 2 | Comparative example 1 | Comparative example 2 | ||
| Material resin | HPP-1 | 95 | 95 | 100 | 95 |
| HSBR | 5 | ||||
| メロンセン LL-1 | 5 | ||||
| メロンセン LL-2 | 5 | ||||
Sym-propene polymer resin-1 (HPP-1)
Grade: E-304GP (bright dipping petrochemistry (strain) system)
Isotactic pentad divide rate: 0.90
MFR:3.0g/10 minute
Hydrogenation styrene butadiene ribber (HSBR)
Grade: ダ イ Na ロ Application 1320P (JSR (strain) system)
Density: 890kg/m
3
MFR:3.5g/10 minute
Class of metallocenes ethene-alpha-olefin copolymer-1 (メ ロ Application セ Application LL-1)
Grade: カ-ネ Le KF370 (Japanese polyethylene (strain) system)
Density: 905kg/m
3
MFR:3.5g/10 minute
Fusing point: 97 ℃
Class of metallocenes ethene-alpha-olefin copolymer-2 (メ ロ Application セ Application LL-2)
Grade: カ-ネ Le KF480 (Japanese polyethylene (strain) system)
Density: 918kg/m
3
MFR:4.0g/10 minute
Fusing point: 109 ℃
Wherein, the density of material resin is to measure according to the method for JIS-K7112 (23 ℃), and in addition, molten flow velocity degree (MFR) is to measure according to the method for JIS K7210.
In addition, isotactic pentad branch rate specifically is to use JNM-FX-200 (NEC's (strain) system, 13C-nuclear resounce frequency 50.1MHz), under following measuring condition, carry out after the 13C-NMR measurement, the difference of the chemical shift that produces according to the stereoregularity of methyl, promptly appear at the areal intensity ratio at each peak of the mmmm～mrrm in 22.5-19.5ppm zone, measure pentad branch rate and the value obtained, measuring condition is as follows:
Measurement pattern: the complete decoupling method of proton, pulse is wide: 6.9 μ s (45 °), pulse-recurrence time: 3s, cumulative frequency: 10000 times, solvent: 1,2,4-trichloro-benzenes/heavy benzol (90/10 capacity %), sample solution concentration 250mg/2.5ml solvent is measured temperature: 130 ℃.
mmmm：21.86ppm
mmmr：21.62ppm
mmrr：21.08ppm
mmrm+rrmr：20.89ppm
rrrr：20.36ppm
mrrm：19.97ppm
Above-mentioned resin combination in embodiment 1,2 and the comparative example 1,2 is used the manufacturing installation 1 that is shown in Fig. 1, be resin temperature settings that 240 ℃, die lip temperature are set to melt extrude under 280 ℃ the condition and are laminar resin combination 2a, this laminar resin combination 2a is carried out planar crimping between endless conveyor 25 on first chill roll 21 and second chill roll 22 (15 ℃ of design temperatures) and carries out chilling while being clipped in, with 17m/ minute speed, obtain the transparent polypropylene resinoid thin slice 2 of sheet thickness 0.4mm.To the transparent polypropylene resinoid thin slice 2 that obtains, measure (1) tensile properties, (2) turbidity, (3) glossiness, (4) Du Pont impact strength under the following conditions.This results are shown in the table 2.
(1) tensile properties
As tensile properties, tensile elasticity rate, yield strength, fracture strength and extensibility have been measured according to JIS K7113.
In addition, measurement is to carry out with respect to the vertical direction (TD direction) of extruding direction (MD direction) and MD direction that is shaped.
(2) turbidity
According to JIS K7105, use turbidimetric apparatus (Japanese electric look industry (strain) system) to measure.In addition, as turbidity,, also measured inner turbidity except total turbidity.
In addition, the total turbidity H that calculates with above-mentioned formula (1) during for 0.4mm at thickness is 15.6.
(3) glossiness
According to JIS K7105, use self-action colour examining colour-difference-metre (ス ガ test instrument (strain) system) to measure (face side: roller side, rear side: the band side).
(4) Du Pont's impact strength
Under condition, measure according to JIS K7211.
[table 2]
| The thin slice | Embodiment | 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | ||
| Tensile properties | Tensile elasticity rate (MPa) | MD | 1160 | 1490 | 1200 | 900 | |
| TD | 1110 | 1420 | 1210 | 966 | |||
| Yield strength (MPa) | MD | 22.5 | 25.9 | 22.2 | 20.2 | ||
| TD | 21.8 | 24.9 | 22.2 | 20.5 | |||
| Fracture strength (MPa) | MD | 51.7 | 52.7 | 49.5 | 48.4 | ||
| TD | 46.1 | 49.1 | 44.8 | 45.7 | |||
| Extensibility (%) | MD | 489 | 469 | 457 | 483 | ||
| TD | 535 | 547 | 511 | 537 | |||
| Turbidity (%) | Total turbidity H | 13.6 | 7.0 | 26.4 | 18 | ||
| Inner turbidity | 12.5 | 5.4 | 24.4 | 16.9 | |||
| Glossiness (%) | Face side | 113 | 121 | 105 | 109 | ||
| Rear side | 112 | 116 | 105 | 111 | |||
| Du Pont impacts (J) | 0℃ | 0.5 | 0.5 | 0.25 | 0.5 | ||
Then, use the transparent polypropylene resinoid thin slice 2 that obtains, form, obtain formed products (lid of food containers) with the vacuum pressure forming machine.
To the formed products that obtains, measure (2) turbidity, (3) glossiness same as described abovely, measure (5) buckling strength simultaneously under the following conditions.This results are shown in the table 3.
(5) buckling strength
The maximum stress (buckling strength) that produces when using plate jig to push with certain speed from a side relative with container body, is measured up as described below in the inside that makes lid (formed products).
Status adjustment: in 23 ℃, the atmosphere of 50%RH, place test specimen more than 48 hours.
Measure number of times: 5 times
Crosshead (cross head) speed: 10mm/ minute
Writing speed: 20mm/ minute
Device: Instron (イ Application ス ト ロ Application) tension test instrument 5564 types (Instron system)
Circular plate jig (Instron system)
Automatic analyzer メ Le リ Application series IX (Instron system)
[table 3]
| The formed products rerum natura | | Embodiment 2 | Comparative example 1 | Comparative example 2 | |
| Turbidity (%) | Total turbidity H | 8.1 | 6.5 | 8.8 | 5.8 |
| Inner turbidity | 5.1 | 3.3 | 5.5 | 4.0 | |
| Glossiness (%) | Face side | 116 | 121 | 125 | 129 |
| Rear side | 117 | 120 | 123 | 127 | |
| Buckling strength (J) | 0℃ | 181 | 190 | 180 | 166 |
In addition, the formed products that obtains is placed on 4 minutes 30 seconds in the thermostat layer that is set at 80-130 ℃, confirms that formed products has or not whiting, when confirming to whiten, measure after taking out by thermostat layer under 23 ℃ the temperature environment and return to the transparent required time.This results are shown in the table 4.
In addition, for what confirm not whiten, represent with " zero " in the table.In addition, the numerical value in the table returns to the transparent required time.
[table 4]
| Heat treatment temperature (℃) | ||||||||
| 80 | 90 | 95 | 100 | 105 | 110 | 120 | 130 | |
| | ○ | ○ | 5 | 10 seconds | 20 | 25 | 25 | 30 seconds |
| Embodiment 2 | ○ | ○ | ○ | ○ | ○ | 5 | 10 seconds | 20 seconds |
| Comparative example 1 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
| Comparative example 2 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | ○ |
Above-mentioned the present invention is as illustrated in below and comparison known technology, and can bring into play can't be by the effect of known technology prediction.
For example, in above-mentioned patent documentation 3, disclose utilization and first embodiment of the invention and similarly used the device of chill roll and endless conveyor, the thin slice that composition by polypropylene and metallocene class straight chain shape low density polyethylene (LDPE) is constituted carries out the method for transparence, but in the method, if metallocene class straight chain shape low density polyethylene (LDPE) is mixed with polypropylene, then promptly use chill roll and endless conveyor to carry out chilling, the transparency also can demonstrate identical or descend a little (referring to Patent Document 3 comparative example 1 and embodiment).
In addition, in above-mentioned patent documentation 5, the method that to carry out chilling with chill roll with the composition that the present invention similarly is made up of polypropylene and class of metallocenes straight chain shape low density polyethylene (LDPE) and form thin slice is disclosed, and shown the transparency, the good aim of resistance to impact, but owing to mixed polyethylene, the degree that the transparency of thin slice improves not is so high (perhaps identical) (referring to Patent Document 5 comparative example 1 and embodiment 1).
In addition, though the transparency of disclosed thin slice is known in the patent documentation 5, also nothing but general effect.In the time of will chemically belonging to different types of mixed with resin, both objectionable interminglings, the transparency of composition can descend and (refers to Patent Document 5 comparative example 1,4-7) usually.
Consider these, if embodiments of the invention and comparative example are compared, then in the present invention, not only improved the transparency dramatically, although mixed the class of metallocenes ethene-alpha-olefin copolymer (b) more soft than polypropylene-based resin (a), the tensile elasticity rate of extrusion molding direction (MD direction) is also identical, has perhaps improved some.This is by the inscrutable effect of known technology.
More than, for the present invention preferred embodiment being illustrated, but the present invention is not limited in above-mentioned embodiment, certainly carries out various changes within the scope of the invention.
Industrial utilizability
Transparent polypropylene resinoid thin slice of the present invention can mainly be used as hot forming product thin slice, wherein, as the thermoformed container thin slice, also is particularly suitable for requiring the purposes of the transparency, for example, and the lid of food containers etc.
Claims (22)
1. the manufacture method of a transparent polypropylene resinoid thin slice, it is characterized in that, with contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-925kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % melt extrudes for laminar, afterwards by (1) at chill roll be wound between the endless conveyor of at least two rollers and carry out planar crimping, perhaps (2) make it by cooling water flows through below 40 ℃ slit being arranged and/or by below 40 ℃ in the cooling water, and cooling has melt extruded and is laminar described resin combination rapidly.
2. the manufacture method of transparent polypropylene resinoid thin slice as claimed in claim 1, wherein said polypropylene-based resin (a) do not contain makes the nuclear agent.
3. transparent polypropylene resinoid thin slice, it is characterized in that, by contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and be that tensile elasticity rate on the MD direction is more than the 800MPa in the extrusion molding direction, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)。
4. transparent polypropylene resinoid thin slice as claimed in claim 3, the impact strength of this thin slice under 0 ℃ is more than the 0.1J.
5. as any one described transparent polypropylene resinoid thin slice among the claim 3-4, the fusing point of wherein said class of metallocenes ethene-alpha-olefin copolymer (b) is more than 105 ℃.
6. as any one described transparent polypropylene resinoid thin slice among the claim 3-4, the fusing point of wherein said class of metallocenes ethene-alpha-olefin copolymer (b) is lower than 100 ℃.
7. formed products, it is characterized in that, constitute by transparent polypropylene resinoid thin slice, described transparent polypropylene resinoid thin slice by contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)。
8. formed products as claimed in claim 7, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
9. as any one described formed products among the claim 7-8, the fusing point of wherein said class of metallocenes ethene-alpha-olefin copolymer (b) is more than 105 ℃.
10. as any one described formed products among the claim 7-8, the fusing point of wherein said class of metallocenes ethene-alpha-olefin copolymer (b) is lower than 100 ℃.
11. formed products, it is characterized in that, constitute by transparent polypropylene resinoid thin slice, described resin flake is formed by the resin combination that contains polypropylene-based resin and class of metallocenes ethene-alpha-olefin copolymer at least, and has a following characteristic, promptly formed products whitens under the temperature before and after the described class of metallocenes ethene-alpha-olefin copolymer fusing point, the surface temperature that shows formed products on specified temp still beneath.
12. formed products as claimed in claim 11, it is made of following transparent polypropylene resinoid thin slice, described transparent polypropylene resinoid thin slice by contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)。
13. formed products as claimed in claim 12, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
14. as any one described formed products among the claim 11-13, wherein based on described characteristic, the temperature sensor during with the heating of effect micro-wave oven.
15. the method for a formed products whiting that prevents to constitute by transparent polypropylene resinoid thin slice, it is characterized in that, it is when reaching arbitrarily temperature M ℃ by the surface temperature that the formed products that transparent polypropylene resinoid thin slice constitutes is heated to described formed products, be used to prevent the method for described formed products whiting, wherein following transparent polypropylene resinoid thin slice is configured as described formed products, described transparent polypropylene resinoid thin slice is 85-99% by containing isotactic pentad branch rate at least, molten flow velocity degree is that MFR is 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses metalloscene catalyst to make, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)，
Simultaneously the fusing point of described class of metallocenes ethene-alpha-olefin copolymer (b) is more than (M+3) ℃.
16. the method for the formed products whiting that prevents to be made of transparent polypropylene resinoid thin slice as claimed in claim 15, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
17. the temperature determination methods of a formed products that constitutes by transparent polypropylene resinoid thin slice, it is characterized in that, for promptly arbitrarily N ℃ of the surface temperature that can with the naked eye judge the heated formed products that constitutes by transparent polypropylene resinoid thin slice, following transparent polypropylene resinoid thin slice is configured as described formed products, and described transparent polypropylene resinoid thin slice is 85-99% by containing isotactic pentad branch rate at least, molten flow velocity degree is that MFR is 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses metalloscene catalyst to make, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)，
Simultaneously the fusing point of described class of metallocenes ethene-alpha-olefin copolymer (b) is [N～(N+3)] ℃.
18. the temperature determination methods of the formed products that is made of transparent polypropylene resinoid thin slice as claimed in claim 17, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
19. formed products, it is characterized in that, it constitutes for the transparent polypropylene resinoid thin slice that the whiting temperature M ℃ time the arbitrarily is prevented from by being heated to surface temperature, following transparent polypropylene resinoid thin slice be shaped and form, described transparent polypropylene resinoid thin slice by contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)，
Simultaneously the fusing point of described class of metallocenes ethene-alpha-olefin copolymer (b) is more than (M+3) ℃.
20. formed products as claimed in claim 19, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
21. formed products, it is characterized in that, it is i.e. N ℃ the formed products that is made of transparent polypropylene resinoid thin slice arbitrarily of surface temperature that can with the naked eye judge formed products, following transparent polypropylene resinoid thin slice be shaped and form, described transparent polypropylene resinoid thin slice by contain at least isotactic pentad branch rate be 85-99%, molten flow velocity degree be MFR be 0.1-30g/10 minute polypropylene-based resin (a) 70-97 quality % and uses the metalloscene catalyst manufacturing, density is 880-920kg/m
3, molten flow velocity degree is that MFR is that the resin combination of 1-30g/10 minute class of metallocenes ethene-alpha-olefin copolymer (b) 30-3 quality % constitutes, and the extrusion molding direction is that tensile elasticity rate on the MD direction is more than the 800MPa, total turbidity H when sheet thickness is t satisfies following formula (1), the unit of t is mm
H≤130t
2-63t+20……(1)，
Simultaneously the fusing point of described class of metallocenes ethene-alpha-olefin copolymer (b) is [N～(N+3)] ℃.
22. formed products as claimed in claim 21, the impact strength of wherein said transparent polypropylene resinoid thin slice under 0 ℃ is more than the 0.1J.
Applications Claiming Priority (2)
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|---|---|---|---|
| JP2005127149 | 2005-04-25 | ||
| JP2005127149A JP4549224B2 (en) | 2005-04-25 | 2005-04-25 | Method for producing transparent polypropylene-based resin sheet, transparent polypropylene-based resin sheet, molded product, method for preventing whitening of molded product comprising transparent polypropylene-based resin sheet, and temperature discrimination method |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102905897A (en) * | 2010-05-28 | 2013-01-30 | 出光统一科技株式会社 | Multilayer sheet, thermally molded container, and easy-open packaging material |
| CN102924816A (en) * | 2012-08-23 | 2013-02-13 | 上海金发科技发展有限公司 | Special welded polypropylene composite for automotive carbon tanks and preparation method thereof |
| CN101801639B (en) * | 2007-09-21 | 2013-04-03 | 住友化学株式会社 | Process for producing raw film for retardation film made of polypropylene resin |
| CN103459121A (en) * | 2011-04-01 | 2013-12-18 | 出光统一科技株式会社 | Method for producing transparent recycled sheet, and transparent recycled sheet |
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| JP2007231036A (en) * | 2006-02-27 | 2007-09-13 | Prime Polymer:Kk | Composition for forming high-transparency polypropylene sheet having radiation resistance, and package comprising the same and having excellent radiation resistance and electron beam sterilization |
| JP5865577B2 (en) | 2010-03-12 | 2016-02-17 | 出光ユニテック株式会社 | Method for producing transparent laminated sheet and transparent laminated sheet |
| JP5331754B2 (en) * | 2010-06-08 | 2013-10-30 | 日本ポリプロ株式会社 | Polypropylene resin composition for extrusion molding and molded resin molded body thereof |
| JP5691572B2 (en) * | 2011-02-02 | 2015-04-01 | 住友化学株式会社 | Olefin resin composition, sheet and thermoformed article |
| JP6595141B2 (en) * | 2019-06-19 | 2019-10-23 | キョーラク株式会社 | Packaging bag |
| WO2022249843A1 (en) * | 2021-05-26 | 2022-12-01 | 株式会社プライムポリマー | Injection molded article made of propylene-based polymer composition |
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| JPS6148315A (en) * | 1984-08-17 | 1986-03-10 | 株式会社豊田中央研究所 | Temperature display container |
| JPH0681698B2 (en) * | 1986-03-31 | 1994-10-19 | 出光石油化学株式会社 | Method for producing polypropylene yarn sheet |
| JP3446104B2 (en) * | 1993-12-28 | 2003-09-16 | キョーラク株式会社 | Plastic containers for chemicals |
| CA2218970A1 (en) * | 1996-10-22 | 1998-04-22 | Kenichi Fujiwara | Soft transparent polyolefin resin sheet and method for producing the same |
| JP3677365B2 (en) | 1997-01-13 | 2005-07-27 | 萩原工業株式会社 | Reversible thermochromic polyolefin fiber |
| JP3874501B2 (en) | 1997-09-02 | 2007-01-31 | 出光興産株式会社 | Polypropylene resin composition and film thereof |
| JP2002105257A (en) * | 2000-02-28 | 2002-04-10 | Grand Polymer Co Ltd | Polypropylene resin composition, and container and medical appliance made of the same |
| JP2002212358A (en) * | 2001-01-19 | 2002-07-31 | Grand Polymer Co Ltd | Polypropylene resin composition for container, method for producing container and container |
| JP2003170485A (en) | 2001-12-07 | 2003-06-17 | Idemitsu Unitech Co Ltd | Transparent polypropylene sheet and method for producing the same |
| HUE037330T2 (en) * | 2002-05-03 | 2018-08-28 | The Government Of The Us Secretary Department Of Health And Human Services | A rDEN3/4delta 30(ME), rDEN2/4delta30(ME) or rDEN1/4delta30(ME) recombinant chimeric dengue virus containing a 30 nucleotide deletion (delta30) in a section of the 3' untranslated region of dengue type 4 genome, wherein said 30 nucleotide deletion cor... |
| CN1938144B (en) * | 2004-03-26 | 2010-06-16 | 出光统一科技株式会社 | Method for producing transparent polypropylene based sheet and transparent polypropylene based sheet |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801639B (en) * | 2007-09-21 | 2013-04-03 | 住友化学株式会社 | Process for producing raw film for retardation film made of polypropylene resin |
| CN102905897A (en) * | 2010-05-28 | 2013-01-30 | 出光统一科技株式会社 | Multilayer sheet, thermally molded container, and easy-open packaging material |
| CN102905897B (en) * | 2010-05-28 | 2015-01-21 | 出光统一科技株式会社 | Multilayer sheet, thermally molded container, and easy-open packaging material |
| CN103459121A (en) * | 2011-04-01 | 2013-12-18 | 出光统一科技株式会社 | Method for producing transparent recycled sheet, and transparent recycled sheet |
| CN102924816A (en) * | 2012-08-23 | 2013-02-13 | 上海金发科技发展有限公司 | Special welded polypropylene composite for automotive carbon tanks and preparation method thereof |
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| Publication number | Publication date |
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| JP4549224B2 (en) | 2010-09-22 |
| KR20060111855A (en) | 2006-10-30 |
| CN100581786C (en) | 2010-01-20 |
| KR101244999B1 (en) | 2013-03-18 |
| JP2006297876A (en) | 2006-11-02 |
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