CN101903256A - High-gloss multilayered plastic container - Google Patents
High-gloss multilayered plastic container Download PDFInfo
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- CN101903256A CN101903256A CN2008801212715A CN200880121271A CN101903256A CN 101903256 A CN101903256 A CN 101903256A CN 2008801212715 A CN2008801212715 A CN 2008801212715A CN 200880121271 A CN200880121271 A CN 200880121271A CN 101903256 A CN101903256 A CN 101903256A
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- China
- Prior art keywords
- transparent
- resin
- layer
- plastic container
- resin layer
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- 229920003023 plastic Polymers 0.000 title claims abstract description 89
- 239000004033 plastic Substances 0.000 title claims abstract description 59
- 239000000088 plastic resin Substances 0.000 claims abstract description 35
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims description 179
- 239000011347 resin Substances 0.000 claims description 179
- 229920000098 polyolefin Polymers 0.000 claims description 67
- -1 vinyl-vinyl Chemical group 0.000 claims description 29
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 229920001903 high density polyethylene Polymers 0.000 claims description 5
- 239000004700 high-density polyethylene Substances 0.000 claims description 5
- 229920005673 polypropylene based resin Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 abstract description 15
- 239000004840 adhesive resin Substances 0.000 abstract description 7
- 229920006223 adhesive resin Polymers 0.000 abstract description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 229920006026 co-polymeric resin Polymers 0.000 abstract description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 169
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 38
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 37
- 239000000049 pigment Substances 0.000 description 21
- 238000010008 shearing Methods 0.000 description 19
- 238000000465 moulding Methods 0.000 description 11
- 239000002184 metal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- RZXDTJIXPSCHCI-UHFFFAOYSA-N hexa-1,5-diene-2,5-diol Chemical compound OC(=C)CCC(O)=C RZXDTJIXPSCHCI-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- CVOFKRWYWCSDMA-UHFFFAOYSA-N 2-chloro-n-(2,6-diethylphenyl)-n-(methoxymethyl)acetamide;2,6-dinitro-n,n-dipropyl-4-(trifluoromethyl)aniline Chemical compound CCC1=CC=CC(CC)=C1N(COC)C(=O)CCl.CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O CVOFKRWYWCSDMA-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000004026 adhesive bonding Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 206010018612 Gonorrhoea Diseases 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 210000004276 hyalin Anatomy 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/406—Bright, glossy, shiny surface
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
- B32B2439/70—Food packaging
Landscapes
- Laminated Bodies (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Wrappers (AREA)
Abstract
high-gloss multilayered plastic container comprising (1) an outer transparent plastic resin layer, (2) a transparent adhesive resin layer, and (3) a colored polyolefin resin layer in this order from the outside. The outer transparent plastic resin layer has a surface roughness satisfying Ra<=0.2 [mu]m. The interface between the outer transparent plastic resin layer (1) and the transparent adhesive resin layer (2) has a roughness of 15 [mu]m or less, and the interface between the transparent adhesive resin layer (2) and the colored polyolefin resin layer (3) has a roughness of 15 [mu]m or less. The outer transparent plastic resin layer (1) is preferably formed from a transparent ethylene/vinyl alcohol copolymer resin. This multilayered plastic container has an even and smooth surface, a deep color tone with a high gloss, and a highly excellent appearance.
Description
Technical field
The high multilayer plastic container of surface gloss that the present invention relates to have excellent outward appearance and the degree of depth is arranged.
Background technology
All the time, multilayer plastic container is widely used as the packing container of various contents such as holding cosmetics, hygienic articles, various beverage, seasonings or food.
In the above-mentioned laminated vessel, consider, preserve the various characteristics of going up requirement, be used in combination various raw materials for plastics production in order to satisfy content from forming characteristics or manufacturing cost aspect.As the outer field resin that constitutes multilayer plastic container, use based on the polyolefin resins such as polyester resin, polyamide-based resin, polyethylene or polypropylene of polyethylene terephthalate (PET) usually etc.On the other hand, from forming characteristics or hygienic characteristic and the consideration of cost aspect, the internal layer of container uses wire olefine kind resins such as polyethylene or polypropylene more.
In addition, for anti-block sees through wall of container, the known all the time resistance oxygen resin bed that in multilayer plastic container, is provided with.As this gas barrier resin, for example use ethylene-vinyl alcohol copolymer (ethylene-acetidin copolymer saponification material), polyamide, polyvinylidene chloride resinoid, polyvinyl alcohol, fluorocarbon resin etc.
About making up the layer structure of the multilayer plastic container that these resins form, various technical schemes have been proposed also.For example known multilayer plastic container (for example with reference to patent documentation 1,2) with the layer structure that forms from outside face one side of container lamination (1) polyester resin, (2) adhering resin and (3) polyolefin resin successively.
In addition, also known multilayer plastic container (for example with reference to patent documentation 3,4) with the layer structure that forms from outside face one side of container lamination (1) polypropylene-based resin, (2) adhering resin, (3) gas barrier resin, (4) adhering resin and (5) polypropylene-based resin successively.
[patent documentation 1] Japanese kokai publication hei 6-79842 communique
[patent documentation 2] Japanese kokai publication hei 6-106606 communique
[patent documentation 3] Japanese kokai publication hei 5-8355 communique
[patent documentation 4] Japanese kokai publication hei 5-42641 communique
But, having in the multilayer plastic container of this layer structure, the resin that constitutes each layer of container there are differences aspect the shaping characteristics such as molten resin viscosity.Therefore, for example after forming the multilayer parison, when making hollow container, might produce bad order problems such as ripples pattern between outer or each layer at the resin of vessel surface by blow molding.In addition, it is inhomogeneous also to become on the form and aspect, the bad problems of form and aspect such as striated pattern might occur taking place.Therefore, can not realize high glaze for example, the multilayer plastic container of the such outward appearance excellence of the container of even metal tone of the degree of depth is arranged.
And, if process vessel surface and reduce the roughness of mould inner surface successfully, then when container formation, produce air pit (owing to be involved in air between mould and moulding product surface, residual mold shape is not transferred phenomenon partly).The result exists vessel surface to produce the concavo-convex bad problem of moulding that waits of part.
Summary of the invention
Therefore, the objective of the invention is to, provide and eliminate the distinctive problem of this multilayer plastic container, have even and smooth surface and high glaze, the tone of the degree of depth arranged, the multilayer plastic container that outward appearance is very excellent.
The inventor finds, by reducing the outer field roughness of surface of plastic resin, making resin skin and the concavo-convex of its inboard adhering resin bed interface simultaneously is below the 15 μ m, and making the concavo-convex of the adhering resin layer colored polyolefin resinoid bed interface inboard with it is below the 15 μ m, can address the above problem, thereby finish the present invention.
That is the technical scheme of employing following 1～9 among the present invention.
1. high-gloss multilayer plastic container, it is the multilayer plastic container that has (1) transparent plastic resin skin, (2) transparent adhering resin layer and (3) colored polyolefin resinoid layer from outside face one side successively, it is characterized in that, the outer field roughness of surface of transparent plastic resin is Ra≤0.2 μ m, above-mentioned (1) transparent plastic resin skin is below the 15 μ m with the concavo-convex of above-mentioned (2) transparent adhering resin bed interface, and the concavo-convex of above-mentioned (2) transparent adhering resin layer and above-mentioned (3) colored polyolefin resinoid bed interface is below the 15 μ m.
2. the high-gloss multilayer plastic container of record is characterized in that above-mentioned (1) transparent plastic resin contains transparent vinyl-vinyl alcohol copolymer resinoid in above-mentioned 1.
3. the high-gloss multilayer plastic container of record is characterized in that above-mentioned (3) colored polyolefin resinoid layer contains flitter in above-mentioned 1 or 2.
4. the high-gloss multilayer plastic container of any record is characterized in that in above-mentioned 1～3, and above-mentioned (3) colored polyolefin resinoid layer contains the block polypropylene resinoid.
5. the high-gloss multilayer plastic container of any record is characterized in that in above-mentioned 1～3, and above-mentioned (3) colored polyolefin resinoid layer contains the high-density polyethylene vinyl resin.
6. the high-gloss multilayer plastic container of any record in above-mentioned 1～4, it is characterized in that the layer structure of multilayer plastic container is to have (1) transparent vinyl-vinyl alcohol copolymer resinoid skin, (2) transparent polypropylene class adhering resin layer, (3) successively from outside face one side to contain the coloured polypropylene resinoid layer of flitter, the polypropylene-based resin layer that (4) do not contain flitter.
7. the high-gloss multilayer plastic container of any record in above-mentioned 1～3 or 5, it is characterized in that the layer structure of multilayer plastic container is to have (1) transparent vinyl-vinyl alcohol copolymer resinoid skin, (2) transparent polyethylene class adhering resin layer, (3) successively from outside face one side to contain the pigmented polyethylene resinoid layer of flitter, the polythylene resin layer that (4) do not contain flitter.
8. the high-gloss multilayer plastic container of any record is characterized in that in above-mentioned 1～7, and multilayer plastic container further has the polyolefin resin internal layer.
9. the high-gloss multilayer plastic container of any record is characterized in that in above-mentioned 1～8, and the outer gross thickness with above-mentioned (2) transparent adhering resin layer of above-mentioned (1) transparent plastic resin is 30～200 μ m.
According to the present invention, can not produce the bad problem of moulding and obtain efficiently having bad order problems such as no ripples pattern or foaming smooth surface and high glaze, the multilayer plastic container of the even metal tone of the degree of depth is arranged.
Description of drawings
[Fig. 1] is the schematic cross-section of an example of the layer structure of expression high-gloss multilayer plastic container of the present invention.
Nomenclature
A transparent vinyl-EVOH skin
The transparent adhering resin layer of B
C contains the colored polyolefin resinoid layer of flitter
D does not contain the polyolefin type resin layer of flitter
The specific embodiment
Among the present invention, the layer structure of multilayer plastic container is to have (1) transparent plastic resin skin, (2) transparent adhering resin layer and (3) colored polyolefin resinoid layer successively from outside face one side.In addition, the outer field roughness of surface of transparent plastic resin is Ra≤0.2 μ m.Further, it is characterized in that, by adopting the shearing stress of each resin of constituting container such as is adjusted at technological means, making (1) transparent plastic resin skin is below the 15 μ m with the concavo-convex of (2) transparent adhering resin bed interface, and (2) transparent adhering resin layer is below the 15 μ m with the concavo-convex of (3) colored polyolefin resinoid bed interface.
Wherein, define the term that uses among the present invention is following.
(surface roughness Ra of container)
Among the present invention, (1) the outer field surface roughness Ra of transparent plastic resin refers to, according to JISB0601, use contact pin type roughness profile measuring machine, is measuring of 4mm to the wall of container par beyond the spray nozzle part with each measured length, carries out the roughness of surface (Ra) that arithmetic average obtains.
(resin bed interface concavo-convex)
Concavo-convex and (2) transparent adhering resin layer of and (2) transparent adhering resin bed interface outer to (1) transparent plastic resin is during with concavo-convex mensuration of (3) colored polyolefin resinoid bed interface, and the concavo-convex big part in interface is got as sample in the wall of container par beyond spray nozzle part.Then, use rotary microtom, the container section of the sample that obtains is cut off as sightingpiston.Further, sample thickness and sightingpiston with 30 μ m on the direction vertical with sightingpiston cut off abreast as sample, will observe concavo-convex as the resin bed interface of the maxim of measuring the concavo-convex value obtain to sightingpiston with optical microscope.
(thickness of skin+transparent adhering resin layer)
When the outer gross thickness with (2) transparent adhering resin layer of (1) transparent plastic resin is measured, similarly concavo-convex with above-mentioned resin bed interface made with the cross section of the container side wall vertical direction that obtains with wall of container par beyond the spray nozzle part sample as sightingpiston.And, with optical microscope sightingpiston is observed, measure the thickness of (1) transparent plastic resin skin and (2) transparent adhering resin layer.
As the outer field preferred transparent plastic resin that constitutes multilayer plastic container, can enumerate ethylene-vinyl alcohol copolymerization resinoid.
As this ethylene-vinyl alcohol copolymerization resinoid (EVOH),, then do not limit especially as long as have the outer necessary diaphaneity that constitutes container.As preferred ethylene-vinyl alcohol copolymerization resinoid, can enumerate ethylene contents and be 20～60 moles of %, saponified in particular for the vinyl-vinyl acetate copolymer of 25～50 moles of %.
As outer field other resin that constitutes multilayer plastic container, can enumerate amilan, polycarbonate resin, ionomer resin etc.
In addition, (1) plastic resin is outer so long as transparent, then can non-coloring or painted.But, preferably avoid adding the pigment of the roughness of surface increase that makes plastic resin etc.
In addition, in (1) plastic resin skin, under the degree of not damaging the transparency, can also add known additive.For example can add thermoplastic elastomer, other thermoplastic base resin, rubber resin, inorganic filler, pigment, plasticizer, antioxidant, antistatic additive, light stabilizer, anti-caking agent, lubricant, dyestuff etc.
Below, be example to use EVOH as the outer field situation of (1) transparent plastic resin, multilayer plastic container of the present invention is further detailed.
In order to make the outer field roughness of surface of (1) transparent plastic resin is Ra≤0.2 μ m, and the roughness of surface that uses the blow mold inside face is the blow mold about 0.2 μ m≤Ra≤0.8 μ m.By using the mould of having handled like this, also be the container of Ra≤0.2 μ m even can obtain the outer field roughness of surface maximum of container.If the surface roughness Ra of container surpasses 0.2 μ m, the reflected light confusion on the vessel surface then, gloss reduces in appearance.
If reduce the roughness of surface of blow mold inside face, then when the moulding of plastic container, produce air pit, might produce the concavo-convex bad problem of moulding that waits of part surface.In addition, the concavo-convex increase of (3) colored polyolefin resinoid bed interface of concavo-convex or (2) transparent adhering resin layer and its inboard of (2) transparent adhering resin bed interface of (if 1) transparent EVOH and its inboard, it is inhomogeneous then to become on the form and aspect, might produce the bad problems of form and aspect such as striated pattern.
Among the present invention, by adopting water ratio to be adjusted into below the 5000ppm, to be preferably about 500～2500ppm with transparent EVOH, simultaneously the shearing stress of each resin of constituting container such as is adjusted at technological means, making the maximum concavo-convex of above-mentioned each resin bed interface is below the 15 μ m, prevents the bad problem of this moulding.If the water ratio of transparent EVOH surpasses 5000ppm, then when the moulding of container, produce foaming.
The adhesive bonding property of EVOH and polyolefin resin is little, and shaping characteristics such as melt viscosity there are differences.Therefore, if with EVOH be outer, be that internal layer comes the moulding multilayer plastic container with the polyolefin resin, then outer or each bed interface might produce bad order problems such as ripples pattern at the EVOH of vessel surface.
Ripples pattern refers to the relief pattern that produces at the interface of the interface of (2) transparent adhering resin layer of (1) transparent EVOH skin and its inboard or (2) transparent adhering resin layer and (3) colored polyolefin resinoid layer.If this is concavo-convex from the container sidewall surfaces, then can see at the continuous ripples shape that forms of the circumferencial direction of container.If observe the cross section of multilayer plastic container sidewall, then producing on the concavo-convex interface, the resin of the layer of inside face one side in the resin of the layer of outside face one side with wavy projection.Concavo-convex can the observation well from the short transverse cross section of container side wall mostly is the concavo-convex of the hundreds of μ m of width, protuberance thickness 15～50 μ m.Concavo-convex generation is agnogenio really, but think when making the multilayer parison, owing to uneven resin flows in the portion of molten resin interflow produces.
Among the present invention,, remedy the difference of the outer shaping characteristic with polyolefin type resin layer of EVOH by the shearing stress of each layer resin of constituting multilayer plastic container and the melt flow rate (MFR) that constitutes the resin of transparent adhering resin layer are adjusted.Thereby can reduce outer (2) the transparent adhering resin bed interface with its inboard of (1) transparent EVOH concavo-convex, and (3) colored polyolefin resinoid bed interface of (2) transparent adhering resin layer and its inboard is concavo-convex, obtain the outward appearance excellence and prevented the also multilayer plastic container of excellence of proterties such as peeling off etc. between resin bed, Dent resistance.
As transparent adhering resin, can use the known resin that EVOH and polyolefin resin both is had gleyness.For example, can use ethylene ' alpha '-olefin copolymer resins and their acid modified resin, alkene and acid copolymer resins, contain the resin of glycidyl etc.In addition, in order to improve gleyness, can also in these resins, add known tackifier.
As copolymer, can use the copolymer for preparing in any bonding mode such as random, block, grafting.As acid modified resin, for example use and utilize unsaturated carboxylic acids such as acrylic acid, methyl acrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, or their acid anhydrides carries out graft modification and the resin that obtains.When using acid modified resin as adhering resin, the acidic group chemical bonding of the hydroxyl of EVOH and acid modified resin, outer adhesive bonding property with the adhering resin layer improves, so preferred.These resins can use separately, in the hybrid resin mode more than 2 kinds, to use with the hybrid resin mode of other resin.As tackifier, for example can enumerate rosin based resin, terpenoid resin, petroleum resin etc.These resins can use separately or mix 2 kinds with on use.As adhering resin, be preferably the polyolefin resin that has carried out sour modification especially.
In addition, in transparent adhering resin layer, can add known additive.For example, can add thermoplastic elastomer, other thermoplastic base resin, rubber resin, inorganic filler, pigment, plasticizer, antioxidant, antistatic additive, light stabilizer, antiblocking agent etc.
In addition, the clear adhesive resin is so long as transparent, then can non-coloring or painted, can contain flash of light property pigment.When painted, for example by making the colored polyolefin layer contain flash of light property pigment, the transparent painted adhesive linkage of light transmission by the reflection of flash of light property pigment obtains the metal sense of the uniqueness of the degree of depth, so preferred with the adhering resin layer.In addition, by changing the tone of clear adhesive and polyolefin layer, can also obtain special form and aspect effect sometimes.As the colorant that uses in the transparent adhering resin layer, only otherwise the infringement transparency does not then limit especially.As this colorant, for example can use organic pigments such as azo class pigment, phthalocyanine pigment, fused polycycle class pigment, dyeing color lake class pigment.
(1) interface of (3) colored polyolefin resinoid layer of concavo-convex and (2) transparent adhering resin layer and its inboard of outer (2) the transparent adhering resin bed interface with its inboard of transparent EVOH is concavo-convex, can make it satisfy following (a) simultaneously by the resin of adjusting each layer of formation multilayer plastic container and (b) reduces.
(a) constitute the shearing stress (unit: KPa) satisfy " (3) colored polyolefin resinoid-55≤(2) transparent adhering resin≤(1) transparent EVOH+70 " of the resin of each layer.
Wherein, the shearing stress of resin refers to the K7199 according to JIS, is under the condition of L=10mm, D=diameter 1mm in the hole of 210 ℃ of temperature, velocity of shear 50/ second, resin extruded portion, the particle before the fusion of employed resin is measured the value that obtains.
If the shearing stress of clear adhesive resin is lower than " (3) colored polyolefin resinoid-55 ", then produce the ripples pattern of concavo-convex inequality at the interface of transparent adhering resin layer and colored polyolefin resin bed.On the other hand, if the shearing stress of transparent adhering resin layer surpasses " (1) transparent EVOH+70 ", then produce the ripples pattern of concavo-convex inequality at the interface of transparent plastic resin layer and transparent adhering resin layer.
(b) melt flow rate (MFR) that constitutes the resin of transparent adhering resin layer (g/10min) satisfies " 1.0≤MFR≤2.5 ".
Wherein, the melt flow rate of resin refers to the K7210 according to JIS, under 190 ℃ of temperature, load 2.16Kg the particle before the fusion of employed resin is measured the value that obtains.
The MFR of clear adhesive resin is during less than 1.0 (g/10min), produces the ripples pattern of concavo-convex inequality at the interface of transparent evoh layer and transparent adhering resin layer.On the other hand, if the MFR of clear adhesive resin surpasses 2.5, then produce the ripples pattern of concavo-convex inequality at the interface of transparent adhering resin layer and colored polyolefin resin bed.
In the multilayer plastic container of the present invention, the outer gross thickness with (2) transparent adhering resin layer of (1) transparent plastic resin is preferably about 30～200 μ m, is preferably especially about 60～150 μ m.
If this thickness is less than 30 μ m, then moulding causes that vessel surface becomes coarse, surface gloss is poor, produces problems such as plastic resin skin disconnection during moulding.In addition, if this thickness surpasses 200 μ m, then hyaline membrane is blocked up, gonorrhoea occurs, and diaphaneity might reduce.
And by making the outer gross thickness with transparent adhering resin layer of transparent plastic resin in this scope, owing to reflect knifeedge from the reflected light of the colored polyolefin resinoid layer that is in internal layer one side, the degree of depth appears in form and aspect or gloss.In addition, when in colored polyolefin resinoid layer, cooperating flitter to make the container of metal tone,, preferably make the major diameter of the gross thickness of (1) transparent plastic resin skin and (2) transparent adhering resin layer greater than pigment in order to obtain required roughness of surface.
The resin of formation as (3) colored polyolefin resinoid layer of the internal layer of (2) transparent adhering resin layer do not limited especially.For example can use known low density polyethylene (LDPE), wire low density polyethylene (LDPE), medium density polyethylene, high density polyethylene (HDPE), polypropylene, propylene-ethylene copolymers, vinyl-vinyl acetate copolymer, carry out in the polyolefin resin classes such as polyolefin resin of graft modification any one with vinyl unsaturated carboxylic acid or its acid anhydrides.As particularly preferred polyolefin resin, can enumerate propylene-ethylene block copolymer.These polyolefin resins can use separately or mix 2 kinds with on use.In addition, the backflow product (salvage material) that produced in the time of can also the mixer moulding etc. use.
Colored polyolefin resinoid layer can be in transparent dyed layer or the opaque coloured layer any one.In addition, not only can also constitute the dyed layer more than 2 layers for 1 layer of dyed layer.The inside face resin bed that is for example formed by polyolefin resin of interlayer that is formed by other resin etc. or the inside face that constitutes container can also further be set in internal layer one side of colored polyolefin resinoid layer in addition.
The colorant that is engaged in (3) colored polyolefin resinoid layer is not limited especially, can use organic pigments such as azo class pigment, phthalocyanine pigment, fused polycycle class pigment and dyeing color lake class pigment, or flitters such as alumina type flitter, mica group flitter, Glass flitter such as polarized light pearlescent pigment etc.These colorants can use a kind or make up 2 kinds with on use.In addition, combinations such as these colorants and extender pigment can also be used.
When in (3) colored polyolefin resinoid layer, cooperating flitter, the layer that the reflected light of flitter is outer by (1) transparent plastic resin and (2) transparent adhering resin layer combines can obtain having the multilayer plastic container of the metal tone of the reflecting feel that the degree of depth is arranged thus.
When particularly (3) colored polyolefin resinoid layer being formed the multiple-structure that constitutes by the pigmentary resin layer that contains flitter with the transparent pigmentary resin layer of (2) transparent adhering resin layer adjacency and layer one side that set within it, obtain the metal sense of the uniqueness as on the metal bottom, being printed with transparent ink, so preferred with degree of depth.
[embodiment]
Then high-gloss multilayer plastic container of the present invention is described, but the present invention is not limited by following concrete example by embodiment.
Fig. 1 is the schematic cross-section of an example of the layer structure of expression multilayer plastic container of the present invention.This container has the outer A of (1) transparent plastic resin (EVOH), (2) transparent adhering resin layer B, (3) successively from outside face one side and contains the colored polyolefin resinoid layer C of flitter and the polyolefin type resin layer D that (4) do not contain flitter.(2) transparent adhering resin layer B can add tinting pigment etc. and make transparent painted adhering resin layer in the scope of not damaging the transparency.
In following example, following manufacturing has the container of layer structure shown in Figure 1.Difference potting resin in four extruders (the following extruder that will constitute the resin of each resin bed A, B, C, D is called extruder A, extruder B, extruder C, extruder D).When being heated, each resin carries out plasticized and mixing and extrude, use the multilayer head, form from outside face one side comprise (1) transparent EVOH outer A, (2) transparent painted adhering resin layer B successively, (3) contain the colored polyolefin resinoid layer C of flitter and the multilayer parison that (4) do not contain the polyolefin type resin layer D of flitter.Then, clip parison with the mould with die cavity, to the parison blowing compressed air, the manufacturing capacity is the hollow container of the square tube type of 500mL.The inside surface roughness of the mould that uses is Ra=0.6 μ m.
In the following example, measure each physics value by the method for having put down in writing.In addition, the water ratio of transparent EVOH is measured by the particle of Ka Er-Fischer aquametry before to fusion.When carrying out the mensuration of each physics value, contact pin type roughness profile measuring machine uses " the industrial Surfcom1400A-3DF-12 of the smart machine in Tokyo ".In addition, rotary microtom uses " ラ イ カ system inspection RM2125RT ", optical microscope use " オ リ Application パ ス system measuring microscope STM5-321 ", resin shearing stress analyzer uses " the キ ヤ ピ ロ グ ラ Off 1D that the smart mechanism work in Tokyo is produced ".
In addition, the surface roughness Ra of multilayer plastic container be the big part of roughness of surface that the flat beyond the spray nozzle part of container is obtained directly or the size that cuts 15mm * 15mm be used for measuring.And " thickness of skin+transparent adhering resin layer " is that top, middle part, the bottom at the container trunk distinguished in a circumferential direction with 8 points of 45 ° of measuring spaces, adopts its aviation value.Further, the gloss evaluation of container be whole flats with the container beyond the nozzle as object, the visual observation.
(embodiment 1)
To bore be fill shearing stress 100 (KPa) among the extruder A of 40mm, water ratio is transparent vinyl-vinyl alcohol copolymer resinoid (EVOH) of 1500ppm.To bore be fill among the extruder B of 40mm MFR be 1.6 (g/10min), shearing stress be 100 (KPa) clear, colorless sour modified polypropylene resin and as the azo class red pigment of 0.3 weight % of tinting pigment.To bore be fill among the extruder C of 50mm MFR be 0.8 (g/10min), shearing stress be 120 (KPa) clear, colorless the ethylene-propylene block copolymerized resin and as the pearl red (mean grain size is the mica group pigment of 21 μ m) of 1.0 weight % of flitter, as the azo class red pigment of 0.3 weight % of tinting pigment.To bore is the ethylene-propylene block copolymerized resin of filling above-mentioned clear, colorless among the extruder D of 40mm.Carry out plasticized and mixing when resin in each extruder heats to being filled into, extrude from the multilayer head and form the multilayer parison.Then, clip parison with the mould with die cavity, to the parison blowing compressed air, the capacity of obtaining is the hollow bottle of the square tube type of 500mL.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.11 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 6 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 7 μ m, and the surface gloss of bottle is good.
(embodiment 2)
In embodiment 1, using shearing stress as outermost resin A is 60 (KPa), the water ratio EVOH as 1200ppm, in addition obtains same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.18 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 15 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 8 μ m, and the surface gloss of bottle is good.
(embodiment 3)
In embodiment 2, using MFR as transparent painted adhering resin B is that 2.5 (g/10min), shearing stress are the sour modified polypropylene resin of 65 (KPa), clear, colorless, in addition obtains same hollow bottle similarly to Example 2.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.12 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 7 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 15 μ m, and the surface gloss of bottle is good.
(embodiment 4)
In embodiment 1, using MFR as transparent painted adhering resin B is that 1.4 (g/10min), shearing stress are the sour modified poly ethylene resinoid of the clear, colorless of 110 (KPa).And as the resin of the clear, colorless of flash of light colored polyolefin resinoid C and transparency polyolefin resinoid D, using MFR is that 0.36 (g/10min), shearing stress are the high-density polyethylene resin of 120 (KPa).Other condition obtains same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.12 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 6 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 8 μ m, and the surface gloss of bottle is good.
(embodiment 5)
In embodiment 1, using shearing stress as outermost resin A is 70 (KPa), the water ratio EVOH as 1500ppm, using MFR as transparent pigmentary resin B is that 1.0 (g/10min), shearing stress are the sour modified polypropylene resin of the clear, colorless of 120 (KPa), in addition obtains same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.20 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 15 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 7 μ m, and the surface gloss of bottle is good.
(embodiment 6)
In embodiment 1, change the discharge-amount of extruder A and B, in addition obtain same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 13 μ m, transparent painted adhering resin layer B are that 17 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.12 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 7 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 8 μ m, and the surface gloss of bottle is good.
(embodiment 7)
In embodiment 1, change the discharge-amount of extruder A and B, in addition obtain same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 85 μ m, transparent painted adhering resin layer B are that 115 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.11 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 5 μ m, and the interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 6 μ m, and the surface gloss of bottle is good.
(comparative example 1)
In embodiment 1, using shearing stress as outermost resin A is 30 (KPa), the water ratio EVOH as 1600ppm, in addition obtains same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.22 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 18 μ m, interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 7 μ m, produces ripples pattern between outer A of EVOH and transparent painted adhering resin layer B.
(comparative example 2)
In embodiment 1, using MFR as transparent painted adhering resin B is that 3.5 (g/10min), shearing stress are the sour modified polypropylene resin of the clear, colorless of 48 (KPa), in addition obtains same hollow bottle similarly to Example 1.
Each layer thickness of this bottle is that outer A is that 50 μ m, transparent painted adhering resin layer B are that 70 μ m, flash of light colored polyolefin resinoid layer C are that 710 μ m, transparency polyolefin resinoid layer D are 170 μ m.In addition, the surface roughness Ra of bottle is 0.12 μ m, interface between outer A of transparent EVOH and the transparent painted adhering resin layer B is concavo-convex to be 7 μ m, interface between transparent painted adhering resin layer B and the flash of light colored polyolefin resinoid layer C is concavo-convex to be 17 μ m, produces ripples pattern at the interface of transparent painted adhering resin layer B and flash of light colored polyolefin resinoid layer C.
The application of this world requires Japanese patent application 2007-325397 number preceence of application on December 18th, 2007, here cites Japanese patent application 2007-325397 number full content.
Claims (9)
1. high-gloss multilayer plastic container, it is the multilayer plastic container that has (1) transparent plastic resin skin, (2) transparent adhering resin layer and (3) colored polyolefin resinoid layer from outside face one side successively, it is characterized in that, the outer field roughness of surface of transparent plastic resin is Ra≤0.2 μ m, described (1) transparent plastic resin skin is below the 15 μ m with the concavo-convex of described (2) transparent adhering resin bed interface, and the concavo-convex of described (2) transparent adhering resin layer and described (3) colored polyolefin resinoid bed interface is below the 15 μ m.
2. high-gloss multilayer plastic container as claimed in claim 1 is characterized in that, described (1) transparent plastic resin contains transparent vinyl-vinyl alcohol copolymer resinoid.
3. high-gloss multilayer plastic container as claimed in claim 1 or 2 is characterized in that, described (3) colored polyolefin resinoid layer contains flitter.
4. as any described high-gloss multilayer plastic container in the claim 1～3, it is characterized in that described (3) colored polyolefin resinoid layer contains the block polypropylene resinoid.
5. as any described high-gloss multilayer plastic container in the claim 1～3, it is characterized in that described (3) colored polyolefin resinoid layer contains the high-density polyethylene vinyl resin.
6. as any described high-gloss multilayer plastic container in the claim 1～4, it is characterized in that the layer structure of multilayer plastic container is to have (1) transparent vinyl-vinyl alcohol copolymer resinoid skin, (2) transparent polypropylene class adhering resin layer, (3) successively from outside face one side to contain the coloured polypropylene resinoid layer of flitter, the polypropylene-based resin layer that (4) do not contain flitter.
7. as any described high-gloss multilayer plastic container in claim 1～3 or 5, it is characterized in that the layer structure of multilayer plastic container is to have (1) transparent vinyl-vinyl alcohol copolymer resinoid skin, (2) transparent polyethylene class adhering resin layer, (3) successively from outside face one side to contain the pigmented polyethylene resinoid layer of flitter, the polythylene resin layer that (4) do not contain flitter.
8. as any described high-gloss multilayer plastic container in the claim 1～7, it is characterized in that multilayer plastic container further has the polyolefin resin internal layer.
9. as any described high-gloss multilayer plastic container in the claim 1～8, it is characterized in that the outer gross thickness with described (2) transparent adhering resin layer of described (1) transparent plastic resin is 30～200 μ m.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007325397 | 2007-12-18 | ||
| JP2007-325397 | 2007-12-18 | ||
| PCT/JP2008/072337 WO2009078311A1 (en) | 2007-12-18 | 2008-12-09 | High-gloss multilayered plastic container |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101903256A true CN101903256A (en) | 2010-12-01 |
| CN101903256B CN101903256B (en) | 2012-06-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801212715A Active CN101903256B (en) | 2007-12-18 | 2008-12-09 | High-gloss multilayered plastic container |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5428863B2 (en) |
| KR (1) | KR20100100804A (en) |
| CN (1) | CN101903256B (en) |
| WO (1) | WO2009078311A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110678328A (en) * | 2017-05-29 | 2020-01-10 | 东洋制罐株式会社 | Decorative multi-layer extrusion blow-molded bottle |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7260333B2 (en) * | 2019-02-28 | 2023-04-18 | メビウスパッケージング株式会社 | Direct blow multilayer container |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0538787A (en) * | 1991-08-07 | 1993-02-19 | Toyo Seikan Kaisha Ltd | Multilayer plastic vessel having excellent surface glossiness |
| JPH0639350A (en) * | 1992-07-24 | 1994-02-15 | Asahi Glass Co Ltd | Fluorine resin coated transportation equipment |
| JP2570082B2 (en) * | 1993-01-05 | 1997-01-08 | 東洋製罐株式会社 | Colored multilayer blow molded container |
| JPH06239350A (en) * | 1993-02-05 | 1994-08-30 | Toyo Seikan Kaisha Ltd | Plastic container having color-metallic appearance |
| JPH06305102A (en) * | 1993-04-28 | 1994-11-01 | Toppan Printing Co Ltd | Multilayer resin container |
| JP2985677B2 (en) * | 1994-09-09 | 1999-12-06 | 東洋製罐株式会社 | Colored liquid packaging |
-
2008
- 2008-12-09 WO PCT/JP2008/072337 patent/WO2009078311A1/en active Application Filing
- 2008-12-09 CN CN2008801212715A patent/CN101903256B/en active Active
- 2008-12-09 JP JP2009546227A patent/JP5428863B2/en active Active
- 2008-12-09 KR KR1020107010830A patent/KR20100100804A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110678328A (en) * | 2017-05-29 | 2020-01-10 | 东洋制罐株式会社 | Decorative multi-layer extrusion blow-molded bottle |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009078311A1 (en) | 2009-06-25 |
| CN101903256B (en) | 2012-06-20 |
| JPWO2009078311A1 (en) | 2011-04-28 |
| JP5428863B2 (en) | 2014-02-26 |
| KR20100100804A (en) | 2010-09-15 |
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