CN101475745A - Nano composite material and its production method - Google Patents
Nano composite material and its production method Download PDFInfo
- Publication number
- CN101475745A CN101475745A CNA2008101894985A CN200810189498A CN101475745A CN 101475745 A CN101475745 A CN 101475745A CN A2008101894985 A CNA2008101894985 A CN A2008101894985A CN 200810189498 A CN200810189498 A CN 200810189498A CN 101475745 A CN101475745 A CN 101475745A
- Authority
- CN
- China
- Prior art keywords
- composite material
- layered silicate
- nano composite
- nylon
- organising
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 55
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 50
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims abstract description 21
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims abstract description 21
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 15
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 11
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 9
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 46
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000010445 mica Substances 0.000 claims description 8
- 229910052618 mica group Inorganic materials 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical group O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910000271 hectorite Inorganic materials 0.000 claims description 4
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- 229910000273 nontronite Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 229910000275 saponite Inorganic materials 0.000 claims description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 230000004888 barrier function Effects 0.000 abstract description 31
- 229920000572 Nylon 6/12 Polymers 0.000 abstract description 2
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 2
- 229920001577 copolymer Polymers 0.000 abstract 1
- 229910052615 phyllosilicate Inorganic materials 0.000 abstract 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 abstract 1
- 229920005989 resin Polymers 0.000 description 28
- 239000011347 resin Substances 0.000 description 28
- 239000010410 layer Substances 0.000 description 25
- 239000011229 interlayer Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 239000004677 Nylon Substances 0.000 description 12
- 238000000071 blow moulding Methods 0.000 description 12
- 229920001778 nylon Polymers 0.000 description 12
- 238000010107 reaction injection moulding Methods 0.000 description 12
- 229920000139 polyethylene terephthalate Polymers 0.000 description 11
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 239000005020 polyethylene terephthalate Substances 0.000 description 11
- 238000005507 spraying Methods 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 230000035699 permeability Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 235000013361 beverage Nutrition 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000004927 fusion Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 244000269722 Thea sinensis Species 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000013405 beer Nutrition 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000002632 lipids Chemical class 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000004901 spalling Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000227653 Lycopersicon Species 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000019993 champagne Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical group O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 235000021577 malt beverage Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000003003 spiro group Chemical group 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 235000015193 tomato juice Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
- Wrappers (AREA)
Abstract
The invention relates to a nano composite material compound and a manufacturing method thereof, more specifically to a nano composite material compound used for manufacturing a multi-layer container having excellent durability, transparency, gas barrier property and strip resistance, and a manufacturing method thereof. The invention is characterized in (a) adding relative 10 parts by weight of mixture and 0.5-10 parts by weight of phyllosilicate organically treated into a mixture of 60wt%-99wt% of polyamide resin MXD6 containing metaxylol or MXDI containing metaxylol and m-phthalic acid, and 40wt%-1wt% of more than one of nylon 6, nylon66, nylon 6/12, 6I/6T and copolymers thereof.
Description
Technical field
The present invention relates to nano composite material and preparation method thereof, more specifically relate to nano composite material that is used to make laminated vessel and preparation method thereof with excellent durability, the transparency, gas barrier property, antistripping.
Background technology
The existing container of being made by the PET resin is owing to have good formability, the transparency, chemical resistance, thermotolerance, physical strength etc., so be widely used as the film of wrap food, beverage, medicine or container etc.But because the gas barrier property of described PET resin is limited, its as the application in field that gas barrier property is had relatively high expectations such as the beverage (coffee, tea) of tomato composition goods (tomato-sauce, tomato juice), juice (fruit juice and dish juice), alcohol soda pop (beer, malt beverage, champagne) and use heating container in be restricted.
One of scheme that solves described problem is the manufacturing laminated vessel.Promptly be manufactured on and form the laminated vessel of one deck barrier material in the thermoplastic polyester layer, with the maximization gas barrier property as the middle layer.
Day disclosure special permission bulletin discloses for clear 56-64839 number outer and internal layer is a pet layer, and the multilayered structure prefabricated component that the middle layer is made of the polyamide resin that contains the m-xylene base reaches the method by two-way stretch blow molding manufacturing laminated vessel.MXD6 nylon is owing to the fusing point of its fusing point near PET, by showing good formability with polyester combination.Again because the free temperature of two resins is close, so when draw blow molding, set the forming temperature that is fit to easily.
Although use the conventional choke resin (MXD6 that uses, Aegis) etc. the laminated vessel of making is more excellent than single-layer PET container gas barrier property, but because when it is used for described high-grade drink to gas sensitization (being beverages such as beer, coffee, tea), need to increase the content of the choke resin that uses, to strengthen the gas barrier property of laminated vessel, cause cost to increase, also can expedite the emergence of the problem of cycling and reutilization, and increase along with the barrier resins amount, cause amalgamation to reduce, thereby (MDX6, Aegis) antistripping with pet layer weakens to cause barrier resins.
Therefore, when the method for using described patent disclosure is made prefabricated component, the tackiness of polyester layer and aramid layer is relatively poor, the formation of prefabricated component is not in good state, cause the final laminated vessel weather resistance variation that is shaped, thereby take place separating of polyester layer and aramid layer, and the formability variation of laminated vessel.Moreover, because a little less than its barrier, thereby need to use a large amount of barrier materials to keep the gas barrier property of the beverage that gas barrier property is had relatively high expectations, so cost is higher.
Summary of the invention
The problem that the invention quasi-solution is determined
The present invention is intended to address the above problem, and it is low both to aim to provide in laminated vessel usage quantity, also can keep good gas barrier property, also is difficult for from what other layer peeled off being used to nano composite material for preparing barrier material and preparation method thereof.
The method of dealing with problems
The nano composite material with good antistripping that is used to make laminated vessel of the present invention is characterised in that, 60wt%-99wt% contained the polyamide resin MXD6 of m-xylene base or contain the m-xylene base and the MXDI of m-phthalic acid is selected from 40wt%-1wt% and adds the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
Another preferred feature of the present invention is, the described layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, maleate, succinate, acrylate, benzylic hydrogens and oxazoline more than one.
Another preferred feature of the present invention is, layered silicate is selected from montmorillonite, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
The method for preparing nano composite material of the present invention comprises: the MXDI and the 40wt%-1wt% that i) 60wt%-99wt% are contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid are selected from more than one blended mixtures dry 4-5 hour drying stage to water content 50-400ppm under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof; Ii) in the mixture of described drying, add the layered silicate through organising and handling of 0.5-10 weight part, make described mixture and layered silicate blended mix stages through organising and handling; And iii) use extruding machine described mixture and the layered silicate handled through organising to be made the preparatory phase of the nano composite material that contains layered silicate.
Another preferred feature of the present invention is that described water content is 50-200ppm.
Below describe the present invention in detail.
Nano composite material of the present invention is characterised in that, 60wt%-99wt% contained the polyamide resin MXD6 of m-xylene base or contain the m-xylene base and the MXDI of m-phthalic acid is selected from 40wt%-1wt% and adds the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
MXD6 is the polyamide resin that contains the m-xylene base, makes by metaxylylene diamine and lipid acid, since good to the gas barrier property of gases such as oxygen, carbonic acid gas, water vapour, be widely used in film for packaging and laminated vessel.Again because the MXD-6 resin shows the consistency good with vibrin, and its second-order transition temperature, fusing point, crystallization velocity be near polyester, therefore the resin for being suitable for being used in combination with vibrin.
MXDI is the polymer resin that contains m-xylene base and m-phthalic acid, makes MXD6 by MXDI and lipid acid that metaxylylene diamine and m-phthalic acid reaction generate.
Described MXD6 or MXDI are resins well known in the art, can prepare by means commonly known in the art or commercially available, and its weight percent is 60wt%-99wt%.If the content of MXD6 or MXDI surpasses 99wt% in the nano composite material, then uncontrollablely raise by the degree of crystallinity due to the organising of layered silicate, cause making that the degree of crystallinity in the IR heat-processed sharply raises in bottle industry, thereby reduce the weather resistance and the stability of the final container that is shaped.In contrast, if when the content of MXD6 or MXDI is lower than 60wt%, then since in the composition ratio of aromatics nylon reduce, cause gas barrier property sharply to reduce.
Through the layered silicate of handling that organises is thick 1nm, the clay of long 500-1000nm left and right sides nanometer scale.Layered silicate is because interlayer gravitation is strong, cause being difficult to it is peeled off, is scattered in macromolecule resin, for addressing this problem, it can be by organising between the laminate structure that the low-molecular-weight agent that organises is embedded silicate, thereby obtain the layered silicate handled through organising.Layered silicate has montmorillonite, hectorite, beidellite, saponite, nontronite, mica, fluoronated mica etc., preferred choosing wherein more than one; Organism is preferably the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, maleate, succinate, acrylate, benzylic hydrogens and oxazoline.
The described layered silicate of handling through organising can prepare by means commonly known in the art or be commercially available, and its weight percent is that the described mixture of relative 100 weight parts closes the 0.5-10 weight part.If the laminar silicic acid salts contg of handling through organising surpasses 10 weight parts of nano composite material, embedding formula thin layer between then the layered silicate of nanometer scale can not peel off and form in macromolecule resin, thereby cause transparency to descend by the degree of crystallinity rising, instead can not guarantee the gas barrier property of aspiration level.And if be lower than 1 weight part, then be difficult to obtain effect of the present invention.
Polymeric amide is meant the synthetic macromolecule that the monomer that constitutes its main chain is formed by connecting by amide group, will be called nylon by the polymeric amide that the unit is mainly aliphatic monomers that constitutes that amide group connects.
Nylon is divided into nylon mn and nylon m again, and the former is the situation that dicarboxylic acid and diamine reactant generate amide group, and wherein that diamines is contained carbonatoms is expressed as m, and the carbonatoms that dicarboxylic acid is contained is expressed as n.In addition, amide group also can be formed by the monomer that has amino and carboxyl concurrently, and be expressed as m with monomer institute carbon atom quantity this moment, and this kind polymeric amide is called nylon m.
By nylon 6 is made in the hexanolactam ring-opening polymerization.Prepare nylon 66 by polycondensation by cyclohexanediamine and lipid acid.By nylon 12 is made in the laurolactam ring-opening polymerization.Prepare 6I/6T by polycondensation by cyclohexanediamine, m-phthalic acid and terephthalic acid.Prepare multipolymer by the inferior nylon raw material more than 2 kinds, described multipolymer is owing to crystallinity reduces, thereby fusing point reduces, and the transparency raises.
The laminated vessel that comprises the interlayer that is made of described nano composite material of the present invention is characterised in that and comprises: (a) comprise the MXDI and the 40wt%-1wt% that 60wt%-99wt% are contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid and be selected from nylon 6, nylon 66, nylon 6/12, add in more than one blended mixtures in 6I/6T and the multipolymer thereof that relative 100 weight part mixtures close the layered silicate of handling through organising of 0.5-10 weight part and the interlayer of the nano composite material made; And (b) polyester resin layer more than one deck that the one or both sides of described interlayer form.
The laminated vessel that comprises the interlayer that contains described nano composite material of the present invention is characterised in that, is included in the above polyester resin layer of one deck of the one or both sides formation of described interlayer.
Vibrin is as the dicarboxylic acid composition with terephthalic acid, with ethylene glycol as the dihydroxyl composition, the resin of making by esterification (or transesterify), liquid polycondensation and solid-phase polymerization well known in the art, be selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate or its multipolymer more than one, be more preferably polyethylene terephthalate.
Described laminated vessel is to be the center with described interlayer, engages the form of polyester resin layer more than 1 layer at its one or both sides, preferably is the center respectively engages one deck vibrin on the two sides 3-tier architecture with the interlayer.
The method for preparing nano composite material of the present invention comprises:
I) MXDI and the 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid is selected from more than one blended mixtures dry 4-5 hour drying stage to water content 50-400ppm under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof;
Ii) in the mixture of described drying, add the layered silicate through organising and handling of 0.5-10 weight part, make described mixture and layered silicate blended mix stages through organising and handling; And
Iii) use extruding machine described mixture and the layered silicate handled through organising to be made the preparatory phase of the nano composite material that contains layered silicate.
In drying stage, if the water content of nylon composite is lower than 50ppm, then thermolysis takes place in nylon in extruding the course of processing; And if water content is higher than 400ppm, then extrudes and take place in the course of processing to cause preparing generation problem in the laminated nm-silicate composite material by the hydrolysis due to the water.
If dry nylon resin was less than 4 hours under 80-90 ℃ of condition, then can't reach the suitable water content about 50ppm, cause in extruding the course of processing, layered silicate appropriateness in macromolecule resin is peeled off with interlayer embed, also quicken thermolysis.In contrast, if dry above 5 hours under 80-90 ℃ of condition, the aging of nylon resin itself being taken place then, therefore will observe described drying conditions.
In mix stages, if the content of nano composite material surpasses 10 weight parts, embedding formula thin layer between then the layered silicate of nanometer scale can not peel off and form in macromolecule resin, thus cause transparency to reduce by the degree of crystallinity rising, instead can not guarantee the gas barrier property of aspiration level.And if be lower than 1 weight part, then be difficult to obtain effect of the present invention.
Extruding machine is a twin screw extruder machine, and L/D is greater than 35 (L: spiro rod length, D: screw diameter); For peeling off the layered silicate of nanometer scale, increase its dispersity between MXD6 and MXDI, need comprise kneading piece and the inverse block more than 2 more than 4.Also extruder rate to be set at more than the 300RPM, so that nano layered silicate that peels off and MXD6 or MXDI are fully mixing.
Set the temperature of extruding machine as table 1.With after nano layered silicate mixes in extruding machine, make extrudate pass through profiled sheeting MXD6 or MXDI, in tank, cool off again, and finally make nano composite material.
Table 1
The laminated vessel that comprises the interlayer that contains described nano composite material of the present invention is characterised in that, is included in the above polyester resin layer of one deck of the one or both sides formation of described interlayer.
Vibrin is as the dicarboxylic acid composition with terephthalic acid, with ethylene glycol as the dihydroxyl composition, the resin of making by esterification (or transesterify), liquid polycondensation and solid-phase polymerization well known in the art, be selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, Polyethylene Naphthalate or its multipolymer more than one, be more preferably polyethylene terephthalate.
Described laminated vessel is to be the center with described interlayer, engages the form of the above polyester resin layer of one deck at its one or both sides, preferably is the center respectively engages one deck vibrin on the two sides 3-tier architecture with the interlayer.
The manufacture method that comprises the laminated vessel of the interlayer that is made of nano composite material of the present invention is the method that comprises fusion, the injection of multilayer prefabricated component, multilayer prefabricated component reheat and the manufacturing laminated vessel in blow molding stage, comprising:
I) described nano composite material is maintained 50-400ppm in 80～90 ℃ of drying machine inner dryings 4-5 hour to water content before injection, more preferably maintain the pretreatment stage of the drying nano matrix material of 50-200ppm; And
Ii) in the course of processing of multilayer prefabricated component, with the injection temperature of 290-295 ℃ (polyester bucket) and 270-285 ℃ (nano composite material) the described resin of fusion separately, and respectively with the spraying pressure of 1300-1900psi (polyester) and 1000-1200psi (nano composite material) stage of reaction-injection moulding multilayer prefabricated component simultaneously.
Dewatered nano composite material and vibrin are transported to from drying machine in the funnel of injector, quantitatively supply in the reciprocating screw reaction-injection moulding device, after fusion plasticising, make its reaction-injection moulding in mould.Need certain hour owing to finish to spray, with the resin of residual a great deal of, absorb moisture again in the injector funnel, preferably it is incubated, more preferably it is incubated in more than 160 ℃ in more than 100 ℃ for preventing it.And the interior temperature of injector funnel that will deliver nano composite material is controlled at more than 70 ℃, thereby prevents to be raise by the degree of crystallinity due to the moisture.
If the water content of nano composite material is lower than 50ppm, then in the melting process of the basal component MXD6 of nano composite material, take place by the loss due to the friction, if and water content is increased to 400ppm when above, moisture in the nano composite material plays the effect of crystallization nucleating agent, make the prefabricated component excessive crystallization of reaction-injection moulding, peel off when causing blow molding.
If the temperature of bucket is too high when reaction-injection moulding, then take place spraying the back prefabricated component, to cool off incomplete possibility higher, increase the crystallinity of prefabricated component, thereby expedite the emergence of the problem of peeling off after the blow molding, if the temperature of bucket is low excessively, then appropriately fusion of macromolecule resin is sheared viscous thereby over-drastic takes place, and causes carrying out continuous injection and is shaped.
Besides spraying pressure if the spraying pressure of PET is lower than 1300psi, then can not form the prefabricated component of target weight and model, and " short penetrating " phenomenon promptly takes place; And if spraying pressure is higher than 1900psi, then, causes spraying and compare the more PET of volume of jet particle size, thereby cause " bar " quality problems such as (bar) because spraying pressure is excessive.The position of prefabricated component internal portioning layer and the speed decision of thickness by the interlayer of relative pet layer.Thus, when the spraying pressure of interlayer is excessive or too small, be difficult to appropriately regulate obstruct speed, thereby be difficult to the position of interlayer from being adjusted to below the support of prefabricated component below the joint line of bottom.
The present invention has used Kostec48 die cavity multiple nozzle spraying former (Fig. 2).The multiple nozzle spraying device be utilize 2 screw rods with 2 kinds of polyester and as the nano composite material of barrier resins simultaneously with the open intravital shaping system in described chamber that is ejected into, it uses following reaction-injection moulding condition to make the preformed articles prefabricated component.As shown in Figure 2, prefabricated component is the structure that comprises between polyester outer layer as the internal layer of the nano composite material of barrier material.Table 2 has been listed the reaction-injection moulding condition of multiple nozzle spraying former.
Table 2
Use prefabricated component heating unit shown in Figure 3 to reach 104 ℃ with heater heats to the temperature of multilayer prefabricated component according to the prefabricated component of above-mentioned condition reaction-injection moulding, through the 1st pressure 9bar, the condition of the 2nd pressure 40bar is carried out draw blow molding.The stretch ratio of keeping transverse axis is more than 2 times, and the stretch ratio of the longitudinal axis is more than 4 times.
The invention effect
The laminated vessel that contains nano composite material of the present invention is compared the laminated vessel that uses existing known barrier resins to make, and gas barrier property and antistripping improve, thereby have good weather resistance and morphological stability.In addition,, therefore do not expedite the emergence of the problem of cycling and reutilization yet, and have the competitive power on the price, and have the advantage that to use existing injection/blowing processing units etc. owing to can reduce the usage quantity of barrier resins.Therefore applicable to the beer container of dissolving carbonic acid, require the coffee of hotness, the heating container of tea, the container of oxygen beverage etc.
The accompanying drawing summary
Fig. 1 is shown the cyclogenic ultrathin section(ing) photo of dispersiveness of the nano silicate of the shaping print that affirmation obtains by embodiments of the invention and Comparative Examples;
Fig. 2 shows the mode chart of Kortec 48 die cavity multilayer spray devices;
Fig. 3 shows the mode chart of prefabricated component heating unit.
The embodiment of invention
Followingly be described in more detail formation of the present invention and effect, but these embodiment only understand the present invention auxiliary more definite, are not to be intended to limit scope of the present invention according to specific embodiment and Comparative Examples.
Embodiment
The degree of scatter of the layered silicate of following evaluation nano composite material prepared in accordance with the present invention and laminated vessel and weather resistance (spalling improvement), gas barrier property.
1) to the evaluation of the dispersiveness of the nano material of nano composite material
Use the cyclogenic ultrathin sectioning will make the print of 30 μ m sizes, and use the nano silicate dispersion of particles degree in the FE-TEM mensuration MXD6 resinous substrates through the nano composite material resin that extrudes processing.
2) to the crystalline evaluation of prefabricated component interlayer
The prefabricated component of reaction-injection moulding bottom is cut off, utilize X ray to estimate degree of crystallinity after obtaining the print of interlayer according to crystallite size and intermolecular distance.
3) DSC of mensuration prefabricated component interlayer
Estimate crystallization according to the fusing point Tm that uses differential scanning calorimeter detected maximum value definition by the absorption peak due to the crystallization dissolving in process with from the difference of molten state crystallized temperature Tc2 of detected maximum value definition by the emission peak due to the crystallization with 10 ℃/minute cooling rate refrigerative process with 20 heat-up rate heating.
4) to the evaluation of prefabricated component interlayer mist degree
To cut off through the prefabricated component of reaction-injection moulding bottom, obtain the mist degree of measuring print behind the print of interlayer.
5) weigh down the bottle experiment
After will highly falling from 50cm through the laminated vessel of blow molding, detect laminated vessel and whether peel off.
6) detect the oxygen permeability
To place device (the Mocon company that measures the oxygen permeability through the laminated vessel of blow molding, OX-TRAN 2/20) go up after, at 23 ℃, stablize 24 hours with nitrogen under the temperature of 50RH% after, measure the oxygen permeability when the oxygen transit dose reaches equilibrium state.
7) permeability of detection carbonic acid gas
To place device (the Mocon company that measures the carbonic acid gas permeability through the laminated vessel of blow molding, PermatranC 4/41) go up after, use plastic lousing at outside 100% carbon dioxide atmosphere that forms of laminated vessel, and at 23 ℃, stablize laminated vessel after inner 24 hours with nitrogen under the temperature of 50RH%, measure the carbonic acid gas permeability when the carbonic acid gas of multilayer external container sees through internal tank and reaches equilibrium state.
Embodiment and Comparative Examples
Polyamide resin 90 ℃ of dryings after 4 hours, is joined the polymeric amide and the layered silicate of the amount of kind as shown in table 3 in the agitator, stir with the speed of 50rpm, to be carried out pre-treatment by nano layered silicate at the polyamide surface bag.With the resin L/D of preparation is 35 delivery screw rod, under 245 ℃ of temperature condition, processes with the extruder rate shown in the table 3, makes extrudate pass through profiled sheeting, cools off in tank again, finally makes nano composite material.
Selected intrinsic viscosity is that the polyethylene terephthalate of 0.8dl/g is following dry 4 hours in 160 ℃, the nano composite material resin of the ratio of components shown in the dry following table uses the described dry resin of crossing so that the content of nano composite material reaches 7% reaction-injection moulding multilayer prefabricated component.
Make the surface temperature of multilayer prefabricated component reach 104 ℃ with heater heats, with the 1st pressure 9bar, the condition draw blow molding of the 2nd pressure 40bar.
Table 3
Shown that layered silicate flakes off into the nano composite material phase, thereby be scattered in the state (embodiment) in the MXD6 resinous substrates; Layered silicate is not dispersed in the Comparative Examples 3 in the polymer, because when using nano composite material shaping multilayer bottle, gas barrier property synergy is very little, and layered silicate plays the effect of crystallization nucleating agent, thereby becomes the reason that the multilayer bottle peels off.
Table 4. crystal analysis/DSC/ mist degree
Annotate:
C.S
The crystallite size of nanometer composite layer, degree of crystallinity are high more, and this value is big more.
D002
Distance between the molecular chain of nanometer composite layer, orientation degree (degree of crystallinity) is high more, and this value is big more.
Tm-Tc2: because in the general reaction-injection moulding process, temperature head is more little, crystallization velocity is fast more, thereby owing to forms crystallization, degree of crystallinity height easily.
As above shown in the table, along with the difference of Tm-Tc2 reduces the tensility variation during blow molding, thereby the spalling variation of container after the blow molding.
The present invention confirms, when the exploitation nano composite material, and time of drying and temperature condition that can be by regulating barrier material and regulate injection conditions and improve the problem (weakness of laminated vessel) of peeling off, thereby the weather resistance of improvement container.
Table 5 Gas permeability/antistripping
| Oxygen-barrier property (cc/pack.day) | Carbonic acid gas barrier (cc/pack.day) | The experiment (peel off/all sample) of falling | |
| Embodiment 1 | 0.0045 | 0.432 | 0/5 |
| Embodiment 2 | 0.0051 | 0.466 | 1/5 |
| Embodiment 3 | 0.0046 | 0.421 | 0/5 |
| Embodiment 4 | 0.0049 | 0.443 | 0/5 |
| Embodiment 5 | 0.0044 | 0.423 | 1/5 |
| Embodiment 6 | 0.0043 | 0.453 | 0/5 |
| Comparative Examples 1 | 0.0061 | 0.782 | 0/5 |
| Comparative Examples 2 | 0.0070 | 0.912 | 4/5 |
| Comparative Examples 3 | 0.0066 | 0.872 | 3/5 |
| Comparative Examples 4 | 0.0075 | 0.977 | 1/5 |
Although Comparative Examples 1 has good antistripping, gas barrier property is not good.The container that can have good antistripping and gas barrier property according to the formation manufacturing of described exploitation.
Claims (7)
1. be used to make the nano composite material of the good antistripping of having of laminated vessel, it is characterized in that, 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contain the m-xylene base and the MXDI of m-phthalic acid and 40wt%-1wt% are selected from and add the layered silicate through organising and handling that relative 100 weight part mixtures close the 0.5-10 weight part in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof in more than one blended mixtures.
2. the nano composite material that is used to make the good antistripping of having of laminated vessel of claim 1, it is characterized in that, the described layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, maleate, succinate, acrylate, benzylic hydrogens and oxazoline more than one.
3. the nano composite material that is used to make the good antistripping of having of laminated vessel of claim 2, it is characterized in that layered silicate is selected from montmorillonite, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
4. the method for preparing nano composite material is characterized in that comprising:
(i) MXDI and the 40wt%-1wt% that 60wt%-99wt% is contained the polyamide resin MXD6 of m-xylene base or contain m-xylene base and m-phthalic acid is selected from more than one blended mixtures dry 4-5 hour drying stage to water content 50-400ppm under 80-90 ℃ of condition in nylon 6, nylon 66, nylon 6/12,6I/6T and the multipolymer thereof;
(ii) in the mixture of described drying, add the layered silicate through organising and handling of 0.5-10 weight part, make described mixture and layered silicate blended mix stages through organising and handling; And
(iii) use extruding machine described mixture and the layered silicate handled through organising to be made the preparatory phase of the nano composite material that contains layered silicate.
5. the preparation of claim 4 is used to make the method for the nano composite material of the good antistripping of having of laminated vessel, it is characterized in that, the described layered silicate of handling through organising is that organism is embedded layered silicate, and wherein said organism is selected from the organism that contains the functional group that is selected from quaternary ammonium salt, monovalence phosphorus, maleate, succinate, acrylate, benzylic hydrogens and oxazoline more than one.
6. the preparation of claim 5 is used to make the method for the nano composite material of the good antistripping of having of laminated vessel, it is characterized in that layered silicate is selected from montmorillonite, hectorite, beidellite, saponite, nontronite, mica, the fluoronated mica more than one.
7. the preparation of claim 4 is used to make the method for the nano composite material of the good antistripping of having of laminated vessel, it is characterized in that described water content is 50-200ppm.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-141621 | 2007-12-31 | ||
| KR1020070141621A KR100885617B1 (en) | 2007-12-31 | 2007-12-31 | Manufacturing method of nanocomposite for multi layer container having excellent resistance against exfoliation |
| KR102007141621 | 2007-12-31 | ||
| KR1020070141594A KR100896401B1 (en) | 2007-12-31 | 2007-12-31 | Nanocomposite for multi layer container having excellent resistance against exfoliation |
| KR102007141594 | 2007-12-31 | ||
| KR10-2007-141594 | 2007-12-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101475745A true CN101475745A (en) | 2009-07-08 |
| CN101475745B CN101475745B (en) | 2012-02-29 |
Family
ID=40836526
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008101894985A Active CN101475745B (en) | 2007-12-31 | 2008-12-29 | Nano composite material synthetic compound and its production method |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR100896401B1 (en) |
| CN (1) | CN101475745B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589351A (en) * | 2015-10-14 | 2017-04-26 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic transparent nylon material PA6I and preparing method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023506A1 (en) | 1998-10-16 | 2000-04-27 | Wolff Walsrode Aktiengesellschaft | Transparent high strength polyamide film |
| WO2003064503A1 (en) * | 2002-01-30 | 2003-08-07 | Ems-Chemie Ag | Method for the production of polyamide nanocomposites, corresponding packaging materials and moulded bodies |
| JP2005067637A (en) * | 2003-08-21 | 2005-03-17 | Mitsubishi Gas Chem Co Inc | Hollow container |
| KR100671666B1 (en) * | 2004-12-30 | 2007-01-19 | 주식회사 효성 | The method of manufacturing a preform for multi-layered plastic bottle |
| CN1865349B (en) * | 2006-05-08 | 2010-05-12 | 陶光 | Polyamide polymerization or co polymerization / clay nano composite materials and process for preparing same |
-
2007
- 2007-12-31 KR KR1020070141594A patent/KR100896401B1/en active IP Right Grant
-
2008
- 2008-12-29 CN CN2008101894985A patent/CN101475745B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106589351A (en) * | 2015-10-14 | 2017-04-26 | 上海杰事杰新材料(集团)股份有限公司 | Semi-aromatic transparent nylon material PA6I and preparing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101475745B (en) | 2012-02-29 |
| KR100896401B1 (en) | 2009-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2402396B1 (en) | Oxygen scavenging plastic material | |
| CN100513137C (en) | Multi-layered biaxial stretch blow molded bottle and method for production thereof | |
| CA2466451C (en) | Multilayer container | |
| US20050009976A1 (en) | Delamination-resistant, barrier polyamide compositions for 3-layer pet beverage bottles | |
| EP1974901B1 (en) | Multi-layer bottle | |
| EP2505354B1 (en) | Multi-layered bottle | |
| TWI571485B (en) | Oxygen scavenging plastic material | |
| JP7327388B2 (en) | Multi-layer bodies and multi-layer containers | |
| JP5315599B2 (en) | Resin composition and multilayer structure | |
| JP4720102B2 (en) | Multi-layer container | |
| CN101475745B (en) | Nano composite material synthetic compound and its production method | |
| CN101474892A (en) | Multi-layer container containing nano composite material and its production method | |
| US20040214981A1 (en) | Methods for making polyethylene terephthalate (pet) preforms and containers such as food bottles, containers and intermediate preforms obtained | |
| JP2004338163A (en) | Multilayered container improved in delamination | |
| JP2017508849A (en) | Oxygen scavenging composition for plastic materials | |
| EP1889704B1 (en) | Dry blend having oxygen-scavenging properties, and the use thereof for making a monolayer packaging article | |
| KR100885617B1 (en) | Manufacturing method of nanocomposite for multi layer container having excellent resistance against exfoliation | |
| RU2412095C2 (en) | Method of producing multilayer container containing nanocomposite material | |
| JPS6279258A (en) | Polyester bottle and production thereof | |
| RU2430939C2 (en) | Nanocomposite and production method thereof | |
| JPH03175032A (en) | Coinjection multi-layered construction | |
| JP2004351716A (en) | Multi-layer device | |
| JP2004323053A (en) | Multi-layered container improved in delamination | |
| KR20090073721A (en) | Manufacturing method of multi layer container comprising nanocomposition having excellent resistance against exfoliation | |
| KR20090021521A (en) | Manufacturing method for preform for multi-layered bottle having excellent transparency and gas barrier properties |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: ASEPSYS GLOBAL CORP. Free format text: FORMER OWNER: HYOSUNG CORP. Effective date: 20150127 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20150127 Address after: Seoul, South Kerean Patentee after: (strain) ASEPSYS Global Address before: Gyeonggi Do city Dongan District South Korea Anyang hogye Dong 183-2 Patentee before: Hyosung Corp. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161227 Address after: Seoul, South Kerean Patentee after: Miyaki packaging company Address before: Seoul, South Kerean Patentee before: (strain) ASEPSYS Global |