WO1990012061A1 - Gas-sealed material - Google Patents
Gas-sealed material Download PDFInfo
- Publication number
- WO1990012061A1 WO1990012061A1 PCT/FI1990/000105 FI9000105W WO9012061A1 WO 1990012061 A1 WO1990012061 A1 WO 1990012061A1 FI 9000105 W FI9000105 W FI 9000105W WO 9012061 A1 WO9012061 A1 WO 9012061A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gas
- polyolefin
- acid
- sealed material
- ethylene
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention concerns a gas-sealed material and products 5 containing gas-sealed material.
- the present invention concerns a gas-sealed material containing polyolefine and polyvinyl alcohol, and products containing the same.
- Polyolefins are widely used, for instance, in packaging industry for -JQ manufacturing various film products. Advantages of polyolefins are in particular appropriate strength and water resistance properties. Among the drawbacks may be mentioned permeability to certain gases and liquids, concerning particularly oxygen and hydrocarbon dis ⁇ solvents. Therefore, the usability of polyolefin films is limited to -
- multiple layer structures may contain layers which form a good barrier against gases, such as oxygen, and layers which provide other properties for the product, such as strength properties.
- multiple layer structures may contain other layers which generate for instance adhesion between
- Polyvinyl alcohol is one of such polymers which has a low oxygen permeability property. Said property has most often been utilized in
- polyolefin-PVA-mixtures are provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen
- the object of the present invention is a polyvinyl alcohol containing polyolefin, in which the moisture sensitivity of the product to oxygen sealing is reduced, the lightness of the product has increased, and the migration of the plasticizers has lessened.
- the invention concerns a gas-sealed material containing polyolefin and polyvinyl alcohol.
- the gas-sealed material of the invention is characterized in that it is produced by mixing 1 to 99 per cent by weight of polyolefin and 99 to 1 per cent by weight of
- the term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains polyglycol groups (polyether
- plasticizer groups are connected into a chain by copolymerizing, branching or by means of reactive compounding.
- Vinex polymer trade name, Air Products and Chemicals Inc.
- 5 is used an ester of methacrylic acid and polyethylene glycol.
- Said internally plasticized vinyl alcohol polymers may be manu ⁇ factured, for instance in the manner as disclosed in the US. patent No. 4,708,999.
- Said patent presents that the product is provided 20 with good oxygen sealing and that it Is appropriate for cast, injection moulding and extrusion products, and that it is characterized by good water solubility and therefore, it is particu ⁇ larly well appropriate for manufacturing films which are required to possess water solubility.
- the vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol mixture of the invention is advantageously such in which in the poly(alkyleneoxy)ester derivative for use as a comonomer the alkylene of the alcohol component is ethylene or propylene, and the acid 30 component is acrylic acid or methacrylic acid.
- Said modified vinyl alcohol polymers may be manufactured, for instance, by polymerizing vinyl acetate monomer and poly(alkyleneoxy)acrylate comonomer, and hydrolyzing the copolymer thus obtained in order to produce an in ⁇ ternally plasticized vinyl alcohol polymer.
- the amount of the internally plasticized vinyl alcohol polymer in the polyethylene-polyvinyl alcohol mixture of the invention may be 1 in the range of from 1 to 99 per cent by weight, preferably in the range of from 10 to 90 per cent by weight. In smaller quantities, the effect on oxygen permeability is, however, smaller, while the colour of the product may, nevertheless, be maintained good. In some
- 0 may be based on homopolymers or copolymers of the olefins. There ⁇ fore, it may be low density polyethylene (LDPE) , medium density polyethylene or high density polyethylene (HDPE) , polypropylene or polybutene.
- the polyolefin may also be a copolymer of ethylene to ⁇ gether with other olefins, such as propylene, butene, hexene and -j5 octene.
- the polyolefin may also be an olefin-ester copolymer, such as ethylene-vinyl acetate copolymer, ethylene-acrylate-ester copolymer or ethylene-methacrylate ester copolymer, or it may be a thermoplastic olefin-based elastomer, such as EP or EPD rubber.
- an olefin-ester copolymer such as ethylene-vinyl acetate copolymer, ethylene-acrylate-ester copolymer or ethylene-methacrylate ester copolymer
- thermoplastic olefin-based elastomer such as EP or EPD rubber.
- the polyolefin in the process according to the invention may also be a homopolymer or a copolymer of the above-mentioned olefins which has been modified with the aid of carboxylic acid.
- a modified olefin polymer is copolymerized or grafted 0.1 to 10 per cent by weight of carboxylic acid.
- the carboxylic acid may comprise any
- the polyolefin grafted or copolymer ⁇ ized with carboxylic acid may also be a mixture containing a poly ⁇ olefin modified in the manner described above, and un unmodified polyolefin.
- the quantity of the polyolefin in the gas-sealed material of the invention may be in the range from 1 to 99 per cent by weight, but preferably in the range from 10 to 90 per cent by weight of the quantity of the entire mixture.
- the gas-sealed material of the invention may further contain 1 to 15 per cent by weight of plasticizers.
- a plasticizer may be selected from any material used for polyvinyl alcohol plasticizer or a mixture thereof. As examples of such may be mentioned ethylene glycol, tri- methylene glycol, propylene glycol, triethylene glycol, neopenthyl glycol and 2,2,4-trimethyl-l,3-pentane diol and sorbitol.
- a preferable plasticizer is glycerol.
- the gas-sealed polyolefin/PVA mixture of the invention may be manu ⁇ factured mixing the polyolefin component, the vinyl alcohol/polymer component and a potential plasticizer component in a melt mixer simultaneously as a dry mixture, premixed in solid or molten state, or then various components are added separately.
- the addition of plasticizers may also be carried out after the compounding. Also such procedure may be adopted in which a plasticizer is added in the PVA component, whereby the advantage is gained that the entire mixture need not be plasticized.
- polyolefin/PVA mixture of the invention various products may be prepared by combining the mixture with polyolefins, other plastics or other materials, such as fibre-based materials.
- Multiple layer products may be manufactured by coextrusion, (co)extrusion coating, (co)extrusion lamination, adhesion lamination, or using other techniques, and these production procedures may also be com ⁇ bined.
- a gas-sealed material of the invention e.g. films, moulded-blown bottles and containers, plates, tubes, injection moulded vessels, deep-drawn films and plates, liquid packaging card ⁇ boards, etc.
- Sealed multiple-layer products are generally used for packaging food stuffs, when oxygen sealing is desired also in moist circumstances, but the sealing of carbon dioxide or some other gas may be thought of.
- fat, chemical and odour sealing may be desired both in food stuff packages and technical products.
- the oxygen permeability of the films was measured with an OX-TRAN 1000 apparatus (ASTM D 3985) .
- the polyolefins and the vinyl alcohol polymers used in the tests of the examples are presented in the table below.
- P01 LDPE (low density polyethylene), density 922 kg/m 3 , molten index (MI) 1.8 g/min (190°C)
- P02 PP (propylene block copolymer), MI 3.3 g/10 min
- P03 PB (polybutene), MI 1.4 g/10 min (190°C)
- P04 EVA (ethylene-vinyl acetate copolymer), vinyl acetate content 5%
- P05 EBA (ethylene-butyl acrylate copolymer), MI 1.0 g/10 min (190°C) , butyl acrylate content 7%
- P06 LLDPE (linear low density polyethylene) , grafted with 0.25% maleic acid anhydride (MHA) , MI 0.5 g/10 min (190°C) P07 - PP (propylene block copolymer), MI 3.3 g/10 min
- P010 - PB P05
- grafted with 0.25% itaconic acid P011 - EVA (ethylene-vinyl acetate copolymer) vinyl acetate content 5%
- P012 EVA (P07)
- grafted with 0.1% fumaric acid P013 - EBA (ethylene-butyl acrylate copolymer), MI 1.0 g/10 min (190°C)
- butyl acrylate content 7% P014 - EBA P09
- grafted with 0.4 % acrylic acid P015 - EEA ethylene-acrylic acid copolymer
- PVAl - vinyl alcohol copolymer wherein the comonomer is an ester of methacryl acid and polyethylene glycol (Vinex 4004, Air Products and Chemicals)
- Polyolefin-PVA mixtures of the invention were prepared by mixing polyolefin and polyvinyl alcohol in molten state by the aid of a Berstorff mixer which was provided with a flat film nozzle.
- the temperature profile was 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 220 to 220, and the temperature of the melt was 220°C.
- the production rate was 10 kilograms per hour.
- the thicknesses of the obtained films were 100 to 170 ⁇ m.
- the com ⁇ pounds thereof are presented in the accompanying Table 1 A.
- the properties of the films are presented in the accompanying Table 1 B.
- the oxygen permeability values of the films are calculated for 25 ⁇ m thickness.
- the lightnesses of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
- Plasticizer type % by weight type, % by w.
- Polyolefin-PVA mixtures were prepared in which various polyolefins and polyvinyl alcohol (Vinex) were used in molten state, by the aid of a Berstorff mixer which was provided with a flat film nozzle.
- the temperature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 220 to 220 and the temperature of the melt was 220°C.
- the production rate was 10 kilograms per hour.
- the thicknesses of the obtained films were 120 to 160 urn.
- the com ⁇ pounds thereof are presented in the accompanying Table 2 A.
- the properties of the films are presented in the accompanying Table 2 B.
- Polyolefin-PVA mixtures of the invention were prepared by mixing polyolefin and polyvinyl alcohol, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
- the temperature profile was 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 220 to 220, and the temperature of the melt was 220°C.
- the production rate was 10 kilograms per hour.
- the thicknesses of the obtained films were 100 to 260 ⁇ m.
- the com- pounds thereof are presented in the accompanying Table 3 A.
- the properties of the films are presented in the accompanying Table 3 B.
- the oxygen permeability values of the films are calculated for 25 ⁇ m thickness.
- the lightness of the films was measured as a so-called yellowness index conforming to the standard ASTM D 1925-70 with the Ultra Scan apparatus of Hunter Lab.
- the polyvinyl does not contain a plasticizer
- polyolefin-PVA mixtures in which poly ⁇ olefin unmodified with an acid or modified with an acid, and ordinary unmodified polyvinyl alcohol were used (except test 12) , in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
- the temperature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 230 to 220 to 220, and the temperature of the melt was 220°C.
- the production rate was 10 kilo ⁇ grams per hour.
- the thicknesses of the obtained films were 130 to 230 ⁇ m.
- the com ⁇ pounds thereof are presented in the accompanying Table 4 A.
- the properties of the films are presented in the accompanying Table 4 B.
- the polyvinyl alcohol does not contain plasticizer the quantity of polyvinyl alcohol contains 6% by weight of a plasticizer, calculated by PVA quantity TABLE 4 B
- Polyolefin/PVA mixtures were prepared in which various polyolefins modified with an acid and internally plasticized polyvinyl alcohol polymer of the invention, or ordinary polyvinyl alcohol were used, in molten state, with the aid of a Berstorff mixer, which was provided with a flat film nozzle.
- the temperature profile was from 25 to 130 to 200 to 200 to 200 to 210 to 230 to 230 to 220 to 220, and the temperature of the melt was 220°C.
- the production rate was 10 kilograms per hour.
- the thicknesses of the obtained films were 120 to 260 ⁇ m.
- the com ⁇ pounds thereof are presented in the accompanying Table 5 A.
- the properties of the films are presented in the accompanying Table 5 B. TABLE 5 A
Abstract
Description
Claims
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI891753 | 1989-04-13 | ||
FI891753A FI86871C (en) | 1989-04-13 | 1989-04-13 | Gas-sealed material containing internally plasticized polyvinyl alcohol |
FI891752A FI86870C (en) | 1989-04-13 | 1989-04-13 | GASTAETT MATERIAL, SOM INNEHAOLLER INVAENDIGT MJUKGJORD POLYVINYLALCOOL |
FI891752 | 1989-04-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1990012061A1 true WO1990012061A1 (en) | 1990-10-18 |
Family
ID=26158537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FI1990/000105 WO1990012061A1 (en) | 1989-04-13 | 1990-04-11 | Gas-sealed material |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0423271A1 (en) |
JP (1) | JPH04500536A (en) |
AU (1) | AU627870B2 (en) |
CA (1) | CA2032121A1 (en) |
WO (1) | WO1990012061A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0832928A2 (en) * | 1996-09-30 | 1998-04-01 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
WO1999054400A1 (en) * | 1998-04-20 | 1999-10-28 | Kwang Myung Pharm. Ind. Co., Ltd. | Compositions of polyolefin and polyvinyl alcohol, and films, sheets and articles processed therefrom and multilayer products using the same |
WO2002024806A1 (en) * | 2000-09-20 | 2002-03-28 | Kuraray Specialtities Europe Gmbh | Plastic composition, method for producing the same and the use thereof, especially as barrier medium |
US20090286906A1 (en) * | 2008-05-14 | 2009-11-19 | Kimberly-Clark Worldwide, Inc. | Water-Sensitive Film Containing an Olefinic Elastomer |
CN107141672A (en) * | 2017-07-06 | 2017-09-08 | 华东理工大学 | A kind of high barrier composition and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975463A (en) * | 1971-06-18 | 1976-08-17 | Toyo Seikan Kaisha Limited | Molded structures containing crystalling polyolefin saponified ethylene vinyl acetate copolymer and carbonyl containing copolymers |
EP0015556A1 (en) * | 1979-03-06 | 1980-09-17 | E.I. Du Pont De Nemours And Company | Laminar articles of polyolefin and a second polymer and process for making them |
EP0152180A2 (en) * | 1984-02-08 | 1985-08-21 | QUANTUM CHEMICAL CORPORATION (a Virginia corp.) | Polyvinyl alcohol alloys |
EP0177762A2 (en) * | 1984-09-06 | 1986-04-16 | Kuraray Co., Ltd. | A resinous composition, molded articles and containers made thereof and its use |
EP0247326A2 (en) * | 1986-03-31 | 1987-12-02 | Kuraray Co., Ltd. | Resin compositions, laminates and block copolymers as components thereof |
EP0255733A2 (en) * | 1986-08-08 | 1988-02-10 | Air Products And Chemicals, Inc. | Copolymers of vinyl acetate and poly(alkyleneoxy) acrylates |
EP0275900A2 (en) * | 1987-01-16 | 1988-07-27 | Air Products And Chemicals, Inc. | Copolymers of vinyl acetate and acrylates |
EP0280455A2 (en) * | 1987-02-25 | 1988-08-31 | Du Pont Canada Inc. | Process for the injection moulding of articles having barrier properties |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3945463A (en) * | 1974-07-27 | 1976-03-23 | Yamaha Hatsudoki Kabushiki Kaisha | Lubrication system for motorcycles |
-
1990
- 1990-04-11 WO PCT/FI1990/000105 patent/WO1990012061A1/en not_active Application Discontinuation
- 1990-04-11 CA CA002032121A patent/CA2032121A1/en not_active Abandoned
- 1990-04-11 AU AU54037/90A patent/AU627870B2/en not_active Ceased
- 1990-04-11 JP JP50563290A patent/JPH04500536A/en active Pending
- 1990-04-11 EP EP19900905546 patent/EP0423271A1/en not_active Withdrawn
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975463A (en) * | 1971-06-18 | 1976-08-17 | Toyo Seikan Kaisha Limited | Molded structures containing crystalling polyolefin saponified ethylene vinyl acetate copolymer and carbonyl containing copolymers |
EP0015556A1 (en) * | 1979-03-06 | 1980-09-17 | E.I. Du Pont De Nemours And Company | Laminar articles of polyolefin and a second polymer and process for making them |
EP0152180A2 (en) * | 1984-02-08 | 1985-08-21 | QUANTUM CHEMICAL CORPORATION (a Virginia corp.) | Polyvinyl alcohol alloys |
EP0177762A2 (en) * | 1984-09-06 | 1986-04-16 | Kuraray Co., Ltd. | A resinous composition, molded articles and containers made thereof and its use |
EP0247326A2 (en) * | 1986-03-31 | 1987-12-02 | Kuraray Co., Ltd. | Resin compositions, laminates and block copolymers as components thereof |
EP0255733A2 (en) * | 1986-08-08 | 1988-02-10 | Air Products And Chemicals, Inc. | Copolymers of vinyl acetate and poly(alkyleneoxy) acrylates |
EP0275900A2 (en) * | 1987-01-16 | 1988-07-27 | Air Products And Chemicals, Inc. | Copolymers of vinyl acetate and acrylates |
EP0280455A2 (en) * | 1987-02-25 | 1988-08-31 | Du Pont Canada Inc. | Process for the injection moulding of articles having barrier properties |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0832928A2 (en) * | 1996-09-30 | 1998-04-01 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
EP0832928A3 (en) * | 1996-09-30 | 1998-12-09 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
US5972447A (en) * | 1996-09-30 | 1999-10-26 | Kuraray Co., Ltd. | Thermoformable multilayer film and thermoformed container |
WO1999054400A1 (en) * | 1998-04-20 | 1999-10-28 | Kwang Myung Pharm. Ind. Co., Ltd. | Compositions of polyolefin and polyvinyl alcohol, and films, sheets and articles processed therefrom and multilayer products using the same |
US6544661B1 (en) | 1998-04-20 | 2003-04-08 | Dong Kweon Lee | Compositions of polyolefin and polyvinyl alcohol, and films, sheets and articles processed therefrom and multilayer products using the same |
WO2002024806A1 (en) * | 2000-09-20 | 2002-03-28 | Kuraray Specialtities Europe Gmbh | Plastic composition, method for producing the same and the use thereof, especially as barrier medium |
US20090286906A1 (en) * | 2008-05-14 | 2009-11-19 | Kimberly-Clark Worldwide, Inc. | Water-Sensitive Film Containing an Olefinic Elastomer |
EP2276800A2 (en) * | 2008-05-14 | 2011-01-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
EP2276800A4 (en) * | 2008-05-14 | 2011-04-20 | Kimberly Clark Co | Water-sensitive film containing an olefinic elastomer |
US8338508B2 (en) * | 2008-05-14 | 2012-12-25 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
AU2009247714B2 (en) * | 2008-05-14 | 2013-09-26 | Kimberly-Clark Worldwide, Inc. | Water-sensitive film containing an olefinic elastomer |
CN107141672A (en) * | 2017-07-06 | 2017-09-08 | 华东理工大学 | A kind of high barrier composition and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
JPH04500536A (en) | 1992-01-30 |
AU5403790A (en) | 1990-11-05 |
EP0423271A1 (en) | 1991-04-24 |
CA2032121A1 (en) | 1991-10-12 |
AU627870B2 (en) | 1992-09-03 |
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