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
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
  • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
• • 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
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/06—Polyethene
• • 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
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
  • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L23/04—Homopolymers or copolymers of ethene
  • C08L23/08—Copolymers of ethene
  • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
  • C08L23/0869—Acids or derivatives thereof

Definitions

• the present invention concerns a gas-sealed material and products containing gas-sealed material.
• the invention concerns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide, and products containing the same.
• Polyolefins are widely used, for instance, in packaging industry in 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 dissolvents. Therefore, the usability of polyolefin films is limited to packaging certain substances, such as foodstuffs, in which minor oxygen perme ⁇ ability is required.
• multiple layer film structures in which materials of different layers are selected for a given purpose. Therefore, such 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. In addition, multiple layer structures may contain other layers which generate, for instance, adhesion between different layers. Products of this kind are, however, expensive to manufacture.
• Polyvinyl alcohol is one of such polymers which has a low oxygen permeability property. Said property has most often been utilized in olefin-vinyl alcohol random-mixed polymers and in olefin-vinyl alcohol segment-mixed polymers. It is also known in the art to manufacture products containing polyolefin and polyvinyl alcohol in the form of mixtures, which have a low oxygen permeability and which therefore are exceedingly appropriate for manufacturing e.g. packaging films. In the Finnish patent application No. 87-5772 is disclosed a mixture of polyolefin and polyvinyl alcohol, moreover containing optionally plasticizers.
• polyolefin-PV -PA mixtures are generally speaking provided with good oxygen sealing properties in dry circumstances, in moist circumstances their oxygen sealing property reduces significantly, so that they are sensitive to moisture.
• mixtures of polyolefins, PVA, and polyamide are mixed in molten state, partial dissolution of PVA and colouring of the product take place.
• plasticizers are used, their stability in the mixture is not as good as possible because of which migration of plasticizers take place in the product.
• One more drawback in conventional PE/PVA/PA mixtures is that the melt index of the product is not low enough.
• the object of the present invention is a material containing polyolefin, polyvinyl alcohol, and polyamide, in which the moisture sensitivity of the product regarding oxygen sealing is reduced, the lightness of the product has increased, and the need for plasticizers has been eliminated, and, in addition, the strength properties of the films manufactured from the product, such as viscosity, tensile strength, impact tensile strength, and resistance to rupture, have improved.
• the invention concerns a gas-sealed material containing polyolefin, polyvinyl alcohol, and polyamide.
• the gas-sealed material of the invention is characterized in that said material is produced by mixing in molten state 3 to 60 per cent by weight of polyolefin, 10 to 96 per cent by weight of internally plasticized vinyl alcohol polymer, and 1 to 50 per cent by weight of polyamide.
• the term 'internally plasticized vinyl alcohol polymer' refers to a vinyl alcohol polymer which contains polyglycol groups (polyether groups) or other groups plasticizing polyvinyl alcohol in the side chains thereof. Said plasticizer groups are connected into a chain by copolymerizing, grafting or by means of reactive compounding.
• One such internally plastizied polyvinyl alcohol is Vinex polymer (trade name, Air Products and Chemicals Inc.) , in which for comonomer is used an ester of methacrylic acid and of polyethylene glycol.
• Said internally plasticized vinyl alcohol polymers may be manu ⁇ factured, for instance in the manner as disclosed in the US. patent No. 4,709,999.
• Said patent presents that the product is provided with good oxygen sealing and that it is appropriate for cast, in ⁇ jection moulding and extrusion products, and that it is characterized by good water solubility, and therefore, it is particularly well appropriate for manufacturing films which are required to possess water solubility.
• the vinyl alcohol polymer used in the polyolefin/polyvinyl alcohol/ polyamide 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 an ethylene or propylene, and the acid component is an acrylic acid or methacrylic acid.
• Said modified vinyl alcohol polymers may be manufactured, for instance, by poly ⁇ merizing vinyl acetate monomer and poly(alkyleneoxy)acrylate co ⁇ monomer, and hydrolyzing the copolymer thus obtained in order to produce an internally plasticized vinyl alcohol polymer.
• the quantity of the internally plasticized vinyl alcohol polymer in the polyethylene-polyvinyl alcohol-polyamide mixture of the invention may be in the range from 10 to 96 per cent by weight, preferably in the range of from 30 to 60 per cent by weight. In some instances, it may be preferable to substitute part of the internally plasticized vinyl alcohol polymer used in the gas-sealed material for unmodified polyvinyl alcohol if the purpose of the product allows.
• the polyolefin in a gas-sealed material of the invention may be based on homopolymers or copolymers of the olefins. Therefore, it may be low density polyethylene (LDPE) , medium density polyethylene (MDPE) or high density polyethylene (HDPE) , polypropylene, or poly- butene.
• LDPE low density polyethylene
• MDPE medium density polyethylene
• HDPE high density polyethylene
• the polyolefin may also be a copolymer of ethylene together with other olefins, such as propylene, butene, hexene and 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 unsaturated carboxylic acid or carboxylic acid anhydride which can be grafted or copolymerized in polyolefin.
• Such acids are, for instance, acrylic acid, methacrylic acid, maleic acid fumaric acid, itaconic acid, crotonic acid, sorbic acid, and anhydrides of the afore-mentioned acids.
• grafting or in copolymerizing one or several above acids may be used.
• 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 30 to 60 per cent by weight of the quantity of the entire mixture.
• a third component in a gas-sealed material of the invention is poly- amide.
• polyamide for instance the following polyamides may be used: polyamide 6, polyamide 8, polyamide 10, polyamide 11, poly ⁇ amide 12, polyamide 6.6, polyamide 6.10, and polyamide 12-elastomers, or mixtures thereof.
• the quantity of polymer in the material of the invention may be selected from the range 1 to 50 per cent by weight.
• the polyamide enhances the viscosity and deep-drawing properties of the mixture of polyolefin and the polyvinyl alcohol copolymer.
• the gas-sealed polyolefin/PVA/PA mixture of the invention can be manufactured mixing the polyolefin component modified with the acid, the vinyl alcohol/copolymer component, and the polyamide component in a melt mixer simultaneously as a dry mixture, premixed in solid or in molten state, or then various components are added separately.
• polyolefin/PVA/PA 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 combined.
• 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 ⁇ board, .etc.
• Sealed multiple-layer products are generally used for packaging foodstuffs, 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 various foodstuff packages and technical products.
• MI 1.8 g/10 min
• P02 - LLDPE linear low density polyethylene
• melt index 0.5 g/10 min
• EAA ethylene-acrylic acid copolymer
• acrylic acid content 6.5%
• PVAl vinyl alcohol copolymer wherein the comonomer is an ester of a methacrylic acid and a polyethy- lene glycol (Vinex 4004, trade name, Air Products and Chemicals Inc.)
• PA1 - polyamide 6
• PA2 polyamide 11
• PA3 polyamide 12
• Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
• the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 215 to 210.
• the production rate was 10 kilograms per hour.
• the thicknesses of the obtained films were 120 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 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. TABLE 1 A
• the quantity of polyvinyl alcohol includes 4.5% glycerol of the PVA quantity.
• Polyolefin/PVA/polyamide mixtures of the invention were prepared by mixing polyolefin, polyvinyl alcohol and polyamide, in molten state, with the aid of a Berstorff mixer which was provided with a flat film nozzle.
• the temperature profile was 130 to 190 to 200 to 210 to 210 to 210 to 220 to 220 to 215 to 210.
• the production rate was 10 kilograms per hour.
• the thicknesses of the obtained films were 130 to 210 ⁇ m.
• 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.
• 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.

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)
• Laminated Bodies (AREA)

Applications Claiming Priority (4)

Publications (1)

Family

ID=26158538

Family Applications (1)

Country Status (5)

Cited By (2)

Citations (10)

Family Cites Families (1)

• 1990
  • 1990-04-11 JP JP50579790A patent/JPH04500537A/ja active Pending
  • 1990-04-11 AU AU54161/90A patent/AU631205B2/en not_active Ceased
  • 1990-04-11 WO PCT/FI1990/000106 patent/WO1990012062A1/en not_active Application Discontinuation
  • 1990-04-11 CA CA002032120A patent/CA2032120A1/en not_active Abandoned
  • 1990-04-11 EP EP19900905541 patent/EP0420954A1/en not_active Withdrawn

Patent Citations (10)

Also Published As

Similar Documents

Legal Events