JPH08244176A - Manufacturing method of laminated body - Google Patents

Abstract

PURPOSE: To provide a laminate having gas barrier properties, fragrance keeping properties and resistance to oils and resistance to chemicals under low humidity and useful for various kinds of packaging by applying polyalcohol solution prepared by reducing a carbon monoxide-ethylene copolymer to a base and drying thereon. CONSTITUTION: Polyalcohol solution prepared by reducing a carbon monoxide- ethylene copolymer is applied onto a base and drying thereon to manufacture a laminate. It is preferable that the repeating unit particularly represented by the formula is 80% or more, more preferably 95% or over is contained in polyalcohol, and further it is optimum that 97% or over is contained therein. As apolyalcohol solvent, methyl alcohol, normal propyl alcohol, isopropyl alcohol or the like is preferable, and electrolyte of 0.01-0.5wt.% (to polymer) can be blended therein for the purpose of lowering viscosity. It is also preferable to apply preliminarily a bonding agent on the surface of the base and dried thereon by the dry lamination method, which is what is called the anchor coating.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention applies a polyalcohol solution obtained by reducing a carbon monoxide-ethylene copolymer,
The present invention relates to a method for producing a laminate having excellent gas barrier properties which is dried and used for packaging films for foods, containers and the like.

[0002]

2. Description of the Related Art Films, sheets, and laminates for food packaging, which require antioxidation of contents or retention of aroma,
A high gas barrier property is required for hollow containers and the like. Further, for vinyl chloride wallpaper, vinyl chloride leather, sheets, etc. made of soft vinyl chloride, a coating material for preventing bleeding of a plasticizer is required. So gas barrier property, aroma retention,
It is widely practiced to satisfy the requirements for oil and chemical resistance.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a laminate having excellent gas barrier properties, particularly gas barrier properties under low humidity.

[0004]

The above object is achieved by applying a polyalcohol solution obtained by reducing a carbon monoxide-ethylene copolymer to a substrate and drying it to obtain a laminate.

The present invention will be specifically described below. In the present invention, the polyalcohol is a polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer, and in particular, the repeating unit represented by the formula (I) is 80
% Of polyalcohol is preferable in terms of gas barrier properties, mechanical properties, and moldability. The repeating unit is 90
% Or more, more preferably 95% or more, and most preferably 97% or more.

[0006]

Embedded image

The above polyketone is a carbon monoxide-ethylene type copolymer, and the carbon monoxide-ethylene type copolymer is obtained by copolymerizing carbon monoxide and ethylene, or Representative examples include those obtained by copolymerizing carbon oxide and ethylene as a main component with an unsaturated compound other than ethylene. Here, as the unsaturated compound other than ethylene, an olefin having 3 to 12 carbon atoms,
Examples thereof include dienes having 4 to 12 carbon atoms, vinyl esters, aliphatic unsaturated carboxylic acids, aliphatic unsaturated carboxylic acid salts, and aliphatic unsaturated carboxylic acid esters. Examples of the copolymer include a random copolymer and an alternating copolymer, and an alternating copolymer having a high carbonyl group content is preferable.

Examples of the olefin having 3 to 12 carbon atoms include propylene, butene-1, isobutene, pentene-
1,4-methylpentene-1, hexene-1, octene-1, dodecene-1, styrene and the like can be mentioned, but propylene, olefin having 4 to 8 carbon atoms, or propylene and olefin having 4 to 8 carbon atoms. A combination system with is preferred. Examples of the diene having 4 to 12 carbon atoms include butadiene, isoprene, 1,5-hexadiene, 1,7-octadiene and 1,9-decadiene. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl pivalate and the like. Also,
Examples of the aliphatic unsaturated carboxylic acid, its salt and its ester include acrylic acid, methacrylic acid, maleic anhydride,
Maleic acid, itaconic acid, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester, itaconic acid diester (as these esters, methyl ester, ethyl ester Alkyl ester such as ester), acrylate,
Examples thereof include maleic acid salts and itaconic acid salts (these salts include monovalent or divalent metal salts).

The polyketone can be produced by known methods, for example, US Pat. No. 2,495,286 and JP-A-53-128690 and JP-A-53-128691.
JP-A-59-197427 and JP-A-61-912.
26, JP-A-62-232434, JP-A-62-5.
3332, JP-A-63-3025, JP-A-63-1
05031, JP-A-63-154737, JP-A-1
The methods described in JP-A-149829, JP-A-1-201333, JP-A-2-67319 and the like can be mentioned, but the method is not particularly limited thereto. Next, as a method for obtaining a polyalcohol by reducing the carbonyl group in the polyketone, a method of reducing a part or all of the carbonyl group in the polyketone with hydrogen, for example,
JP-A-1-149828, JP-A-2-232228
JP-A-5-339367, JP-A-6-49203
And a method of treating a part or all of the carbonyl group in the polyketone with a metal hydrogen compound to reduce the polycarbonyl, for example, the method described in JP-A-1-204929.

The intrinsic viscosity [η] of the polyol is 0.2 to
It is 5 dl / g, preferably 0.5 to 3 dl / g (value measured by Ostwald viscometer at 30 ° C. in a mixed solvent of 15% by weight of water-85% by weight of phenol).

Examples of the polyalcohol solvent include monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol, dihydric alcohols such as ethylene glycol and propylene glycol,
Trihydric alcohols such as glycerin, phenols, phenols such as cresol, amines such as ethylenediamine and trimethylenediamine, monovalent carboxylic acids such as formic acid and acetic acid, dimethylsulfoxide, dimethylacetamide, N
-Methylpyrrolidone and the like, or hydrates thereof and the like can be used alone or in admixture of two or more. Particularly preferred solvents are monohydric alcohols such as methyl alcohol, normal propyl alcohol and isopropyl alcohol.

In the polyalcohol solution, a plasticizer (polyhydric alcohol, etc.), a filler, a reinforcing material (glass fiber, etc.),
A colorant, a polarizing element, an ultraviolet absorber, a surfactant, a modifying resin, boric acid or borax may be added.

In the solution, alkali metal compounds such as sodium hydroxide, sodium chloride, sodium acetate, sodium sulfate and sodium nitrate, calcium hydroxide, calcium chloride, calcium acetate, calcium sulfate, for the purpose of decreasing the viscosity, An alkaline earth metal compound such as calcium nitrate or other electrolyte is added in an amount of 0.01 to 0.
You may mix | blend 5 weight% (with respect to a polymer).

As a method for applying the solution to the surface of the substrate, ejection from a casting head, roll coating,
Air knife coat, gravure roll coat, doctor roll coat, doctor knife coat, curtain flow coat, spray, wire bar, rod coat, dip,
An arbitrary means such as brush coating is exemplified. Examples of the method for drying and heat treating the substrate thus coated include a dry heat treatment method such as an infrared irradiation method and a hot air drying method. These infrared irradiation and hot-air drying may be used alone or in combination. The temperature of the drying / heat treatment is preferably 30 to 180 ° C, and the lower limit is preferably 50 ° C or higher, and most preferably 80 ° C or higher. Also, the drying and heat treatment time is 5 seconds ~
It is preferably 10 minutes, more preferably 1 to 5 minutes. Conditions during drying / heat treatment, such as increasing or decreasing the temperature,
For example, the treatment may be performed at a low temperature at first, and the temperature may be gradually increased. By performing such drying and heat treatment, a film having a particularly excellent low-humidity gas barrier property is formed on the surface of the substrate.

It is preferable to apply an adhesive agent to the surface of the substrate in advance by a dry lamination method or the like, that is, to perform anchor coating. The dry lamination adhesive is not particularly limited as long as it has a sufficient interlayer adhesive force. For example, polyurethane-based and polyester-based adhesives for dry lamination can be mentioned. Further, the surface of the base material may be subjected to corona discharge treatment, sputtering treatment, high frequency treatment, fire treatment, chromic acid treatment, solvent etching treatment, or a combination of these.

Examples of the base material include the following. A film of a thermoplastic resin, for example, a biaxially stretched film containing a homopolymer of propylene as a main component, a homopolymer of ε-caprolactam and a diamine component such as hexamethylenediamine and metaxylylenediamine, and adipic acid as a main raw material. Biaxially stretched film containing nylon as the main component, biaxially stretched film containing ethylene glycol and terephthalic acid or naphthalene dicarboxylic acid as the main raw materials, polyester as the main component, and carbonic acid derivatives such as bisphenol A and phosgene as the main raw materials. A film made of polycarbonate, a biaxially stretched film made of polyvinylidene chloride obtained by copolymerizing vinyl chloride, acrylonitrile, (meth) acrylic acid ester, etc., with vinyl chloride as the main raw material, a homopolymer of styrene and styrene. Raw material and butadiene, acrylonitrile, biaxially oriented film of polystyrene by copolymerizing like, include rolling or biaxially oriented high density polyethylene film or the like.

Various molded products (sheets, cups, bottles, etc.) other than the above-mentioned films are also mentioned as preferable ones, and fiber aggregates (paper, non-woven fabric, woven fabric, fibrous casing, etc.), inorganic substances (cement etc.). ), Metal, polyvinyl chloride resin wallpaper, photographic paper and the like.

The thickness of the film after coating, drying and heat treatment of the solution is preferably 0.5 to 15 μm, more preferably 1 to 10 μm, most preferably 2 to 6 μm.
Is.

Further, the laminated body obtained by the above method is
Other layers can be laminated by a conventionally known method to form a further multilayer. Examples of these methods include an extrusion lamination method and a dry lamination method.

In laminating these layers, a usual method of laminating an adhesive resin layer between the layers is adopted. The adhesive resin is not particularly limited as long as it does not cause delamination at a practical stage, and is not particularly limited, for example, an unsaturated carboxylic acid or an anhydride thereof is an olefin polymer (for example, polyethylene, polypropylene,
Examples thereof include modified olefin-based polymers containing a carboxyl group, which are obtained by chemically (for example, addition reaction or graft reaction) bonding to a polyolefin such as polybutene or a copolymer mainly composed of olefins. Specifically, one selected from maleic anhydride graft modified polyethylene, maleic anhydride graft modified polypropylene, maleic anhydride graft modified ethylene-ethyl acrylate copolymer, maleic anhydride graft modified ethylene-vinyl acetate copolymer or A mixture of the two may be mentioned. Further, glycidyl acrylate, a polymerizable unsaturated compound having a glycidyl group such as glycidyl methacrylate, a polymerizable unsaturated compound having a methacryloxypropyltrimethoxysilane group, a glycidyl group, a modified olefin polymer such as an alkoxysilane group. To be A plurality of these functional groups may be combined. Specifically, glycidyl modified polyethylene, glycidyl modified polypropylene, glycidyl modified ethylene-ethyl acrylate copolymer, glycidyl modified ethylene-vinyl acetate copolymer, alkoxysilane modified polyethylene, alkoxysilane modified polypropylene, alkoxysilane modified ethylene-vinyl acetate. One or a mixture of two selected from copolymers may be mentioned. In addition, polyester resins containing polyvalent carboxylic acids, polyhydric alcohols, and hydroxycarboxylic acids as constituent components can also be used as the adhesive resin.

When the dry laminating method is adopted,
The same dry laminating adhesive as described above can be used and is not particularly limited.

Containers (bags, cups, tubes, trays, bottles, etc.) composed of the laminates (films, sheets, etc.) produced by these methods are used for general food packaging,
Very suitable for pharmaceutical packaging and retort food packaging.

The present invention will be described below with reference to examples.
The present invention is not limited thereby.

[0024]

【Example】

Example 1 Polyalcohol obtained by reducing carbon monoxide-ethylene copolymer {Repeating unit represented by formula (I) 96%, other 4
%, And 10 parts by weight of intrinsic viscosity [η] 0.8 dl / g} (parts by weight will be simply referred to as “parts”) were dissolved in 90 parts of methyl alcohol with heating and stirring at 70 ° C. to obtain a solution. Biaxially oriented polypropylene film (film thickness 20μ
Urethane-based anchor coating agent (Toyo Morton Co., Ltd. AD33) on the primer-treated surface of Tokyo Cellophane Paper Co., Ltd.
5A / CAT10) was applied by the gravure coating method and dried and heat-treated at 110 ° C. for 5 minutes to obtain a multilayer film (polyalcohol layer thickness 3 μm).
Then, the oxygen barrier property (Modern) of the multilayer film
OX-TRAN 10 / 50A from Control Co. was used, and the measurement conditions were 20 ° C. and 65% RH. The result was 0.4 cc / m ↑ 2 · day · atm, which was a very good barrier property as a food packaging material. (Hereinafter, the measurement conditions and units of the oxygen transmission amount are the same).

When the coated film was dipped in benzene and ethyl methyl ketone at 20 ° C. for 10 days, there was no change in appearance.

Example 2 Polyalcohol obtained by reducing carbon monoxide-ethylene copolymer {90% of repeating units represented by the formula (I), other 1
0%, (Intrinsic viscosity [η] 1.2 dl / g)} 1
0 parts by weight (parts by weight are simply referred to as "parts") was dissolved in 90 parts of methyl alcohol by heating at 70 ° C with stirring to obtain a solution. Using this solution as a base material, a urethane-based anchor coating agent (Toyo Morton Co., Ltd. A) was applied to the primer-treated surface of a biaxially oriented polypropylene film (20 μm thickness, Tokyo Cellophane Paper Co., Ltd.).
D335A / CAT10) was applied and applied by the gravure coating method, and dried and heat-treated at 110 ° C. for 5 minutes to obtain a multilayer film (polyalcohol layer thickness 3 μm).
m). When the oxygen barrier property of the multilayer film was measured, it was 0.6 cc / m ↑ 2 · day · atm, which was a very good barrier property as a food packaging material (hereinafter, the measurement conditions and units of oxygen permeation amount were the same. is there).

When the coated film was dipped in benzene and ethyl methyl ketone for 10 days at 20 ° C., no change in appearance was observed.

[0028]

As described above, according to the present invention, it exhibits extremely excellent gas barrier properties, particularly gas barrier properties under low humidity, aroma retention and oil / chemical resistance, and is used for various packaging. A useful laminate is obtained.

Claims (1)

[Claims] 1. A method for producing a laminate, which comprises applying a polyalcohol solution obtained by reducing a carbon monoxide-ethylene copolymer to a substrate and drying the solution.