JPH08259801A - Resin composition - Google Patents

Abstract

(57) [Summary] [Structure] Resin composition comprising polyalcohol (A) obtained by reducing polyketone comprising carbon monoxide-ethylene copolymer and polyketone (B) comprising carbon monoxide-ethylene copolymer Stuff. [Effect] According to the present invention, a resin composition having heat resistance and water resistance and having a high gas barrier property can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition having excellent gas barrier properties, water resistance and heat resistance.

[0002]

2. Description of the Related Art A polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer has a high gas barrier property such as an ethylene-vinyl alcohol copolymer (EVOH) or a polyvinylidene chloride resin (PVDC). Similar to resin, it has excellent gas barrier properties, so it is a film for packaging foods, etc., especially foods that require barrier properties against oxygen, odor, flavor, etc., food packaging for products that require aroma retention, etc. It is known to be used for the purpose of material (JP-A-6-226925,
6-255057). However, polyalcohol has a drawback of poor water resistance as compared with EVOH or PVDC.

On the other hand, a polyketone composed of a carbon monoxide-ethylene copolymer is also expected to be used in the field of food packaging materials because of its excellent gas barrier property (Japanese Patent Laid-Open No. 158036). In addition, since polyketone has a high melting point of around 240 ° C., it is expected to be used as a heat-resistant container having a gas barrier property, and since it has a low water absorption rate, it can be expected as a water-resistant resin. However,
From the viewpoint of gas barrier properties, polyketone is not a high gas barrier resin such as ethylene-vinyl alcohol copolymer (EVOH) or polyvinylidene chloride resin (PVDC), and is a gas such as polyethylene terephthalate or nylon. It has a barrier property within the range of a medium resin.

[0004]

DISCLOSURE OF THE INVENTION The present invention was devised in order to solve the above-mentioned drawbacks of the prior art, and provides a resin composition having excellent gas barrier properties and water resistance. To aim.

[0005]

[Means for Solving the Problems] The above object is to provide a polyalcohol (A) obtained by reducing a polyketone comprising a carbon monoxide-ethylene copolymer and a polyketone (B) comprising a carbon monoxide-ethylene copolymer. It is achieved by providing a resin composition comprising

In the present invention, the blend composition ratio (weight) of the polyalcohol (A) and the polyketone (B) is preferably (A) / (B) = 95/5 to 5/95.
(A) / (B) = 95/5 to 50/50, especially 95/5
In the case of 60/40, the water resistance and heat resistance of the polyalcohol are improved, and (A) / (B) = 50 / 50-5.
In the case of / 95, especially 40/60 to 5/95, the gas barrier property of the polyketone is improved.

In the present invention, the polyalcohol is a polyalcohol obtained by reducing a polyketone consisting of a carbon monoxide-ethylene copolymer, and particularly 80% or more of the repeating unit represented by the formula (I). The polyalcohol containing is preferable from the viewpoint of gas barrier properties, mechanical properties, and moldability.
The content of the repeating unit is more preferably 90% or more, particularly preferably 95% or more, and most preferably 97% or more.

[0008]

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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 a known method, 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).

Further, other additives (plasticizer, heat stabilizer, ultraviolet absorber, antioxidant, colorant, filler, crosslinking agent (boric acid etc.), other resin etc.) are added to the resin composition of the present invention. It is free to use within a range not impairing the object of the present invention. In particular, as a measure for preventing gel formation, one or two of hydrotalcite-based compounds, hindered phenol-based, hindered amine-based heat stabilizers, metal salts of higher fatty acid carboxylic acids (for example, calcium stearate, magnesium stearate, etc.) 0.01 or more seeds
It is preferable to add 1% by weight.

If necessary, the resin composition may contain additives. Examples of such additives may include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other polymeric compounds. It can be blended within a range in which the action and effect of the invention are not impaired. Specific examples of the additives include the following.

Antioxidants: 2,5-di-t-butylhydroxine, 2,6-di-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol), 2, 2'-methylene-bis- (4-methyl-6-
t-butylphenol), octadecyl-3- (3 ′,
5'-di-t-butyl-4'-hydroxyphenyl) propionate, 4,4'-thiobis- (6-t-butylphenol) and the like.

UV absorber: ethylene-2-cyano-
3,3'-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole,
2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5) '-Methylphenyl) 5-
Chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone and the like.

Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphoric acid ester and the like. Antistatic agent: pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins,
Polyethylene oxide, carbowax, etc. Lubricants: ethylene bis stearamide, butyl stearate, etc. Coloring agent: carbon black, phthalocyanine, quinacridone, indoline, azo pigment, red iron oxide, etc.

The method of blending the polyketone (A) and the polyalcohol (B) of the present invention is not particularly limited, but both are dry blended and used as they are, or more preferably a Banbury mixer. , Pelletizing and drying with a single-screw or twin-screw extruder. Alternatively, (A) and (B) can be dissolved in a common solvent (metacresol or the like) and blended. Further, at the time of blending and pelletizing, it is free to use the above-mentioned additives within a range not impairing the object of the present invention.

The resin composition of the present invention comprises a single-layer film,
It is used for at least one layer of a laminate, especially as an intermediate layer, and for solution coating. In the film formation, an unstretched film or a stretched film is formed by a usual method, and the production conditions thereof are not particularly limited. When used as part of a laminate,
If necessary, a recovery layer may be provided for effectively utilizing an unused portion generated when the container is molded from the laminate (sheet).

One of the preferred multilayer forms of the present invention is to have the composition as an intermediate layer, and to have a layer of a moisture resistant thermoplastic resin on both sides thereof. In the case where the layer of the moisture-resistant thermoplastic resin is provided only on one side of the composition layer, for example, heat and moisture act simultaneously in retort sterilization treatment, that is, when used under high temperature and high humidity, storage In some cases, it is not possible to obtain a package having excellent properties and appearance. As a resin forming the layer of the moisture-resistant thermoplastic resin, a hydrophobic resin, particularly the above-mentioned polyolefin resin is representatively mentioned. Examples of the polyolefin resin include high-density, medium-density or low-density polyethylene, high-density, medium-density or low-density polypropylene, polybutene, vinyl acetate, acrylate ester, butene, hexene, 4-methyl-1-
Polyethylene copolymerized with α-olefins such as pentene, ionomer resin, polypropylene homopolymer, polypropylene grafted with ethylene, or copolymerized with α-olefins such as ethylene, hexene and 4-methyl-1-pentene polypropylene,
Poly-1-butene, poly-4-methyl-1-pentene,
Alternatively, it contains a modified polyolefin obtained by reacting maleic anhydride with the above-mentioned polyolefin. Of these, polypropylenes (PP) are most suitable.

Further, the resin forming the layer of the moisture-resistant thermoplastic resin is represented by poly (ethylene terephthalate), poly (ethylene naphthalate), poly (butylene terephthalate), poly (ethylene terephthalate / isophthalate) and the like. Polystyrene resin such as polyester resin, polystyrene, styrene-butadiene copolymer, styrene-isoprene copolymer, or polycarbonate resin, nylon-6 and nylon-6,6
And the like, or a mixture thereof.

The resin forming the layer of the moisture-resistant thermoplastic resin may be the same as or different from the inner and outer layers. Furthermore, in addition to the resin composition layer of the present invention, other barrier material, such as polyvinyl alcohol,
An ethylene-vinyl alcohol copolymer, polyvinylidene chloride or the like may be further laminated.

The resin composition of the present invention can be easily laminated with these thermoplastic resins, and by further laminating these thermoplastic resins, the resin composition of the present invention is protected and reinforced, and under high humidity. It also prevents deterioration of the gas barrier property of and also imparts excellent mechanical strength.

When the interlayer adhesion between these resins and the resin composition of the present invention is not sufficient, it is preferable to provide an adhesive resin layer. The adhesive resin is not particularly limited as long as it does not cause delamination at a practical stage, and is not particularly limited. An unsaturated carboxylic acid or an anhydride thereof may be an olefin polymer (for example, polyethylene, polypropylene, polyolefin such as polybutene, Modified olefin polymers containing a carboxyl group, which are obtained by chemically (eg, addition reaction, graft reaction) bonding to an olefin-based copolymer). 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 is mentioned as a suitable one. It is also possible to mix a polyalcohol with these adhesive resins as long as the effects of the present invention are not impaired.

The method for obtaining a laminate having at least one resin composition layer of the present invention is not particularly limited, but coextrusion method, coinjection method, sand lamination method, solution coating method, extrusion lamination method, dry method. The lamination method etc. are mentioned. In the co-extrusion method, after melt-kneading with an extruder corresponding to each resin layer, it is extruded into a predetermined shape through a multi-layer multi-die such as a T-die and a circular die.
Further, in the co-injection method, after melt-kneading with an injection machine corresponding to each resin layer, the mixture is injected into a mold to produce a multilayer container or a preform for a container. The resin composition of the present invention,
Secondary processing by heat stretching can be carried out as a single layer or a laminate by a usual method to obtain a heat stretched multilayer structure. Here, the heat-stretched multilayer structure in the present invention,
A cup, a container such as a bottle, a sheet, or a film obtained by heating and stretching is a film, and heating means that the multilayer structure is allowed to stand for a predetermined time at a temperature necessary for heating and stretching, and the multilayer structure is thermally It is a method of operating by heating with a heater so as to be almost uniform.

A molded product of the resin composition of the present invention, particularly the above-mentioned multilayer structure, is used as a packaging material for foods, particularly retort foods, medical products, and also for fuel pipes and tanks, floor heating pipes, bag-in-boxes. , Useful for agricultural films.

[0027]

EXAMPLES Next, the present invention will be described in more detail with reference to synthesis examples, examples and comparative examples, but the present invention is not limited to these examples.

Example 1 A polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer {90% of the repeating unit represented by (I), and 10% of others, and an intrinsic viscosity [η].
80 parts by weight of 1.2 dl / g} (A) and 20 parts by weight of the above polyketone (linear alternating copolymer) (B) were put into a twin-screw type extruder, and under a nitrogen gas atmosphere at 270 ° C.
Was extruded and pelletized. 2 using the above pellets
A 0 μ film was prepared and the oxygen gas barrier property of the film was measured. The oxygen barrier property at 20 ° C.-65% RH was 0.4 cc / m ↓ 2 · day · atm. Also, in order to evaluate the water resistance, the film was
When a dipping test in water at ℃ was carried out, there was no shrinkage of the film and the shape retention was good.

Example 2 A polyalcohol obtained by reducing a polyketone composed of a carbon monoxide-ethylene copolymer {96% of the repeating unit represented by (I), and 4% of others, and an intrinsic viscosity [η] 0. ．
30 parts by weight of 8 dl / g} (A) and 70 parts by weight of the polyketone (B) used in Example 1 were put into a twin-screw type extruder and extruded at 270 ° C. under a nitrogen gas atmosphere to pelletize. . A film having a thickness of 20 μm was produced using the above pellets, and the oxygen gas barrier property of the film was measured. The oxygen barrier property at 20 ° C-65% RH is
It was 80 cc / m ↓ 2 · day · atm. Further, when the film was subjected to a dipping test in water at 20 ° C.,
There was no shrinkage of the film and the shape retention was good.

Comparative Example 1 The polyketone used in Example 1 was extruded at 270 ° C. using a single screw type extruder to prepare a 20 μ film. In order to evaluate the water resistance, the film was subjected to a dipping test in water at 20 ° C. As a result, the film did not shrink and the shape retention was good. However,
The oxygen barrier property at 20 ° C-65% RH is 500.
It was cc / m ↓ 2 ・ day ・ atm.

Comparative Example 2 The polyalcohol used in Example 1 was extruded at 200 ° C. using a single screw type extruder to prepare a 20 μ film. The oxygen barrier property at 20 ° C. and 65% RH was 0.1 cc / m ↓ 2 · day · atm. However, when the film was subjected to a water immersion test at 20 ° C., the film shrank and the shape retention was poor.

[0032]

EFFECTS OF THE INVENTION According to the present invention, a resin composition having high gas barrier properties having heat resistance and water resistance can be obtained.

Claims (1)

[Claims] 1. A resin composition comprising a polyalcohol (A) obtained by reducing a polyketone comprising a carbon monoxide-ethylene copolymer and a polyketone (B) comprising a carbon monoxide-ethylene copolymer.