JP6148500B2 - Gas barrier coating composition - Google Patents

Description

The present invention relates to a gas barrier coating composition.

In the packaging resin film, particularly in the food packaging field, gas barrier properties are an important required characteristic for long-term storage of contents. Polyvinyl alcohol (PVA) is used as a resin having an excellent gas barrier property, but the gas barrier property is lowered at the time of moisture absorption and is not particularly suitable for packaging of foods containing a large amount of moisture.

When using a resin film as a packaging material under high humidity, not only gas barrier properties but also water resistance (water-insoluble) is required. In order to improve the water resistance of PVA and improve the humidity dependency of gas barrier properties, a method is known in which a hydroxyl group of PVA and a carboxyl group of poly (meth) acrylic acid are crosslinked by an esterification reaction (for example, Patent Document 1). ). However, heat treatment at a high temperature of about 200 ° C. is necessary for sufficient gas barrier properties and water resistance, and there is a problem that the resin is colored and the appearance is impaired.

Furthermore, among food packaging applications, in applications where retort processing is performed, it is not sufficient to simply improve the humidity dependency of oxygen permeability, and surface conditions and adhesion (retort resistance) after retort processing are major issues. Become. In the gas barrier coating composition containing polyvinyl alcohol and poly (meth) acrylic acid known so far, the retort resistance could not be sufficiently improved.

JP-A-6-220221

The present invention improves the above-mentioned problems, is a relatively simple production method, has no gas barrier property or coloring problem due to baking at high temperature, has low humidity dependency of oxygen permeability, and is also resistant to retort. An object of the present invention is to provide a coating composition that gives a gas barrier film with improved slag.

As a result of intensive studies to solve the above problems, the present inventors have introduced a branched structure into poly (meth) acrylic acid in a gas barrier coating composition containing polyvinyl alcohol and poly (meth) acrylic acid. As a result, it was found that the retort resistance can be improved, and the present invention has been completed.

That is, the present invention relates to a gas barrier coating composition containing polyvinyl alcohol and branched poly (meth) acrylic acid.

The branched poly (meth) acrylic acid is preferably poly (meth) acrylic acid obtained by copolymerizing alkylene glycol di (meth) acrylate.

Moreover, this invention relates to the manufacturing method of the gas barrier film including the process of apply | coating the said gas barrier coating composition and heat-processing, and the gas barrier film manufactured by this manufacturing method.

In this invention, since the branched poly (meth) acrylic acid is used, while improving the change by the humidity of the gas barrier property resulting from polyvinyl alcohol, the gas barrier film excellent also in retort resistance can be obtained.

The gas barrier coating composition of the present invention includes polyvinyl alcohol and branched poly (meth) acrylic acid.

The polyvinyl alcohol used in the present invention is not particularly limited as long as it has at least two vinyl alcohol units in the molecule, and a copolymer containing other monomer units can also be used. Examples of the copolymerizable monomer include olefins having 2 to 10 carbon atoms such as ethylene, propylene and 1-butene, and unsaturated carboxylic acids having 3 to 30 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid and fumaric acid. Examples thereof include unsaturated nitriles having 3 to 10 carbon atoms such as acids, acrylonitrile and methacrylonitrile, and vinyl ethers having 3 to 10 carbon atoms such as methyl vinyl ether and ethyl vinyl ether. Among these, polyvinyl alcohol (PVA) or ethylene-vinyl alcohol copolymer is preferable.

The degree of saponification of polyvinyl alcohol is not particularly limited, but is preferably 90 to 100%, more preferably 95 to 100%. If it is less than 90%, the barrier properties and water resistance tend to be lowered.

The number average polymerization degree of polyvinyl alcohol is not particularly limited, but is preferably 50 to 5000, and more preferably 300 to 2000. If it is less than 50, mechanical strength is inferior, and if it exceeds 5000, the liquid viscosity tends to be high and workability tends to be lowered.

The poly (meth) acrylic acid used in the present invention is not particularly limited as long as it is a polymer having at least two acrylic acid or methacrylic acid units in the molecule. A homopolymer of acrylic acid or methacrylic acid In addition, copolymers of acrylic acid and methacrylic acid, and copolymers containing other monomer units can also be used. Examples of the copolymerizable monomer include olefins having 2 to 10 carbon atoms such as ethylene, propylene, and 1-butene, and unsaturated carboxylic acids having 3 to 10 carbon atoms such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and fumaric acid. Examples thereof include unsaturated nitriles having 3 to 10 carbon atoms such as acids, acrylonitrile and methacrylonitrile, and vinyl ethers having 3 to 10 carbon atoms such as methyl vinyl ether and ethyl vinyl ether. In addition, poly (meth) acrylic acid obtained by neutralizing all or part of carboxylic acid groups with an alkali or alkaline earth metal hydroxide, ammonium hydroxide, organic ammonium hydroxide, or the like can also be used. Among these poly (meth) acrylic acids, poly (meth) acrylic acid or a partially neutralized product thereof is preferable, and polyacrylic acid (PAA) or a partially neutralized product thereof is particularly preferable. Here, poly (meth) acrylic acid means polymethacrylic acid and polyacrylic acid.

Especially, the homopolymer of acrylic acid or methacrylic acid, or its partial neutralization thing is preferable at the point from which the compatibility with polyvinyl alcohol is high and the dry film excellent in transparency is obtained.

The method for introducing a branched structure into poly (meth) acrylic acid is not particularly limited. For example, polyfunctional (meth) acrylate is introduced during polymerization such as solution polymerization, emulsion polymerization, soap-free emulsion polymerization, suspension polymerization. A method is mentioned. Among them, a method of introducing polyfunctional (meth) acrylate during solution polymerization is preferable in that a fine soft gel can be generated.

Examples of the polyfunctional (meth) acrylate include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and ethylene glycol di (meth) acrylate. , Alkylene glycol di (meth) acrylate such as triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, diethylene glycol bis β- (Meth) acryloyloxypropinate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate Dipentaerythritol hexa (meth) acrylate, tri (2-hydroxyethyl) isocyanate di (meth) acrylate, pentaerythritol tetra (meth) acrylate, 2,3-bis (meth) acryloyloxyethyloxymethyl [2.2 .1] Heptane, poly-1,2-butadiene di (meth) acrylate, 1,2-bis (meth) acryloyloxymethylhexane, nonaethylene glycol di (meth) acrylate, tetradecanethylene glycol di (meth) acrylate, 10- Examples include decanediol (meth) acrylate and 3,8-bis (meth) acryloyloxymethyltricyclo [5.2.10.] Decane. These compounds can be used alone or in combination of two or more. Of these, alkylene glycol di (meth) acrylate is preferable. Such branched poly (meth) acrylates are present as particles in the coating composition.

The copolymerization amount of the polyfunctional (meth) acrylate is not particularly limited, but is preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. If it is less than 0.5% by weight, particle formation does not occur, and if it exceeds 20% by weight, it tends to be difficult to mix with polyvinyl alcohol.

The number average molecular weight of the branched poly (meth) acrylic acid is not particularly limited, but is preferably 3000 to 50000, more preferably 5000 to 20000. If it is less than 3000, mechanical strength will fall, and if it exceeds 50000, a viscosity will rise and there exists a tendency for workability | operativity to fall.

The blending amount of polyvinyl alcohol and branched poly (meth) acrylic acid is not particularly limited, but the blending amount of branched poly (meth) acrylic acid is 5 to 400 parts by weight with respect to 100 parts by weight of polyvinyl alcohol. Preferably, 50-100 weight part is more preferable. If it is less than 5 parts by weight, the water resistance is lowered, and if it exceeds 400 parts by weight, the barrier properties and the water resistance tend to be lowered.

When mixing polyvinyl alcohol and branched poly (meth) acrylic acid, a catalyst can be added to cause an esterification reaction between them. As the esterification catalyst, an acid, an alkali, a metal catalyst, or the like can be used. Of these, alkali is preferable from the viewpoint of neutralizing poly (meth) acrylic acid. It does not specifically limit as an alkali, Sodium hydroxide, potassium hydroxide, ammonia etc. are mentioned. The addition amount of the alkali is not particularly limited, but may be added so as to neutralize 1 to 20% with respect to the acid.

An inorganic layered compound or the like can be added to the gas barrier coating composition of the present invention. The inorganic layered compound is an inorganic compound in which ultrathin unit crystal layers overlap to form one layered particle, and those that swell and cleave in a solvent are preferable. Among these, a viscosity compound having a swelling property to a solvent is particularly preferably used. Typical examples are kaolinite, halloysite, montmorillonite, verculite, dickite, nacrite, antigolite, pyrophyllite, hectorite, beidellite, margite, talc, tetrasilic mica, muscovite, phlogopite. Chlorite and the like. Of these, montmorillonite is preferable in terms of barrier properties.

As a compounding quantity of an inorganic layered compound, 5-100 weight part is preferable with respect to a total of 100 weight part of polyvinyl alcohol and branched poly (meth) acrylic acid, and 20-50 weight part is more preferable. If the amount is less than 5 parts by weight, the barrier property is not sufficiently exhibited, and if it exceeds 100 parts by weight, the coating tends to become cloudy.

A solvent can be added to the gas barrier coating composition of the present invention. Although it does not specifically limit as a solvent, For example, C1-C30 alcohols, such as water, methanol, ethanol, and propanol; C4-C30 aliphatic, such as n-hexane, n-heptane, toluene, and xylene Or aromatic hydrocarbons; halogen-containing aliphatic or aromatic hydrocarbons having 1 to 30 carbon atoms such as dichloromethane, chloroform, chlorobenzene, o-dibromobenzene; aliphatics having 2 to 30 carbon atoms such as diethyl ether and diphenyl ether Or aromatic ethers; aliphatic or aromatic esters having 2 to 30 carbon atoms such as ethyl acetate and butyl propionate; aliphatic or aromatic amide compounds having 2 to 30 carbon atoms such as dimethylformamide and dimethylacetamide; Acetonitrile, benzonitrile Like aliphatic or aromatic nitriles having 2 to 30 carbons such. These solvents can be used alone or in combination of two or more.

Although the usage-amount of a solvent is not specifically limited, 1-10000 weight part is preferable with respect to 100 weight part of the mixture of polyvinyl alcohol and branched poly (meth) acrylic acid, and 10-1000 weight part is more preferable.

The method for producing a gas barrier film of the present invention includes a step of applying the gas barrier coating composition to a substrate and heat-treating it. Although a base material is not specifically limited, For example, a glass plate, a metal plate, a thermoplastic resin film, a thermosetting resin film etc. are mentioned. Subsequently, after forming a film on a support body, it heat-processes. Although heat processing temperature is not specifically limited, 150-250 degreeC is preferable and 150-200 degreeC is more preferable. If the temperature is lower than 150 ° C., the reaction does not proceed sufficiently, so that a film having low water resistance is likely to be obtained. If the temperature exceeds 250 ° C., a film having low adhesion tends to be obtained.

The film thickness of the gas barrier film is not particularly limited, but is preferably 0.5 to 20 μm, and more preferably 1 to 5 μm. If the thickness is less than 0.5 μm, it tends to be difficult to obtain a defect-free thin film.

The gas barrier film can be laminated with other thermoplastic resin films. The thermoplastic resin film is not particularly limited, and examples thereof include polyolefin resin films such as polyethylene and polypropylene, polyamide resin films such as nylon 6 and nylon 66, and polyester resin films such as polyethylene terephthalate and polyethylene naphthalate.

The application of the gas barrier coating composition of the present invention is not particularly limited, and can be applied to applications where conventional gas barrier materials have been used. In particular, films (deep-drawn bags, bag making), bottles, tubes, standing pouches, retort bags, paper containers, back-in boxes, film containers for heavy bags such as resin bags, foods such as cans, and industrial materials It can be used as a packaging material such as a floor heating pipe and a part of its structural material.

Next, the paint of the present invention will be described based on examples, but the present invention is not limited thereto.

Production Example 1
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Then, 1 part of ethylene glycol dimethacrylate EG (light ester EG, manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.3% and a viscosity of 400 cps. The viscosity was measured using a B-type viscometer and a rotor No. 2 was measured at 25 ± 0.5 ° C. The number average molecular weight of the obtained acrylic resin was 18000.

Production Example 2
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Thereafter, 1 part of polyethylene glycol dimethacrylate (light ester 4EG-A, PEG # 200 (EG tetramer), manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.1% and a viscosity of 250 cps. The number average molecular weight of the obtained acrylic resin was 13000.

Production Example 3
Polymerization was conducted with stirring for 19 hours under a nitrogen stream using 19 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst. Thereafter, 1 part of 1,6-hexanediol methacrylate (light ester 1.6HX, manufactured by Kyoeisha Chemical Co., Ltd.) was added and stirred at the same temperature for 5 hours to obtain an acrylic resin solution. The obtained acrylic resin solution had a solid content of 20.0% and a viscosity of 350 cps. The number average molecular weight of the obtained acrylic resin was 15000.

Production Example 4
Using 20 parts of methacrylic acid, 80 parts of ethanol, and azobisisobutyronitrile (AIBN) as a catalyst, polymerization was conducted with stirring at 70 ° C. for 6 hours under a nitrogen stream. The obtained acrylic resin solution had a solid content of 20.4% and a viscosity of 200 cps. The number average molecular weight of the obtained acrylic resin was 10,000.

Examples 1 to 3 and Comparative Example 1
Add 50 g of acrylic resin polymerized in Production Examples 1 to 4 (solid content 20%) and 0.44 g of sodium hydroxide to 50 g of 20% aqueous solution of polyvinyl alcohol (OKS-8049, Nihon Gosei Co., Ltd.) and stir well. The paints of Examples 1 to 3 and Comparative Example 1 were prepared.

Example 4
250 parts by weight of mica water swelling slurry (concentration 8%, Somasif MEB-3, average particle diameter of 2 to 3 μ, manufactured by Coop Chemical Co., Ltd.) with respect to 100 parts by weight of the solid content of the paint obtained in Example 2 The mixture was mixed and mixed well to prepare a paint.

Comparative Example 2
50 g of 20% aqueous solution of polyvinyl alcohol (OKS-8049, manufactured by Nihon Gosei Co., Ltd.), 50 g of polyacrylic acid aqueous solution (Aquaric HL-415, manufactured by Nippon Shokubai Co., Ltd.) with a solid content of 20%, 0.44 g of sodium hydroxide Was added and stirred well to prepare a coating material of Comparative Example 2.

The paints obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were applied on a base material of 0.250 mm thick A5052 aluminum material (manufactured by Kobe Steel) and baked at 200 ° C. for 3 minutes. Using the obtained coated plate, pencil hardness and water resistance were evaluated by the following methods. The evaluation results are shown in Table 1.

The paint obtained in Example 2 and Comparative Example 2 was applied on the corona surface of a biaxially stretched polyester film (25 μ, E5107, manufactured by Toyobo Co., Ltd.) with a dry film thickness of 3 μ, baked at 200 ° C. for 3 minutes, and 200 Bake at 10 ° C. for 10 minutes. Each of the obtained films was visually checked for coloration, and the oxygen permeability was measured by the method described below. The evaluation results are shown in Table 2.

The paints obtained in Examples 2 and 4 were applied at a dry film thickness of 3 μm on the corona surface of a biaxially stretched polyester film (25 μm, E5107, manufactured by Toyobo Co., Ltd.) and baked at 200 ° C. for 3 minutes. Using each of the obtained films, the oxygen transmission rate was measured at 23 ° C. under the conditions of 65% and 80% humidity by the following method. The evaluation results are shown in Table 3.

<Pencil hardness>
Based on the method described in JIS K-5400 (1990), the measurement was performed using Uni (trade name) manufactured by Mitsubishi Pencil Co., Ltd.
<Adhesion>
In accordance with the method described in JIS K-5400 (1990), the coated plate was cut with a cutter knife on the painted plate at intervals of 1 mm so as to reach the substrate, and 100 grids (10 × 10) were cut create. Nichiban cello tape (registered trademark) was completely adhered to this, and it peeled off rapidly in the direction of 90 ° with respect to the coating surface. The state of the coating film was visually observed and evaluated based on the following criteria.

<Water resistance>
About 80 degreeC 30 minute process, after performing immersion process for 30 minutes to a 80 degreeC water bath, the surface condition and adhesiveness were evaluated on the following references | standards. About 30 minutes of retort processing, after performing the retort processing for 30 minutes at 125 degreeC, the surface condition and adhesiveness were evaluated on the following references | standards. The evaluation results are shown in Table 1.
Surface condition ○ ・ ・ ・ No change.
○ △ ・ ・ Slightly whitening or change in surface condition.
Δ: The surface is whitened or slightly melted.
X: The coating film was dissolved by the treatment.

Adhesion ○ ・ ・ ・ No change.
○ Δ ························································································ −
Δ: Half of the squares peeled off.
X: The whole peeled off.

<Oxygen permeability>
Based on the method described in JIS K 7126B, the oxygen permeability from the sample surface to the back surface was measured twice under the condition of 23 ° C. × 65% RH, and the average value was calculated.

From the results in Table 1, when unbranched poly (meth) acrylic acid is used, as shown in Comparative Example 1, the adhesion is greatly reduced. On the other hand, when branched poly (meth) acrylic acid is used, as shown in Examples 1 to 3, the surface state and adhesion are maintained even after 30 minutes of retorting.

From the results shown in Table 2, the gas barrier coating composition containing poly (meth) acrylic acid into which no branched structure was introduced was yellowed when baked at 200 ° C. for 10 minutes as shown in Comparative Example 2. On the other hand, in the gas barrier coating composition containing poly (meth) acrylic acid into which a branched structure was introduced, as shown in Example 2, no coloring was observed even after baking at 200 ° C. for 10 minutes.

From the results in Table 3, when mica was blended, the humidity dependency of oxygen permeability was greatly improved.

A gas barrier film excellent in retort resistance can be obtained, and can be suitably applied to food packaging, particularly retort foods.

Claims (2)

A gas barrier coating composition comprising polyvinyl alcohol and branched poly (meth) acrylic acid ,
A gas barrier coating composition in which the branched poly (meth) acrylic acid is poly (meth) acrylic acid obtained by copolymerizing alkylene glycol di (meth) acrylate . The manufacturing method of the gas barrier film including the process of apply | coating and heat-treating the gas barrier coating composition of Claim 1 .