JP2002206068A - Resin composition and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition, taking environmental problems into consideration, without containing acrylonitrile, vinyl chloride and vinylidene chloride, capable of exhibiting excellent gas barrier properties, resultantly useful as a coating agent for various kinds of packaging materials and building materials and applicable to food packaging materials, medicinal packaging materials and deterioration preventing materials for building structures utilizing its excellent gas barrier properties when the resin composition is applied to a coating composition. SOLUTION: This gas barrier film-forming resin composition comprises (A) a specific resin, (B) a specific resin and (C) a cross-linking agent, and it is characterized in that the acrylontrile, vinyl chloride and vinylidene chloride are not contained in all the monomers constituting the resin (A) and the resin (B).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a gas-barrier film-forming resin composition. The present invention relates to a method for producing a gas barrier film-forming resin composition. The present invention relates to a gas barrier structure and a gas barrier film obtained by coating a gas barrier film-forming resin composition. The gas-barrier structure and the gas-barrier film obtained according to the present invention correspond to environmental problems.

[0002]

[Prior art] [Technical background] In recent years, diversification of food culture
Due to the sophistication and diversification of medicines, the need to protect the contents of foods and medicines from deterioration and decay for a long period of time has been increasing year by year. Therefore, a high gas barrier property has been required year by year for a plastic film used for a packaging material.

[0003] Conventionally, when a gas barrier property is imparted to a plastic film such as polyethylene, polypropylene, polyethylene terephthalate, polynylon, cellophane or paper, or the like, a gas barrier resin layer is formed on the film. Have been. As a typical example, a gas barrier coating film is formed by applying polyvinylidene chloride (hereinafter referred to as PVDC) on a biaxially stretched film made of a polypropylene film or the like, followed by drying by heating. ing. JP-A-3-5021
No. 1 (applicant; Mitsubishi Yuka Birdish Co., Ltd.)
A technique for producing an aqueous dispersion of a vinylidene chloride polymer having excellent gas barrier properties and printability is disclosed. This technique uses vinylidene chloride 85 as a monomer mixture (1).
After polymerizing 1 to 95% by weight of a monomer selected from methyl methacrylate, methyl acrylate and acrylonitrile, or 5 to 15% by weight of a mixture thereof, methacrylic acid was obtained as a monomer mixture (2). Monomers 20 to 65 selected from the group consisting of methyl and vinyl aromatic compounds
% By weight, and 35 to 80% by weight of a monomer selected from the group consisting of alkyl acrylate, alkyl methacrylate, and vinyl ester, and 0.2 to 5% by weight of a hydroxyl group-containing monomer. In a legal manner, the monomer mixture (2) was added to 100 parts by weight of the monomer mixture (1).
Is a technique for producing a vinylidene chloride-based polymer by using 0.5 to 20 parts by weight of a polymer.

[0004] However, in recent years, the flow of dechlorination has begun to accelerate in the packaging material industry, starting with the environmental problem caused by the dioxin problem. Polyacrylonitrile and polyvinyl alcohol (hereinafter, PVA) have been used as substitute coating agents for PVDC. Etc. have begun to be used.

However, when polyacrylonitrile is used, since acrylonitrile as a monomer has toxicity, it is necessary to remove acrylonitrile monomer remaining without being polymerized with great effort. Further, if the application to be used is in the food field, a gas barrier resin which does not use such highly toxic acrylonitrile monomer as a raw material as much as possible has been desired. In addition, PVA is generally applied as an aqueous solution, but is applied at a low concentration because it tends to have a high viscosity. However, when applied at a low concentration, a long drying time and a large amount of drying energy are required, and there is a problem that productivity is reduced due to poor coating property due to a specific viscosity. The present inventors have already found that a film coated with a resin composition having a specific composition has gas barrier properties in order to solve the above problem (Japanese Patent Application No. 11-141590). However, the requirements for gas barrier properties are becoming more stringent year by year, and further improvement in gas barrier properties has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a resin composition having excellent environmental compatibility, excellent workability and gas barrier properties, a gas barrier structure, and the like. For the purpose.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and have found that vinylidene chloride,
Even without using acrylonitrile and vinyl chloride monomers as raw materials, polypropylene can be obtained by using a crosslinking agent (C) in combination with a resin composition comprising a resin (A) and a resin (B) each containing a specific amount of a carboxyl group. It has been found that when a resin is coated on a film or the like, the gas barrier properties are further improved, and the present invention has been completed. That is, the present invention is specified by the matters described below. (1) A gas-barrier film-forming resin composition comprising a resin (A), a resin (B), and a crosslinking agent (C), wherein the resin (A) has a carboxyl group-containing monomer (a −
1) Based on the total weight of the hydroxyl group-containing monomer (a-2) and the other monomer (a-3), the carboxyl group-containing monomer (a-1) 5 to 5 100% by weight, 0 to 95% by weight of a monomer containing a hydroxyl group (a-2)
And other monomers (a-3) in an amount of 0 to 95% by weight (co)
A polymer (B), wherein the resin (B) is a monomer (b-1) containing a carboxyl group and a monomer (b-
2) and a monomer (b-1) containing a carboxyl group based on the total weight of the other monomers (b-3)
96 to 1% by weight of the total of the monomer (b-2) containing a hydroxyl group and / or the other monomer (b-3) is 0 to 4% by weight.
A (co) polymer of 00% by weight, and the crosslinking agent (C) is used in an amount of 0.05 to 2 molar equivalents relative to the total molar amount of the carboxyl groups and / or hydroxyl groups of the resin (A) and the resin (B). And a gas-barrier film-forming resin composition characterized in that all monomers constituting the resin (A) and the resin (B) do not contain acrylonitrile, vinyl chloride or vinylidene chloride. (2) The carboxyl group-containing monomer (a-1) and / or (b-1) is an unsaturated carboxylic acid, and the hydroxyl group-containing monomer (a-2) and / or (b-2) ) Is a hydroxyl group-containing unsaturated carboxylic acid ester or a hydroxyl group-containing unsaturated ether, and the other monomer (a-3) and / or (b-3) is an alkyl acrylate, an alkyl methacrylate, or an aromatic monomer. At least one selected from the group consisting of monomers, amide group-containing monomers, epoxy group-containing monomers, butadiene, ethylene, and vinyl acetate, wherein the crosslinking agent (C) is chemically bonded to a carboxyl group and / or a hydroxyl group. The gas-barrier film-forming resin composition according to (1), which is a compound that reacts and / or adsorbs. (3) A gas barrier film-forming resin composition comprising the resin (A), the resin (B) and the crosslinking agent (C) is a mixture of the resin (A), the resin (B) and the crosslinking agent (C). The gas-barrier film-forming resin composition according to (1) or (2), wherein: (4) The gas-barrier film-forming resin composition containing the resin (A), the resin (B) and the crosslinking agent (C) is chemically bonded to the resin (A), the resin (B) and the crosslinking agent (C). as well as/
Or the gas-barrier film-forming resin composition according to (1) or (2), which is adsorbed. (5) A film formed from the gas-barrier resin composition has a temperature of 20 ° C. and a relative humidity of 65% with respect to oxygen or carbon dioxide at 20 × 10 ⁻¹³ cm ³ · cm / cm ^2.
The gas-barrier film-forming resin composition according to any one of (1) to (4), which exhibits gas barrier properties of not more than / s / mmHg. (6) 10 to 95% by weight of resin (A) and 90% of resin (B) based on the total weight of resin (A) and resin (B).
(1) to (5).
The gas-barrier film-forming resin composition according to any one of the above. (7) the crosslinking agent (C) is at least one selected from the group consisting of metals and salts thereof, methylol compounds, isocyanate compounds, aldehyde compounds, and glycidyl group-containing epoxy compounds; (6) The gas barrier film-forming resin composition according to any of (6). (8) a carboxyl group-containing monomer (a-1) and / or a carboxyl group-containing monomer (b-1)
The gas-barrier film-forming resin composition according to any one of (1) to (7), which contains acrylic acid and / or methacrylic acid. (9) The monomer containing a hydroxyl group (a-2) and / or the monomer containing a hydroxyl group (b-2) contain 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate. The resin composition for forming a gas barrier film according to any one of (1) to (8). (10) The other monomer (a-3) and / or the other monomer (b-3) are selected from the group consisting of alkyl acrylate, alkyl methacrylate, styrene, vinyl acetate, acrylamide and methacrylamide. The gas-barrier film-forming resin composition according to any one of (1) to (9), which is at least one kind. (11) The method for producing a gas barrier film-forming resin composition according to any one of (1) to (10), wherein the resin (B) is polymerized in the presence of the resin (A), and a crosslinking agent ( A method for producing a gas-barrier film-forming resin composition, comprising mixing C). (12) The method for producing a gas barrier film-forming resin composition according to any one of (1) to (10), wherein the resin (A) is polymerized in the presence of the resin (B), and a crosslinking agent ( A method for producing a gas-barrier film-forming resin composition, comprising mixing C). (13) A gas barrier structure obtained by coating a substrate with the gas barrier film-forming resin composition according to any one of (1) to (10). (14) A gas barrier film obtained by coating a film with the gas barrier film-forming resin composition according to any one of (1) to (10). (15) A gas barrier film having a gas barrier layer and a thermoplastic resin film sandwiching the gas barrier layer from above and below, wherein the gas barrier layer is composed of (1) to (10).
A gas barrier film, characterized by being a layer formed by forming the gas barrier film-forming resin composition according to any one of the above. (16) Gas barrier property imparting, wherein the gas barrier property is imparted to the substrate by applying the gas barrier film-forming resin composition according to any one of (1) to (10) to the substrate. Method. (17) The method for providing gas barrier properties according to (16), wherein the substrate is a film.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

[Gas Barrier Property] The gas barrier property in the present invention is determined according to ASTM D-3985 or JIS K7.
The gas barrier property of the present invention can be measured by the method specified in No. 126, and the numerical value of the gas barrier property of the present invention means a transmission coefficient measured at a temperature of 20 ° C. and a relative humidity of 65%. The oxygen or carbon dioxide permeability coefficient of the resin composition film obtained by the present invention is 20 × 10 ⁻¹³ cm ³ · cm / cm ² / s / mmHg.
Below, more preferably 10 × 10 ^-13 cm ³ · cm / cm
² / s / mmHg or less, more preferably 5 × 10 ⁻¹³ c
m ³ · cm / cm ² / s / mmHg or less, most preferably 2 × 10 ⁻¹³ cm ³ · cm / cm ² / s / mmHg or less.

[Monomer Containing a Carboxyl Group] In the present invention, a monomer containing a carboxyl group (a-
1) · (b-1) is not particularly limited as long as it contains a carboxyl group. Specific examples of the carboxyl group-containing monomers (a-1) and (b-1) in the present invention include, for example, unsaturated acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, and fumaric acid. Carboxylic acids are mentioned, among which acrylic acid, methacrylic acid, maleic acid, and itaconic acid are preferable, acrylic acid,
Methacrylic acid is particularly preferred. These monomers can be selected alone or in combination of two or more.

[Hydroxyl-Containing Monomer] In the present invention, hydroxyl-containing monomers (a-2) and (b-2)
Is not particularly limited as long as it contains a hydroxyl group. The hydroxyl group-containing monomer (a-2) · (b) in the present invention
Specific examples of -2) include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, -Hydroxy vinyl ether, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, a hydroxyl group-containing unsaturated carboxylic acid ester such as polypropylene glycol monomethacrylate or a hydroxyl group-containing unsaturated ether, and these monomers are , Alone or in combination of two or more. Among these, those containing 2-hydroxyethyl acrylate and / or 2-hydroxyethyl methacrylate are particularly preferred. This is because it is excellent in water solubility and good polymerization stability can be obtained.

[Other Monomer (a-3)] In the present invention, the other monomer [other copolymerizable monomer other than (a-1) and (a-2)] (a -3) is other than acrylonitrile, vinylidene chloride and vinyl chloride,
There is no particular limitation. Specific examples of the other copolymerizable monomer (a-3) in the present invention include, for example, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl Acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate, alkyl acrylate such as 2-ethylhexyl methacrylate, Alkyl methacrylate; aromatic monomers such as styrene, α-methylstyrene, divinylbenzene, etc .; acrylamide, methacrylamide, N-methylacryl Amide group-containing monomers such as amide and N-methyl methacrylamide; epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate; styrene sulfonic acid and salts thereof, 2-acrylamide-2-methylpropane sulfonic acid and the like Sulfonic acid group-containing monomers such as salts; butadiene; ethylene; vinyl acetate, and the like. These monomers can be selected alone or in combination of two or more. Among these, at least one selected from the group consisting of alkyl acrylates, alkyl methacrylates, styrene, vinyl acetate, acrylamide and methacrylamide is preferable, and those containing alkyl acrylate and / or alkyl methacrylate are particularly preferable. This is because good polymerization stability can be obtained.

[Other monomer (b-3)] Other monomers [other copolymerizable monomers other than (b-1) and (b-2)] (b-3) Preferred are methyl methacrylate, methyl acrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl acrylate , 2-ethylhexyl methacrylate and styrene.

[Resin (A)] Resin (A) in the present invention
Is a (co) of a monomer (a-1) containing a carboxyl group, a monomer (a-2) containing a hydroxyl group, and another copolymerizable monomer (a-3). It is a polymer. The amount of the monomer (a-1) is 5 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the monomers (a-1), (a-2) and (a-3). % By weight, more preferably 3%
5 to 100% by weight, more preferably 40 to 100% by weight
And The amount of the monomer (a-2) is 0 to 95% by weight, preferably 0 to 60% by weight, based on the total weight. The amount of the other monomer (a-3) is from 0 to 9
5% by weight, preferably 0 to 60% by weight. With such an amount, a sufficient gas barrier property can be obtained.

The total amount of the monomers (a-1) and (a-2) is preferably from 50 to 10 based on the above total amount.
0% by weight, more preferably 70 to 100% by weight, most preferably 90 to 100% by weight. With such a total amount, a sufficient gas barrier property can be obtained. The hydroxyl group-containing monomer (a-2) and the other copolymerizable monomer (a-3) are appropriately selected according to the performance required for the resin. If necessary, a carboxyl group-containing monomer (a-1) 5 to 80
% By weight, 20 to 95% by weight of a hydroxyl group-containing monomer (a-2), and 0 to 75% by weight of another copolymerizable monomer (a-3). The monomer (a-1) is 5 to 50% by weight, the hydroxyl group-containing monomer (a-2) is 50 to 95% by weight, and the other copolymerizable monomer (a-3) is 0 to 45% by weight. More preferably, there is.

[Glass Transition Temperature of Resin (A)] The theoretical glass transition temperature of the resin (A) is not particularly limited, but is generally 0 ° C. to 200 ° C. When the glass transition temperature of the resin (A) is significantly lower than room temperature, for example, below freezing point, there is a problem that the formed film becomes sticky. On the other hand, when the temperature exceeds 200 ° C., in order to prevent film formation failure, It is necessary to remarkably increase the drying temperature during molding, which is a problem.

[Weight-Average Molecular Weight of Resin (A)] The weight-average molecular weight of the resin (A) is not particularly limited, but is generally preferably from 1,000 to 1,000,000. When the molecular weight is less than 1,000, there is a problem that the water resistance of the formed film is reduced. When the molecular weight is more than 1,000,000, the viscosity of the resin increases and there is a problem that handling becomes difficult.
The molecular weight can be measured by GPC (gel permeation chromatography).

[Resin (B)] Resin (B) in the present invention
Is the total weight of the carboxyl group-containing monomer (b-1), the hydroxyl group-containing monomer (b-2), and the other copolymerizable monomer (b-3). As a reference, 0 to 4% by weight of a monomer (b-1) containing a carboxyl group
And a monomer selected from the group consisting of a hydroxyl group-containing monomer (b-2) and another copolymerizable monomer (b-3).
It consists of a copolymer with at least one or more monomers of 96 to 100% by weight. When the amount of the monomer (b-1) exceeds 4% by weight, the viscosity of the resin increases, and handling may be difficult. The amount of the monomer (b-3) is preferably from 70 to 100, based on the total weight of the monomer (b-1), the monomer (b-2) and the monomer (b-3). % By weight, more preferably 85-100% by weight, most preferably 96-100% by weight. By doing so, the resin (B) can be obtained with good production stability, and the workability of the obtained resin composition is improved.

When water resistance is particularly required, 0 to 2% by weight of a monomer (b-1) containing a carboxyl group,
The hydroxyl group-containing monomer (b-2) is preferably 0 to 20% by weight, and the other copolymerizable monomer (b-3) is preferably 78 to 100% by weight, more preferably a carboxyl group-containing monomer. (B-1) 0% by weight, hydroxyl group-containing monomer (b-2) 0 to 10% by weight, and other copolymerizable monomer (b-3) 90 to 100% by weight.

[Glass transition temperature of resin (B)] The theoretical glass transition temperature of the resin (B) is not particularly limited, but is generally -50 ° C to 200 ° C. The glass transition temperature is appropriately selected under drying conditions when the composition of the present invention is used, and under conditions that allow sufficient film formation.

[Weight Average Molecular Weight of Resin (B)] The weight average molecular weight of the resin (B) is not particularly limited, but is generally 10,000 to 10,000,000.

[Crosslinking agent (C)] The crosslinking agent (C) in the present invention improves the water resistance of a film formed from the resin composition and, in some cases, improves the density of the resin composition film. It plays a role in improving gas barrier properties under humidity conditions. The crosslinking agent (C) may be any compound that chemically reacts with and / or adsorbs a carboxyl group and / or a hydroxyl group. Specific examples thereof include iron, zinc, tin,
Metals such as copper, aluminum and zirconium and salts thereof; inorganic acids such as hydrochloric acid and sulfuric acid and salts thereof; organic acids such as phosphoric acid and acetic acid and salts thereof; methylol compounds such as melamine; isocyanate compounds; epoxy containing a glycidyl group Compounds; aldehyde compounds such as glyoxal;
Oxidizing agents such as peroxides; imines such as ethyleneimine; imide group-containing compounds; oxazoline group-containing compounds; aziridinyl group-containing compounds. Among these compounds, particularly preferred as the crosslinking agent (C) are metal salts and salts thereof, methylol compounds, isocyanate compounds,
An epoxy compound, an aldehyde compound, and an imide group-containing compound.

The rate of addition of these crosslinking agents is 0.05 to 2 molar equivalents based on the total molar amount of the carboxyl groups and / or hydroxyl groups of the resin (A) and the resin (B), but is more preferably. , 0.1 to 1 molar equivalent. In general, the optimum addition amount differs depending on the addition ratio of the crosslinking agent and the type of the crosslinking agent. However, when the addition amount is less than 0.05 molar equivalent, the water resistance effect due to the addition of the crosslinking agent may not be exhibited, and 2 mol If the amount is more than the equivalent, an unreacted crosslinking agent remains in the resin film, so that the gas barrier property may decrease. The crosslinking agent to be used is, among the above compounds, alone
Alternatively, two or more kinds can be used in combination.

[Carboxyl group contained in resin (A) and resin (B)] Carboxyl group contained in resin (A) and resin (B) is a metal salt such as potassium or sodium; ammonia, amine The organic bases can neutralize part or all of the organic base. Organic bases are preferred as the neutralizing agent from the viewpoint of improving gas barrier properties and water resistance of the film.

A monomer containing a carboxyl group (a-
The total amount of 1) and (b-1) is preferably 10 to 9 based on the total weight of the resin (A) and the resin (B).
The content is 5% by weight, more preferably 20 to 80% by weight. By doing so, good gas barrier properties can be obtained.

[Gas Barrier Film-Forming Resin Composition Containing Resin (A), Resin (B) and Crosslinking Agent (C)] Resin (A), resin (B) and crosslinking agent (C) according to the present invention. ) Is a gas barrier film-forming resin composition comprising a resin (A), a resin (B), and a crosslinking agent (C),
Or a chemically bonded composition, the chemical bond is a covalent bond, an ionic bond, a hydrogen bond, a coordinate bond, and the like,
This also includes the adsorption phenomenon. The ratio of the resin (A) to the resin (B) is 10 to 95% by weight of the resin (A) and the resin (B) based on the total weight of the resin (A) and the resin (B).
It is preferably 90 to 5% by weight. Resin (A) is 1
If the amount is less than 0% by weight, the gas barrier property of the formed film may decrease, and if it exceeds 95% by weight, the water resistance of the film may decrease. More preferably, it is 30 to 90% by weight of the resin (A) and 70 to 10% by weight of the resin (B). Most preferably, it is 40 to 90% by weight of the resin (A) and 60 to 10% by weight of the resin (B).

The resin (A), the resin (B) and the resin (C) in the present invention are preferably dissolved or dispersed in a solvent in terms of handling. The resin (A) is dissolved in the solvent, the resin (B) is dispersed in the solvent as resin particles, and the crosslinking agent (C)
Is more preferably dissolved or dispersed in a solvent, and the resin particles containing the resin (A) and the resin (B) in the same particle are dispersed in water, and the crosslinking agent (C) is dissolved or dispersed in water. Most preferred. In addition, “the resin particles containing the resin (A) and the resin (B) in the same particle are dispersed in water” means that the resin (B) is dispersed in water and the surface of the resin (B) is A) refers to a state in which A) is adsorbed or bound, for example, a form of a composite emulsion or the like comprising a hydrophobic core made of an acrylic polymer and a water-soluble shell made of a water-soluble polymer.

As described above, a water-soluble polymer such as PVA is effective as a gas-barrier material, but has a problem that the viscosity increases when it is made into an aqueous solution. This is considered to be due to entanglement between molecular chains of the water-soluble polymer in water. In contrast, when the form of the composite emulsion is adopted, the water-soluble polymer is adsorbed or bonded to the surface of the hydrophobic resin dispersion, so that the entanglement between the molecular chains of the water-soluble polymer is suppressed, and the viscosity increases. Can be suppressed. For this reason,
As compared with the case where the form of the aqueous solution is adopted, good workability can be obtained even when the concentration of the water-soluble polymer is increased.

The solvent used is not particularly restricted but includes, for example, water; alcohols such as methanol, ethanol, isopropyl alcohol and butanol; water-soluble solvents such as ketones such as methyl ethyl ketone and acetone, glycols and ethers. Organic solvents; water-insoluble solvents such as toluene and xylene can be used alone or in combination of two or more. In particular, a solvent containing water as a main component is preferable from the viewpoint of environmental problems.

[Production Method of Resin (A), Resin (B) and Gas Barrier Film-Forming Resin Composition Containing Crosslinking Agent (C)] Resin (A), Resin (B) and Crosslinking According to the Present Invention The production method (polymerization method) of the resin (A) and the resin (B) in the gas-barrier film-forming resin composition containing the agent (C) is not particularly limited, but is usually the polymerization heat. Polymerization is carried out in a solvent due to the problem of control of the polymerization. Generally, radical polymerization is preferred.

[Initiator] Specific examples of the initiator used in the case of performing the radical polymerization include, for example, hydrogen peroxide;
Persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate; cumene hydroperoxide, t-
Organic peroxides such as butyl hydroperoxide, benzoyl peroxide, t-butylperoxy-2-ethylhexanoate and t-butylperoxybenzoate; azo compounds such as azobisisobutyronitrile; Redox initiators in combination with metal ions such as ions and reducing agents such as sodium sulfoxylate, formaldehyde, sodium pyrosulfite, sodium bisulfite, L-ascorbic acid, Rongalite and the like. The amount of the initiator used at the time of radical polymerization is generally 0.1 to 20% by weight based on the total weight of the monomers.

[Molecular weight regulator] If necessary, t
Mercaptans such as -dodecylmercaptan and n-dodecylmercaptan; allyl compounds such as allylsulfonic acid, methallylsulfonic acid and soda salts thereof can also be used as molecular weight regulators.

[Surfactant] Further, in order to improve the stability of the resin particles, it is possible to use a surfactant used in ordinary emulsion polymerization. Particularly, when the solvent is mainly composed of water. It is suitable for. Examples of such a surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and other reactive surfactants. One or more of these surfactants may be used in combination. Can be.

Nonionic surfactant Specific examples of the nonionic surfactant include, for example, polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene oleyl phenyl ether, polyoxyethylene nonyl phenyl ether, Oxyethylene / oxypropylene block copolymer, tert-octylphenoxyethyl polyethoxyethanol, nonylphenoxyethyl polyethoxyethanol, and the like are included.

Specific examples of the anionic surfactant include, for example, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, stearic acid Sodium, potassium oleate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, tert -Octylphenoxyethoxy polyethoxyethyl sulfate sodium salt, etc. It is.

Cationic surfactant Specific examples of the cationic surfactant include lauryltrimethylammonium chloride, stearyltrimethylammonium chloride and the like.

[Average Particle Diameter of Resin Particles] In the present invention, the average particle diameter of the resin particles constituting the resin composition is as follows:
It is preferably from 1 to 1000 nm, more preferably from 1 to 50 nm.
0 nm. When the particle size exceeds 1000 nm,
There are problems such as a loss of smoothness of the formed film and a decrease in gas barrier properties.

[Polymerization method] At the time of polymerization, the above-mentioned various monomers are mixed with a solvent in a lump or divided.
Alternatively, it is continuously added dropwise and polymerized at a temperature of 0 ° C. to 200 ° C. in the presence of the initiator described above.

The resin composition of the present invention comprises a resin (A)
And the resin (B) and the crosslinking agent (C) are mixed or chemically bonded. After the resin (A) and the resin (B) are polymerized by the method described above, the resin (A) and the resin (B) are polymerized. ) And a cross-linking agent (C); a method of polymerizing the resin (B) in the presence of the resin (A) and mixing and stirring the cross-linking agent (C); a method of mixing the resin (B) in the presence of the resin (B). A desired resin composition can be obtained by, for example, a method of polymerizing A) and mixing and stirring the crosslinking agent (C). As the polymerization performed at this time, it is possible to use the above-described polymerization method, solvent, initiator, molecular weight modifier, and surfactant.

[Additives] Various additives may be added to the resin composition of the present invention, if necessary. As various additives, for example, pigments, film-forming aids, wetting agents, defoamers, preservatives, thickeners, heat stabilizers, ultraviolet absorbers, lubricants,
Examples include a coloring agent, an antistatic agent, an antiblocking agent, and an inorganic salt. Among them, a wetting agent is preferably used in combination when coating the resin composition on a polyolefin film. Further, the pigment can improve various performances of the formed film, and thus is preferably used in combination.

[Pigment] Specific examples of the pigment include kaolinite, halloysite, montmorillonite, vercurite, dickite, nacryte, antigolite, pyrophyllite, hectorite, beidellite, margarite, talc, and tetrasilyl. Inorganic layered compounds such as mica, muscovite, phlogopite, chlorite; inorganic compounds such as kaolin, calcium carbonate, titanium oxide, silicon oxide, calcium fluoride, lithium fluoride, alumina, barium sulfate, zirconia, calcium phosphate; Organic fillers such as polystyrene-based particles can be used. The addition ratio of these pigments is generally 1 to 30% by weight based on the total weight of the monomers. Furthermore, 1 to 15% by weight
Is more preferred. When the addition ratio of the pigment exceeds 30% by weight, fine gaps are formed in the formed film, and the gas barrier property may decrease. When the addition ratio is less than 1% by weight, the effect of the addition may not be obtained. is there.

[Third Component] In addition to the resin (A), the resin (B) and the crosslinking agent (C), a known water-soluble resin can be used in combination as the third component. Known water-soluble resins include, for example, polyalcohol polymers, sugars, amino acids, polyethylene oxides, polyethylene glycols, celluloses, and the like.

[Coating Composition] A coating composition containing the resin composition of the present invention is applied to various substrates, for example, films, papers, and building boards made of thermosetting resins, thermoplastic resins and the like. A film and a structure having gas barrier properties can be obtained by applying the composition to a building or a building structure to form a film. In particular, by coating and forming a film on a thermoplastic resin film or paper,
A gas barrier film for packaging can be obtained. Also,
When the film and the structure having gas barrier properties have a multilayer structure, the layer coated with the coating agent composition containing the resin composition according to the present invention is used for any of the upper layer, the lower layer, and the intermediate layer. It does not matter.

[Thermoplastic resin film] Specific examples of the thermoplastic resin film include polyolefins such as polyethylene and polypropylene; polyethylene terephthalate;
Polybutylene terephthalate, polyethylene-2,6-
Polyesters such as naphthalate; polyamides such as nylon 6 and nylon 12; ethylene-vinyl acetate copolymer or saponified product thereof; polystyrene; polycarbonate; polysulfone; polyphenylene oxide; polyphenylene sulfide; aromatic polyamide; polyimide; polyamideimide; A polyvinyl alcohol, and a copolymer thereof. From the viewpoints of cost performance, transparency, gas barrier properties, and the like, films of polyolefin, polyester, polyamide, and the like are preferable.

[Gas Barrier Film] The gas barrier film of the present invention is obtained by coating a film with the gas barrier film-forming resin composition of the present invention. Above all, a gas barrier film having a gas barrier layer and a thermoplastic resin film sandwiching the gas barrier layer from above and below, wherein the gas barrier layer is formed by forming the gas barrier film-forming resin composition of the present invention. It is preferable to have a configuration as follows. For example, a first layer made of a thermoplastic resin film, a second layer formed by forming the gas barrier film-forming resin composition of the present invention, and a third layer made of a thermoplastic resin film are laminated in this order. A preferred embodiment is a multilayer film having the above structure. By adopting such a structure, it is possible to effectively prevent the film layer made of the resin composition for forming a gas barrier film of the present invention from being damaged or absorbing water, thereby deteriorating the film properties. The thickness of the layer made of the gas-barrier film-forming resin composition is appropriately set. For example, the thickness is about 0.1 to 20 μm, preferably about 0.5 to 10 μm (thickness after film formation and drying). be able to. As a film forming method, any generally known method can be used without any particular problem.
For example, a film can be formed by uniformly coating the resin composition on one surface of a thermoplastic resin film using a bar coater, a roll coater, or the like, and then evaporating the solvent using a hot-air dryer or the like.

[Building Boards / Building Structures]
By coating and forming a film on a building board or a building structure, it is possible to obtain an effect of preventing oxidation deterioration due to oxygen and neutralization due to carbon dioxide gas. Examples of building board components include gypsum board, cement board, wool cement board, asbestos cement board, fiber board, calcium silicate board, particle board, plywood, and specific examples of building structures. Examples include concrete, steel frames, walls, beams, floors and the like.

[Method of imparting gas barrier properties] The resin composition of the present invention is applied to various substrates, for example, films, papers, architectural boards, architectural structures and the like made of thermosetting resins, thermoplastic resins and the like. By forming a film, a gas barrier property can be imparted to the substrate.

[0048]

Next, the present invention will be described more specifically with reference to examples. Hereinafter, all parts and percentages are based on weight.

Example 1 746 parts of deionized water was charged into a reaction vessel and heated to 80 ° C. under a nitrogen stream. Separately, 2-hydroxyethyl methacrylate 290
And a mixture of 194 parts of acrylic acid were neutralized with 108 parts of a 20% aqueous sodium hydroxide solution, and 49 parts of potassium persulfate was added and dissolved in a reaction vessel as an initiator. The mixture was dropped into the reaction vessel in 2 hours,
Thereafter, the temperature was further maintained at the same temperature for 2 hours to complete the polymerization.
Thereafter, 590 parts of ion-exchanged water is added to the reaction vessel, and 80
The temperature was raised to ° C. Separately, 57 parts of n-butyl acrylate, 2 parts of 2-hydroxyethyl methacrylate,
A mixed solution of 1 part of methacrylic acid was prepared, and 0.3 part of ammonium persulfate was added and dissolved as an initiator in the reaction vessel. After that, the monomer mixture was dropped into the reaction vessel in 3 hours. The mixture was maintained at the same temperature for 1 hour, 0.1 part of ammonium persulfate was added as a catalyst, and further maintained at the same temperature for 2 hours to complete the polymerization. The solid content of the obtained resin is 30%, pH
Is 4.8, and the weight average particle diameter by light scattering measurement is 0.3.
μm. Cymel C350 (Mitsui Cytec Co., Ltd.) was added to the obtained resin as a melamine-based cross-linking agent at 165.
Was added and stirred and mixed well to obtain a gas-barrier film-forming resin composition.

The obtained resin was applied on a polyethylene terephthalate film (hereinafter referred to as PET) having a thickness of 23 μm so that the film thickness after drying was 2 μm.
After drying with a hot air drier for 1 minute to evaporate water, the film was further heated with a hot air drier at 150 ° C. for 3 minutes to prepare an evaluation film, and the oxygen gas permeability at a temperature of 20 ° C. and a relative humidity of 65%. Was measured. Thereafter, the oxygen gas permeability and oxygen gas permeability coefficient of the resin film alone were calculated by the following formulas. The results are shown in Table 1. 1 / P <total> = 1 / P <film> + 1 / P <
PET> P <total>: Oxygen gas permeability of a laminated film obtained by laminating a PET film and a resin composition film P <film>: Oxygen gas permeability of a resin composition single film P <PET>: Polyethylene terephthalate film (PET) Oxygen gas permeability of a single substance Gas permeability coefficient = 1.523 × 10 ⁻¹² × P <film>
× dd: thickness of resin composition unit film (mm) [Example 2] 635 parts of deionized water was charged into a reaction vessel,
The temperature was raised to 80 ° C. under a nitrogen stream. Separately, 40 parts of 2-hydroxyethyl methacrylate, 3 parts of acrylic acid
63 parts of a mixed solution was prepared, and 41 parts of potassium persulfate was added as an initiator to the reaction vessel and dissolved.
The mixture was dropped into the reaction vessel over a period of time, and then kept at the same temperature for 2 hours to complete the polymerization. Then, ion-exchanged water 55
6 parts and 222 parts of a 20% aqueous sodium hydroxide solution were added to the reaction vessel, and the temperature was raised to 80 ° C. Separately, a mixed solution of 105 parts of n-butyl acrylate, 3 parts of 2-hydroxyethyl methacrylate, 2 parts of methacrylic acid, and 0.2 part of n-dodecyl mercaptan was prepared, and ammonium persulfate was added to the reaction vessel as an initiator. After charging and dissolving 0.6 part, the above monomer mixture was dropped into the reaction vessel in 3 hours, and then further kept at the same temperature for 1 hour, and 0.1 part of ammonium persulfate was added as a catalyst, Further, the temperature was maintained at the same temperature for 2 hours to complete the polymerization. The solid content of the obtained resin is 30%, pH
Is 4.2 and the weight average particle diameter by light scattering measurement is 0.3.
μm. 58 parts of Cymel C350 (manufactured by Mitsui Cytec Co., Ltd.) was added to the obtained resin as a melamine-based crosslinking agent, and the mixture was thoroughly stirred and mixed to obtain a gas-barrier film-forming resin composition. Thereafter, an evaluation film was prepared in the same manner as in Example 1, the oxygen gas permeability was measured, and the oxygen gas permeability coefficient was calculated. The results are shown in Table 1.

Comparative Example 1 After the same resin composition as in Example 1 was polymerized, an evaluation film was prepared in the same manner as in Example 1 without adding a crosslinking agent, and the oxygen gas permeability was measured. ,
The oxygen gas permeability coefficient was calculated. The results are shown in Table 1.

[Comparative Example 2] After the same resin composition as in Example 2 was polymerized, an evaluation film was prepared in the same manner as in Example 2 without adding a crosslinking agent, and the oxygen gas permeability was measured. ,
The oxygen gas permeability coefficient was calculated. The results are shown in Table 1.

[0053]

[Table 1]

[0054]

According to the present invention, the resin composition according to the present invention is a resin composition containing no acrylonitrile, vinyl chloride, and vinylidene chloride, and exhibits extremely excellent gas barrier properties. Therefore, it is useful as a coating agent for various packaging materials and building materials. When the resin composition according to the present invention is applied to a coating composition, it can be applied to a food packaging material, a pharmaceutical packaging material, and a building structure deterioration preventing material by utilizing the excellent gas barrier properties. Summarizing the above, the present invention exhibits at least the effects of the following inventions. Respond to environmental issues. Demonstrates excellent gas barrier properties. It is useful as a coating agent for various packaging materials and building materials.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09D 133/02 C09D 133/02 133/14 133/14 F term (Reference) 4F100 AB01H AC05A AK01A AK01B AK01C AK11A AK24A AK25A AK25K AK31H AK36 AK36H AK42 AK51H AK53H AL07A AT00B BA02 BA03 BA06 BA10B BA10C CA02A DE01A EH462 GB15 JB09A JB16B JB16C JD02A JD14A JM02A 4J038 CC02 CH1 CG12 CG CG CG CG CG CG CG CG JB38 KA02 KA03 LA02 MA08 MA09 MA10 NA08 PB04 PC08

Claims (17)

[Claims] 1. A gas-barrier film-forming resin composition comprising a resin (A), a resin (B) and a crosslinking agent (C), wherein the resin (A) is a monomer having a carboxyl group. (A-1), a hydroxyl-containing monomer (a-2),
And a carboxyl-containing monomer (a-1) 5 to 100 based on the total weight of the other monomers (a-3).
% By weight, a (co) polymer of 0 to 95% by weight of a monomer (a-2) containing a hydroxyl group and 0 to 95% by weight of another monomer (a-3), wherein the resin (B) is A monomer containing a carboxyl group (b-1), a monomer containing a hydroxyl group (b-2),
And 0 to 4% by weight of a monomer (b-1) containing a carboxyl group and a monomer (b-2) containing a hydroxyl group, based on the total weight of the other monomers (b-3) And / or 96 to 100% by weight of a (co) polymer as a total of the other monomers (b-3), and the crosslinking agent (C) contains the carboxyl groups of the resin (A) and the resin (B) and Acrylonitrile, vinyl chloride, vinylidene chloride is added to all monomers constituting the resin (A) and the resin (B) in an amount of 0.05 to 2 molar equivalents with respect to the total molar amount of the hydroxyl groups. A gas-barrier film-forming resin composition, which does not contain any gas. 2. The carboxyl group-containing monomer (a-1) and / or (b-1) is an unsaturated carboxylic acid, and contains a hydroxyl group-containing monomer (a-2) and / or (b). -2)
Is a hydroxyl group-containing unsaturated carboxylic acid ester or a hydroxyl group-containing unsaturated ether, and the other monomer (a-3)
And / or (b-3) is selected from the group consisting of alkyl acrylates, alkyl methacrylates, aromatic monomers, amide group-containing monomers, epoxy group-containing monomers, butadiene, ethylene, and vinyl acetate. The gas-barrier film-forming resin composition according to claim 1, wherein the crosslinking agent (C) is a compound that chemically reacts with and / or adsorbs a carboxyl group and / or a hydroxyl group. . 3. A gas-barrier film-forming resin composition comprising a resin (A), a resin (B) and a crosslinking agent (C), comprising a resin (A), a resin (B) and a crosslinking agent (C). The gas-barrier film-forming resin composition according to claim 1, which is a mixture. 4. A gas-barrier film-forming resin composition comprising a resin (A), a resin (B) and a crosslinking agent (C), wherein the resin (A), the resin (B) and the crosslinking agent (C) are The gas-barrier film-forming resin composition according to claim 1, wherein the resin composition is chemically bonded and / or adsorbed. 5. A film formed from the gas-barrier resin composition, at a temperature of 20 ° C. and a relative humidity of 65%.
20 × 10 ^-13 cm ³ · cm per oxygen or carbon dioxide
The gas-barrier film-forming resin composition according to any one of claims 1 to 4, wherein the resin composition exhibits gas barrier properties of not more than / cm ² / s / mmHg. 6. The resin (A) is 10 to 95% by weight based on the total weight of the resin (A) and the resin (B), and the resin (B)
The gas-barrier film-forming resin composition according to any one of claims 1 to 5, wherein the content is 90 to 5% by weight. 7. The cross-linking agent (C) is at least one selected from the group consisting of metals and salts thereof, methylol compounds, isocyanate compounds, aldehyde compounds, and glycidyl group-containing epoxy compounds. 7. The gas-barrier film-forming resin composition according to any one of 1 to 6. 8. The resin according to claim 1, wherein the resin (A) and the resin (B) are dissolved or dispersed in water, and the crosslinking agent (C) is dissolved or dispersed in water. A gas barrier film-forming resin composition according to any one of the above. 9. The resin (A) is dissolved in water, the resin (B) is dispersed in water as resin particles, and the crosslinking agent (C) is dissolved or dispersed in water. Items 1 to 7
The gas-barrier film-forming resin composition according to any one of the above. 10. The method according to claim 1, wherein the resin particles containing the resin (A) and the resin (B) in the same particle are dispersed in water, and the crosslinking agent (C) is dissolved or dispersed in water. Item 8. The gas-barrier film-forming resin composition according to any one of Items 1 to 7. 11. The method for producing a gas-barrier film-forming resin composition according to any one of claims 1 to 10, wherein
A method for producing a gas-barrier film-forming resin composition, comprising polymerizing a resin (B) in the presence of a resin (A) and mixing a crosslinking agent (C). 12. The method for producing a gas-barrier film-forming resin composition according to any one of claims 1 to 10, wherein
A method for producing a gas-barrier film-forming resin composition, comprising polymerizing a resin (A) in the presence of a resin (B) and mixing a crosslinking agent (C). 13. A gas-barrier structure obtained by coating a substrate with the gas-barrier film-forming resin composition according to any one of claims 1 to 10. 14. A gas-barrier film obtained by coating a film with the gas-barrier film-forming resin composition according to any one of claims 1 to 10. 15. A gas barrier film comprising a gas barrier layer and a thermoplastic resin film sandwiching the gas barrier layer from above and below, wherein the gas barrier layer is formed with a gas barrier film according to any one of claims 1 to 10. A gas barrier film, which is a layer formed by forming a conductive resin composition. 16. A gas-barrier property imparting to a substrate by applying the gas-barrier film-forming resin composition according to any one of claims 1 to 10 to the substrate. Method. 17. The method according to claim 16, wherein the substrate is a film.