JP6527402B2 - Polyolefin resin aqueous dispersion and packaging material - Google Patents

Description

   The present invention relates to an aqueous polyolefin resin dispersion suitable as an anchor coat agent for extrusion lamination.

Polyolefin resins are widely used in large quantities in various fields such as electricity, electronics, automobiles, and packaging because they are excellent in mechanical properties, chemical properties and recycling properties. Polyolefin resins are known as poorly adhesive resins because they do not have polar groups in their molecules, and their use in applications requiring coating or adhesion has been difficult. So far, coating agents specialized for polyolefin resin substrate applications have been developed, and among them, many methods for using the acid-modified polyolefin resin as a coating agent by aqueous dispersion are proposed.
It has also been conventionally practiced to add additives to the acid-modified polyolefin resin aqueous dispersion for the purpose of enhancing the performance and imparting functionality. In such a technique, suppression of thickening and gelation over time is one of the problems. On the other hand, the prior art of applying a water-insoluble plasticizer to the acid-modified polyolefin resin aqueous dispersion has not been found so far.

   As one application of the acid-modified polyolefin resin aqueous dispersion, an anchor coating agent used for producing a packaging material is known, and by using the same for adhesion and content resistance (in packaging material, the content of It is known that a packaging material excellent in the ability to suppress the phenomenon in which the adhesive strength between the base material layer and the sealant layer decreases with time or during peeling during storage can be obtained (Patent Documents 1 to 4). 3). Patent documents 1 to 3 have various laminated constitutions obtained by extruding and laminating a polyolefin resin using an acid-modified polyolefin resin aqueous dispersion containing a specific crosslinking agent as an anchor coating agent, and the content resistance Excellent packaging materials have been proposed.

JP, 2010-5802, A JP, 2010-5803, A JP, 2011-73728, A

   However, when an anchor coating agent comprising an aqueous polyolefin resin dispersion proposed in Patent Documents 1 to 3 is applied to a base material layer comprising a barrier layer, a thermoplastic resin layer, etc. and dried to form a coating film And warping of the base material may occur. The base material layer in which warpage has occurred has a problem that the processability at the time of manufacturing the packaging material and the handleability of the resulting packaging material are deteriorated.

Moreover, when extrusion laminating as a sealant layer a polyethylene resin by the method proposed by patent documents 1-3, if extrusion temperature is not set as high temperature as 300 degreeC or more, expression of adhesion performance etc. is inadequate. The If the extrusion temperature is high, the smoke at the time of lamination becomes intense, which causes the environment at the production site to be deteriorated. In addition, the resulting packaging material has a unique odor derived from polyethylene resin (sometimes referred to by those skilled in the art as "poly odor") generated by the oxidation of polyethylene resin, and the poly odor in the content to be packaged Had the problem that odor transfer occurred.
On the other hand, low temperature sealability is required for some packaging materials, in which case ethylene copolymers are generally used as sealants. Since the ethylene-based copolymer has a melting point lower than that of a general polyethylene resin, a setting of 240 ° C. or less is adopted as the extrusion temperature. However, at such a low extrusion temperature, sufficient adhesion can not be obtained even if an anchor coating agent comprising an aqueous dispersion of polyolefin resin proposed in Patent Documents 1 to 3 is used.

   Furthermore, in the polyolefin resin aqueous dispersions of Patent Documents 1 to 3, the adhesion may be insufficient when the line speed during extrusion lamination is as high as 50 m / min or more. That is, there is also a problem in increasing the line speed of the extrusion laminating process, that is, productivity.

   With respect to the above problems, in the packaging material produced by extrusion lamination, there is no warp of the substrate while maintaining good adhesion and content resistance, and there is no smoke or poly odor during processing. Another object of the present invention is to provide an aqueous dispersion of a polyolefin resin which can lower the extrusion temperature and lower the line speed at the time of extrusion lamination, and a laminate using the same.

   As a result of intensive studies to solve the above problems, the present inventors have found that aqueous dispersions containing an acid-modified polyolefin resin of a specific structure, an epoxidized vegetable oil, and an aqueous medium have stable liquid properties and are extruded. The present invention has been found to be suitable as an anchor coating agent for lamination.

That is, the gist of the present invention is as follows.
(A) an acid-modified polyolefin resin (A) having an unsaturated carboxylic acid content of 0.1 to 10% by mass, an epoxidized vegetable oil (B), and an aqueous medium; A polyolefin resin aqueous dispersion characterized in that the content of (a) is in the range of 0.01 to 30 parts by mass.

ADVANTAGE OF THE INVENTION According to this invention, the wettability to a base material is favorable, and even when it preserve | saves for a long period of time, a viscosity increase is suppressed, and the aqueous dispersion which has uniform characteristics is provided. Moreover, when the aqueous dispersion of the present invention is applied to a substrate and dried to form a coated film, warping of the substrate is unlikely to occur, and a highly transparent coated film can be obtained.
The aqueous dispersion of the present invention is suitable as an anchor coat agent for extrusion lamination, and it is possible to obtain a packaging material excellent in content resistance even when extrusion lamination of a polyethylene resin at a low temperature of 300 ° C. or less. it can. As the extrusion temperature is lowered, it is also possible to suppress smoke at the time of lamination and the generation of poly-odor of the packaging material. Furthermore, even when an ethylene-based copolymer requiring extrusion lamination at a low temperature is extrusion-laminated at 240 ° C. or less, it is possible to obtain a packaging material excellent in content resistance.
Furthermore, since it is possible to exhibit sufficient adhesiveness even for speeding up of the extrusion laminate production line, the productivity of the packaging material is also excellent.

   Hereinafter, the present invention will be described in detail.

   The aqueous polyolefin resin dispersion of the present invention contains an acid-modified polyolefin resin (A), an epoxidized vegetable oil (B), and an aqueous medium.

   The acid-modified polyolefin resin (A) contains an olefin component as a main component, and as the olefin component, carbon such as ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene and the like The number 2 to 6 alkenes are preferred, and mixtures of these may be used. Among them, from the viewpoint of improving adhesion, alkenes having 2 to 4 carbon atoms such as ethylene, propylene, isobutylene and 1-butene are more preferable, ethylene and propylene are particularly preferable, and ethylene is further preferable.

   The content of the olefin component in the acid-modified polyolefin resin (A) is preferably 45 to 99.9% by mass, more preferably 55 to 99.8% by mass, and 60 to 99.7% by mass Is more preferably 70 to 99.5% by mass, and most preferably 80 to 99.0% by mass. When the content of the olefin component is out of the range of 45 to 99.9% by mass, it is difficult to make the aqueous dispersion described later, the adhesiveness is lowered, or the epoxidized vegetable oil (B) is contained in the aqueous dispersion. Evenly, the effect of dissolving and / or dispersing tends to deteriorate.

The acid-modified polyolefin resin (A) contains an unsaturated carboxylic acid component from the viewpoints of improving the adhesiveness and also improving the dispersibility of the aqueous dispersion and mixing with the epoxidized vegetable oil (B). is necessary.
Examples of the unsaturated carboxylic acid component include acrylic acid, methacrylic acid, (anhydride) maleic acid, (anhydride) itaconic acid, fumaric acid, crotonic acid and the like, as well as half esters and half amides of unsaturated dicarboxylic acids. Among them, acrylic acid, methacrylic acid and (anhydride) maleic acid are preferable, and (anhydride) maleic acid is particularly preferable. In addition, "(anhydride)-acid" means "-acid or anhydride-acid." That is, (anhydride) maleic acid means maleic acid or maleic anhydride.
The unsaturated carboxylic acid component may be copolymerized with the olefin component, and the form thereof is not limited. As the state of copolymerization, for example, random copolymerization, block copolymerization, graft copolymerization (graft modification), etc. Can be mentioned.

   The content of the unsaturated carboxylic acid component needs to be in the range of 0.1 to 10% by mass of the acid-modified polyolefin resin (A). As a minimum of content, 0.2 mass% or more is preferable, 0.5 mass% or more is more preferable, 1 mass% or more is more preferable, 2 mass% or more is particularly preferable. The upper limit of the content is preferably 8% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and particularly preferably 3% by mass or less. When the content of the unsaturated carboxylic acid component is less than 0.1% by mass, adhesion is reduced or it is difficult to form an aqueous dispersion, and when the content exceeds 10% by mass, When the adhesiveness or water-resistant adhesiveness (adhesiveness when the adhesive layer comes in contact with moisture) is lowered or when it is made an aqueous dispersion, the epoxidized vegetable oil (B) is dissolved and / or uniformly in the aqueous dispersion. Or the dispersing effect tends to deteriorate.

The acid-modified polyolefin resin (A) is an epoxidized vegetable oil (B as a more excellent adhesive property or aqueous dispersion by further copolymerizing components other than the above-mentioned olefin component and unsaturated carboxylic acid component) Stability can be imparted.
As such other components, specifically, (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethyl maleate, diethyl maleate Maleic acid diesters such as dibutyl maleate, alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, and vinyl esters Examples thereof include vinyl alcohol obtained by saponification with a basic compound and the like, (meth) acrylic acid amides and the like, and mixtures thereof. Among them, (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate, vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and the like The vinyl esters component of is preferred, and (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate and butyl (meth) acrylate are more preferred. In addition, "(meth) acrylic acid ~" means "acrylic acid ~ or methacrylic acid ~".
These other components may be copolymerized in the acid-modified polyolefin resin (A), and the form thereof is not limited. As the state of copolymerization, for example, random copolymerization, block copolymerization, graft co-polymerization, etc. Polymerization (graft modification) etc. are mentioned.

   The content of these other components is preferably 1 to 45% by mass, more preferably 2 to 35% by mass, and still more preferably 3 to 25% by mass of the acid-modified polyolefin resin (A). Preferably, it is 4 to 18% by mass. When the content of the other components is less than 1% by mass, the effect of improving the adhesion and mixing stability with epoxidized vegetable oil (B) is small, and when the content exceeds 45% by mass, the water-resistant adhesion and The heat-resistant adhesion (hot adhesion under heating atmosphere) tends to decrease.

   In the present invention, specific examples of the acid-modified polyolefin resin (A) include ethylene- (meth) acrylic acid ester- (anhydride) maleic acid copolymer, ethylene-propylene- (meth) acrylic acid ester- (anhydride) maleic acid Acid copolymer, ethylene-butene- (meth) acrylic acid ester- (anhydride) maleic acid copolymer, propylene-butene- (meth) acrylic acid ester- (anhydride) maleic acid copolymer, ethylene-propylene-butene -(Meth) acrylic acid ester-(anhydride) maleic acid copolymer, ethylene-(meth) acrylic acid copolymer, ethylene-(anhydride) maleic acid copolymer, ethylene-propylene-(anhydride) maleic acid copolymer Combined, ethylene-butene- (anhydride) -maleic acid copolymer, propylene-butene- (anhydride) -maleic acid copolymer, Examples thereof include lene-propylene-butene- (maleic anhydride) -maleic acid copolymer, ethylene-vinyl acetate-maleic acid (maleic anhydride) copolymer, ethylene-vinyl acetate-acrylic acid (maleic anhydride) copolymer, etc., among which ethylene -(Meth) acrylic acid ester-(anhydride) maleic acid copolymer is preferable from the viewpoint of adhesiveness.

   Ethylene- (meth) acrylic acid ester- (anhydride) maleic acid copolymers are described, for example, in the methods described in, for example, British Patent No. 2091745, U.S. Pat. No. 4,617,366 and U.S. Pat. No. 4,644,044. The person skilled in the art can easily manufacture it by referring to.

   In the present invention, the melting point of the acid-modified polyolefin resin (A) is preferably 50 ° C. or more, more preferably 60 to 250 ° C., and particularly preferably 80 to 200 ° C. When the melting point of the acid-modified polyolefin resin (A) is less than 50 ° C., the heat resistant adhesion tends to be lowered.

   The weight-average molecular weight of the acid-modified polyolefin resin (A) is preferably 20,000 to 100,000, more preferably 25,000 to 70,000, still more preferably 30,000 to 50,000, and particularly preferably 3,500 to 50,000. preferable. When the weight average molecular weight of the acid-modified polyolefin resin (A) is less than 20000, the adhesiveness tends to be lowered. On the other hand, when the weight average molecular weight exceeds 100,000, the aqueous dispersion tends to be difficult to obtain.

   In general, polyolefin resins are poorly soluble in solvents, which may make it difficult to measure molecular weight. In such a case, it is preferable to use a melt flow rate value that indicates the fluidity of the molten resin as a measure of the molecular weight.

   The melt flow rate value (190 ° C., 21.2 N load according to ISO 1133) of the acid-modified polyolefin resin (A) is preferably 1 to 300 g / 10 min, more preferably 2 to 200 g / 10 min 3 to 100 g / 10 min is more preferable, and 3 to 80 g / 10 min is particularly preferable. When the melt flow rate value exceeds 300 g / 10 min, the adhesion tends to decrease. On the other hand, when the melt flow rate value is less than 1 g / 10 minutes, it tends to be difficult to obtain an aqueous dispersion.

   In the present invention, the acid-modified polyolefin resin (A) is not particularly required to be chlorinated for the purpose of improving adhesiveness and water dispersibility, and does not contain chlorine from the viewpoint of environmental protection and simplification of the production process. preferable. However, the acid-modified polyolefin resin (A) may be chlorinated if required for its purpose of use. As a method for chlorination, after dissolving the acid-modified polyolefin resin (A) in a chlorine-based solvent, it may be carried out by blowing in gaseous chlorine while irradiating ultraviolet light or in the presence of a radical generator. it can.

The epoxidized vegetable oil (B) used in the present invention is a compound obtained by epoxidizing the unsaturated bond part of the fatty acid of vegetable oil. As a vegetable oil, a vegetable oil generally extracted from plant seeds, fruits and the like can be used. Specifically, soybean oil, linseed oil, rice bran oil, soy sauce, sesame oil, sesame oil, coconut oil, castor oil, safflower oil, Corn oil, cotton seed oil, palm oil, sunflower oil, almond oil, cashew nut oil, hazelnut oil, pine seed oil and the like can be mentioned. These may be one kind or a mixture of two or more kinds. In general, vegetable oils are mainly composed of unsaturated fatty acids such as linoleic acid, linolenic acid and oleic acid. In the present invention, epoxidized soybean oil and epoxidized linseed oil are preferable, and epoxidized large oil is preferable from the viewpoint of making various properties such as mixing stability with the aqueous dispersion of the acid-modified polyolefin resin (A) and adhesiveness good. Bean oil is more preferred.
It should be noted that the presence of a certain amount of non-epoxidized or epoxidized insufficient oil contained in the epoxidized vegetable oil does not interfere with the purpose and essence of the present invention.

   The oxirane oxygen concentration of the epoxidized vegetable oil (B) is preferably in the range of 5 to 10%, more preferably in the range of 6 to 8%. When the oxirane oxygen concentration is out of the above-mentioned preferable range, the effect of dissolving and / or dispersing the epoxidized vegetable oil (B) uniformly in the aqueous dispersion tends to deteriorate.

   The epoxidized vegetable oil (B) has an iodine value of preferably 10.0 Ig / 100 g or less, more preferably 7.0 Ig / 100 g or less, and 5.0 Ig / 100 g or less from the viewpoint of making various performances such as adhesiveness better. More preferably, 3.0 Ig / 100 g or less is particularly preferred. The acid value is preferably 1.5 KOHmg / g or less, more preferably 0.5 KOHmg / g. The ester value is preferably in the range of 170 to 195 KOHmg / g, and more preferably in the range of 175 to 190 KOHmg / g. The viscosity at 25 ° C. is preferably in the range of 100 to 1000 mPa · s, and more preferably in the range of 200 to 700 mPa · s. The appearance of the epoxidized vegetable oil (B) is usually a transparent liquid with a slight yellow color.

   Content of the epoxidized vegetable oil (B) in the aqueous dispersion of this invention is the range of 0.01-30 mass parts with respect to 100 mass parts of acid-modified polyolefin resin (A). The lower limit of the content is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, still more preferably 0.5 parts by mass or more, and particularly preferably 1 parts by mass or more. As an upper limit, 15 mass parts or less are preferable, 10 mass parts or less are more preferable, 8 mass parts or less are more preferable, 5 mass parts or less are especially preferable. If the amount is less than 0.01 parts by mass, the effect of the addition is small and the effect of the present invention is hardly obtained. If it exceeds 30 parts by mass, the mixing stability in the aqueous dispersion, the transparency of the coating film, and the adhesion tend to be deteriorated.

The aqueous dispersion of the present invention is inhibited from phase separation despite containing the water-insoluble epoxidized vegetable oil (B), and the epoxidized vegetable oil (B) is dissolved and / or uniformly in the aqueous dispersion. Or decentralization has been achieved. By suppressing phase separation as an aqueous dispersion, it becomes possible to form a coating film excellent in transparency.
Although the clear mechanism of such a phenomenon in which phase separation is suppressed is unknown, the long chain fatty acid which is a component of the epoxidized vegetable oil has a structure similar to that of the polyolefin, and both are low polar materials. Therefore, the affinity to the olefin skeleton of the acid-modified polyolefin resin (A) is excellent. On the other hand, it is considered that the acid-modified polyolefin resin (A) and the epoxidized vegetable oil (B) contain polar groups (unsaturated carboxylic acid group and epoxy group) in a specific range, and their affinity is also high. Thus, in the case where the molecule has a portion with high affinity in each part and the content and ratio of both polar groups satisfy certain conditions, that is, the acid-modified polyolefin resin (A) In addition to the saturated carboxylic acid content and the ratio of (A) and (B) being in the range defined in the present invention, especially when the oxirane oxygen concentration of the epoxidized vegetable oil (B) is within the preferable range, Good solubility and / or dispersibility.
The fact that the epoxidized vegetable oil (B) is homogeneously dissolved and / or dispersed in the aqueous dispersion means that no precipitation or phase separation is found in the aqueous dispersion in terms of the appearance of the aqueous dispersion. And. It is most preferable that a portion where the concentration of the epoxidized vegetable oil (B) locally differs from other portions is not found.

   The aqueous medium used in the present invention is water or a liquid containing water as a main component, and may contain a basic compound or an organic solvent described later.

   The aqueous medium preferably contains a basic compound. The carboxyl group of the acid-modified polyolefin resin (A) contained in the aqueous dispersion is neutralized by the basic compound, and the electric repulsion between the produced carboxyl anions prevents the aggregation between the fine particles, thus the aqueous dispersion Is given dispersion stability. Moreover, it also has an effect as a catalyst at the time of the carboxyl group which acid-modified polyolefin resin (A) contains, and the epoxy group which epoxidized vegetable oil (B) contains. The basic compound is preferably a volatile compound from the viewpoint of drying when the aqueous dispersion is dried to form a coating film, and the boiling point is more preferably 200 ° C. or less. When the boiling point exceeds 200 ° C., it tends to remain in the obtained coating film, and various performances such as adhesion may be deteriorated.

   As the basic compound, ammonia or an organic amine is preferred in consideration of the effect of neutralizing a carboxyl group and the effect as a catalyst. Specific examples of organic amines include triethylamine, N, N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxypropylamine, 3- Diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine, pyrrole And pyridine. Among them, triethylamine and N, N-dimethylethanolamine which are excellent in the catalytic effect are preferable.

   The content of the basic compound is preferably 0.5 to 10 times equivalent to the carboxyl group in the acid-modified polyolefin resin (A), more preferably 0.8 to 5 times equivalent, 0 It is particularly preferable that it is 0.9 to 3 times equivalent, most preferably 0.9 to 2 times equivalent. When the content of the basic compound is less than 0.5 times equivalent, the addition effect of the basic compound is not recognized, while when the content exceeds 10 times equivalent, when forming a coating film from the aqueous dispersion Drying time may be prolonged, or the stability of the aqueous dispersion may be reduced.

The aqueous medium may contain an organic solvent, and preferably contains a water-soluble organic solvent. The wettability to a substrate can be improved by containing an organic solvent. Further, by adding an organic solvent in the aqueous dispersion of the acid-modified polyolefin resin (A) described later, the aqueous dispersion can be promoted and the dispersed particle diameter can be reduced. Furthermore, the effect of dissolving and / or dispersing the epoxidized vegetable oil (B) uniformly in the aqueous dispersion is improved, and the effect of forming a transparent coating film is improved.
The solubility of the water-soluble organic solvent in water at 20 ° C. is preferably 100 g / L-H ₂ O or more, more preferably 200 g / L-H ₂ O or more, 300 g / L-H more preferably at _{2 O} or more, particularly preferably at 500 g / L-H 2 _O or more, and most preferably completely soluble in any amount. If it is 100 g / L-H ₂ O or more, the effect of uniformly dissolving and / or dispersing the epoxidized vegetable oil (B) in the aqueous dispersion tends to be improved.
Further, the boiling point of the organic solvent is preferably 200 ° C. or less from the viewpoint of drying property when the aqueous dispersion is dried to form a coating film. When the boiling point exceeds 200 ° C., it tends to remain in the obtained coating film, and various performances such as adhesion may be deteriorated.

   As the water-soluble organic solvent, for example, alcohols such as methanol, ethanol, n-propanol, isopropanol, sec-butanol, tert-butanol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1-propanol and the like , Ketones such as methyl ethyl ketone, ethers such as tetrahydrofuran, esters, glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, etc. Is 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol Methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1,2-dimethyl glycerin, 1,3-dimethyl glycerin, trimethyl glycerin. Among them, ethanol, n-propanol and isopropanol, which have high solubility in water at 20 ° C., promote the aqueous dispersion of the acid-modified polyolefin resin (A), and uniformly disperse the epoxidized vegetable oil (B) in the aqueous dispersion. It is preferable from the viewpoint of the effect of dissolving and / or dispersing. The organic solvents may be used alone or in combination of two or more.

   The content of the water-soluble organic solvent is preferably in the range of 5 to 95% by mass with respect to the whole aqueous dispersion, and the lower limit of the content is more preferably 10% by mass or more, and still more preferably 15% by mass or more. 20 mass% or more is especially preferable, and 25 mass% or more is the most preferable. As an upper limit of content, 90 mass% or less is more preferable, 85 mass% or less is more preferable, 80 mass% or less is especially preferable, and 70 mass% or less is the most preferable. When the content is less than 5% by mass, the wettability, the effect of uniformly dissolving and / or dispersing the epoxidized vegetable oil (B) in the aqueous dispersion, and the effect of forming a transparent coating film deteriorate. If the content exceeds 95% by mass, the dispersion stability of the acid-modified polyolefin resin (A) in the aqueous dispersion tends to deteriorate.

   The aqueous dispersion of the present invention preferably contains substantially no nonvolatile aqueous dispersion aid. The present invention does not exclude the use of the non-volatile aqueous dispersion aid, but without using the aqueous dispersion aid, the acid-modified polyolefin resin (A) and the epoxidized vegetable oil (B) in an aqueous dispersion. Can be dissolved and / or dispersed uniformly. The aqueous dispersion is substantially free of the non-volatile aqueous dispersion aid, and thus is excellent in adhesion, content resistance and water resistance, and these performances hardly change even in the long run.

   Here, the term "aqueous dispersion aid" refers to a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing aqueous dispersion in the production of aqueous dispersion, and "non-volatile" Indicates that it does not have a boiling point at normal pressure, or has a high boiling point (eg, 300 ° C. or higher) at normal pressure.

   By "substantially free of non-volatile aqueous dispersion aids" is meant that such aids are not used during the preparation of the aqueous dispersion and the resulting aqueous dispersion consequently does not contain this aid. . Therefore, although it is most preferable that the content of the aqueous dispersion aid is zero, it may be contained within a range not to impair the effects of the present invention. For example, to the acid-modified polyolefin resin (A) 5 mass% or less, preferably 2 mass% or less, more preferably 1 mass% or less, particularly preferably 0.5 mass% or less may be contained.

   Examples of the non-volatile aqueous dispersion aid as referred to in the present invention include an emulsifying agent described later, a compound having a protective colloid action, modified waxes, and an acid modified compound having a high acid value.

   As an emulsifier, a cationic emulsifier, an anionic emulsifier, a nonionic emulsifier, or an amphoteric emulsifier is mentioned, In addition to what is generally used for emulsion polymerization, surfactant is also contained. For example, as an anionic emulsifier, sulfates of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfosuccinic acid And nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide propylene oxide block copolymer, polyoxyethylene fatty acid amide, ethylene oxide-propylene oxide Compounds having a polyoxyethylene structure such as a copolymer, and sorbitan derivatives such as polyoxyethylene sorbitan fatty acid ester And examples of the amphoteric emulsifiers, lauryl betaine, lauryl dimethyl amine oxide, and the like.

   Compounds having a protective colloid action, modified waxes, and acid-modified compounds with high acid value include carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl pyrrolidone, polyacrylic acid and salts thereof, carboxyl group-containing polyethylene wax, Acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less such as carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax, and salts thereof, acrylic acid-maleic anhydride copolymer and salts thereof, styrene- (meth) Acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, etc. Carboxyl group-containing polymer having a saturated carboxylic acid content of 10% by mass or more and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, gum arabic, casein, etc. The compound etc. which are used as an agent are mentioned.

   The aqueous dispersion of the present invention preferably further contains a polyurethane resin (C). By containing the polyurethane resin (C), it is possible to improve the adhesiveness, content resistance and the like. The content of the polyurethane resin (C) is preferably in the range of 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, with respect to 100 parts by mass of the acid-modified polyolefin resin (A) in the aqueous dispersion. The range of -30 parts by mass is more preferable. When the content of the polyurethane resin is less than 1 part by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A) in the aqueous dispersion, the improvement of the coating film performance may not be sufficient. And resistance to content may deteriorate.

The polyurethane resin (C) is a polymer containing a urethane bond in the main chain, and is obtained, for example, by the reaction of a polyol compound and a polyisocyanate compound.
The polyurethane resin (C) preferably has an anionic group from the viewpoint of adhesiveness and dispersibility in an aqueous medium. The anionic group is a functional group which becomes an anion in an aqueous medium, and examples thereof include a carboxyl group, a sulfonic acid group, a sulfuric acid group and a phosphoric acid group. Among these, it is preferable to have a carboxyl group.

   The polyurethane resin (C) is preferably a polycarbonate-type polyurethane resin, a polyether-type polyurethane resin, or a polyester-type polyurethane resin from the viewpoint of adhesiveness and content resistance, more preferably a polycarbonate-type polyurethane resin and a polyether-type polyurethane resin. Ether-type polyurethane resins are particularly preferred.

   The method for incorporating the polyurethane resin (C) as described above into the aqueous dispersion of the present invention is not particularly limited, but an aqueous dispersion or an aqueous solution of the polyurethane resin (C) is prepared beforehand It is convenient and preferable to mix the aqueous dispersion of the invention so that the content is within the defined range.

   The aqueous dispersion of the present invention preferably further contains polyvinyl alcohol (D). The content resistance can be further improved by containing polyvinyl alcohol (D). The content of polyvinyl alcohol (D) is preferably in the range of 0.01 to 10 parts by mass, and in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A) in the aqueous dispersion. The range of 0.1 to 3 parts by mass is more preferable, the range of 0.2 to 2 parts by mass is particularly preferable, and the range of 0.3 to 1 parts by mass is the most preferable. When the content of polyvinyl alcohol (D) is less than 0.01 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A) in the aqueous dispersion, the improvement in content resistance may not be sufficient, 10 If the amount is more than 10 parts by mass, the content resistance and water resistance may be reduced.

   The polyvinyl alcohol (D) is not particularly limited, but those obtained by completely saponifying or partially saponifying a vinyl ester polymer can be preferably used. As a saponification method, a known alkali saponification method or acid saponification method can be adopted. Among them, the method of alcoholysis using alkali hydroxide in methanol is preferable.

   Examples of the vinyl ester include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and the like, and these can be optionally used. Among these, vinyl acetate is the most industrially preferred.

   The saponification degree of the polyvinyl alcohol (D) is not particularly limited, but from the viewpoint of improving the chemical resistance of the coating, 80 to 99.9 mol% is preferable, 90 to 99.9 mol% is more preferable, and 95 to 95 99.9 mol% is more preferable. If the amount is less than 80% by mole, the content resistance tends to be lowered.

   Although the average degree of polymerization of polyvinyl alcohol (D) is not particularly limited, it is preferably 100 to 3,000, more preferably 300 to 2,000, even more preferably 500 to 1,500, and particularly preferably 500 to 1,000. If it is less than 100, the resistance to content may tend to deteriorate, and if it exceeds 3,000, the viscosity of the aqueous dispersion may tend to be too high.

In the present invention, it is particularly preferable to use a polyvinyl alcohol having a degree of saponification of 80 to 99.9 mol% and an average degree of polymerization of 100 to 3,000, from the viewpoint of content resistance.
It is possible to copolymerize another vinyl compound with a vinyl ester within the range not impairing the effects of the present invention. Other vinyl compounds that are vinyl compounds include unsaturated monocarboxylic acids such as crotonic acid, acrylic acid, methacrylic acid and the like, esters, salts, anhydrides, amides, nitriles, etc .; maleic acid, itaconic acid, fumaric acid And unsaturated dicarboxylic acids and salts thereof; α-olefins having 2 to 30 carbon atoms such as ethylene; alkyl vinyl ethers; vinyl pyrrolidones; and diacetone acrylamide.
When ethylene is copolymerized, that is, in the case of an ethylene-vinyl alcohol copolymer, the content of ethylene is preferably 50 mol% or less, more preferably 40 mol% or less from the viewpoint of content resistance.

   A commercially available thing can be used as polyvinyl alcohol (D). Specifically, “J-Poval” manufactured by Nippon Shokubai B. Poval, “Klare Poval” “EXEVAL” manufactured by Kuraray Co., Ltd., “Denka Poval” manufactured by Denki Kagaku Kogyo Co., Ltd., and the like can be suitably used.

   The method for incorporating the polyvinyl alcohol (D) as described above into the aqueous dispersion of the present invention is not particularly limited, but an aqueous solution of polyvinyl alcohol (D) is prepared beforehand, and the aqueous dispersion of the present invention is prepared. The method of mixing in the body so that the content is within the specified range is simple and preferable.

   The aqueous dispersion of the present invention is, besides the acid-modified polyolefin resin (A), the epoxidized vegetable oil (B), the polyurethane resin (C) and the polyvinyl alcohol (D), in order to further improve the performance according to the purpose. And additives such as resins, crosslinking agents, inorganic particles, pigments, and dyes.

   Other resins include, for example, polyethylene resin, polyester resin, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene- (meth) acrylic acid copolymer, styrene-maleic acid resin , Styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, poly (meth) acrylonitrile resin, (meth) acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, modified nylon resin, tackiness such as rosin type or terpene type Resin, phenol resin, silicone resin, epoxy resin etc. are mentioned. A plurality of things may be mixed and used as needed. The addition amount of the other resin may be appropriately selected in consideration of the effects of the present invention and the purpose of addition, but it is 1 to 100 parts by mass of 100 parts by mass of the acid-modified polyolefin resin (A). The range is preferable, and 1 to 50 parts by mass is more preferable.

As the crosslinking agent, a crosslinking agent having a self-crosslinking property, a crosslinking agent having a plurality of functional groups that react with carboxyl groups in the molecule, a metal complex having a polyvalent coordination site, or the like can be used. Specifically, oxazoline type crosslinking agents, isocyanate type crosslinking agents (including block type), amine type crosslinking agents, carbodiimide type crosslinking agents, melamine type crosslinking agents, urea type crosslinking agents, epoxy type crosslinking agents, zirconium salt compounds, A silane coupling agent, an organic peroxide, etc. are mentioned.
Among them, a crosslinking agent having a plurality of functional groups that react with carboxyl groups in the molecule is more preferable. As such a crosslinking agent, an oxazoline type crosslinking agent, a carbodiimide type crosslinking agent, an epoxy type crosslinking agent, an isocyanate type crosslinking agent, an amine type crosslinking agent, a melamine type crosslinking agent, etc. are mentioned. A plurality of these may be used in combination.
The addition amount of the crosslinking agent may be appropriately selected in consideration of the effects of the present invention and the purpose of addition, but it is 1 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A). The range is preferable, and 1 to 30 parts by mass is more preferable.

   Examples of inorganic particles include metal oxides such as magnesium oxide, zinc oxide and tin oxide, inorganic particles such as calcium carbonate and silica, and layered inorganic compounds such as vermiculite, montmorillonite, hectorite, hydrotalcite and synthetic mica. Be The average particle diameter of these inorganic particles is preferably 0.005 to 10 μm, and more preferably 0.005 to 5 μm, from the viewpoint of the stability of the aqueous dispersion. Although the addition amount is suitably set according to the objective, the range of 0.01-30 mass parts is usually preferable with respect to 100 mass parts of acid-modified polyolefin resin (A). A plurality of inorganic particles may be mixed and used. Zinc oxide can be used for ultraviolet shielding and tin oxide can be used for antistatic purposes.

   Examples of pigments and dyes include titanium oxide, zinc white, carbon black and the like, and any of disperse dyes, acid dyes, cationic dyes, reactive dyes and the like can be used. Although the addition amount is suitably set according to the objective, the range of 0.01-30 mass parts is usually preferable with respect to 100 mass parts of acid-modified polyolefin resin (A).

   To the aqueous dispersion of the present invention, various agents such as leveling agent, antifoaming agent, anti-slip agent, pigment dispersant, UV absorber, thickener, weathering agent, flame retardant and the like are further added, as necessary. It is also possible.

   The additives as described above may be used alone or in combination of two or more. The additive is preferably water-soluble or water-dispersible from the viewpoint of ease of addition to the aqueous dispersion and mixing.

   In the aqueous dispersion of the present invention, the components as described above are uniformly dissolved and / or dispersed in an aqueous medium. The number average particle diameter of dispersed particles in such an aqueous dispersion is preferably 0.5 μm or less, and preferably 0.001 to 0.3 μm, from the viewpoint of storage stability and easiness of forming a thin film. Is more preferable, 0.01 to 0.2 μm is more preferable, and 0.02 to 0.1 μm is particularly preferable.

   The content of nonvolatile components such as acid-modified polyolefin resin (A) and epoxidized vegetable oil (B) in the aqueous dispersion of the present invention can be appropriately selected according to the coating conditions, coating film thickness, storage stability, performance, etc. Although it is not particularly limited, it is preferably in the range of 1 to 50% by mass, more preferably in the range of 2 to 20% by mass, from the viewpoint of facilitating application at the time of application. The range of 10% by mass is more preferable, and the range of 5 to 10% by mass is particularly preferable.

   The viscosity of the aqueous dispersion of the present invention is preferably in the range of 4 to 10000 mPa · s, preferably 5 to 1000 mPa · s, when measured with a B-type viscometer at 20 ° C. from the viewpoint of coating workability and the like. The range of 5 to 300 mPa · s is more preferable. Also, the pH of the aqueous dispersion is not particularly limited, but is preferably 6 to 12.

Although the coating obtained from the aqueous dispersion can not generally be mentioned depending on the purpose of use, it is generally preferred that it is transparent. The coating obtained from the aqueous dispersion of the present invention is transparent, and the haze value of the coating having a thickness of 10 μm is preferably 9% or less, more preferably 7% or less, and 6% or less. It is more preferably present, particularly preferably 5% or less, and most preferably 4% or less. The haze value is obtained by applying an aqueous dispersion to a 50 μm thick polyethylene terephthalate film (transparent type) to form a 10 μm coating, and using a turbidimeter (cloudiness meter) according to JIS K7136: 2000. The light was made incident from the coated surface side and measured in the thickness direction of the film.
Here, the "coating film" in the present invention is obtained by applying an aqueous dispersion to a substrate and drying it.

Next, the method for producing the aqueous dispersion of the present invention will be described.
As a method of producing the aqueous dispersion of the present invention, a method of producing an aqueous dispersion of the acid-modified polyolefin resin (A) in advance, adding an epoxidized vegetable oil (B) to the aqueous dispersion and mixing is preferable.

The manufacturing method of the aqueous dispersion of acid-modified polyolefin resin (A) is demonstrated.
As a method for producing the aqueous dispersion of the acid-modified polyolefin resin (A), known methods such as a self emulsification method and a forced emulsification method can be used. Among known methods, a method which substantially does not use a non-volatile aqueous dispersion aid is preferred. Specifically, the acid-modified polyolefin resin (A) and an aqueous medium (optionally containing an organic solvent such as a water-soluble organic solvent, a basic compound, etc.) are heated and stirred in a sealable container The method is mentioned.
The aqueous dispersion of the acid-modified polyolefin resin (A) obtained by the method substantially not using the non-volatile aqueous dispersion aid neutralizes the unsaturated carboxylic acid component of the acid-modified polyolefin resin (A) with a basic compound A homogeneous aqueous dispersion is obtained, which is an anionic aqueous dispersion.

When the aqueous dispersion of the present invention is produced using a water-soluble organic solvent or the like, some or all of the organic solvent is distilled out of the system by a desolvation treatment called "stripping" after the aqueous dispersion. It is also possible to reduce the content of the organic solvent.
As a method of stripping, there is a method of heating while stirring the aqueous dispersion under normal pressure or reduced pressure and distilling off the organic solvent. In addition, since the solid content concentration of the aqueous dispersion is increased by distilling off the aqueous medium, for example, when the viscosity is increased and the workability is lowered, the aqueous medium is added in advance. It can be adjusted.

   Although the acid-modified polyolefin resin (A) can be dispersed in an aqueous medium by the above-mentioned aqueous dispersion production method, the aqueous dispersion is used as an apparatus to remove foreign matter in the container and undispersed resin slightly remaining. At the time of disbursing, a filtration step may be provided. Although the filtration method is not limited, for example, a method of pressure filtration (for example, air pressure 0.5 MPa) with a stainless steel filter (wire diameter 0.035 mm, plain weave) of 300 mesh may be mentioned. By providing such a filtration step, even if foreign matter or undispersed resin remains, they can be removed, so the obtained aqueous dispersion can be used practically without any problem. The appearance of the aqueous dispersion of the acid-modified polyolefin resin (A) is usually a milky white liquid.

As a method for producing the aqueous dispersion of the present invention, a method is preferable in which an epoxidized vegetable oil (B) is added to and mixed with the aqueous dispersion of the acid-modified polyolefin resin (A). At this time, the epoxidized vegetable oil (B) is diluted beforehand with a water-soluble organic solvent so that the concentration of the epoxidized vegetable oil (B) becomes 5 to 70% by mass, and then the acid-modified polyolefin resin (A) is More preferably, a water-soluble organic solvent dilution of epoxidized vegetable oil (B) is added while stirring the aqueous dispersion. The epoxidized vegetable oil (B) is preferably added in the range of 0.01 to 30 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A) in the aqueous dispersion.
By adopting the mixing method as described above, the epoxidized vegetable oil (B) can be more uniformly dissolved and / or dispersed in the aqueous dispersion. Furthermore, a more transparent coating film can be formed, and the performance such as adhesion can be improved.
The aqueous dispersion of the acid-modified polyolefin resin (A) may be previously diluted with an organic solvent. Further, an organic solvent may be further added for the purpose of adjusting the solid content concentration and the organic solvent content of the aqueous dispersion.

   A polyurethane resin (C) or polyvinyl alcohol (D) can be further added to the aqueous dispersion of the present invention for the purpose of improving adhesion strength and content resistance. In the aqueous dispersion of the present invention, the method of adding the polyurethane resin (C) and the polyvinyl alcohol (D) is not particularly limited, but an aqueous dispersion or an aqueous solution of the polyurethane resin (C) and the polyvinyl alcohol (D) is prepared in advance. In addition, there is a method of adding to a target content.

   The use of the aqueous polyolefin resin dispersion of the present invention is not particularly limited, and it can be used for adhesives, coatings, binders for paints, etc., but it is particularly suitable for anchor coats for extrusion lamination, and packaging materials It is preferable to use as an anchor coat agent for extrusion lamination in the case of manufacturing.

   Next, a packaging material obtained by using the aqueous polyolefin resin dispersion of the present invention as an anchor coating agent for extrusion lamination, in which a base material layer / anchor coat layer / a sealant layer is laminated at least in this order will be described.

   Examples of the base material layer in the packaging material of the present invention include barrier materials, thermoplastic resins, paper, rubber, non-woven fabrics, woven and knitted materials, etc., as long as they can be applied to the aqueous polyolefin resin dispersion of the present invention. Among them, barrier materials and thermoplastic resins are preferable from the viewpoint of function.

   Examples of thermoplastic resins include polyester resins such as polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and mixtures thereof; polycapronamide (nylon 6, Polyamide resins such as polyhexamethylene adipamide (nylon 66), poly-p-xylylene adipamide (MXD6 nylon), and mixtures thereof, hereinafter sometimes referred to as “Ny6”; polyethylene resins, Polypropylene resins, and polyolefin resins such as blends thereof may be mentioned. Among these, PET, Ny6 and polypropylene resin which are excellent in mechanical properties when used as a packaging material are preferable.

   When using a thermoplastic resin as a base material layer, the form of a film is preferable. As the thermoplastic resin film, one produced by a generally known method can be used, and either a non-oriented film or a stretched film may be used, but from the viewpoint of imparting transparency and glossiness, uniaxial or biaxial Stretched films are preferred, and biaxially stretched films are more preferred. The thickness of the film is not particularly limited, but usually 5 to 500 μm is used.

   When using a thermoplastic resin film as a base material layer, in order to improve adhesion, it is preferable that surface activation treatment is performed on the surface on which the anchor coat layer is provided. The surface activation treatment includes, for example, corona discharge treatment, flame plasma treatment, atmospheric pressure plasma treatment, low pressure plasma treatment, ozone treatment, electron beam irradiation treatment, ultraviolet irradiation treatment, chemical treatment, solvent treatment, etc. From the balance of the adhesion effect, corona discharge treatment is preferred.

The barrier material may be composed of any material capable of blocking liquid or gas. For example, organic barriers made of soft metals such as aluminum, vapor deposited films such as aluminum vapor deposition, silica vapor deposition, alumina vapor deposition, alumina vapor deposition, silica alumina binary vapor deposition, vinylidene chloride resin, modified polyvinyl alcohol, ethylene vinyl alcohol copolymer, MXD nylon etc. Materials and the like can be used.
When using a barrier material as a base material layer, it is preferable that it is thin film forms, such as metal foil, a film, and a vapor deposition film.

   When using metal foil as a barrier material, aluminum foil is preferable because it is inexpensive and excellent in processability. The thickness of the metal foil is preferably in the range of 3 to 50 μm.

   When a vapor deposition film is applied as a barrier material, it is convenient and preferable to use a film having a vapor deposition layer. As a film having a vapor deposition layer, for example, "IB series" manufactured by Dainippon Printing Co., Ltd., "GL, GX series" manufactured by Toppan Printing Co., Ltd., "Barrier Rocks" "VM-PET" "YM manufactured by Toray Film Processing Co., Ltd. -"CPP" "VM-OPP", "Tec Barrier" made by Mitsubishi Plastics, "Metaline" made by Tosoh Cello, "MOS" "Terayite" "Bee Brite" made by Oike Kogyo, "C" made by Eiko Examples include Diaraster, "Sun mirror", "High raster" and "Fine barrier". In these, a protective coating layer may be provided on the surface of the vapor deposition layer film.

   When an organic barrier material is applied as a barrier material, it is convenient and preferable to use a film made of an organic barrier material or a laminated film having a layer made of an organic barrier material (hereinafter referred to as an organic barrier layer). In the case of a laminated film having an organic barrier layer, one obtained by coating a film with a coating agent containing a resin having a barrier property, and one obtained by laminating the above-mentioned resin by a co-extrusion method can be used. Moreover, as a commercially available film having an organic barrier layer, "Klarista" and "Evar" manufactured by Kuraray Co., Ltd., "Vesela" manufactured by Toba Chemical Industry Co., Ltd., "Super Neal" manufactured by Mitsubishi Plastics and "Corrier" manufactured by Kojinsha "UNBLON M", "Embron E", "emblem DC", "emblet DC", "emblem NV", "Sevix" manufactured by UNITIKA, "K-OP" "A-OP" manufactured by Higashi-Sero, manufactured by Daicel "Seneshi" etc. is mentioned and it is convenient and it is easy to use these.

About the barrier property in a barrier material, an optimal range may be suitably selected according to the content to pack, storage period, etc. Among them, the water vapor transmission rate under conditions of 40 ° C. and 90% RH is preferably 100 g / m ² · day or less, more preferably 20 g / m ² · day or less, further preferably 10 g / m ² · day or less, 1 g Particularly preferred is not more than / m ² · day. Moreover, as oxygen permeability under 20 ° C., 90% RH conditions, 100 ml / m ² · day · MPa or less is preferable, 20 ml / m ² · day · MPa or less is more preferable, 10 ml / m ² · day · MPa The following is more preferable, and 1 ml / m ² · day · MPa or less is particularly preferable.

   The surface of the barrier material on which the anchor coat layer is to be provided may be subjected to surface activation treatment to improve adhesion. The surface activation treatment includes, for example, corona discharge treatment, flame plasma treatment, atmospheric pressure plasma treatment, low pressure plasma treatment, ozone treatment, electron beam irradiation treatment, ultraviolet ray irradiation treatment, chemical treatment, solvent treatment, chemical conversion treatment and the like. Be

   The anchor coat layer is formed by applying and drying an anchor coat agent comprising the aqueous dispersion of the present invention on at least one surface of the base layer.

   The anchor coating agent is applied to the surface of the substrate layer by a known method such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating method, etc. It can be coated uniformly. Moreover, after setting at about room temperature as necessary, heat treatment for drying treatment or drying may be performed to form a uniform coating film in close contact with the surface of the base material layer.

   When using a plurality of layers as described below as the base material layer, after laminating on one of the surfaces, an anchor coating agent may be applied to at least a part of the other surface and dried.

   The thickness of the anchor coat layer is preferably 0.001 to 5 μm, more preferably 0.01 to 3 μm, still more preferably 0.02 to 2 μm, and 0.03 to 1 μm. Are particularly preferred, and most preferably 0.05 to 0.5 μm. If the thickness of the anchor coat layer is less than 0.001 μm, sufficient adhesion and resistance to content property tend not to be obtained, while if it exceeds 5 μm, it tends to be economically disadvantageous.

   After application of the anchor coating agent, it is preferable to dry most or all of the aqueous medium from the viewpoint of improving adhesion and resistance to storage. The drying conditions are not particularly limited, but may be suitably selected in the range of 40 to 200 ° C. as the drying temperature and in the range of 1 to 600 seconds as the drying time, in consideration of the drying property and the performance.

   The laminate in which the anchor coat layer is laminated on the base material layer by the above method may be subjected to the extrusion laminating step directly in-line, or may be subjected to the extrusion laminating step while being wound once taken up on a roll. Good.

   As described above, in the laminate in which the coating film obtained from the aqueous dispersion of the present invention is laminated on the surface of the base material layer, the occurrence of warpage is suppressed, and the processability when processing into a packaging material, Handling of the packaging material is improved.

For example, a polyolefin resin can be used as the sealant layer. Examples of the polyolefin resin include polyethylene resins such as low density polyethylene, linear low density polyethylene, high density polyethylene, acid-modified polyethylene, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer, Ethylene- (meth) acrylic acid copolymer, ethylene-based copolymer such as polyethylene-based ionomer, homopolypropylene, polypropylene such as random polypropylene, acid-modified polypropylene, polypropylene-based copolymer such as terpolymer, cyclic polyolefin (COP) And cyclic polyolefin copolymers (COC). These may be used alone or in combination of two or more.
The sealant layer is preferably a polyethylene resin from the viewpoint of processability and cost. Furthermore, when low-temperature sealability is required, the sealant layer contains an ethylene-based copolymer such as ethylene-vinyl acetate copolymer, ethylene- (meth) acrylate copolymer, ethylene- (meth) acrylate copolymer, etc. It is preferred to use coalescence.

As a method of forming a sealant layer, a method of extrusion laminating a molten polyolefin resin on an anchor coat layer provided on a base material layer can be mentioned.
Immediately after extruding and laminating the molten polyolefin resin, it is preferable to provide a cooling roll to solidify by cooling. The resin temperature at the time of melt extrusion is preferably in the range of 150 to 360 ° C. from the viewpoint of improving adhesion and content resistance. The lower limit of the resin temperature during melt extrusion is preferably 180 ° C. or more, more preferably 200 ° C. or more, particularly preferably 220 ° C. or more, and most preferably 230 ° C. or more. As the upper limit, less than 340 ° C. is more preferable, less than 330 ° C. is more preferable, less than 320 ° C. is more preferable, less than 310 ° C. is particularly preferable, and less than 300 ° C. is most preferable. If the temperature is less than 150 ° C., the processability tends to be poor, and the adhesion tends to be insufficient. If the temperature is 360 ° C. or more, the processability is poor, and the problems of smoke generation and poly odor become remarkable.

   When melt-extruding a polyolefin resin, processing such as ozone treatment may be performed. In the case of extrusion lamination, a sand lamination method or a coextrusion lamination method may be used in combination for the purpose of providing another layer further inside the sealant layer.

   The line speed at the time of extrusion laminate manufacturing (rolling speed of laminated laminate) is preferably 50 to 400 m / min, more preferably 70 to 300 m / min, and 100 to 200 m / min. It is further preferred that When the line speed is less than 50 m / min, productivity is low, and when it exceeds 400 m / min, laminating becomes difficult.

   The thickness of the sealant layer constituting the packaging material of the present invention is not particularly limited, but is preferably in the range of 10 to 60 μm and more preferably in the range of 15 to 40 μm in consideration of processability to the packaging material and heat sealability. Moreover, it is possible to provide slipperiness and tearability of a packaging material to a sealant layer by providing an unevenness | corrugation with an elevation difference of 5-20 micrometers in a sealant layer.

   The packaging material of the present invention is usually packaged with the base layer outside and the sealant layer inside (content side). Also, in consideration of the use as a packaging material, required performance (easiness to tear or hand-cut), rigidity and durability required as a packaging material (for example, impact resistance, pinhole resistance, etc.), etc. Another layer can be laminated to the base material layer as needed. When a metal foil or an organic barrier layer is used as the substrate layer, it can be used together with a thermoplastic resin layer, a paper layer, a second sealant layer, a non-woven layer and the like outside the metal foil or the organic barrier layer. When using a vapor deposition layer as a base material layer, a thermoplastic resin layer, a paper layer, a 2nd sealant layer, a nonwoven fabric layer etc. can be used for the outer side of a vapor deposition layer. When using a thermoplastic resin layer as a base material layer, it can be used with a barrier layer, a thermoplastic resin, a paper layer, a 2nd sealant layer, a nonwoven fabric layer, etc. on the outer side of a thermoplastic resin layer.

   As a method of laminating other layers in addition to the base material layer, the anchor coat layer and the sealant layer, known methods can be used. For example, an adhesive layer may be provided between the other layers and laminated by a dry lamination method, a thermal lamination method, a heat sealing method, an extrusion lamination method, or the like. As the adhesive, a one-component urethane adhesive, a two-component urethane adhesive, an epoxy adhesive, an aqueous dispersion of acid-modified polyolefin, or the like can be used. The aqueous dispersion of the present invention may also be used as an adhesive.

   As a laminate constitution of the packaging material of the present invention, thermoplastic resin layer / barrier layer / anchor coat layer / sealant layer or the like, which can be suitably used for general packaging material, lid material, refill container, etc .; , First layer capable of being used suitably for paper cups, etc., first sealant layer / paper layer / barrier layer / anchor coat layer / second sealant layer, first sealant layer / paper layer / polyolefin resin layer / thermoplastic resin Layer / barrier layer / anchor coat layer / second sealant layer, paper layer / barrier layer / anchor coat layer / sealant layer, thermoplastic resin layer / paper layer / barrier layer / thermoplastic resin layer / anchor coat layer / sealant layer And a first sealant layer / barrier layer / anchor coat layer / second sealant layer and the like which can be suitably used for a tube container and the like. These laminates only have to have the above-described layer configuration laminated in the above order at least, and may have other layers such as a printing layer and a top coat layer as needed.

   Examples of the paper layer include natural paper and synthetic paper. The first and second sealant layers can be formed of the same material as the above-described sealant layer.

   Each layer constituting the laminate may contain known additives and stabilizers such as an antistatic agent, an easily adhesive coating agent, a plasticizer, a lubricant, an antioxidant and the like. In addition, each layer may be subjected to corona treatment, plasma treatment, ozone treatment, chemical treatment, solvent treatment, etc., as a pretreatment, in order to improve adhesion when laminating with other materials. Good. The thickness of each layer is not particularly limited as long as it is determined in consideration of the suitability as a packaging material and the processability in the case of laminating, and a range of 1 to 300 μm is preferable practically. However, depending on the application, those larger than 300 μm may be employed.

   Embodiments of the packaging material of the present invention include a three-sided sealed bag, a four-sided sealed bag, a gusset packaging bag, a pillow packaging bag, a Goebel top type bottomed container, a tetra-crash, a bruck type, a tube container, a paper cup, a lid material, etc. There are various types. Among them, as a paper cup, a blank plate of a barrel and a bottom is manufactured, and using the blank plate, a tubular barrel is formed by a cup forming machine, and the bottom of one open end of the barrel is formed. And a heat-bonded paper cup.

   The packaging material of the present invention may be subjected to an easy-opening treatment. Specifically, processing such as cut lines, half cut lines, perforations and the like may be performed. Moreover, you may provide a notch (notch) suitably in an opening position. Moreover, you may provide a resealable means suitably. Specifically, an adhesive may be applied to the sealant layer of the innermost layer to make it re-sealable, or a zipper made of polyethylene resin or polypropylene resin may be provided to make a packaging bag with a chuck. The anchor coating agent of the present invention is also excellent in adhesion when the packaging material is provided with such a chuck. Furthermore, the anchor coating agent of the present invention is also suitable for deep drawing.

   It is preferable that the zippered packaging bag has an opening at one end of the packaging bag, and the sealant layer of the innermost layer in the vicinity of the opening be provided with a resin chuck. In the case where the content of the packaging material of the present invention is an alcoholic beverage, bath agent, spice, poultice, patch, etc., it is advantageous that a chuck is provided from the viewpoint of long-term storage after opening. . By providing the chuck, the contents can be easily put in and out. The chuck is generally composed of a pair of chuck bodies, and the male mold portion of one chuck body is fitted with the female mold portion of the other chuck body, whereby the packaging bag is sealed. The male part and the female part are usually joined with the sealant layer of the respective opposing packaging material. The packaging bag with a chuck is capable of accommodating the contents for a long period of time by containing the contents and manufacturing it in a state in which the outside of the opening provided with the chuck is sealed. . And in such a packaging bag, it is preferable that the tearing part which can be cut | disconnected or torn at the time of content use is provided between a sealing part and a chuck | zipper.

As a material which comprises a chuck | zipper, a polyolefin resin is preferable, Among them, from the point which is cheap, what has a polyethylene resin or a polypropylene resin as a main component is more preferable, and what has a polyethylene resin as a main component is especially preferable. Among them, LDPE and LLDPE are particularly preferable.
The male part and the female part of the chuck body are preferably manufactured separately by extrusion, and are preferably made of LDPE having a flexural modulus of 50 to 500 MPa. If the bending elastic modulus is less than 50 MPa, the fitting strength of the chuck becomes weak, or the delivery during bag making becomes difficult. On the other hand, if it exceeds 500 MPa, the strength at the time of repeated opening and the strength after resealing will fall, or breakage of a chuck will occur.
The LDPE preferably has a melt flow rate (MFR) of 1 to 15 g / 10 min, more preferably 2 to 8 g / 10 min. When MI is less than 1 g / 10 min, melt fracture tends to occur, and when it exceeds 15 g / 10 min, moldability (mold retention) is deteriorated. For the chuck body, polypropylene other than LDPE, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, etc. can be used.

   Since the packaging material of the present invention uses the anchor coating agent of the present invention, it has good resistance to various contents. Therefore, the packaging material of the present invention is particularly suitable as a packaging material for volatile contents and highly irritating contents. Among them, it is most suitable as a packaging material for products having a fragrant ingredient, a spice ingredient and a medicinal ingredient. Specifically, alcohol (for example, high concentration alcohol with an alcohol concentration of 50% by mass or more), red wine, white wine, sake, alcoholic beverages such as shochu, antioxidants, sulfites, fragrances, fragrances, bath agents (liquids Type, powder type), spice (cledge, pepper), poultice, patch, medicine, battery electrolyte, toiletry product, surfactant, shampoo, rinse, detergent, car cleaner, perm liquid, insect repellent, insecticidal Agent, antiseptic solution, deodorant, hair restorer, vinegar, toothpaste, cosmetics, developer, hair dye, tooth powder, mustard, vinegar, oil, curry, powdered kimchi powder, tabasco (condiment made from red pepper ), Those containing basic substances, and those containing acidic substances are suitably used as packaging materials.

   The packaging material of the present invention can be suitably used to package an osmotic component-containing liquid substance among the above contents. Here, the permeable component-containing liquid material is a liquid containing an irritant component, an aroma component, a medicinal component, a highly volatile component, an oil component, etc. which may penetrate the sealant layer and / or the anchor coat layer and deteriorate the adhesiveness. Means substance. Specifically, alcoholic beverages such as wine, liquid detergents, shampoos, rinses, battery electrolytes, vinegar, oils and the like can be mentioned.

   Moreover, the packaging material of this invention can be suitably used also in order to package an osmotic component containing paste-like substance, such as cosmetics, pharmaceuticals, seasonings, and food, among the above-mentioned contents. The packaging material to be used for this application is preferably a tube container from the viewpoint of the handleability of the permeable component-containing paste-like substance of the contents. The tube container is, for example, formed into a tubular shape with the packaging material of the present invention, one of the openings is sealed with a heat seal or the like, and the other opening is a head having a shoulder and an opening. It can manufacture by providing. A nozzle, a hinge cap, a check valve, a sealing material, etc. may be provided in the mouth.

   Furthermore, the packaging material of the present invention can be suitably used also for packaging a volatile component-containing solid such as a spice and a bathing agent among the above-mentioned contents. Examples of the shape of the contents include powder, flakes, pellets, blocks, cubes, tablets, crumbles, holes, granules, granules, plates, spheres, threads, and the like.

   The packaging material of the present invention can be suitably used as a packaging material for refilling for packaging contents to be refilled into a container. In that case, in order to easily transfer the contents to another container such as a bottle at the time of refilling, it is preferable that a spout is provided in part of the packaging material. The mounting position of the pouring spout is not particularly limited, but it is preferable to provide the spout at the upper center or the corner portion of the packaging material from the viewpoint of facilitating the pouring operation of the contents. The shape of the spout is not particularly limited, and may be provided so as to project without break from the bag body, and may be made of a material different from the bag body. In addition, a screw cap or the like may be attached to the spout.

   From the viewpoint of storing the contents for a long time, it is preferable that the outer periphery of the tip of the pouring spout be heat sealed. And in order to make opening easy, it is preferable that the easy-opening process is given to the heat seal part of the pouring nozzle tip. Specifically, processing such as cut lines, half cut lines, perforations and the like may be performed. Moreover, you may provide a notch (notch) suitably in an opening position.

   The packaging material of the present invention is excellent in the interlayer adhesion between the base material layer and the sealant layer. The preferable adhesive strength between the base material layer and the sealant layer varies depending on the material adopted for the base material layer and the sealant layer, and can not be generally mentioned, but generally considering the suitability as a packaging material, The peel strength is preferably 1.0 N / 15 mm or more when T-peel is performed at a rate of 200 mm / min between the base material layer and the sealant layer of the test piece cut into a width of 15 mm. / 15 mm or more is more preferable, 3.0 N / 15 mm or more is more preferable, 5.0 N / 15 mm or more is particularly preferable, and peeling is most preferable. In addition, it is a state which can not peel off the interface of a base material layer and a sealant layer, or a state where a base material layer or a sealant layer cuts during a peeling test, since interlayer adhesion strength is too strong. Also, the packaging material of the present invention has high adhesiveness retention even when the content is enclosed, and has the above adhesive strength even after the content is enclosed. Is preferred.

   The invention is illustrated by the following examples. However, the present invention is not limited by these.

1. Properties of acid-modified polyolefin resin (1) Composition and structure of acid-modified polyolefin resin
^It calculated | required from the <1> H-NMR analyzer (Nihon Denshi make, ECA500, 500 MHz). The measurement was carried out at 120 ° C. using tetrachloroethane (d ₂ ) as a solvent.
(2) Weight Average Molecular Weight The weight average molecular weight was measured at 40 ° C. using a GPC apparatus (HLC-8020 GPC manufactured by Tosoh Corporation, column: TSK-GEL). It calculated | required from TSK standard polystyrene conversion, using an ortho dichlorobenzene as an eluting solvent. In addition, when not melt | dissolving in trichlorobenzene and a weight average molecular weight can not be measured, the melt flow rate value of following (3) was made into the parameter | index of molecular weight.
(3) Melt flow rate value (MFR) of acid-modified polyolefin resin
It measured by 190 degreeC and 21.2N load according to the method of ISO1133.
(4) Melting | fusing point of acid-modified polyolefin resin It measured by DSC method using Perkin-Elmer DSC7.

2. Properties of epoxidized vegetable oil (1) Oxygen concentration of oxygen (%)
Determined by chemical titration using the hydrogen bromide method according to the Japan Oil Chemistry Association established "Standard oil and fat analysis test method" 2013 edition (1) 2.3.7.1.

3. Properties of aqueous dispersion (1) Number average particle diameter of dispersed particles in aqueous dispersion It was determined using a microtrack particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., UPA 150, MODEL No. 9340, dynamic light scattering method). The refractive index of the resin used for particle diameter calculation was 1.50.
(2) Appearance The aqueous dispersion immediately after production is placed in a transparent glass container of about 100 ml in volume of about 80 ml and allowed to stand for 5 minutes, after which the state of the aqueous dispersion is visually observed and dissolved and / or dispersed according to the following criteria. The degree was evaluated.
"Excellent": distribution of components, no separation, uniform milky white.
"Good": Some fine oil droplets consisting of epoxidized vegetable oil are observed near the liquid surface, but they are almost uniform milky white.
"Normal": Fine oil droplets consisting of epoxidized vegetable oil are confirmed near the liquid surface, but no phase separation is confirmed, and it is roughly homogeneous milky white.
"Slightly inferior": Oil droplets consisting of epoxidized vegetable oil are confirmed near the liquid surface, but no phase separation is confirmed, and the whole is milky white.
"Poor": phase separation by epoxidized vegetable oil can be confirmed, but the separation interface is unclear (the lower phase is a milky white phase derived from dispersed particles of acid-modified polyolefin resin and becomes transparent as it approaches the upper phase, the upper layer Is a clear phase consisting of epoxidized vegetable oil and becomes milky white as it approaches the lower phase).
"Poor": phase separation by epoxidized vegetable oil can be confirmed, and the separation interface is clear (the lower phase is a milky white phase derived from dispersed particles of acid-modified polyolefin resin, and the upper layer is transparent composed of epoxidized vegetable oil) Phase).
(3) Viscosity The rotational viscosity (mPa · s) at a temperature of 20 ° C. was measured using a B-type viscometer (DVI-BII digital viscometer manufactured by Tokimec Co., Ltd.).
a) Initial value: Measured after 1 hour of storage at 25 ° C. after preparing the aqueous dispersion of each example.
b) After 30 days: measured after 30 days of storage at 25 ° C. after preparing the aqueous dispersion of each example.
(4) Transparency of Coating Film Aqueous dispersion of a 50 μm thick PET film (manufactured by Unitika, Emblet TAG-50, transparent grade, 2% haze value) so that the amount of the coating after drying becomes 10 μm The body was applied and dried at 100 ° C. for 120 seconds. Then, according to JIS K 7136: 2000, using a turbidimeter (cloudiness meter), light was incident from the coated film side of the PET film, and the haze value (%) in the thickness direction of the film was measured. In this measurement, the haze value including the PET film is adopted. The test was performed 5 times and evaluated by the average value of 5 times.
(5) Warpage suppressing effect of base material layer An aqueous dispersion was applied to a biaxially stretched PET film with a thickness of 12 μm so that the thickness of a coated film after drying was 1 μm, and dried at 100 ° C. for 120 seconds. Next, the coated film-provided laminate was cut into a square of 100 mm × 100 mm, and this was placed on a horizontal flat table with the coated surface facing up. Then, after holding at 20 ° C. and 65% RH for 1 hour, the distance between the highest position of the laminate and the tabletop surface was measured, and the degree of warpage of the base material layer was evaluated based on the following criteria. The test was conducted at n = 5, and the value of warpage was an average value. In this test, it can be judged that the degree of warpage is larger as the distance is longer.
"Excellent": distance is less than 5 mm "good": distance is 5 mm or more and less than 10 mm "normal": distance is 10 mm or more and less than 15 mm "poor": distance is 15 mm or more and less than 20 mm "bad": Distance is 20 mm or more

4. Properties of packaging material (1) Laminate strength (initial strength)
From the laminate film obtained in each example, a test piece with a width of 15 mm is collected, and using a tensile tester (Intesco precision universal material testing machine 2020 type), in an atmosphere at 20 ° C., 65% RH, tensile speed The strength required to peel off the interface between the base material layer of the test piece and the sealant layer under the condition of 200 mm / min was measured by a T-peel test. The measurement was carried out with 10 samples, and the average value was taken as the laminate strength.
In addition, since the interlayer adhesion strength is too strong with "not peelable" of the evaluation result, the base layer or the sealant layer is cut during the state where the base layer and the interface of the sealant layer can not be peeled or the peeling test. The situation is

(2) Lamination strength after content resistance test The packaging material obtained in each example was charged with 12 g of red wine (including sulfite) or 12 g of kerosene as the content, and sealed by heat sealing. At the time of heat sealing, the packaging material was sealed so as to prevent air from entering as much as possible. The packaging material sealed with the contents was stored at 50 ° C. for 4 weeks. Thereafter, the package was opened to remove the contents, and the laminate strength was measured in the same manner as the above (1). The measurement was carried out with 10 samples, and the average value was taken as the laminate strength after the content resistance test.

The following raw materials were used as raw materials used in Examples and Comparative Examples.
An aqueous dispersion of acid-modified polyolefin resin (A) was produced by the following method.

<Production of aqueous dispersion of ethylene-ethyl acrylate- (anhydride) maleic acid copolymer>
Based on the method described in British Patent 2091745, US Patent 4617366 and US Patent 4644044, "PO1", "PO2" of acid-modified polyolefin resin (A) which is ethylene-ethyl acrylate-maleic anhydride copolymer And produced "PO3". The characteristics of "PO1", "PO2" and "PO3" are shown in Table 1.
Next, 50 g of “PO1”, “PO2” or “PO3” obtained above, 150 g of n-propanol, 3 g of 2-dimethylaminoethanol were distilled in a 2-liter glass container equipped with a stirrer and a heater We charged 297 g of water. When stirring was performed with the rotational speed of the stirring blade set to 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the resin was in a floating state. Then, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature inside the system was maintained at 130 ° C., and the mixture was further dispersed for 120 minutes with stirring. Thereafter, the system was cooled to about 80 ° C. with stirring at a rotational speed of 300 rpm, and the system was gradually depressurized to remove n-propanol and water. After removing 300 g or more of n-propanol and water, when the system internal temperature reaches 35 ° C., add water so that the concentration of the acid-modified polyolefin resin (A) in the aqueous dispersion becomes 20 mass%. Adjusted, pressure-filtered through a 180 mesh stainless steel filter, and milky white uniform dispersions of acid-modified polyolefin resin (A) of “A-1”, “A-2” and “A-3” were respectively prepared. Obtained. In the production of any of the aqueous dispersions, no undispersed resin was found in the stainless steel filter after filtration.

<Production of Aqueous Dispersion of Ethylene-Methacrylic Acid Copolymer>
As ethylene-methacrylic acid copolymers, commercially available products: nucrel AN42115C (hereinafter referred to as AN42115C) manufactured by DuPont Polychemicals, nucrel N0903HC manufactured by DuPont Polychemicals (hereinafter referred to as N0903HC), and Mitsui Dupont The acid-modified polyolefin resin (A) aqueous dispersions “A-4” to “A-6” were produced by the following method using Nuclell N1560 (hereinafter referred to as N1560) manufactured by Polychemical Co., Ltd. The characteristics of “AN 42115 C”, “N0903 HC”, and “N 1560” are shown in Table 1.
Next, 75 g of “AN 42115 C” or “N0903 HC”, 175 g of n-propanol, 20 g of 2-dimethylaminoethanol, and 230 g of distilled water were charged into a 2-liter glass container equipped with a stirrer and a heater. When stirring was performed with the rotational speed of the stirring blade set to 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the resin was in a floating state. Then, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature inside the system was kept at 150 ° C., and stirring was further carried out for 120 minutes for dispersion. Then, after cooling to about 80 ° C. while stirring at a rotational speed of 300 rpm, 200 g of water was added, and then the system was gradually depressurized to remove n-propanol and water. After removing 350 g or more of n-propanol and water, when the system internal temperature reaches 35 ° C., water is added to adjust the solid content concentration of the aqueous dispersion to 20 mass%, and stainless steel of 180 mesh. The mixture was pressure-filtered with a filter made of a filter to obtain a milky white uniform acid-modified polyolefin resin (A) aqueous dispersion of "A-4" or "A-5".
When "N1560" is used as the acid-modified polyolefin resin (A), 75 g of "N1560", 50 g of isopropanol, 7 g of 2-dimethylaminoethanol are distilled in a 1-liter glass container equipped with a stirrer and a heater. We charged 368 g of water. When stirring was performed with the rotational speed of the stirring blade set to 300 rpm, no precipitation of resin particles was observed at the bottom of the container, and it was confirmed that the resin was in a floating state. Then, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature inside the system was maintained at 130 ° C., and the mixture was further dispersed for 120 minutes with stirring. Thereafter, the system was cooled to about 80 ° C. with stirring at a rotational speed of 300 rpm, and the pressure in the system was gradually reduced to remove isopropanol and water. After removing 125 g or more of isopropanol and water, when the system temperature reaches 35 ° C., water is added to adjust the solid content concentration of the aqueous dispersion to 20 mass%, and a 180 mesh stainless steel filter The reaction mixture was pressure-filtered with the above to obtain a milky white homogeneous acid-modified polyolefin resin (A) aqueous dispersion of "A-6". In the production of any of the aqueous dispersions, no undispersed resin was found in the stainless steel filter after filtration.

<Production of aqueous dispersion of propylene- (anhydride) maleic acid copolymer>
A polypropylene obtained by subjecting a homopolypropylene resin having an isotactic structure (MFR = 0.1 g / 10 min-170 ° C. · 2,160 g) to 360 ° C. × 80 min thermal decomposition treatment under nitrogen gas flow under normal pressure. 1000 g of the resin was put in a jacketed reactor, purged with nitrogen, heated to 180 ° C. to melt, and then 125 g of maleic anhydride was added and uniformly mixed. Thereto, 125 g of xylene in which 6.3 g of dicumyl peroxide was dissolved was dropped, and the mixture was reacted by stirring at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure, and the obtained reaction product was poured into 3 kg of acetone to solidify the resin. This resin was finely cut, processed into pellets, washed twice with acetone, and then dried under reduced pressure to obtain an acid-modified polypropylene resin "PO4". The characteristics of “PO4” are shown in Table 1.
Then, using a stirrer equipped with a sealable pressure resistant 2 L glass container with a heater, 150.0 g of acid-modified polypropylene resin “PO4”, 60.0 g of isopropanol, 340.0 g of tetrahydrofuran, 30.0 g of dimethyl Aminoethanol and 420.0 g of distilled water were charged in a glass container and stirred at a rotational speed of a stirring blade of 300 rpm. No resin precipitation was observed at the bottom of the container, confirming that it was in a floating state. The Then, while maintaining this state, the heater was turned on and heated after 10 minutes. Then, the temperature inside the system was kept at 150 ° C., and after stirring for additional 60 minutes, the power of the heater was turned off and natural cooling was carried out.
When the internal temperature cooled to 80 ° C., the container was opened, and a raw material consisting of 120.0 g of tetrahydrofuran, 20.0 g of dimethylaminoethanol and 100.0 g of distilled water was additionally charged. After that, the container was sealed, the power of the heater was turned on, and the stirring blade was again heated (reheated) at a rotational speed of 300 rpm. After the system temperature was maintained at 140 ° C. and the stirring was continued for additional 60 minutes, the output of the heater was adjusted to an internal temperature of 80 ° C.
When the internal temperature cooled to 80 ° C., the system was gradually depressurized using a vacuum pump to remove isopropanol, tetrahydrofuran and water. After 800g or more of tetrahydrofuran, isopropanol and water are removed, the heater is turned off, and when the system temperature reaches 35 ° C, water is added to make the concentration of "PO4" in the aqueous dispersion 20% by mass. The mixture was adjusted as above, and pressure-filtered through a 180 mesh stainless steel filter to obtain a uniform aqueous dispersion “A-7” of “PO4”. In addition, undispersed resin was not confirmed by the stainless steel filter after filtration.

   The characteristics of the acid-modified polyolefin resin used as a raw material are shown in Table 1.

   The content of n-propanol in the acid-modified polyolefin resin (A) aqueous dispersions “A-1” to “A-5” is determined by gas chromatography and all are below the lower limit of determination (5 ppm), and acid-modified With regard to the aqueous polyolefin resin dispersions "A-6" and "A-7", the contents of isopropanol and tetrahydrofuran were determined by gas chromatography and all were below the lower limit of determination (5 ppm).

The following were used as epoxidized vegetable oil (B).
・ B-1: Epoxidized soybean oil (Adeka company make, Adekasizer O-130P, oxirane oxygen concentration 6.6%)
・ B-2: Epoxidized linseed oil (Adeka company make, Adekasizer O-180A, oxirane oxygen concentration 9.1%)
・ B-3: Epoxidized linseed oil (Shin Nippon Rika Co., Ltd., Sanssoizer E-9000H, oxirane oxygen concentration 8.4%)
· B-4: Epoxidized cottonseed oil (manufactured according to the method described in JP-A-6-107652, oxirane oxygen concentration 5.1%)
· B-5: Epoxidized rice bran oil (manufactured according to the method described in JP-A-6-107652, oxirane oxygen concentration 4.8%)

The following additives were used as additives other than epoxidized vegetable oil.
-EX-411: pentaerythritol polyglycidyl ether (manufactured by Ganase Chemtex, Denacol EX-411, tetrafunctional epoxy compound, epoxy value 229 g / eq)
SR-TMP: trimethylolpropane polyglycidyl ether (Sakamoto Yakuhin Kogyo Co., Ltd. SR-TMP, trifunctional epoxy compound, epoxy value 140 g / eq)
・ ADH liquid: suspension of adipic acid dihydrazide (water made in adipic acid dihydrazide manufactured by Nippon Kasei Chemical Co., Ltd., suspended therein, adipic acid dihydrazide concentration is 20% by mass)

As a substrate layer for extrusion lamination, an aluminum substrate, a PET substrate, an Ny6 substrate, and a biaxially oriented polypropylene (referred to as OPP) substrate shown below were used. The values in parentheses indicate the thickness (in μm).
Aluminum base: A laminate in which a 12 μm-thick biaxially stretched PET film is laminated on one side of a 9 μm-thick aluminum foil by a dry lamination method. That is, the composition is aluminum foil (9) / dry laminating adhesive / PET (12). Hereinafter, this laminate is used as an Al base.
-PET substrate: 20 μm thick paper, 12 μm thick biaxially stretched PET by dry lamination on the 12 μm thick biaxially stretched PET film side with an aluminum deposited film adjacent on one side A laminated body in which a film is laminated. That is, a composition is PET (12) / aluminum vapor deposition film / dry lamination adhesive / paper (20) / dry lamination adhesive / PET (12).
Hereinafter, this laminate is used as a PET substrate.
-Ny 6 base material: 20 μm thick paper, 12 μm thick biaxially stretched PET by dry lamination on the side of the 15 μm thick biaxially stretched Ny 6 film having an aluminum deposited film adjacent to one side. A laminated body in which a film is laminated. That is, a composition is Ny6 (15) / aluminum vapor deposition film / dry lamination adhesive / paper (20) / dry lamination adhesive / PET (12). Hereinafter, this laminate is referred to as a Ny6 substrate.
-OPP base material: A laminated body in which a 20 μm-thick non-oriented polypropylene film is laminated by dry lamination on a vapor-deposited side of a 15 μm-thick biaxially oriented polypropylene film having an aluminum deposited film adjacent on one side. . That is, a structure is a biaxially-stretched polypropylene film (15) / aluminum vapor deposition film / dry lamination adhesive agent / non-stretching polypropylene film (20). Hereinafter, this laminate is referred to as an OPP substrate.

Example 1
"A-1" was used as an aqueous dispersion of acid-modified polyolefin resin (A), and "B-1" was used as an epoxidized vegetable oil (B). In advance, “B-1” was diluted with ethanol (the solubility in water at 20 ° C. was completely dissolved in any amount) to prepare an ethanol solution with a “B-1” concentration of 20 mass%. Then, the aqueous dispersion of “A-1” is epoxidized vegetable oil (B) “B-1” so that “B-1” is 10 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin “PO1” Solution of ethanol was added. Under the present circumstances, the ethanol solution of "B-1" was gradually added over 2 minutes, stirring the aqueous dispersion of "A-1". Subsequently, ethanol was added to the aqueous dispersion, and the content of ethanol in the aqueous dispersion was adjusted to 25% by mass to obtain an aqueous dispersion E-1.

Examples 2 to 6, Comparative Examples 1 and 3 to 5
Instead of the acid-modified polyolefin resin (A) aqueous dispersion “A-1”, “A-2” in Example 2, “A-3” in Example 3, and “A-4” in Example 4 In Example 5, “A-5” in Example 5, “A-7” in Example 6, “A-6” in Comparative Example 1, and an aqueous dispersion of polyurethane resin in Comparative Example 3 (ester type polyurethane resin Aqueous dispersion of Adeka, Adekabon titer HUX 380, diluted with water to adjust the resin concentration to 20% by mass, containing no organic solvent), and Comparative Example 4 an aqueous dispersion of polyacrylic resin (Kushimoto An aqueous dispersion of SBR (styrene butadiene in Comparative Example 5) prepared by diluting Neokryl XK-12 manufactured by Kasei Chemical Co., Ltd. with water to adjust the resin concentration to 20 mass%, containing no organic solvent, and having an acid value of 11 mg KOH / g). Rubber latex, Japan A & L The ethanol content is 25 in the same manner as in Example 1 except that the resin concentration is adjusted to 20% by mass by diluting NaIrustar SR-116 manufactured by water with water and using no organic solvent). Aqueous dispersions “E-2” to “E-6”, “E-22”, and “E-24” to “E-26” of mass% were obtained, respectively.

Examples 7 to 10
"B-1" is 0.01 parts by mass (Example 7), 0.1 parts by mass (Example 8), and 0.5 parts by mass (Example 9) with respect to 100 parts by mass of "PO2" Or the ethanol solution of the epoxidized vegetable oil (B) "B-1" was added to the acid-modified polyolefin resin (A) aqueous dispersion "A-2" so as to be 2 parts by mass (Example 10) In the same manner as in Example 2, aqueous dispersions “E-7” to “E-10” each having an ethanol content of 25% by mass were obtained.

Example 11
The aqueous dispersion of “A-2” was used as the aqueous dispersion of the acid-modified polyolefin resin (A), and “B-1” was used as the epoxidized vegetable oil (B). In advance, "B-1" was diluted with ethanol to prepare an ethanol solution having a "B-1" concentration of 50% by mass. Subsequently, the said ethanol solution of "B-1" was added to the aqueous dispersion of "A-2" so that "B-1" might be 15 mass parts with respect to 100 mass parts of "PO2." Under the present circumstances, the ethanol solution of "B-1" was gradually added over 2 minutes, stirring the aqueous dispersion of "A-2." Subsequently, ethanol was added to the aqueous dispersion, and the content of ethanol in the aqueous dispersion was adjusted to 25% by mass to obtain an aqueous dispersion “E-11”.

Example 12, Comparative Example 7
Acid-modified polyolefin resin (A) aqueous solution so that “B-1” is 30 parts by mass with respect to 100 parts by mass of “PO2” (Example 11) or 40 parts by mass (Comparative Example 7) An aqueous dispersion having a content of ethanol of 25% by mass in the same manner as in Example 11 except that an ethanol solution of epoxidized vegetable oil (B) "B-1" was added to dispersion "A-2" E-12 "and" E-28 "were obtained respectively.

Examples 13 to 16 and Comparative Examples 8 and 9
Instead of epoxidized vegetable oil (B) "B-1", Example 13 "B-2", Example 14 "B-3", Example 15 "B-4", Example In the same manner as in Example 2, except that “B-5” was used in 16, “EX-411” in Comparative Example 8, and “SR-TMP” in Comparative Example 9, Aqueous dispersions “E-13” to “E-16”, “E-29”, and “E-30” having a content of 25% by mass were obtained, respectively.

Example 17
"A-2" was used as an aqueous dispersion of acid-modified polyolefin resin (A), and "B-1" was used as an epoxidized vegetable oil (B). Epoxidized vegetable oil (B) with no dilution solvent in the acid-modified polyolefin resin (A) aqueous dispersion of "A-2" so that "B-1" is 10 parts by mass with respect to 100 parts by mass of "PO2""B-1" (stock solution) was added. Under the present circumstances, the aqueous dispersion of "A-2" was gradually added "B-1" over 2 minutes, stirring, and aqueous dispersion "E-17" was obtained. The aqueous dispersion does not contain a water-soluble organic solvent.

Comparative example 2
No water-soluble organic solvent was contained in the same manner as in Example 17 except that “A-6” was used instead of “A-2” as the aqueous dispersion of the acid-modified polyolefin resin (A) An aqueous dispersion "E-23" was obtained.

Example 18
"A-2" was used as an aqueous dispersion of acid-modified polyolefin resin (A), and "B-1" was used as an epoxidized vegetable oil (B). First, "B-1" is diluted with isobutanol (the solubility in water at 20 ° C is 87 g / L-H ₂ O), and a "B-1" concentration is 20% by mass in an isobutanol solution. Made. Subsequently, the isobutanol solution of "B-1" was added to the aqueous dispersion of "A-2" so that "B-1" might be 10 mass parts with respect to 100 mass parts of "PO2." At this time, while stirring the aqueous dispersion of "A-2", an isobutanol solution of "B-1" was gradually added over 2 minutes or more. Subsequently, ethanol was added to the aqueous dispersion, and the total content of isobutanol and ethanol in the aqueous dispersion was adjusted to 25% by mass to obtain an aqueous dispersion "E-18".

Example 19
An aqueous dispersion of a polyurethane resin (an aqueous dispersion of an ester type polyurethane resin, Adekabon Titer HUX 380 manufactured by Adeka diluted with water to adjust the resin concentration to 20% by mass) to an aqueous dispersion “E-2” Was added. The amount of addition was such that the polyurethane resin contained in HUX 380 was 5 parts by mass with respect to 100 parts by mass of "PO2" contained in the aqueous dispersion. After the addition, the mixture was stirred to obtain an aqueous dispersion "E-19".

Example 20
In aqueous dispersion “E-2”, an aqueous solution of polyvinyl alcohol (PVA) [VC-10 (polymerization degree 1000, degree of saponification 99.5 mol%) made by Nippon Shokubai-Bi-Pobar, is dissolved in water, 5 What was adjusted to the concentration by mass, hereinafter referred to as an aqueous solution of VC-10] was added. The addition amount was such that VC-10 was 0.5 parts by mass with respect to 100 parts by mass of "PO2" contained in the aqueous dispersion "E-2." After addition, the mixture was stirred to obtain an aqueous dispersion "E-20".

Example 21
An aqueous VC-10 solution was further added to the aqueous dispersion "E-19". The amount of addition was such that VC-10 was 0.5 parts by mass with respect to 100 parts by mass of "PO2" contained in the aqueous dispersion "E-19". After the addition, the mixture was stirred to obtain an aqueous dispersion "E-21".

Comparative example 6
Epoxidized vegetable oil (B) was not used in Example 2. That is, “A-2” is used as the aqueous dispersion of the acid-modified polyolefin resin (A), ethanol is added thereto, and the content of ethanol in the aqueous dispersion is adjusted to 25 mass%, An aqueous dispersion "E-27" was obtained.

Comparative example 10
"A-2" was used as an acid-modified polyolefin resin (A) aqueous dispersion, and "ADH liquid" was used as a crosslinking agent. "WS700" was added as an additive to the aqueous dispersion "A-2" so that the adipic acid dihydrazide component of "ADH liquid" was 5 parts by mass with respect to 100 parts by mass of "PO2". At this time, the aqueous dispersion "A-2" was gradually added with the "ADH solution" over 2 minutes while being stirred. Subsequently, ethanol was added to the aqueous dispersion, and the content of ethanol in the aqueous dispersion was adjusted to 25% by mass to obtain an aqueous dispersion “E-31”.

Comparative example 11
100 parts by mass of "PO2" and 10 parts by mass of "B-1" were mixed with 600 parts by mass of toluene. Then, it was stirred while heating, and "PO2" and "B-1" were dissolved in toluene (the generated toluene vapor was refluxed by a condenser). Thus, the toluene solution "E-32" which contained 10 mass parts of "B-1" with respect to 100 mass parts of "PO2" was obtained. Also with respect to this toluene solution, the transparency of the coating film and the warpage suppressing effect of the base material layer were evaluated.

   Table 2 shows the composition and evaluation results of the aqueous polyolefin resin dispersion obtained in Examples 1 to 21. Composition and evaluation of the aqueous dispersion obtained in Comparative Examples 1 to 10, and the toluene solution obtained in Comparative Example 11 The results are shown in Table 3.

Example 22
For extrusion lamination on aluminum foil surface of Al substrate, PET surface of PET film adjacent to vapor deposited film of PET substrate, Ny6 film surface of Ny6 substrate, or biaxially oriented polypropylene film surface of OPP substrate Using the aqueous dispersion obtained in Example 1 as an anchor coating agent, it was applied and dried at 100 ° C. for 10 seconds. The amount of application was such that the thickness of the anchor coat layer after drying was 0.3 μm.
Then, using an extrusion laminating apparatus equipped with a T-die, low density polyethylene resin (Sumitomo Chemical Co., Ltd .: Sumikasen L211, hereinafter sometimes referred to as PE) or the surface of the anchor coat layer provided on each substrate layer Melt-extrusion of ethylene-vinyl acetate copolymer (manufactured by Tosoh Corp., Ultracene 541, vinyl acetate content: 10% by mass, hereinafter sometimes referred to as EVA), laminating a 30 μm-thick sealant layer, and laminating film Obtained. The line speed at the time of extrusion lamination (rolling up speed of laminated film) was 150 m / min. Also, set the extrusion temperature so that the molten resin temperature just below the T die when extrusion laminating EVA will be 230 ° C. so that the molten resin temperature just below the T die when extrusion laminating PE will be 280 ° C. did. In addition, the extrusion lamination of EVA uses only Al base material and PET base material, and does not implement Ny6 base material and OPP base material.
Then, cut out 2 sheets of each obtained laminate film in a size of 90 mm × 90 mm, overlap the 2 sheets so that the sealant layer is inside, heat seal 3 sides of 3 sides of it, and make 90 mm × 90 mm I got a size packaging material.
In this way, a packaging material comprising at least a base layer / anchor coat layer / sealant layer laminated in this order, wherein any one of the aluminum base, the PET base, the Ny6 base and the OPP base is used as a base Obtained.

Examples 23 to 42, Comparative Examples 12 to 22
A packaging material was obtained in the same manner as in Example 1 except that the anchor coat agent shown in Table 4 was used instead of the aqueous dispersion E-1 as the anchor coat agent for extrusion lamination.
In Comparative Example 17, extrusion coating was not performed because an anchor coating agent was applied to the surface of the two-oriented polypropylene film of the OPP substrate, and repelling occurred and an anchor coating layer could not be formed.

   The characteristics of the packaging materials obtained in Examples 22 to 42 and Comparative Examples 12 to 22 are shown in Table 4.

In the aqueous dispersions E-1 to E-21 obtained in Examples 1 to 21, the epoxidized vegetable oil (B) is uniformly dissolved and / or dispersed in the aqueous dispersion, and the obtained coating film is It was transparent and had the effect of suppressing the warping of the substrate. Also, thickening during storage was suppressed. Above all, these effects are improved as the unsaturated carboxylic acid content of the acid-modified polyolefin resin (A) and the oxirane concentration of the epoxidized vegetable oil (B) are the preferred concentrations of the present invention.
On the other hand, in the aqueous dispersions E-22 to E-26 obtained in Comparative Examples 1 to 5, phase separation is remarkable, and thickening occurs even during storage, and the transparency of the obtained coating film is also obtained. It was inferior and there existed a case where the suppression effect of the curvature of a base material was not acquired.
The aqueous dispersions E-27 and E-31 obtained in Comparative Examples 6 and 10 were inferior to the warpage suppression of the base material.
With respect to the aqueous dispersions E-28 to E-30 obtained in Comparative Examples 7 to 9, phase separation of the aqueous dispersion and thickening during storage were confirmed, and the transparency of the obtained coating film was also inferior, and the substrate In some cases, the effect of suppressing warpage can not be obtained.
Moreover, in Comparative Example 11, although the ratio containing the acid-modified polyolefin resin (A) and the epoxidized vegetable oil (B) was equivalent to that of Example 2, it was inferior to the warpage suppression of the base material. In Comparative Example 11, the medium was toluene, not an aqueous medium, and was a toluene solution, not an aqueous dispersion, so it was considered that sufficient reactivity between the carboxyl group of (A) and the epoxy group of (B) was not obtained. Be
In the aqueous dispersions E-1 to E-21 of Examples 1 to 21, no increase in viscosity was confirmed even when stored at room temperature for 1 month after production.

Examples 22 to 42 are packaging materials obtained using the aqueous dispersions E-1 to E-21 obtained in Examples 1 to 21 as anchor coating agents. When producing these packaging materials, the extrusion laminate was at a low extrusion temperature such as 280 ° C., and the line speed was as high as 150 m / min, but had sufficient laminate strength. In the case of using an ethylene-based copolymer such as ethylene-vinyl acetate copolymer as the sealant resin, although the extrusion temperature was lower (240 ° C.), the laminate strength and the content resistance were excellent. In particular, in Examples 40 to 42 in which an aqueous dispersion containing a polyurethane resin (C) and a polyvinyl alcohol (D) was used as an anchor coating agent, the content resistance was improved.
On the other hand, the anchor coating agents used in Comparative Examples 12 and 13 were inferior in both laminate strength and content resistance because the unsaturated carboxylic acid content was out of the scope of the present invention.
The anchor coating agent used in Comparative Examples 14 to 16 was inferior in both laminate strength and content resistance, since it did not contain an acid-modified polyolefin resin.
Since the anchor coating agent used in Comparative Examples 17 and 19 to 21 does not contain an epoxidized vegetable oil, it is inferior in content resistance, and in particular, it can not be applied poorly to OPP substrates, laminate strength and resistance It was inferior to the content physical property.
In the anchor coating agent used in Comparative Example 18, the content of the epoxidized vegetable oil deviates from the scope of the claims of the present invention, so both the laminate strength and the content resistance are inferior.
The anchor coating agent used in Comparative Example 22 was not a water-based medium, but was a toluene solution, so it was particularly inferior in content resistance.
In addition, although kerosene is used as a content in evaluation of an Example, generally it is rare to enclose kerosene in the packaging material which consists of laminate films. However, kerosene has a very high effect of deteriorating the adhesion between the base material layer and the sealant layer, and the packaging material whose content resistance is confirmed using kerosene is as opposed to the other contents exemplified in this specification. However, it can be evaluated as having resistance to content.
In addition, the poly-odor of the packaging material obtained by extrusion-laminating polyethylene resin at 280 degreeC as sealant resin in each Example was hardly sensed.

Claims (15)

   (A) an acid-modified polyolefin resin (A) having an unsaturated carboxylic acid content of 0.1 to 10% by mass, an epoxidized vegetable oil (B), and an aqueous medium; A polyolefin resin aqueous dispersion characterized in that the content of (a) is in the range of 0.01 to 30 parts by mass.    The aqueous polyolefin resin dispersion according to claim 1, wherein the acid-modified polyolefin resin (A) contains a (meth) acrylic acid ester component in the range of 1 to 45% by mass as a copolymerization component.    The aqueous dispersion of polyolefin resin according to claim 1 or 2, wherein the oxirane oxygen concentration of the epoxidized vegetable oil (B) is in the range of 5 to 10%.    The aqueous polyolefin resin dispersion according to any one of claims 1 to 3, wherein the epoxidized vegetable oil (B) is an epoxidized soybean oil.    The polyolefin according to any one of claims 1 to 4, wherein the aqueous medium contains a water-soluble organic solvent, and the content of the water-soluble organic solvent is in the range of 5 to 95% by mass of the whole aqueous dispersion. Resin aqueous dispersion.    Furthermore, the polyurethane resin (C) is contained in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A), The aqueous dispersion of polyolefin resin according to any one of claims 1 to 5 body.    The polyolefin resin according to any one of claims 1 to 6, further comprising polyvinyl alcohol (D) in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the acid-modified polyolefin resin (A). Aqueous dispersion.    The polyolefin resin aqueous dispersion according to any one of claims 1 to 7, wherein a haze value of a coating film having a thickness of 10 μm obtained from the aqueous dispersion is 9% or less.   The polyolefin resin according to any one of claims 1 to 8, wherein an epoxidized vegetable oil (B) previously diluted with a water-soluble organic solvent is added while stirring an aqueous dispersion of the acid-modified polyolefin resin (A). Method of producing an aqueous dispersion.    An anchor coating agent for extrusion lamination, comprising the aqueous polyolefin resin dispersion according to any one of claims 1 to 8.    The laminated body on which the coating film obtained from the polyolefin resin aqueous dispersion in any one of Claims 1-8 was laminated | stacked on at least one part of the at least single side | surface of a base material layer.    A packaging material comprising a base material layer / anchor coat layer / a sealant layer laminated at least in this order, wherein the anchor coat layer comprises a coating of the anchor coat agent for extrusion lamination according to claim 10, and a sealant layer Is a polyolefin resin laminated by extrusion lamination.    The packaging material according to claim 12, wherein the base material layer is a barrier layer or a thermoplastic resin layer.    The packaging material according to claim 12, wherein a paper layer is laminated further to the outside of the base material layer. The method for producing a packaging material according to any one of claims 12 to 14, wherein a line speed at the time of extrusion laminating of a polyolefin resin which is a sealant layer is 50 to 400 m / min.