JPH0723460B2 - Adhesive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to an adhesive resin composition and a gas barrier resin,
In particular, it relates to an adhesive resin composition for laminating a saponified ethylene-vinyl acetate copolymer resin and a hydrophobic thermoplastic resin.

B. Conventional Technology and Its Problems Recent technological innovations in the food packaging industry have been remarkable. For example,
It is well known that hydrophobic thermoplastic resins such as polyethylene are being used for food packaging for the purpose of hygiene, beautiful appearance, and weight reduction for reducing transportation costs. However, these polyethylene-based resins have low barrier properties against oxygen, carbon dioxide, etc., and are not suitable for long-term storage of foods, carbonated drinks, etc., and glass bottles, metal cans, etc. are often used. There are many problems such as the pollution caused by throwing away all of them and the cost required to recover the pins, and the development of alternative packaging container materials has been struggling.

An ethylene-vinyl acetate copolymer saponified resin with an ethylene content of 20 to 55 mol% is a material that has melt moldability, high transparency, and excellent gas barrier properties, and is excellent as a food container or packaging material. It has characteristics. However, there are drawbacks in other physical properties such as rigidity and moisture resistance, and they are not satisfactory.

On the other hand, hydrophobic thermoplastic resins, especially polyethylene-based resins, are excellent in moldability, balance of impact resistance and rigidity, hygiene, etc., but they do not have sufficient gas barrier against oxygen, carbon dioxide, etc. However, there are restrictions on its use as packaging material.

Therefore, in order to obtain a food container and a packaging material having both good gas barrier properties of an ethylene-vinyl acetate copolymer saponified resin and excellent mechanical properties of a hydrophobic thermoplastic resin such as a polyethylene resin, in order to obtain both of these, It is conceivable to stack resins. However, these resins have little affinity for each other and it is not possible to obtain a laminate by simple thermal bonding.

By grafting an ethylene-vinyl acetate copolymer saponified resin with a hydrophobic thermoplastic resin such as a polyethylene-based resin by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component onto the polyethylene-based resin, adhesion is achieved. It is well known that a laminate having properties can be formed. However, there are many problems in industrial application of an adhesive resin obtained by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component onto the above-mentioned polyethylene resin. The largest example is the molding speed. In industrial applications, the molding speed is one of the major factors that influence the manufacturing cost. That is, even if it has a good adhesive performance as a basic ability, since the adhesiveness decreases as the molding speed is increased, the molding speed must be extremely slowed down. As a result, the manufacturing cost becomes too high and the industrial application may be greatly limited. Since the various molding conditions affect each other, the take-up speed is not determined independently, but for example, the higher the take-up speed, the faster the molding speed and the reduction in manufacturing cost, and the industrial cost. The application has great significance. In the adhesive resin obtained by grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component to the above-mentioned polyethylene-based resin, there is often a large limitation on the take-up speed of the extruded laminated resin. That is, even if the adhesive has sufficient adhesiveness when the take-up speed is slow, the adhesiveness often decreases when taken-off at a high speed, which is a major obstacle to industrial application.

Further, JP-B-39-6810 discloses that a copolymer obtained from at least one α-olefin and at least one α, β-ethylenically unsaturated carboxylic acid having one or two carboxyl groups is used in one or more waters. There is known a method for producing an ionic copolymer obtained by reacting an ionic metal compound that is soluble in water.
Therein, suitable base copolymers are those obtained by directly copolymerizing ethylene with a monocarboxylic acid monomer with or without the presence of a third copolymerizable monoethylenically unsaturated monomer. Are preferred. And the above-mentioned base copolymer, by neutralizing 10% or more of the acid groups with metal ions such as Na ⁺ , rubber elasticity, flexibility, thermal stability,
It shows that it has desirable physical properties in the solid state such as toughness and wear resistance, and melt flowability, and claims its superiority. On the other hand, it is disclosed that the base copolymer can also be obtained by grafting an α-olefin and an acid monomer to the base of the polyolefin, but this method is not limited to olefins having a molecular weight larger than ethylene, such as propylene, It is described that it is suitable when a polyolefin obtained from butene-1 or the like is used, and there is no disclosure that it can be suitably applied to a polyethylene-based copolymer resin as a polyolefin. And the present invention is a resin having a melting coefficient (MI) of 0.1 to 100 g / 10 minutes to improve the physical properties as described above,
It has been shown that it becomes a resin for adhesives and laminates only when the melting coefficient (MI) is 100g / 10 minutes or more.

However, a copolymer obtained from one or more α-olefins and one or more α, β-ethylenically unsaturated carboxylic acids having one or two carboxyl groups,
The ionic copolymer obtained by reacting one or more water-soluble ionic metal compounds shows little adhesiveness to the gas barrier resin, probably because the carboxyl group is in the main chain. is there. Propylene and butene-1
As a base copolymer polyolefin obtained from
A resin grafted with an acid monomer and neutralized with a metal ion has no adhesiveness to polyethylene. Further, when the MI is 100 g / 10 min or more, there is a problem that molding cannot be performed because the MI is too large. Therefore, it cannot be a substantially useful adhesive resin.

C. Problems to be Solved by the Present Invention In view of such circumstances, the present inventors have considered various physical properties of an adhesive resin and co-extrusion adhesion based on consideration of necessary properties of the adhesive resin during industrial co-extrusion. , The relationship between the moldability and the moldability is earnestly studied, industrial co-extrusion molding is performed at high speed, and an adhesive resin composition having sufficient adhesiveness even when taken at high speed is obtained,
Further, it is intended to obtain a laminate having a good appearance by using it.

D. Means for Solving the Problem The present invention is based on the consideration of the required properties of the adhesive resin during industrial coextrusion, and has made a thorough study of the relationship between the physical properties of the adhesive resin, the coextrusion adhesiveness, and the moldability. As a result, when a polyethylene compound having a specific density is grafted with a specific compound and then an adhesive resin composition containing a specific range of a specific metal compound is used, it is industrially co-extruded at high speed. The inventors of the present invention have found that a laminate having a good appearance can be obtained with sufficient adhesiveness even when molded and taken at a high speed, and the present invention has been completed.

That is, the present invention has a density of 0.91 to 0.86 g / cm ³ grafted an ethylenically unsaturated carboxylic acid or a carboxylic acid anhydride to a polyethylene-based polymer, to an ethylenically unsaturated carboxylic acid or a carboxylic acid anhydride component. For 0.02 to 0.
Adhesiveness of 3 equivalents of a metal compound consisting of a hydroxide or salt of a Group Ia or IIa metal of the periodic law, or a mixture of the metal compound and a polyethylene polymer having a density of 0.91 to 0.86 g / cm ³ . A resin composition and a gas barrier resin, particularly an adhesive resin composition for laminating an ethylene-vinyl acetate copolymer saponified resin and a hydrophobic thermoplastic resin.

E. Effect of the Invention The adhesive resin composition of the present invention satisfies both the adhesiveness and the high-speed moldability required for the coextrusion adhesive resin by using the modified polyethylene resin having a specific density. It's a brutal thing. Further, the obtained laminate has not only an excellent appearance but also excellent mechanical properties and gas barrier properties, and is extremely useful as a food container or a packaging material.

In the present invention, the most important thing is that the density is in a specific range. By grafting an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride onto a polyethylene-based copolymer having a density of 0.91 to 0.86 g / cm ³ , an adhesive resin capable of high-speed extrusion molding was obtained. The reason is not always clear, but it is thought that the crystallinity of the resin may be involved, but vinyl acetate, ethyl acrylate, propylene, butene-1, hexene-
A copolymer having a density of 0.93 to 0.97 g / cm ³ obtained by controlling the crystallinity by copolymerizing α-olefin such as 1,4-methylpentene-1 and octene-1 with ethylene The effect of the present invention cannot be enjoyed. This means that the polyethylene-based resin is graft-polymerized with an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component to form an ethylene-vinyl acetate copolymer saponified resin and a polyethylene-based resin. It is difficult to reach the present invention only by analogy with the prior art, such as the fact that it is well known in the industry that a laminate having adhesiveness can be formed in combination with a hydrophobic thermoplastic resin such as a resin. Is something
It's truly amazing.

The next important thing is 0.02 to 0.3 for the grafted ethylenically unsaturated carboxylic acid or the carboxylic anhydride component.
By adding an equivalent amount of a metal compound consisting of a hydroxide or salt of a metal of Group Ia or IIa of the periodic law, stable molding was possible even under severe molding conditions. The reason is not clear, but Ia or Periodic Table
By blending a metal compound consisting of a hydroxide or salt of a Group IIa metal in a specific range, in the coextrusion molding process, particularly at the time of melting, the interface between the adhesive resin composition layer and the hydrophobic thermoplastic resin layer and / or Alternatively, it is considered that interfacial chemical interaction and chemical reaction at the interface between the adhesive resin composition layer and the gas barrier resin layer are involved. Surprisingly, nothing can be expected from the above statement that metal ions improve the solid state.

F. More Detailed Description of the Invention The greatest feature of the present invention is to use a polyethylene-based polymer having a density of 0.91 to 0.86 g / cm ³ as a base. If the density exceeds 0.91 g / cm ³ and is large, the adhesiveness during high-speed molding, which is the effect of the present invention, is insufficient and the density is 0.86 g / cm ^3.
A polyethylene-based polymer having a size of less than cm ³ is not suitable because it does not have sufficient permeability in the manufacturing process and industrially stable supply cannot be achieved. In order to enjoy the effect of the present invention more preferably, the density is
Desirably, it is based on 0.905 to 0.87 g / cm ³ polyethylene polymer. The method for producing such a polyethylene polymer is not limited, but there is, for example, a method of copolymerizing ethylene and α-olefin at a polymerization temperature of 10 to 80 ° C. using a Ziegler type catalyst. As the α-olefin, those having 3 to 8 carbon atoms are used, and examples thereof include propylene, butene-1, hexene-1, 4-methylpentene-1, and octene-1. The copolymerization ratio varies depending on the type of α-olefin, but is often 7 to 30 mol%. Furthermore, butadiene as the third monomer, 1.4-
It is also possible to copolymerize by adding various dienes such as hexadiene, 1.5-hexadiene, vinyl norbornene, ethylidene norbornene and dicyclopentadiene. Examples of commercially available products include Tuffmer A-4085, Tuffmer A-4090, Tuffmer P-0180, Tuffmer P-0480 marketed by Mitsui Petrochemical Co., Ltd., and Flex Resin DFDA marketed by Nippon Unicar Co., Ltd. −
1137NT7, Flex Resin DFDA-1138NT, etc.

Examples of the ethylenically unsaturated carboxylic acid or carboxylic acid anhydride used for grafting include ethylenically unsaturated carboxylic acids such as maleic acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride, or the like. Although there are carboxylic acid anhydrides and the like, maleic anhydride is preferable among them. Upon grafting, co-grafting can be carried out simultaneously with a comonomer such as ethylene, styrene, vinyl acetate or vinyl ether. Graft amount is 0.
The amount may be 001 to 6% by weight, but 0.01 to 5% by weight is more preferable in terms of adhesiveness and moldability.

The grafting method is not particularly limited, but an ethylene-based unsaturated carboxylic acid or a carboxylic acid anhydride, a dibenzoyl peroxide, a dibutyl peroxide, a dicumyl peroxide, a t-butyl perbenzoate are added to a polyethylene-based copolymer. , T-butyl hydroperoxide,
There is a method in which an organic peroxide such as cumene hydroperoxide is allowed to coexist and a heating reaction is performed so that a chemical bond is formed between the two. The reaction is, for example, benzene, toluene, xylene, chlorobenzene, t-butylbenzene,
100-240 ℃ in the presence or absence of solvent such as cumene
However, it is more preferable to carry out the treatment at 110 to 200 ° C. in the presence of a solvent such as toluene or xylene because a uniform product can be obtained.

In carrying out the present invention, the graft copolymer obtained above is an ethylenically unsaturated carboxylic acid or 0.02 to 0.3 equivalent of a hydroxide of a periodic group Ia or IIa metal with respect to the carboxylic acid anhydride component. Alternatively, it is necessary to add a metal compound consisting of a salt. By blending such a metal compound, it is possible to widen the range in which the temperature conditions of each part of the molding machine can be set, and to prevent resin deterioration in the stagnant part of the molding machine. Becomes At this time, the addition amount of the metal compound is
If it is less than 0.02 equivalent, the effect is not remarkable. Also 0.3
If it is added in excess of the equivalent amount, the adhesive resin will be colored or the fluidity will deteriorate, which is not suitable as a molding material.
Examples of the metal compound consisting of a hydroxide or salt of a metal of Group Ia or IIa of the periodic law include sodium carbonate, lithium carbonate, magnesium carbonate, sodium acetate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like. However, among them, metal compounds consisting of hydroxides or salts of periodic group Ia metals such as sodium carbonate, sodium acetate, sodium hydroxide and potassium hydroxide are preferably used, but sodium hydroxide is particularly preferably used. To be This tendency tends to appear when the gas barrier resin is a saponified ethylene-vinyl acetate copolymer resin.

Ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride component of polyethylene polymer in an ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride density 0.91~0.86g / cm ³ in the copolymer obtained by grafting the present invention For 0.02
~ 0.3 equivalents of a modified copolymer containing a metal compound consisting of a metal hydroxide or salt can be industrially used by itself with sufficient performance, but if necessary, a density of 0.91 to 0.86
It can be used by blending with an ethylene-based polymer of g / cm ³ . In that case, the blending ratio of the modified copolymer and the polyethylene-based polymer depends on the characteristics of the modified copolymer and the polyethylene-based polymer, but may be 1:99, but 2:98 to 40:60 In many cases, 5:95 to 30:70 is more preferable in terms of manufacturing cost and moldability.

The adhesive resin composition of the present invention may contain other additives commonly used in thermoplastic resins. Examples of such additives include antioxidants, UV absorbers,
Examples include plasticizers, antistatic agents, lubricants, and fillers.
These can be blended within the range that the effects of the present invention are not impaired. The following are specific examples of the additive. Antioxidants: 2,5-di-t-butylhydroquinone, 2,6-t-butyl-p-cresol, 4,4'-thiobis- (6-t-butylphenol,
2,2'methylene-bis (4-methyl 6-t-butylphenol, tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, octadecyl-3 -(3 ', 5-di-t-
Butyl-4'-hydroxyphenyl) propionate,
4,4'-thiobis- (6-t-butylphenol) and the like.
Ultraviolet absorber: ethyl-2-cyano-3,3-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2'hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-
4-octoxybenzophenone and the like. Plasticizer: dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin, phosphate ester, etc. Antistatic agent: pentaerythritol monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide, carbowax, etc. Lubricants: ethylene bis stearamide, butyl stearate, etc. Coloring agent: carbon black, phthalocyanine, quinacridone, indoline,
Azo pigments, titanium oxide, red iron oxide, etc. Filler: glass fiber, asbestos, mica, ballastonite, etc.

The ethylenically unsaturated carboxylic acid or its carboxylic acid anhydride grafted onto the polyethylene-based polymer having a density of 0.91 to 0.86 g / cm ³ used in the present invention and its content, the periodicity Ia or the water of a Group IIa metal. Regarding the metal compound consisting of an oxide or a salt and the content thereof, one kind or a mixture of two or more kinds may be used.

Ribbon blenders, high speed mixers, kneaders, mixing rolls, Banbury mixers, extruders, etc. are exemplified as means for blending the respective components for obtaining the composition of the present invention.

Next, as the gas barrier resin used in the laminate of the present invention, there are saponified ethylene-vinyl acetate copolymer resins, polyamide resins such as 6 nylon, 6-6 nylon and 6-12 nylon. Component content rate
A saponified ethylene-vinyl acetate copolymer resin having a saponification degree of 20 to 55 mol% and a saponification degree of 90% or more is preferably used. Further, the ethylene treated with a boron compound such as boric acid or borax
Modified resin obtained by saponifying a vinyl acetate copolymer saponified resin, a silicon-containing olefinically unsaturated monomer, α-olefin, N-vinylpyrrolidone and other third components with ethylene and vinyl acetate Also has melt moldability, and the effect of the present invention can be enjoyed as long as it is in a range that does not impair various physical properties as a gas barrier resin.

As the hydrophobic thermoplastic resin, any resin that can be melt-molded by heating can be used, but preferably polyethylene, polypropylene, polyamide, saturated polyester, polycarbonate, vinyl chloride, polystyrene, ethylene-vinyl acetate copolymer resin, ethylene- There are acrylic ester copolymer resins and the like, and among them, polyethylene is more preferably used.

Examples of polyethylene include the following.

i High-pressure polyethylene: a resin polymerized in the presence of a radical initiator under high pressure of 1000 atm or more ii Medium-pressure polyethylene: in the presence of a catalyst such as Cr ₂ O ₃ ,
Resin polymerized at 30 to 40 atm at 100 to 150 ° C iii Low pressure polyethylene: 0 to 7 atm and 60 to 8 atm using a catalyst combining triethylaluminum and titanium tetrachloride
Resin polymerized at 0 ° C. iv LLDPE: A resin obtained by copolymerizing α-olefin by a solution polymerization method or a gas phase fluidized bed polymerization method. In the present invention, a gas barrier resin and a hydrophobic thermoplastic resin are used as an adhesive resin composition. As the structure of the laminated body laminated through, three types of A / B / C three-layer structure A / B / C / B / A, C / B / A / B / C, A / B / C
/ B / A ', C / B / A / B / C' (where A and A'are gas barrier resin, B is adhesive resin composition, C and C'are hydrophobic thermoplastic resin) symmetry or Asymmetrical three-type five-layer structure,
There is a multi-layered structure in which each of A, B, and C is multilayered.
As a method for obtaining a laminated body, there are a laminating method inside a die, a laminating method outside a die, and a method such as thermocompression bonding by a press,
It can be most preferably applied to the in-die laminating method. Further, it is most suitably applicable to the extrusion molding method by the T die method and the ring die method, but is also suitably applicable to the direct blow molding method, the injection blow molding method and the like. The thus obtained laminate has excellent gas barrier properties and excellent mechanical properties, and is useful as a food container (cup, bolt) or packaging material. Furthermore, the laminate thus obtained can be made more useful by undergoing uniaxial or biaxial stretching, deep drawing, blow molding and the like. Further, the laminate obtained in the present invention can be further laminated with a synthetic resin film, metal, paper or the like.

Hereinafter, the present invention will be described in more detail with reference to Examples.

G. Examples Examples 1 to 4 Tuffmer A-4085 (density 0.88 g / cm ³ , MI (190 ° C, 2160
Polyethylene resin (g) was 3.6 g / 10 min, 100 parts by weight of Mitsui Petrochemical Co., Ltd.) and 12 parts by weight of maleic anhydride were dissolved in 720 parts by weight of purified toluene and kept at 180 ° C. 100 parts by weight of a purified toluene solution in which 1.3 parts by weight of cumene hydroperoxide was dissolved was continuously added to this solution in 2.0 hours with stirring. After the addition was completed, the reaction was continued for 30 minutes.
After cooling, the reaction solution was poured into a large amount of acetone to precipitate a polymer. The obtained polymer was purified by reprecipitation using purified toluene as a solvent and acetone as a non-solvent. This product contained 2.1% by weight of maleic anhydride component.

An aqueous solution containing a predetermined amount of sodium hydroxide (NaOH) was uniformly added to the polymer thus obtained, and after partial drying, melt-kneading pelletized while expelling volatiles under reduced pressure with a vented extruder. An adhesive resin composition composed of the modified copolymer was obtained.

A predetermined amount of the adhesive resin composition obtained above was dry blended with the above Tuffmer A-4085, and then melt-kneaded into pellets by an extruder to obtain an adhesive resin blend composition.

Obtained by saponifying 99.6% of the vinyl acetate component of an ethylene-vinyl acetate copolymer having a vinyl acetate component content of 67 mol% [η] = 1.11 (phenol / water = 85/1
5 in solution, 30 ℃, d1 / g) ethylene-vinyl acetate copolymer saponified resin as gas barrier resin, Mirason 27 (low density polyethylene, MI = 2.0g / 10min, manufactured by Mitsui Petrochemical Co., Ltd. Was used as a hydrophobic thermoplastic resin to obtain a laminate by the following method.

Extruder I with inner diameter 120mmφ, Extruder I with inner diameter 60mmφ
I, equipped with an extruder III with an inner diameter of 90 mmφ, the extruder I,
In II, the molten material is branched into two layers, and then the extruder
A feed block type three-kind five-layer co-extruder of the type in which the resin from the extruder II and the resin from the extruder I are sequentially joined to the resin layer melt-extruded from III is used. The hydrophobic thermoplastic resin is used, and (B) the adhesive resin composition is used in the extruder II.
(A) Gas barrier resin is supplied to III, and die temperature 2
C / B / A / B / co-extruded at 20 ℃, take-off speed 25m / min
A three-kind five-layer film of C (30μ / 6μ / 15μ / 6μ / 30μ) was prepared, and the appearance and peel strength were measured.

In Examples 1 and 2 in which 0.05 equivalent of NaOH was added to the grafted maleic anhydride, molded products with good appearance were obtained, and sufficient adhesive strength was obtained. Also, add NaOH to 0.
In Examples 3 and 4 in which 1 equivalent was added, molded products having an extremely good appearance were obtained with sufficient adhesive strength. Even if the content of the modified copolymer adhesive resin composition in the blend composition is 20%, the peel strength is hardly reduced as compared with the case of the modified copolymer adhesive resin group alone. The results are also shown in Table 1.

Comparative Examples 1 to 4 Mirafson 12 (density = 0.927 g / c instead of Tuffmer A-4085)
m ^3, MI = 3.0, except for using Mitsui Petrochemical Co., Ltd.) was carried out co-extrusion in the same manner as in Example 1-4. The obtained molded product had a good appearance, but had an extremely weak adhesive force and was easily peeled off, and had poor commercial value. The results are also shown in Table 1.

Comparative Examples 5 to 8 The same as Examples 1 to 4 except that the addition amount of NaOH was changed. In Comparative Example 5 and Comparative Example 6 in which NaOH is not added, the surface of the molded product has many irregularities, and the adhesive strength also varies, probably because the thickness is not uniform, and the product value is poor. It was When 1.0 equivalent of NaOH was added, the metal-modified copolymer was colored brown (Comparative Example 7), and the blend composition of the metal-modified copolymer resin and Tuffmer A-4085 could not be mixed uniformly, and many brown Not only that, but the whole was colored (Comparative Example 8), which had poor commercial value, and co-extrusion molding was not carried out. The results are also shown in Table 1.

Comparative Example 9 (B) A laminated film was obtained in the same manner as in Example 1 except that Toughmer A-4085 was used for the adhesive resin layer. Although the laminated film had a good appearance, it had an extremely low adhesive force, was easily peeled off, and had poor commercial value.

Examples 5-6 Flex Resin DFDA-1138 instead of Tuffmer A-4085
Using NT (density = 0.90 g / cm ³ , MI = 0.4 g / 10 min, manufactured by Nippon Unicar Co., Ltd.), the amounts of maleic anhydride and cumene hydroperoxide used were changed, and potassium carbonate (K ₂ CO ₃ ) was used in the same manner as in Examples 1 to 4 except that 0.14 equivalent was used to obtain an adhesive resin composition containing 2.4% of a maleic anhydride component.

The adhesive resin composition obtained above and Toughmer P-0180 (density = 0.88 g / cm ³ , MI = 4.5, manufactured by Mitsui Petrochemical Co., Ltd.) were dry blended at 10:90 to obtain a (B) layer resin.

Obtained by saponifying 99.5% of the vinyl acetate component of the ethylene-vinyl acetate copolymer having a vinyl acetate component content of 56 mol% [η] = 0.96 (phenol / water = 85/1
5 saponified ethylene-vinyl acetate copolymer resin (A) at 30 ° C. in a mixed solution of 30 ° C. as a gas barrier resin,
Mirason 151 (low density polyethylene, MI = 2.0, manufactured by Mitsui Petrochemical Co., Ltd.) is used as the (C) hydrophobic thermoplastic resin.

Extruder I with inner diameter of 60mmφ, Extruder I with inner diameter of 40mmφ
I, equipped with an extruder III with an inner diameter of 90 mmφ, and after the molten material from each extruder is spread in one die by each manihole, it is merged in the die and multi-layered type 3 type 3 Using a layer co-extrusion device,
The extruder I is (C) a hydrophobic thermoplastic resin, the extruder II is a (B) adhesive resin composition, and the extruder III.
(A) Gas barrier resin is supplied to the
C / B / A (50
μ / 8μ / 15μ) was prepared. The obtained films had a good appearance, and when the peel strength was measured, all had sufficient adhesive force. The results are also shown in Table 2.

Comparative Examples 10 to 11 Ultzex in place of Flex Resin DFDA-1138NT
3055R (LLDPE, density = 0.935g / cm ³ , manufactured by Mitsui Petrochemical Co., Ltd.)
Instead of Toughmer P-0180, Ult-Zex 2020L (L
LDPE, density = 0.92 g / cm ³ , manufactured by Mitsui Petrochemical Co., Ltd.) was used, and the same procedure as in Examples 5 to 6 was performed. The obtained molded product had a good appearance, but had a very weak adhesive force, was easily peeled off, and had poor commercial value. The results are also shown in Table 2.

Comparative Example 12 Flex Resin DFDA-1138NT and Toughmer P-0180 1
Molding was performed in the same manner as in Example 7 except that the 0:90 mixture was used as the adhesive resin to obtain a laminated film. Although the laminated film had a good appearance, it had an extremely low adhesive force, was easily peeled off, and had poor commercial value. Result is second
Shown according to the table.

Claims (8)

[Claims] 1. An ethylenically unsaturated carboxylic acid or a carboxylic anhydride thereof is grafted onto a polyethylene polymer having a density of 0.91 to 0.86 g / cm ³ to obtain an ethylenically unsaturated carboxylic acid or a carboxylic anhydride component. On the other hand, 0.02 to 0.3 equivalents of a metal compound consisting of a hydroxide or salt of a periodic Ia or IIa metal, or the metal compound and a polyethylene polymer having a density of 0.91 to 0.86 g / cm ³ are blended. Adhesive resin composition. 2. The adhesive resin composition according to claim 1, wherein the ethylenically unsaturated carboxylic acid or the carboxylic acid anhydride is maleic anhydride. 3. The adhesive resin composition according to claim 1 or 2, wherein the metal compound is a metal compound consisting of a hydroxide or salt of a metal of Group 1a of the periodic table. 4. The adhesive resin composition according to claim 1, which is an interlayer adhesive for co-extrusion. 5. A polyethylene polymer having a density of 0.91 to 0.86 g / cm ³ is grafted with an ethylenically unsaturated carboxylic acid or a carboxylic acid anhydride to form an ethylenically unsaturated carboxylic acid or a carboxylic acid anhydride component. On the other hand, 0.02 to 0.3 equivalents of a metal compound consisting of a hydroxide or salt of a periodic Ia or IIa metal, or the metal compound and a polyethylene polymer having a density of 0.91 to 0.86 g / cm ³ are blended. An adhesive resin composition for laminating a gas barrier resin comprising the above composition and a hydrophobic thermoplastic resin. 6. The adhesive resin composition according to claim 5, wherein the metal compound is a metal compound consisting of a hydroxide or salt of a Group Ia metal in the periodic table. 7. A gas barrier resin containing ethylene component
The adhesive resin composition according to claim 5 or 6, which is an ethylene-vinyl acetate copolymer saponified resin having a saponification degree of 20 to 55 mol% and a saponification degree of 90% or more. 8. The adhesive resin composition according to any one of claims 5 to 7, wherein the hydrophobic thermoplastic resin is polyethylene.