JP2019038929A - Adhesive composition, laminate, laminate for packaging, and container for packaging - Google Patents

Abstract

To provide an adhesive composition capable of forming a laminate which has a high initial bond strength and can maintain the bond strength at high level even when being immersed in a chemical for a long period of time, and a material for packaging which is excellent in strong acidity, strong alkalinity and resistance to high-concentration alcohol than conventional one.SOLUTION: An adhesive composition contains 50-99 mass% of a polyolefin resin (A) that has a carboxyl group or an acid anhydride group and has no primary hydroxyl group and 1-50 mass% of a polyolefin resin (B) having a primary hydroxyl group and no carboxyl group or acid anhydride group and in 100 mass% of the total of the polyolefin resin (A) and the polyolefin resin (B), and contains 1-40 pts.mass of a curing agent selected from the group consisting of 0.1-5 pts.mass of a silane compound (C), 0.01-1 pts.mass of a phosphorus compound (D) and an epoxy compound (E) having no -SiH group and an isocyanate compound (F) in 100 mass% of the total of the polyolefin resin (A) and the polyolefin resin (B).SELECTED DRAWING: None

Description

  The present invention relates to adhesive compositions. Further, the present invention relates to a laminate obtained by using the adhesive composition, a laminate for packaging, and a container for packaging.

As the packaging container, there are various containers such as a container made mainly of metal, a container made mainly of glass, and a container made of a laminate in which a barrier layer such as metal foil is laminated on a plastic film. There are various types of containers such as a bottle and a bag.
Also, as familiar contents, in addition to food, hair cosmetic products (shampoo, treatments, conditioners, coloring liquids, perms liquid), alcohol for disinfection, bleaching agents, acidic contents, alkaline contents, etc. are mentioned. And also pesticides.

  Patent Document 1 describes 100 parts by weight of a resin mixture comprising 10 to 90% by weight of a polyolefin resin (A1) modified with α, β-ethylenically unsaturated carboxylic acid and 90 to 10% by weight of an unmodified polyolefin resin (B1). And a polyolefin adhesive composition comprising 1 to 200 parts by weight of an acid neutralizer or acid absorber (C1) is disclosed.

  In Patent Document 2, as an adhesive for producing a flexible printed circuit board, (A) a resin dispersion obtained by dispersing modified polypropylene having specific properties in an organic solvent in a solid state, (B) an epoxy resin, An adhesive composition is disclosed comprising C) an amine modified polyol resin, and (D) a curing agent.

  In Patent Document 3, a polyolefin resin obtained by contacting a copolymer of an alkenylsilane and an α-olefin with a compound selected from a cyclohexyl alcohol and a derivative thereof from an OH-free compound, a C = O containing compound and a C = C containing compound. A composition is disclosed.

  Patent Document 4 discloses an adhesive resin composition for bonding a layer formed of a cyclic polyolefin resin and a layer formed of another thermoplastic resin, which is a differential scanning calorimeter (DSC). The melting start temperature in the endothermic curve (second heating) is in the range of −20 ° C. to + 50 ° C., and the melting end temperature in the endothermic curve is 70 when measured at a heating rate of 20 ° C./min using Disclosed is an adhesive resin composition comprising an adhesive component (A) present in a range of -100 ° C and a polyolefin resin (B) having a half value width of a melting peak in the endothermic curve of 20 ° C or less. There is.

  Furthermore, in Patent Document 5, a polyolefin resin (A) having a carboxyl group or an acid anhydride group and a compound having two or more epoxy groups as an adhesive for forming a packaging material for a power storage device, which is aromatic An adhesive composition is disclosed which comprises an epoxy compound (B) having at least one of a group amino group or a heterocyclic ring having a nitrogen atom as a hetero atom.

JP, 2002-3805, A Japanese Patent Application Laid-Open No. 10-60401 JP-A-2-49048 JP 2008-1760 A JP, 2016-35035, A

Among the laminates for a packaging material for forming a container for containing various contents other than food (hereinafter referred to as chemicals), the simplest one is an outer layer side resin film layer in order from the outer layer side, There may be mentioned a laminate comprising an outer adhesive layer, a barrier layer, an inner adhesive layer and a heat seal layer.
The following performance is mainly required for the inner layer side adhesive layer.
(1) The adhesive strength between the barrier layer and the heat seal layer is high.
(2) The above adhesive layer is resistant to chemicals. That is, even if chemicals are sealed in the packaging container, the adhesive strength between the barrier layer and the heat seal layer can be maintained.
For example, when chemicals such as alkaline perm solution are put in the packaging container, the alkaline perm solution passes through the heat seal layer and reaches the adhesive layer, but the adhesion strength between the heat seal layer and the metal foil which is the barrier foil is It is desirable not to decrease.

  Patent Document 1 contains a polyolefin resin (A) modified with an unsaturated carboxylic acid, an unmodified polyolefin (B), and an acid neutralizing agent or an absorbent (C) to provide a chemical like propylene carbonate. Even if medicines are included, it should be stated that adhesion can be maintained. However, in the adhesive described in Patent Document 1, when the content is strongly acidic or strongly alkaline, or when the content contains an alcohol at a high concentration, the adhesive strength can not be sufficiently maintained.

Patent Document 2 discloses an adhesive for flexible printed circuit boards containing epoxy. However, it does not disclose or suggest chemical packaging materials.
Patent Document 3 does not disclose or suggest a chemical packaging material. And although the initial adhesive strength is described, there is no mention of the durability of the adhesive strength.
Patent Document 4 is a layer composed of a cyclic olefin-based resin which is excellent in transparency and widely used as a material such as a light diffusion sheet by combining a specific adhesive component and a specific polyolefin-based resin, and other heat It is disclosed that adhesion with a layer formed of a plastic resin can be improved, and warpage and surface roughness can be suppressed. However, since the cited reference 4 does not disclose the packaging container in the first place, it does not disclose nor suggest any chemical resistance of adhesive strength.

  Patent Document 5 discloses, as described above, an adhesive for forming a packaging material for an electric storage device. However, in the adhesive described in Patent Document 5, when the content is strongly acidic or strongly alkaline, or when the content contains an alcohol at a high concentration, the adhesive strength can not be sufficiently maintained.

The present invention has been made in view of the above background, and provides a laminate having high initial adhesive strength and capable of maintaining a high level of initial adhesive strength before exposure even after prolonged exposure to chemicals. An object of the present invention is to provide an adhesive composition that can be used. Another object of the present invention is to provide a packaging material capable of maintaining a high level of adhesive strength before being exposed even if exposed to a strongly acidic, strongly alkaline, high concentration alcohol for a long time than before. .
Specifically, the initial adhesive strength is 15 mm width and at least 4 N or more, strongly acidic contents at about pH 3 or less, strongly alkaline contents at about pH 10 or more, and contents of 50 mass% or more of ethanol It is an object of the present invention to maintain the adhesive strength at a high level of 70% or more before being exposed even if the object is exposed to 60 ° C. for 4 weeks or more.

The present invention has solved the above problems by using a specific amount of an acid-modified polyolefin, a primary hydroxyl group-containing polyolefin, and a phosphoric acid compound and a silane compound.
That is, the present invention provides a polyolefin resin (A) having a carboxyl group or an acid anhydride group and having no primary hydroxyl group, and a polyolefin resin (B) having a primary hydroxyl group and having no carboxyl group or acid anhydride group. Containing 50 to 99% by mass of the polyolefin resin (A) and 1 to 50% by mass of the polyolefin resin (B) in 100% by mass in total of
With respect to a total of 100 parts by mass of the polyolefin resin (A) and the polyolefin resin (B),
0.1 to 5 parts by mass of silane compound (C),
0.01 to 1 part by mass of a phosphoric acid compound (D), and
1 to 40 parts by mass of a curing agent (E) selected from the group consisting of an epoxy compound having no —SiH and an isocyanate compound,
The present invention relates to an adhesive composition characterized by containing.

  Furthermore, the present invention relates to an adhesive composition characterized in that the silane compound (C) has an epoxy group.

  Further, the present invention relates to an adhesive composition characterized in that the polyolefin resin (A) is obtained by acid-modifying a copolymer obtained from 1-butene and another olefin.

  The present invention also relates to an adhesive composition characterized in that the polyolefin resin (B) is a polybutadiene having a primary hydroxyl group.

In the present invention, a barrier layer having a permeability of oxygen of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) and a heat seal layer are laminated via an adhesive layer formed of the above adhesive composition. Laminated body to be

Further, the present invention relates to a packaging material in which the outer layer side resin film layer, the outer layer side adhesive layer, the barrier film layer, the inner layer side adhesive layer and the heat seal layer are essential in order from the outer layer,
The present invention relates to a packaging material characterized in that the inner layer side adhesive layer is formed from the above adhesive composition.

  Furthermore, the present invention relates to a packaging container formed from the above-mentioned packaging laminate, wherein the heat seal layer constitutes the inner surface.

  According to the present invention, it has become possible to provide a packaging material having an initial adhesive strength of at least 2N at a width of 15 mm and having excellent resistance to strongly acidic, strongly alkaline and highly concentrated alcohol than conventional.

  Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the description “arbitrary number A to arbitrary number B” means a range larger than the number A and the number A and smaller than the number B and the number B.

Hereinafter, a polyolefin resin (A) having a carboxyl group or an acid anhydride group and a polyolefin resin (B) having a primary hydroxyl group may be simply referred to as a polyolefin resin (A) or a polyolefin resin (B).
The adhesive composition of the present invention is sandwiched between the metal foil layer and the heat seal layer,
Reacting the carboxyl group or acid anhydride group in the polyolefin resin (A) with the primary hydroxyl group of the polyolefin resin (B),
Reacting a carboxyl group or an acid anhydride group in the polyolefin resin (A) with the silane compound (C),
Reacting the carboxyl group or acid anhydride group in the polyolefin resin (A) with the epoxy compound or isocyanate compound in the curing agent (E),
By reacting the primary hydroxyl group in the polyolefin resin (B) with the epoxy compound or isocyanate compound in the curing agent (E), a strong crosslinked structure can be formed, sufficient adhesive strength can be expressed, and a strongly acidic solution or Even if it is immersed in a strongly alkaline solution or a solution containing a high concentration of alcohol for a long period of time, its adhesive strength can be maintained at a high level.

<Polyolefin resin (A) having a carboxyl group or an acid anhydride group>
The polyolefin resin (A) has non-crystallinity because it has the solubility in the solvent used for the adhesive composition, and the dissolved solution can be stably stored without precipitation (having storage stability). preferable. On the other hand, in order to improve the chemical resistance as the adhesive layer in the laminate, it is preferable to have a crystalline site, and the balance is important. The polyolefin resin (A) used in the present invention has a mass average molecular weight of 50,000 to 500,000, a melting point of 60 to 110 ° C., and a melting energy (ΔE) of 15 to 50 (mJ / mg) preferable.

The polyolefin resin (A) has a mass average molecular weight (Mw) of 50,000 to 500,000, and thus, the storage stability as a solution of the polyolefin resin (A) constituting the adhesive composition, and the packaging material for chemicals Chemical resistance, heat sealability, and coatability can be easily achieved at the same time. More preferably, the Mw of the polyolefin resin (A) is 100,000 to 400,000.
In other words, if the Mw of the polyolefin resin (A) is less than 50,000, the entanglement of the polymer chains of the polyolefin resin (A) is insufficient, so the film strength of the adhesive layer may be low and the chemical resistance may be insufficient. . If the Mw is more than 500,000, the storage stability at 25 ° C. as the polyolefin resin (A) solution may be reduced, or the viscosity of the adhesive solution may be too high to deteriorate the coatability.

The polyolefin resin (A) has a melting point of 60 to 110 ° C. and a melting energy (ΔE) of 15 to 50 (mJ / mg), so that the adhesive strength as a packaging material for chemicals (initially after chemical immersion) And heat sealability can be satisfied in a well-balanced manner.
In other words, if the melting point of the polyolefin resin (A) is less than 60 ° C., there is a fear that the adhesive strength and the heat sealability may be deteriorated after being immersed in a strongly acidic solution, a strongly alkaline solution, or a solution containing a high concentration of alcohol. There is. If the melting point is higher than 110 ° C., the adhesive strength (initially, after chemical immersion) may be reduced. More preferably, the melting point of the polyolefin resin (A) is 60 to 90 ° C.
In addition, if the melting energy (ΔE) of the polyolefin resin (A) is less than 15 (mJ / mg), the adhesive strength and heat sealability after chemical immersion decrease, and if it exceeds 50 (mJ / mg), crystallinity And the storage stability as a polyolefin resin (A) solution may be reduced. More preferably, the melting energy (ΔE) of the polyolefin resin (A) is 20 to 50 (mJ / mg), and still more preferably 20 to 40 (mJ / mg).

  In the present invention, "preserves storage stability" means that 10 g of resin is added to 90 g of toluene, and the resin is heated and dissolved to obtain a clear solution, which is then cooled to 25 ° C and one week at the same temperature. Let stand and say what does not form a precipitate.

The polyolefin resin (A) in the present invention may have a carboxyl group or an acid anhydride group. For example, the polyolefin resin (A1) having no carboxyl group or acid anhydride group has an ethylenically unsaturated carboxyl group. Examples thereof include modified polyolefin resins obtained by graft polymerization of a group or an acid anhydride thereof, and copolymers of an olefin monomer and an ethylenically unsaturated carboxylic acid or an acid anhydride thereof. Moreover, the polyolefin which has a carboxyl group can also be obtained by making the acid anhydride group of the polyolefin which has an acid anhydride group, and water and alcohol react. The modified polyolefin resin which graft-polymerized the ethylenically unsaturated carboxyl group or its acid anhydride to polyolefin (A1) which does not have a carboxyl group or an acid anhydride group is preferable. The polyolefin resin (A) may be used alone or in combination of two or more.
The amount of the carboxyl group or the acid anhydride group in the polyolefin resin (A) will be described later.

The graft polymerization method of the polyolefin is not particularly limited, but for example, the method disclosed in JP-A-11-293216 can be used.
The polyolefin resin (A) is not particularly limited. For example, homopolymers of olefin monomers such as ethylene, propylene, 1-butene, butadiene, isoprene, 1-hexene and 1-octene, olefin monomers It refers to a copolymer having a hydrocarbon backbone as a main component, such as a copolymer of one another or a copolymer with another monomer, and a hydride or a halide of the obtained polymer. Copolymers of olefin monomers are preferred.

  As a copolymer of olefin monomers, a copolymer of 1-butene and another olefin monomer is preferable. As other olefins, ethylene and propylene are preferable, and as a copolymer of 1-butene and another olefin monomer, a binary copolymer of ethylene and 1-butene, a binary of propylene and 1-butene Copolymers and terpolymers of ethylene, propylene and 1-butene may be mentioned, and binary copolymers of propylene and 1-butene are more preferred. The copolymerization ratio is preferably propylene: 1-butene = 10: 90-80: 20 (molar ratio), and more preferably 40: 60-80: 20 (molar ratio). In a copolymer of propylene and 1-butene, the melting point may be lower than 60 ° C. when propylene is less than 10 mol%, and the melting point may be higher than 110 ° C. when it is more than 80 mol%.

Other monomers which may be copolymerized with the olefin monomer are not particularly limited, and, for example,
Aromatic vinyl compounds such as styrene, α-methylstyrene, indene;
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, Alkyl (meth) acrylate compounds such as behenyl (meth) acrylate;
(Meth) acrylate compounds having an alicyclic structure such as cyclohexyl (meth) acrylate and isobornyl (meth) acrylate;
(Meth) acrylate compounds having an aromatic ring such as benzyl (meth) acrylate;
A hydroxyl group-containing (meth) acrylate compound such as 2-hydroxypropyl (meth) acrylate;
(Meth) acrylate compounds having an amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl (meth) acrylate and the like;
Acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide and the like;
Examples include (meth) acrylonitrile, acryloyl morpholine and the like.
Styrene, dodecyl (meth) acrylate and stearyl (meth) acrylate are preferred from the viewpoint of graft polymerization and compatibility with the polyolefin.
The ethylenically unsaturated carboxylic acid is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and the like. One of these ethylenically unsaturated carboxylic acids or their acid anhydrides may be used alone, or two or more thereof may be used in combination.

  The polymerization method of the olefin monomer is not particularly limited, but, for example, metal catalysts such as Ziegler-Natta catalyst or metallocene catalyst such as the method disclosed in Japanese Patent Publication No. 07-080948, or (methyl) aluminoxane if necessary Cocatalysts can be added and polymerized.

In addition, Mw of polyolefin resin (A) is calculated | required as follows.
The column temperature was 40 ° C., and the eluent was tetrahydrofuran at a flow rate of 0.35 ml per minute according to HLC-8220 GPC system manufactured by Tosoh Co., Ltd. in which two columns of TSKgel super HZM-N were connected. The sample was prepared by dissolving 2 mg of polyolefin resin (A) in 5 ml of tetrahydrofuran. Moreover, Mw was computed by standard polystyrene conversion.
When 2 or more types of polyolefin resin (A) are used in combination, the weight average molecular weight of the whole mixture is meant.

The melting point and the melting energy (ΔE) can be determined by DSC measurement according to JIS K7121. Specifically, it is determined as follows.
When the diameter or each side of about 10 mg of the polyolefin resin (A) is 0.5 mm or less, it is used as it is, and if it exceeds 0.5 mm, it is cut into 0.5 mm or less and put in a container.
Heat to a temperature of about 30 ° C. above the melting point at 10 ° C. per minute and then cool to a temperature about 50 ° C. below the Tg at 10 ° C. per minute. If no clear Tg is observed, cool to about 50 ° C. below the melting point. Thereafter, it was determined from the peak top of the peak corresponding to the melting that appears when heated to a temperature about 30 ° C. higher than the melting point at 10 ° C./min. Also, ΔE is determined from the area of the portion from the peak corresponding to the melting to the return to the baseline after leaving the baseline.
When two or more types of polyolefin resin (A) are used in combination, the melting point is determined from the peak top of the peak on the high temperature side, and ΔE is calculated from the sum of all peak areas obtained by melting.

  A commercial item can also be used as polyolefin resin (A), For example, Sumifit B1401, H1301, Z9901 (a brand name, Sumitomo Chemical Co., Ltd. make), Unistol P-401, P-802, P-902 ( Trade name) Umex 1001, 1010, 2000 (trade name, Sanyo Chemical Industries, Ltd.), auroren 350S, 351S, 359S, 500S, S-5247S, S-5248S, S-5297S, S-5349S, S-5350S, etc. Can be mentioned.

  In the present invention, in addition to the polyolefin resin (A) having a carboxyl group or an acid anhydride group, a polyolefin resin having no carboxyl group or an acid anhydride group may be used in combination as long as the effects of the invention are not impaired. .

  As a polyolefin resin which does not have a carboxyl group or an acid anhydride group used by the present invention, for example, Sumitomo Chemical Co., Ltd. Tuff Selenium T3712, T3722, T3522 (propylene-based elastomer), Sumitomo Nobrene (polypropylene), Mitsui Chemical Tafmer DF & A, Tafmer H, Tafmer XM, Tafmer BL, Tafmer M (α-olefin copolymer), Kraprene LIR-30 (isoprene polymer) manufactured by Kuraray Co., Ltd., LIR-200 (hydrogenated isoprene polymer) LBR-300 (butadiene polymer), Septon 2002, manufactured by Kuraray Co., Ltd. (more than hydrogenated styrene-isoprene-styrene copolymer), 2104, 4033, HG 252 (more than hydrogenated styrene-isoprene / butadiene- Styrene copolymer) Asaprene T-432, T-437, manufactured by Asahi Kasei Chemicals Corporation, Clayton D 1155 (above, Styrene-Butadiene-Styrene Copolymer, manufactured by Clayton Polymer Japan Co., Ltd.) Partially hydrogenated styrene-butadiene-styrene copolymer), H1052, H1043 (above, hydrogenated styrene-butadiene-styrene copolymer), Superchron C (chlorinated propylene polymer) manufactured by Nippon Paper Chemicals Co., Ltd., Nippon Polyethylene Co., Ltd., Rexpearl EMA (ethylene-methyl acrylate copolymer), Rexpearl EEA (ethylene-ethyl acrylate copolymer), Mitsui-Dupont Polychemical Co., Ltd. Evaflex (ethylene-vinyl acetate copolymer) Polymer), Bond First (ethylene-glycidyl methacrylate copolymer) manufactured by Sumitomo Chemical Co., Ltd., and the like. These may be used alone or in any combination of two or more.

<Polyolefin resin having primary hydroxyl group (B)>
It is desirable that the polyolefin resin (B) used in the present invention has the solubility in the solvent used for the adhesive composition and the compatibility with the polyolefin resin (A). On the other hand, in order to improve the chemical resistance as the adhesive layer in the laminate, having active groups at both ends causes various reactions to cause the adhesive resin composition to have a high molecular weight preferable.

The mass average molecular weight (Mw) of the polyolefin resin (B) is from 10,000 to 50,000 from the point of improvement in storage stability as a solution of the polyolefin resin (B) and improvement in compatibility with the polyolefin resin (A). Is preferably, and more preferably 0.2000 to 10,000.
That is, when the Mw of the polyolefin resin (B) is at least 10,000, the polymer chains of the polyolefin resin (B) are effectively entangled, and the film strength of the adhesive layer is improved. Moreover, compatibility with a polyolefin resin (A) improves because Mw is 50,000 or less.

  The polymerization method of the polyolefin (B) and the method of determining the Mw are the same as described above.

As polyolefin (B), a commercial item can also be used, For example, G series (hydroxyl polybutadiene) of NISSO-PB made by Nippon Soda Co., Ltd., GI series (hydroxyl hydrogenated polybutadiene), Poly bd series manufactured by Idemitsu Co., Ltd. Examples thereof include (hydroxyl-terminated liquid polybutadiene), Polyip series (hydroxyl-terminated liquid polyisoprene), EPOL series (hydroxyl-terminated liquid polyolefin), and Mitsubishi Chemical polytel series (polyhydroxypolyolefin oligomer).
These may be used alone or in any combination of two or more.

  The polyolefin resin (B) may be urethane-ized with an isocyanate to give a hydroxyl group-terminated polyolefin polyurethane resin, if necessary. The type of isocyanate used at that time is not particularly limited.

  In the present invention, a polyolefin resin (A) having a carboxyl group or an acid anhydride group and a polyolefin resin (B) having a primary hydroxyl group are preferred from the viewpoint of the improvement of the wettability during coating and the improvement of the content resistance of the laminate. It is important to contain 50 to 99% by mass of the polyolefin resin (A) and 1 to 50% by mass of the polyolefin resin (B) in a total of 100% by mass.

<Silane Compound (C)>
The silane compound (C) used in the present invention is to improve the adhesion strength to a metal foil, a metal plate, a metal vapor deposited film or the like.
For example, trialkoxysilane having vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane, etc., triaminosilane having amino group such as 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, etc. Trialkoxysilanes having a glycidyl group such as alkoxysilane, 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. may be mentioned. .
A silane compound containing an epoxy group is preferable because it can react with a carboxyl group or an acid anhydride group in the polyolefin resin (A), a primary hydroxyl group in the polyolefin resin (B), or a phosphoric acid compound (D).
The silane coupling agent is 0.1 to 5 parts by mass, preferably 0.5 to 3 parts by mass, with respect to 100 parts by mass in total of the polyolefin resin (A) and the polyolefin resin (B). .

<Phosphoric acid compound (D)>
The phosphoric acid-based compound (D) used in the present invention also further improves the adhesive strength to metal foils, metal plates, metal vapor-deposited films and the like, and in particular maintains high levels of adhesive strength to metals during long-term storage. It is effective in terms of
The phosphoric acid compound (D) may be any one of oxygen acids of phosphorus or derivatives thereof as oxygen acids of phosphorus as long as it has at least one free oxygen acid, for example, hypophosphorous acid And phosphoric acids such as phosphorous acid, orthophosphoric acid and hypophosphoric acid, and condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and ultraphosphoric acid. Moreover, as a derivative of the oxygen acid of phosphorus, what was partially esterified with alcohols etc. in the state which left at least one piece of free oxygen acid of the said oxygen acid of phosphorus etc. is mentioned. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol and phlorogricinol. The oxygen acid of phosphorus or its derivative may be used in combination of 2 or more types.
The addition amount of phosphorus oxygen acid or its derivative is 0.01 to 10% by mass, preferably 0.05 to 5% by mass, preferably 0.1 to 1% by mass based on the solid content of the adhesive. It is more preferable that

<Curing agent (E) selected from the group consisting of an epoxy compound having no —SiH and an isocyanate compound>
The epoxy compound having no -SiH used in the present invention is a carboxyl group or an acid anhydride group in the polyolefin resin (A), a primary hydroxyl group in the polyolefin resin (B), a phosphoric acid compound (D) and the like. The adhesive properties and durability are expressed by the reaction of It can also be used in combination with a polyisocyanate.
Although the structure is not particularly limited, compounds having two or more epoxy groups and having at least one of an aromatic amino group or a heterocyclic ring having a nitrogen atom as a hetero atom are preferable.
As a compound which has two epoxy groups among the compounds which have the said aromatic amino group, for example,
N, N-bis (2,3-epoxypropyl) aniline,
2-Methyl-N, N-bis (2,3-epoxypropyl) aniline,
N, N-diglycidyl aniline ("GAN", manufactured by Nippon Kayaku Co., Ltd.),
N, N- diglycidyl -2- methyl benzene amine ("GOT", Nippon Kayaku Co., Ltd. make) etc. are mentioned.
As a compound which has an epoxy group three or more among the compounds which have the said aromatic amino group, for example,
N, N, N ', N'-tetrakis (2,3-epoxypropyl) -1,4-phenylenediamine,
N, N, N ′, N′-tetrakis (oxirane-2-ylmethyl) -4,4′-methylenebisaniline (alias: tetraglycidyldiaminodiphenylmethane, “jER-604”, manufactured by Mitsubishi Chemical Corporation),
N, N-diglycidyl-4- (glycidyloxy) aniline (alias: N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline, “jER-630”, Mitsubishi Chemical Corporation And the like.
In addition, Araldite MY0600 (trade name, made by Huntsman), Adeka Resin EP-3950S, 3950L, 3980S (trade name, made by Adeka Co., Ltd.), YH-434, YH-434L (trade name, made by Nippon Steel Chemical Co., Ltd.) And the like can also be exemplified as a compound having two or more epoxy groups and an aromatic amino group.

Among the epoxy compounds, as a compound having two or more epoxy groups and a heterocycle having a nitrogen atom as a hetero atom, for example, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, Epoxy compounds having a triazine skeleton such as TEPIC-L, TEPIC-PAS, TEPIC-VL (trade name, Nissan Chemical Industries, Ltd.), 2,4,6-tri (glycidyloxy) -1,3,5-triazine, etc. Can be mentioned.
These may be used alone or in combination of two or more.

Also, a compound obtained by reacting a part of the epoxy group of the above epoxy compound with a compound having reactivity with the epoxy group may be used as an epoxy compound not having -SiH.
Compounds having reactivity with an epoxy group include compounds containing an amino group such as butylamine, hexylamine, octylamine, 2-ethylhexylamine, dibutylamine, ethylenediamine, benzylamine, aniline and the like;
Compounds containing a hydroxyl group such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, octanol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, propylene glycol, benzyl alcohol, phenol and the like;
Compounds having an isocyanate group such as octyl isocyanate, dodecyl isocyanate, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate;
Compounds containing carboxylic acids such as acetic acid, butanoic acid, hexanoic acid, octanoic acid, succinic acid, adipic acid, sebacic acid, phthalic acid and the like can be mentioned.

The isocyanate compound exhibits adhesion performance and durability by reaction with the carboxyl group or acid anhydride group in the polyolefin resin (A), the primary hydroxyl group in the polyolefin resin (B), and the phosphoric acid compound (D). It is It can also be used in combination with an epoxy compound which does not have -SiH.
Without being limited thereto, it is a compound derived from a well-known diisocyanate. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, or water Diisocyanate such as diphenylmethane diisocyanate or the like, or a nurate body thereof, trimethylolpropane adduct body, biuret type, prepolymer having isocyanate residue (a low polymer obtained from diisocyanate and polyol), uretdione body having isocyanate residue And allophanates or complexes thereof, and the like, and these can be used alone or in combination of two or more.

  The adhesive composition of the present invention contains the curing agent (E) in an amount of 1 part by mass or more in terms of chemical resistance with respect to 100 parts by mass in total of the polyolefin resin (A) and the polyolefin resin (B). 40 parts by mass or less is included to ensure strength. It is preferable to include 10 to 30 parts by mass.

  The adhesive composition of the present invention can further contain an epoxy phosphate resin in order to enhance the adhesive strength to the metal foil. The epoxy phosphate ester resin is obtained by reacting the epoxy group of the epoxy resin with phosphoric acid to open the epoxy group, and the epoxy resin portion and the phosphoric acid portion are bound by a phosphate ester bond.

  As an epoxy resin which reacts with phosphoric acid, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, bisphenol AD type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin Examples thereof include resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, heterocyclic epoxy resins, diaryl sulfone type epoxy resins, hydroquinone type epoxy resins, and modified products thereof.

  A commercial item can also be used as an epoxy phosphoric acid ester resin, and, specifically, URAD-DD79 (made by DSM Japan) is preferable. Furthermore, those having characteristic values equivalent to those of URAD-DD79 described above can also be suitably used.

  The adhesive of the present invention can contain catechol or a derivative thereof in order to increase the adhesive strength to the metal foil. Specifically, catechol, t-butyl catechol, adrenalin, noradrenaline, dopamine, nordihydroguayretic acid and the like can be mentioned.

The adhesive composition of the present invention can comprise an organic solvent. The materials used in the present adhesive composition can be dissolved alone or as a mixed solvent, and polyolefin resin (A), polyolefin resin (B), silane compound (C), phosphoric acid compound (D), curing agent (E) and The reactivity is not particularly limited as long as it is inert and can be volatilized and removed by heating in the drying step at the time of adhesive coating. Specific examples of these solvents include, for example, aromatic organic solvents such as toluene and xylene;
Aliphatic organic solvents such as n-hexane and n-heptane;
Alicyclic organic solvents such as cyclohexane and methylcyclohexane;
Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone;
Ester solvents such as ethyl acetate and butyl acetate;
Alcohol solvents such as ethanol, methanol, n-propanol, 2-propanol, butanol and hexanol;
Ether solvents such as diisopropyl ether, butyl cellosolve, tetrahydrofuran, dioxane, butyl carbitol;
Glycol ether solvents such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether;
Examples thereof include glycol ester solvents such as ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, etc. These may be used alone or in combination of two or more.
Among them, from the viewpoint of the storage stability of the solution of the polyolefin resin (A) and (B), a combination of an aromatic organic solvent and a ketone solvent, a combination of an aromatic organic solvent and an alcohol solvent, an alicyclic The combined use of the organic solvent and the ketone solvent, and the combined use of the alicyclic organic solvent and the alcohol solvent are preferable.

In the adhesive composition of the present invention, known additives such as a tackifier and a plasticizer may be blended as needed within the range not impairing the effects of the invention.
Examples of tackifiers that can be used in the present invention include polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymeric petroleum resins, styrene resins, hydrogenated petroleum resins, etc. It is used for the purpose of improving the strength. These may be used alone or in any combination of two or more.
Moreover, as a plasticizer used by this invention, liquid rubber, such as polyisoprene and polybutene, process oil, etc. are mentioned.

  In addition, additives known for adhesives can be incorporated into the main agent, for example, reaction accelerators can be used. For example, metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimaleate; 1,8-diazabicyclo (5,4,0) undecen-7,1,5-diazabicyclo (4,3) And 0) tertiary amines such as nonene-5, 6-dibutylamino-1,8-diazabicyclo (5,4,0) undecen-7; reactive tertiary amines such as triethanolamine; One or two or more reaction accelerators selected from the group consisting of

  A well-known leveling agent or an antifoamer can also be mix | blended with a main ingredient in order to improve the smoothness etc. of an adhesive film.

  As the leveling agent, for example, polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, acrylic copolymer Methacrylic copolymers, polyether-modified polymethylalkyl siloxanes, acrylic acid alkyl ester copolymers, methacrylic acid alkyl ester copolymers, lecithin, mixtures thereof and the like can be mentioned.

  As an antifoamer, well-known things, such as a silicone resin, a silicone solution, the copolymer of alkyl vinyl ether, acrylic acid alkyl ester, and methacrylic acid alkyl ester, or mixtures thereof are mentioned.

The adhesive composition of the present invention is suitably used for laminating a heat seal layer and a barrier layer having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less.
As a barrier layer having an oxygen permeability of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.), a film obtained by vapor-depositing aluminum, SiOx, Al ₂ O ₃ or the like on various plastic films can be mentioned. Is preferred.
Examples of the metal of the metal foil include aluminum, copper, nickel and the like. These metal foils may be subjected to various surface treatments. Examples of the surface treatment include physical treatment such as sandblasting treatment and polishing treatment, degreasing treatment by deposition, etching treatment, and primer treatment for applying a coupling agent and a coating agent.
The treatment agent for forming the surface treatment layer preferably contains a functional group that reacts with an epoxy group, and more preferably contains at least one functional group selected from the group consisting of a carboxylic acid, a hydroxyl group and an amino group. Is preferred. The term "amino group" as used herein means any of a primary amine, a secondary amine, and an imino group. By providing a surface treatment layer containing such functional groups on the surface of the metal foil layer, when the adhesive composition is thermally cured, the epoxy group in the adhesive layer reacts with the functional group in the surface treatment layer. By doing this, a laminate having high adhesive strength can be obtained.

  The heat seal layer is not particularly limited, but is preferably a polyolefin film, and at least one selected from the group consisting of polyethylene, polypropylene, an olefin copolymer, an acid modified product thereof and an ionomer thereof. It is preferable that it is an unstretched film made of a thermoplastic resin. The thickness of the heat seal layer is not particularly limited, but is preferably 20 to 150 μm.

A laminate comprising the adhesive composition of the present invention can be obtained, for example, as follows.
The adhesive composition of the present invention is applied to one surface of a metal foil layer (or heat seal layer), the solvent is volatilized (dried), and an uncured adhesive layer is formed, at 60 to 150 ° C. After laminating a heat seal layer (or metal foil) on the surface of the uncured adhesive layer under pressure, the adhesive layer is sufficiently cured by standing at 40 to 80 ° C. for about 3 to 10 days ( A laminate can be obtained by bonding the metal foil and the heat seal layer together, which is also referred to as aging, curing, and aging).
For coating of the adhesive composition, a general coating machine such as a gravure coater or a comma coater can be used. Moreover, it is preferable that the thickness (amount) of the hardening adhesive layer at the time of dry hardening is about 0.5-10 g / m < ² >.

The packaging material of the present invention is the outer layer side resin through the outer layer side adhesive layer on the other side of the metal foil layer (the side where the inner layer side adhesive layer formed from the adhesive composition of the present invention is not in contact). A film layer can be provided.
The outer layer side resin film layer may be laminated to the metal foil layer using an adhesive composition (which may be the same as or different from the adhesive composition of the present invention) in advance. After the laminate of the metal foil layer and the heat seal layer is obtained using the adhesive composition of the present invention, the outer layer side resin film layer can be laminated on the metal foil layer via the outer layer side adhesive layer. .
As an outer layer side resin film layer to be used, stretched films, such as polyester resin and polyamide resin (nylon), etc. are mentioned.

  Hereinafter, the present invention will be described in more detail by way of examples, but the following examples do not in any way limit the scope of the present invention. In addition, each evaluation in the Example followed the following method. In the examples,% indicates mass% and part indicates mass part.

<Number average molecular weight>
Using an HLC-8220 GPC system manufactured by Tosoh Co., Ltd., in which two columns of TSKgel super HZM-N were connected, tetrahydrofuran was used as the eluent and the column temperature was 40 ° C., and flow rate was measured at 0.35 ml per minute. The sample was prepared by dissolving 2 mg of polyolefin resin (A) in 5 ml of tetrahydrofuran. Moreover, the mass mean molecular weight was computed by standard polystyrene conversion.

<Melting point, melting temperature energy (ΔE)>
The melting point and ΔE can be determined by DSC measurement according to JIS K7121. Specifically, it is determined as follows.
When the diameter or each side of about 10 mg of the polyolefin resin (A) is 0.5 mm or less, it is used as it is, and if it exceeds 0.5 mm, it is cut into 0.5 mm or less and put in a container.
Heat to a temperature of about 30 ° C. above the melting point at 10 ° C. per minute and then cool to a temperature about 50 ° C. below the Tg at 10 ° C. per minute. If no clear Tg is observed, cool to about 50 ° C. below the melting point. Thereafter, it was determined from the peak top of the peak corresponding to the melting that appears when heated to a temperature about 30 ° C. higher than the melting point at 10 ° C./min. In addition, ΔE was determined from the area of the portion from the peak corresponding to melting to the return to the baseline after leaving the baseline

<Copolymer composition ratio>
The copolymerization compositional ratio of the polyolefin was determined by measurement of ¹³ C using NMR (JNM-LA400) manufactured by Nippon Denshi Co., Ltd.
A 20 mg sample was dissolved in 1 ml of heavy chloroform and measured. The ethylene-derived methylene group is contained at 40-50 ppm, the propylene-derived methine group is contained at 25-30 ppm, and the 1-butene-derived methine group is contained at 30-35 ppm. The copolymerization composition ratio was determined from the integral ratio of each peak.

Synthesis Example 1
250 mL of purified toluene in a 500 mL glass autoclave with nitrogen substitution, 0.5 mg of methylaluminoxane in terms of Al atom, dimethylsilyl-bis- (4,5,6,7,8-pentahydroazulen-2-yl) 1.25 μg atom of zirconium dichloride was converted in terms of Zr atom, and the temperature was raised to 40 ° C. Subsequently, 1-butene monomer was continuously supplied to maintain a constant pressure of 1.32 MPa at 40 ° C. while supplying ethylene and propylene at a constant rate of 50 L / hr and 40 L / hr, respectively, and polymerization was initiated. . After polymerization was carried out at 40 ° C. for 8 hours, isopropanol was added to terminate the polymerization. The obtained polymer solution was added to a large amount of methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain a polyolefin copolymerized with ethylene / propylene / 1-butene = 46/33/15 (molar ratio).
20 g of the obtained polyolefin and 20 g of cellosolve acetate were charged, and dissolved by heating under a nitrogen stream to a solution temperature of 110 ° C. A solution of 4 g of maleic anhydride, 2 g of lauryl methacrylate and 0.6 g of benzoyl peroxide in 239.4 g of cellosolve acetate was dropped over 2 hours. The reaction was continued at that temperature for an additional hour after the end of the addition. The obtained polymer solution was added to a large amount of methanol to precipitate a polymer. The precipitated polymer was filtered and dried to obtain a polyolefin resin (A1) having an acid anhydride group.
The Mw, the melting point and the ΔE of the polyolefin resin (A1) were 4700, 103 ° C. and 45 mJ / mg, respectively.

Example 1
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping tank, and a nitrogen gas introduction pipe, 90 parts of a polyolefin resin (A1), G-3000 (manufactured by Nippon Soda Co., Ltd.) as a polyolefin resin (B) having a primary hydroxyl group B-1) 10 parts were heated and dissolved in 600 parts of toluene / MEK = 2/1 (weight ratio).
After cooling to room temperature, 1 part of γ-glycidoxypropyltrimethoxysilane as silane compound agent (C), 0.05 part of phosphoric acid (D), epoxy compound not having -SiH as curing agent (E) An adhesive solution with a solid content of 15% was obtained by blending and stirring 40 parts of a toluene / MEK diluted solution (nonvolatile content 25% by weight) of a Mitsubishi Chemical JER630 2/1 2: 1. Initial adhesive strength, pesticide resistance, alcohol, acid and alkalinity were evaluated using the obtained adhesive solution according to the method described later. The results are shown in Table 1.

<Examples 2 and 3>
Bonding in the same manner as in Example 1 except that G-1000 (B-2) manufactured by Soda Co., Ltd. and G-2000 (B-3) manufactured by Soda Co., Ltd. were used instead of the polyolefin resin (B-1). The agents were obtained, evaluated similarly and the results are shown in Table 1.

Examples 4 and 10, Comparative Example 6
20 parts (Example 4), 40 parts (Example 10), 60 parts (Comparative Example) of an isocyanate compound, Duranate D101 manufactured by Asahi Kasei Chemicals Corporation, instead of an epoxy compound not having -SiH as a curing agent (E) An adhesive was obtained and evaluated in the same manner as in Example 1 except that 6) was used, and the results are shown in Tables 1 and 2.

Examples 5 to 6
An adhesive was obtained and evaluated in the same manner as in Example 1 except that the proportions of the polyolefin resin (A1) and the polyolefin resin (B-1) were changed, and the results are shown in Table 1.

Examples 7 to 8
An adhesive was obtained and evaluated in the same manner as in Example 1 except that the amount of the silane compound agent (C) was changed, and the results are shown in Table 1.

Example 9
An adhesive was obtained and evaluated in the same manner as in Example 1 except that the amount of the epoxy compound not containing —SiH was changed to 20 parts, and the results are shown in Table 1.
Example 11
An adhesive was obtained and evaluated in the same manner as in Example 1 except that polyolefin resin Aurolen 500S (A2) manufactured by Nippon Paper Chemicals Co., Ltd. was used instead of the polyolefin resin (A1), and evaluations were made in the same manner. Shown in 1.

<Comparative Example 1 to Comparative Examples 5, 7, 8>
An adhesive was obtained in the same manner as in Example 1 with the composition shown in Table 2, and evaluated in the same manner. The results are shown in Table 2.

(Creating a three-layer composite laminate)
Adhesive of 3-layer composite laminate of polyethylene terephthalate (PET) film (thickness 12 μm) / aluminum (AL) foil (thickness 9 μm) / unstretched polyethylene (LLDPE) film (thickness 100 μm, surface corona discharge treatment) The solid content coating amount was 3.5 g / m 2 and was prepared by the method described below.
That is, the adhesive solution was first applied to a printing surface of a polyethylene terephthalate film by a laminator at normal temperature, and after the solvent was volatilized, the coated surface was bonded to the aluminum foil surface. Furthermore, an adhesive solution is similarly applied to the aluminum foil surface of the laminate, and after the solvent is volatilized, the coated surface is bonded to an unstretched polyethylene film, and kept at 60 ° C. for 6 days, a three-layer composite laminate It was created.
The appearance of the three-layer composite laminate was observed for adhesion from each of the PET side and the LLDPE side, but floating and peeling were not observed in all the Examples and Comparative Examples, and no repelling was observed.

(Initial adhesive strength test)
Test pieces of 300 mm × 15 mm in size are prepared from the three-layer composite laminate prepared as described above, and peeling is performed by T-type peeling using a tensile tester under conditions of a temperature of 20 ° C and a relative humidity of 65%. The laminate strength (N / 15 mm) between the AL foil / LLDPE film was measured at a speed of 30 cm / min. The numerical values in Tables 1 and 2 are average values of five test pieces.

(Pesticide resistance test)
Using each three-layer composite laminate, prepare a pouch of 9 cm x 13 cm size so that the unstretched polyethylene film is inside, and fill it with PH = 4.0, organophosphorus pesticide as content did. After storage at 60 ° C. for 2 weeks or 4 weeks, the peeling state between the AL foil / CPP film was observed.
◎: no peeling, and the laminate strength is 90% or more of the initial value.
○: no peeling, and the laminate strength is less than 90%, 70% or more of the initial value.
Δ: no peeling, and the laminate strength is less than 70% of the initial value, and 40% or more of the initial value.
X: Exfoliated or laminate strength less than initial value 40%.

(Alcohol resistance test)
A pouch was prepared by the above method and filled with 50%, 75 and 98% aqueous ethanol solutions as contents. After storage at 60 ° C. for 2 weeks or 4 weeks, the peeling state between the AL foil / CPP film was observed, and evaluated on the basis as in the case of the pesticide resistance test.

(Acid resistance test)
A pouch was prepared by the method described above, and filled with PH = 2,9 perm solution as the contents. After storage at 60 ° C. for 2 weeks or 4 weeks, the peeling state between the AL foil / CPP film was observed, and evaluated on the basis as in the case of the pesticide resistance test.

(Alkali resistance test)
A pouch was prepared by the method described above, and filled with PH = 10,2 permanent solution as the contents. After storage at 60 ° C. for 2 weeks or 4 weeks, the peeling state between the AL foil / CPP film was observed, and evaluated on the basis as in the case of the pesticide resistance test.

The adhesive composition according to the present invention is used as a packaging material for forming a laminate capable of maintaining a high level of adhesion strength even when immersed in chemicals such as acids, alkalis, pesticides and solvents for a long time (laminate) Can be used suitably.
In addition, the adhesive composition according to the present invention is not limited to a packaging material for forming a packaging material excellent in chemical resistance, and various industries requiring high adhesive strength and chemical resistance such as construction, medical care and automobiles. It is suitably used for formation of the laminated body in the field.

Claims (7)

100% by mass in total of a polyolefin resin (A) having a carboxyl group or an acid anhydride group and not having a primary hydroxyl group and a polyolefin resin (B) having a primary hydroxyl group and not having a carboxyl group or acid anhydride group In the above, it contains 50 to 99% by mass of the polyolefin resin (A) and 1 to 50% by mass of the polyolefin resin (B),
With respect to a total of 100 parts by mass of the polyolefin resin (A) and the polyolefin resin (B),
0.1 to 5 parts by mass of silane compound (C),
0.01 to 1 part by mass of a phosphoric acid compound (D), and
1 to 40 parts by mass of a curing agent (E) selected from the group consisting of an epoxy compound having no —SiH and an isocyanate compound,
Adhesive composition characterized by containing.   The adhesive composition according to claim 1, wherein the silane compound (C) has an epoxy group.   The adhesive composition according to claim 1 or 2, wherein the polyolefin resin (A) is obtained by acid-modifying a copolymer obtained from 1-butene and another olefin.   The adhesive composition according to any one of claims 1 to 3, wherein the polyolefin resin (B) is a polybutadiene having a primary hydroxyl group. A barrier layer having a permeability of oxygen of 100 CC (m ² , 24 hr, 1 atm, 25 ° C.) or less through an adhesive layer formed of the adhesive composition according to any one of claims 1 to 4 and a heat seal layer A laminated body to be laminated. In the case of the packaging laminate in which the outer layer side resin film layer, the outer layer side adhesive layer, the barrier layer, the inner layer side adhesive layer, and the heat seal layer are essential in order from the outer layer,
A packaging laminate, wherein the inner layer side adhesive layer is formed from the adhesive composition according to any one of claims 1 to 5.   A packaging container comprising the packaging laminate according to claim 6, wherein the heat seal layer constitutes the inner surface.