JP6960422B2 - Adhesive composition and laminate - Google Patents

Description

The present invention relates to a two-component curable polyhydroxyurethane resin adhesive composition and a laminate using the composition as an adhesive layer. More specifically, the present invention relates to a technique for providing an adhesive composition capable of responding to environmental problems and having a formed coating film (adhesive layer) exhibiting gas barrier properties and sufficient adhesive strength.

Films with gas barrier properties (hereinafter referred to as "gas barrier films") are mainly used for the purpose of protecting the contents, and are mainly used as packaging materials for foods and pharmaceuticals in the field of industrial materials. It is also widely used in. As the material for forming the gas barrier layer for the gas barrier film, a resin in which the formed film exhibits gas barrier properties is used. Typical resins include, for example, ethylene-vinyl alcohol copolymer resin (hereinafter abbreviated as EVOH) and vinylidene chloride resin (hereinafter abbreviated as PVDC). These resins having gas barrier properties can be used alone. Generally, as described below, a multilayer film is formed by using another resin material, and is used as a material for forming a gas barrier layer in the multilayer film.

For example, EVOH is used for composite films by co-extruding with a resin such as polypropylene (hereinafter abbreviated as PP), but EVOH is inferior in solubility in organic solvents, so it is a coating method. It is not suitable for producing films and coating films. On the other hand, PVDC can be molded by a coating method and can be applied to various base materials, and therefore is used as a coat film for food packaging and the like. However, since PVDC has a high chlorine content, another problem has been pointed out, such as the generation of dioxins when it is discarded (incinerated).

On the other hand, in recent years, global warming has become a problem, and studies are underway to reduce the use of petroleum-derived materials and use biomass-derived materials as raw materials for polymers. For example, in polyethylene terephthalate (hereinafter abbreviated as PET) used as a packaging material, a manufacturing method using biomass-derived components has almost been established, and studies on using biomass-derived components in polyethylene and PP have also been studied. It is done. However, with respect to resins such as EVOH and PVDC, which are widely used as materials for forming the barrier layer described above, it is difficult to replace them with biomass-derived components due to chemical structural problems, and the current situation is that studies have not progressed. ..

On the other hand, Patent Document 1 proposes the use of polyvinylidene urethane resin as a material for forming a gas barrier layer as a novel environment-friendly gas barrier material having a completely different chemical structure from the above-mentioned EVOH and PVDC. There is. The polyhydroxyurethane resin described in Patent Document 1 is a resin that can cope with environmental problems in that it has an -O-CO- bond derived from carbon dioxide in the chemical structure of the resin. Further, this resin is characterized by a chemical structure having a hydroxyl group in the vicinity of the urethane bond, and the chemical structure having the hydroxyl group exhibits gas barrier properties not found in conventional polyurethane resins.

By the way, in recent years, as a packaging material, a composite flexible film in which different kinds of polymer materials are combined has become mainstream for the reasons such as strength, product protection, workability, and expression of advertising effect by printing and the like. A general composite flexible film is composed of a thermoplastic plastic film layer which is an outer layer having a role of protecting products, a thermoplastic plastic film layer which is a sealant layer, and the like. Then, as a method for adhering these layers, generally, a dry laminating method in which an adhesive is applied to a laminated film to adhere the sealant layer, or an anchor coating agent is applied to the laminated film as needed. An extrusion laminating method is performed in which a plastic film to be a molten sealant layer is pressure-bonded and laminated in the form of a film. Further, as the adhesive used in these methods, since its adhesive performance is high, it is a two-component polyurethane-based adhesive composed of a main agent having an active hydrogen group such as a hydroxyl group and a curing agent having an isocyanate group. Agents are the mainstream (see, for example, Patent Document 2 and Patent Document 3).

However, these two-component polyurethane-based adhesives generally do not have a very fast curing reaction, and therefore, in order to ensure sufficient adhesiveness, it takes 1 to 5 days after the films are bonded. It was necessary to accelerate curing by aging over time. Further, since a curing agent having an isocyanate group is used, when an unreacted isocyanate group remains after curing, the residual isocyanate group reacts with moisture in the atmosphere to generate carbon dioxide, and as a result, lamination is performed. There was a problem that bubbles were generated in the film.

On the other hand, as a method for solving the above problems, Patent Document 4 proposes a polyurethane-based adhesive improved from the prior art, and Patent Document 5 proposes an epoxy-based laminating adhesive. However, since the gas barrier properties of the polyurethane-based adhesives in the above-mentioned prior art and the epoxy-based adhesives proposed in Patent Document 5 are not high, PVDC is required when the packaging material is required to have gas barrier properties. A coat layer, a polyvinyl alcohol (PVA) coat layer, an ethylene-vinyl alcohol copolymer (EVOH) film layer, a metaxylylene adipamide film layer, alumina (Al ₂ O ₃ ), silica (SiO ₂ ), etc. were deposited. It was necessary to separately laminate various gas barrier layers such as an inorganic vapor-deposited film layer. Therefore, it is inferior in terms of the manufacturing cost of the laminated film and the work process in laminating, and it is necessary to improve it in order to use it industrially.

Japanese Unexamined Patent Publication No. 2012-172144 Japanese Unexamined Patent Publication No. 5-51574 Japanese Unexamined Patent Publication No. 9-316422 Japanese Unexamined Patent Publication No. 2000-154365 International Publication No. 99/60068 Pamphlet

Therefore, the present invention has been made in view of the above-mentioned problems of the prior art, and an object thereof is not only to have various excellent performances of the polyhydroxyurethane resin, but also to have a high gas barrier property in the formed adhesive layer. It is an object of the present invention to provide an adhesive composition of a polyhydroxyurethane resin, which has good adhesiveness to a wide variety of materials such as various plastics and inorganic materials. Another object of the present invention is to find an adhesive composition of a polyhydroxyurethane resin that can be effectively used when laminating layers made of a wide variety of materials such as various plastics and inorganic materials, and to obtain a useful laminate. It is to realize the offer.

［一般式（１）中、Ｘは、直接結合か、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基のいずれかであり、該構造中には、エーテル結合、アミノ結合、スルホニル結合、エステル結合、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖を含んでもよい。また、一般式（１）中、Ｙは、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５芳香族炭化水素基であり、該構造中には、エーテル結合、スルホニル結合、水酸基及びハロゲン原子を含んでもよく、且つ、前記繰り返し単位間において、異なる構成のＹが混在してもよい。また、一般式（１）中、Ｚは、下記一般式（３）〜（６）のいずれかを示し、且つ、前記繰り返し単位内及び繰り返し単位間のいずれにおいても、これらの一般式の群から選ばれる１種又は２種以上が混在してもよい。］

［一般式（３）〜（６）中、Ｒはそれぞれ独立に、水素原子又はメチル基を示し、右側の結合手は、一般式（１）中の主鎖の酸素原子と結合し、左側の結合手は、一般式（１）中のＸと結合するか、該Ｘが直接結合の場合は他方のＺと結合する。］ The above object is achieved by the following invention. That is, the present invention provides the following adhesive composition and a laminate using the composition for forming an adhesive layer.
[1] A two-component curable adhesive composition of a polyhydroxyurethane resin composed of at least a component (A) which is a main agent and a component (B) which is a curing agent, and is a main agent. The component (A) is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the following general formula (1), and the component (B) which is a curing agent has one or more functional groups. It is an epoxy compound, and the ratio of the total amine value of the polyhydroxyurethane resin to the epoxy equivalent of the epoxy compound is 0.05 or more and 3.50 or less, and the amino of the polyhydroxyurethane resin. An adhesive composition, wherein the ratio of the active hydrogen of the group to the epoxy group of the epoxy compound is in the range of 0.3 to 3.0.

[In the general formula (1), X is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon having 6 to 40 carbon atoms. Any of the groups, the structure may include an ether bond, an amino bond, a sulfonyl bond, an ester bond, a hydroxyl group, a halogen atom and a polyalkylene glycol chain consisting of 2 to 6 carbon atoms of repeating units 1 to 30. good. Further, in the general formula (1), Y is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms. The structure may contain ether bonds, sulfonyl bonds, hydroxyl groups and halogen atoms, and Ys having different configurations may be mixed between the repeating units. Further, in the general formula (1), Z represents any of the following general formulas (3) to (6), and both within the repeating unit and between the repeating units, from the group of these general formulas. One or more selected species may be mixed. ]

[In the general formulas (3) to (6), R independently represents a hydrogen atom or a methyl group, and the bond on the right side is bonded to the oxygen atom of the main chain in the general formula (1) and is on the left side. The bonder binds to X in the general formula (1), or if the X is a direct bond, it binds to the other Z. ]

［一般式（２）中、Ｙ_１及びＹ_２は、同一でも異なっていてもよく、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５芳香族炭化水素基であり、該構造中には、エーテル結合、スルホニル結合、水酸基及びハロゲン原子を含んでもよい。］ Preferred forms of the adhesive composition of the present invention described above include the following.
[2] The adhesive composition according to the above [1], wherein Y in the general formula (1) has a structure represented by the following general formula (2).

[In the general formula (2), Y ₁ and Y ₂ may be the same or different, and may be an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or a carbon number of carbon atoms. It is a 6 to 15 aromatic hydrocarbon group, and the structure may contain an ether bond, a sulfonyl bond, a hydroxyl group and a halogen atom. ]

[3] The adhesion according to claim 1 or 2, wherein the hydroxyl value of the polyhydroxyurethane resin is 100 mgKOH / g or more and 350 mgKOH / g or less, and the amine value is in the range of 10 mgKOH / g or more and 300 mgKOH / g or less. Agent composition.

[4] The polyhydroxyurethane resin is a compound having two or more 5-membered cyclic carbonate structures synthesized by using carbon dioxide as a raw material in at least a part thereof, and a compound having two or more amino groups. Any of the above [1] to [3], which is an addition reaction product and in which 0.1% by mass or more and 30% by mass or less of the total mass is composed of carbon dioxide-derived -O-CO- bonds. The adhesive composition described.

[5] The formed thickness of the coating film of 20 [mu] m, temperature 23 ° C., an oxygen permeability under constant temperature and humidity ^65%, or less ^{400ml / m 2 · 24h · atm} , and a bonding property and gas barrier property The adhesive composition according to any one of the above [1] to [4].

Further, the present invention provides the following laminate as another embodiment.
[6] Two or more layers made of the same or different materials selected from the group consisting of plastic film, polyolefin sealant, fiber cloth, paper, vapor-deposited plastic film, metal foil, metal and concrete are adhered via an adhesive layer. The laminate is characterized in that the adhesive layer is formed of the adhesive composition according to any one of the above [1] to [5].

According to the present invention, not only the polyhydroxyurethane resin has various excellent performances, but also the formed adhesive layer exhibits a high gas barrier property and also has good adhesiveness to various plastics. A resin adhesive composition can be provided. Further, the adhesive composition of the polyhydroxyurethane resin provided by the present invention can be effectively used when laminating layers made of a wide variety of materials such as various plastics and inorganic materials, and the formed adhesive layer can be used. According to the present invention, a useful laminate can be provided because the gas barrier property and the adhesive property are excellent.

Next, the present invention will be described in more detail with reference to preferred embodiments for carrying out the invention. The adhesive composition of the present invention is a two-component curable, polyhydroxyurethane resin adhesive composition composed of a main agent (A) component and a curing agent (B) component. The component (A) of the main agent is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the above general formula (1), and the component (B) which is a curing agent is It is an epoxy compound having one or more functional groups, and the ratio of the total amine value of the polyhydroxyurethane resin to the epoxy equivalent of the epoxy compound is 0.05 or more and 3.50 or less, and the polyhydroxy It is characterized in that the ratio of the active hydrogen of the amino group of the urethane resin to the epoxy group of the epoxy compound is in the range of 0.3 to 3.0. Hereinafter, the components constituting the present invention and the amount used will be described.

［一般式（１）中、Ｘは、直接結合か、炭素数１〜３０の脂肪族炭化水素基、炭素数４〜４０の脂環式炭化水素基又は炭素数６〜４０の芳香族炭化水素基のいずれかであり、該構造中には、エーテル結合、アミノ結合、スルホニル結合、エステル結合、水酸基、ハロゲン原子及び繰り返し単位１〜３０の炭素数２〜６からなるポリアルキレングリコール鎖を含んでもよい。また、一般式（１）中、Ｙは、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５芳香族炭化水素基であり、該構造中には、エーテル結合、スルホニル結合、水酸基及びハロゲン原子を含んでもよく、且つ、前記繰り返し単位間において、異なる構成のＹが混在してもよい。また、一般式（１）中、Ｚは、下記一般式（３）〜（６）のいずれかを示し、且つ、前記繰り返し単位内及び繰り返し単位間のいずれにおいても、これらの一般式の群から選ばれる１種又は２種以上が混在してもよい。］

［一般式（３）〜（６）中、Ｒはそれぞれ独立に、水素原子又はメチル基を示し、右側の結合手は、一般式（１）中の主鎖の酸素原子と結合し、左側の結合手は、一般式（１）中のＸと結合するか、該Ｘが直接結合の場合は他方のＺと結合する。］

［一般式（２）中、Ｙ_１及びＹ_２は、同一でも異なっていてもよく、炭素数１〜１５の脂肪族炭化水素基、炭素数４〜１５の脂環式炭化水素基又は炭素数６〜１５芳香族炭化水素基であり、該構造中には、エーテル結合、スルホニル結合、水酸基及びハロゲン原子を含んでもよい。］ [Polyhydroxyurethane resin of component (A)]
The component (A), which is the main agent constituting the adhesive composition of the present invention, is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the following general formula (1). In particular, it is preferable that Y in the general formula (1) has a structure represented by the following general formula (2). Further, it is preferable that the hydroxyl value of the polyhydroxyurethane resin is 100 mgKOH / g or more and 350 mgKOH / g or less, and the amine value is 10 mgKOH / g or more and 300 mgKOH / g or less.

[In the general formula (1), X is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon having 6 to 40 carbon atoms. Any of the groups, the structure may include an ether bond, an amino bond, a sulfonyl bond, an ester bond, a hydroxyl group, a halogen atom and a polyalkylene glycol chain consisting of 2 to 6 carbon atoms of repeating units 1 to 30. good. Further, in the general formula (1), Y is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms. The structure may contain ether bonds, sulfonyl bonds, hydroxyl groups and halogen atoms, and Ys having different configurations may be mixed between the repeating units. Further, in the general formula (1), Z represents any of the following general formulas (3) to (6), and both within the repeating unit and between the repeating units, from the group of these general formulas. One or more selected species may be mixed. ]

[In the general formulas (3) to (6), R independently represents a hydrogen atom or a methyl group, and the bond on the right side is bonded to the oxygen atom of the main chain in the general formula (1) and is on the left side. The bonder binds to X in the general formula (1), or if the X is a direct bond, it binds to the other Z. ]

[In the general formula (2), Y ₁ and Y ₂ may be the same or different, and may be an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or a carbon number of carbon atoms. It is a 6 to 15 aromatic hydrocarbon group, and the structure may contain an ether bond, a sulfonyl bond, a hydroxyl group and a halogen atom. ]

<Outline of reaction>
The polyhydroxyurethane resin constituting the adhesive composition of the present invention has, for example, a five-membered cyclic carbonate structure (hereinafter, simply referred to as simply) produced by using carbon dioxide as one of the raw materials and having two or more 5-membered cyclic carbonate structures in one molecule. It can be obtained by using a compound having (also abbreviated as cyclic carbonate) and a compound having two or more amino groups in one molecule as a monomer unit and subjecting them to a double addition reaction. Here, in the reaction between the cyclic carbonate constituting the polymer chain and the amine, it is known that since there are two types of cleavage of the cyclic carbonate as shown below, products having two types of structures can be obtained. ..

Therefore, for example, when a bifunctional compound is reacted, a polymer resin obtained by a double addition reaction of a compound having a two-membered cyclic carbonate structure and an amine compound having two amino groups can be obtained. , Four kinds of chemical structures of the following formulas (1) to (4) are generated, and these are considered to exist at random positions.

［但し、式（１）〜（４）中のＸ、Ｙは、それぞれ独立に、そのモノマー単位由来の脂肪族炭化水素、脂環式炭化水素又は芳香族炭化水素からなる化学構造を示し、該構造中には、酸素原子、窒素原子及び硫黄原子を含んでもよい。］

[However, X and Y in the formulas (1) to (4) independently show a chemical structure composed of an aliphatic hydrocarbon, an alicyclic hydrocarbon or an aromatic hydrocarbon derived from the monomer unit thereof, and the chemical structure thereof. The structure may contain oxygen atoms, nitrogen atoms and sulfur atoms. ]

As illustrated in the above formula, the polyhydroxyurethane resin constituting the present invention is characterized by having a chemical structure having a urethane bond and a hydroxyl group in the main chain. On the other hand, it is impossible to form a structure having a hydroxyl group in the main chain by the addition reaction of the isocyanate compound and the polyol compound in the method for producing a polyurethane resin which has been industrially used conventionally. Therefore, the polyhydroxyurethane resin having the structure illustrated above, which constitutes the present invention, has a structure that is clearly distinguished from the conventional polyurethane resin.

<Five-membered cyclic carbonate compound>
The five-membered cyclic carbonate compound used above (hereinafter, may be simply referred to as a cyclic carbonate compound) is preferably obtained by reacting an epoxy compound with carbon dioxide. That is, it is preferable to use a polyhydroxyurethane resin derived by using the cyclic carbonate compound obtained by the reaction described below as a raw material. Specifically, the cyclic carbonate compound suitable in the present invention is, for example, carbon dioxide obtained by pressurizing an epoxy compound as a raw material at a temperature of 0 ° C. to 160 ° C. to about atmospheric pressure to 1 MPa in the presence of a catalyst. It can be obtained by the following reaction by reacting in an atmosphere for 4 to 24 hours. As a result, a cyclic carbonate compound in which the carbon dioxide used in the reaction is immobilized on the ester moiety is obtained.

By using the cyclic carbonate compound synthesized from carbon dioxide as a raw material as described above, the obtained polyhydroxyurethane resin had an -O-CO- bond in which carbon dioxide was immobilized in its structure. It becomes a thing. The content of carbon dioxide-derived -O-CO- bonds (fixed amount of carbon dioxide) in the polyhydroxyurethane resin should be as high as possible from the standpoint of effective utilization of carbon dioxide. By obtaining as described above, carbon dioxide can be contained in the structure of the polyhydroxyurethane resin in the range of 1 to 30% by mass.

Examples of the catalyst used for the reaction between the epoxy compound and carbon dioxide include halogenated salts such as lithium chloride, lithium bromide, lithium iodide, sodium chloride, sodium bromide, and sodium iodide, and quaternary ammonium salts. Is preferred. The amount used is 1 to 50 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the raw material epoxy compound. Further, in order to improve the solubility of these catalyst salts, triphenylphosphine or the like may be used at the same time.

The reaction between the epoxy compound and carbon dioxide can also be carried out in the presence of an organic solvent. As the organic solvent used at this time, any solvent that dissolves the above-mentioned catalyst can be used. Specifically, for example, amide solvents such as N, N-dimethylformamide, dimethyl sulfoxide, dimethyl acetamide, and N-methyl-2-pyrrolidone, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, and propylene glycol, Ether-based solvents such as ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and tetrahydrofuran are preferred organic solvents.

The above-mentioned compound having two epoxy groups in one molecule, which can be used when synthesizing a compound having two 5-membered cyclic carbonate structures in one molecule from carbon dioxide, is any conventionally known compound. Can also be used. Preferred epoxy compounds that can be used in the present invention are illustrated below.

For example, the following compounds are exemplified as those having two epoxy groups in one molecule and having a benzene skeleton and an aromatic polycyclic skeleton. R in any of the following formulas is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

Further, for example, the following compounds are exemplified as compounds having two epoxy groups in one molecule and having an aliphatic or alicyclic skeleton. R in any of the following formulas is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

<Amine component>
Any conventionally known amine component can be used as the amine component for inducing the polyhydroxyurethane resin. Preferred specific examples include, for example, methylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, N- (2-hydroxyethyl) -1.3-diaminopropane, N. -(2-Hydroxyethyl) -aliphatic diamine compounds such as ethylenediamine; phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis (phenylamine), 4,4'- Aromatic diamine compounds such as diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, xylylene diamine; cyclopentyldiamine, cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 1,3-bis ( Aminomethyl) cyclohexane, piperazine, 2,5-dimethylpiperazine, isophoronediamine and other alicyclic diamine compounds; be able to.

Further, as a compound containing two primary amino groups and one or more secondary amino groups in one molecule, which is a raw material for synthesizing a polyhydroxyurethane resin having a secondary amino group in the main chain, conventional compounds have been used. Any known one can be used. Suitable examples include, for example, diethylenetriamine, triethylenetetramine, iminobispropylamine, N, N'-bisaminopropyl-1,3-propyldiamine and N, N'-bisaminopropyl-1,3-butylenediamine. Such as chain aliphatic diamines can be mentioned.

The method for producing the polyhydroxyurethane resin having the above-mentioned secondary amino group in the main chain is not particularly limited, but can be obtained by, for example, the following method. That is, it can be obtained by mixing the cyclic carbonate compound as described above with the diamine compound and the polyamine compound in the presence of an organic solvent or in the absence of a solvent, and reacting them at a temperature of 40 to 200 ° C. for 4 to 24 hours. can.

The polyhydroxyurethane resin can be produced without using a catalyst as described above, but it can also be produced in the presence of a catalyst as described below in order to promote the reaction. For example, basic catalysts such as triethylamine, tributylamine, diazabicycloundecene (DBU) triethylenediamine (DABCO) and pyridine, and Lewis acid catalysts such as tetrabutyltin and dibutyltin dilaurylate can be used. The preferable amount of these catalysts to be used can be 0.01 to 10 parts by mass with respect to the total amount (100 parts by mass) of the carbonate compound and the amine compound to be used.

[Epoxy compound of component (B)]
Next, the epoxy as the component (B), which is a curing agent, is used in combination with the polyhydroxyurethane resin of the component (A) described above, which constitutes the adhesive composition of the two-component curable polyhydroxyurethane resin of the present invention. A compound (hereinafter, may be referred to as an "epoxy curing agent") will be described. The adhesive composition of the present invention makes it possible to form a pressure-sensitive adhesive layer (coating film) by reacting a polyhydroxyurethane resin with a curing agent at the time of use. The reaction at this time is, for example, in the case where plastic films are adhered to each other via an adhesive layer to form a laminate, the adhesive composition is applied, the diluting solvent is dried, and then 40 ° C. Aging at a moderate temperature for several days completes the process, and as a result, the plastic films can be adhered to each other in a good condition.

The epoxy curing agent constituting the adhesive composition of the present invention may be any one having one or more functional groups, and any conventionally known one can be used. For example, as an epoxy compound suitable in the present invention, which is a bifunctional compound having two epoxy groups in one molecule and has a benzene skeleton and an aromatic polycyclic skeleton, two 5-membered ring rings in one molecule. Any of the compounds described and listed above can be used as they can be used to obtain a compound having a carbonate structure.

Further, for example, for an epoxy compound having two epoxy groups in one molecule and having an aliphatic or alicyclic skeleton, when obtaining a compound having two 5-membered cyclic carbonate structures in one molecule. Any of the epoxy compounds described and listed above can be used.

The epoxy curing agent constituting the adhesive composition of the present invention is not limited to the above, and a trifunctional or higher functional epoxy compound having three or more epoxy groups in one molecule can also be used. For example, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, sorbitol polyglycidyl ether and the like can be mentioned.

A commercially available product that can be used as an epoxy curing agent constituting the adhesive composition of the present invention is Denacol (trade name) manufactured by Nagase ChemteX Corporation. Specifically, EX-211, EX-212, EX-252, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-911, EX-941, EX. Bifunctional type aliphatic epoxy compounds such as -920, EX-313, EX-314, EX-321, EX-411, EX-421, EX-512, EX-521, EX-612, EX-614, Examples thereof include polyfunctional epoxy compounds such as EX-614B, FCA-677 and FCA-678, and bifunctional type aromatic epoxy compounds such as EX-201, EX-711 and EX-721. According to the study of the present inventor, as the epoxy compound constituting the present invention, for example, an epoxy compound having an epoxy equivalent of about 90 to 270 and liquid at room temperature can be preferably used.

What is important in the present invention is that the component (A) and the component (B) are used so as to satisfy the following conditions, as described below, rather than the structure of the epoxy compound used. First, the ratio of the total amine value of the polyhydroxyurethane resin of the component (A) to the epoxy equivalent of the epoxy curing agent of the component (B) is 0.05 or more and 3.50 or less. , The ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) to the epoxy group of the epoxy compound of the component (B) shall be in the range of 0.3 to 3.0. It is characterized by. These will be described below.

[Ratio of total amine value of component (A) to epoxy equivalent of component (B)]
The adhesive composition of the present invention is a two-component curable polyhydroxyurethane resin composed of a polyhydroxyurethane resin as a main component (A) and an epoxy curing agent as a component (B). It is an adhesive composition, and as described above, the ratio of the total amine value of the component (A) to the epoxy equivalent of the component (B) is required to be 0.05 or more and 3.50 or less. .. The amine value / epoxy equivalent ratio specified in the present invention determines the structure and molecular weight of the polyhydroxyurethane resin of the component (A) constituting the present invention, and the molecular weight of the epoxy curing agent of the component (B), and the effect of the present invention. This is to specify the range that can be obtained stably. According to the study of the present inventor, it is more preferable to configure this ratio to be 0.1 or more and 3.0 or less, and further preferably 0.15 or more and 2.5 or less. The adhesive layer formed by adjusting and using the components (A) and (B) constituting the two liquids so that the above ratio is within the range specified in the present invention has sufficient adhesive strength. And, it becomes a good one that has both high gas barrier properties.

Further, the adhesive composition of the present invention is a two-component curing type composed of a polyhydroxyurethane resin as a main component (A) and an epoxy curing agent as a component (B), and is a two-component curing type. It is preferable that the structure is such that the residual unreacted curing agent is reduced when the curing agent is cured. For that purpose, it is conceivable to reduce the amount of the epoxy curing agent used (blended) as much as possible. However, if the amount of the epoxy curing agent used is simply reduced, the curing may be insufficient and the function as an adhesive may not be sufficiently fulfilled. According to the study by the present inventor, it has been found that when a bifunctional epoxy compound is used as the epoxy curing agent, the insufficient adhesive strength becomes remarkable when the amount used is small. Based on these findings, the present invention stipulates that the component (A) and the component (B) are used in the following formulations.

[Ratio of active hydrogen of amino group of component (A) to epoxy group of epoxy compound]
When the adhesive layer is formed from the adhesive composition of the present invention, the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) and the epoxy of the epoxy curing agent of the component (B) constituting the composition are formed. Reacts with the group. Therefore, for example, if the active hydrogen of the amino group of the component (A) and the epoxy group of the component (B) are used in the same equivalent amount, the ratio of these contributing to the reaction is 1: 1. According to the study of the present inventor, the component (A) is such that the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin to the epoxy group of the epoxy compound is in the range of 0.3 to 3.0. The effect of the present invention can be obtained by blending the component (B) into a composition. If it is out of this range, sufficient curing (reaction) cannot be obtained, and there is a concern that the sealing strength and boil resistance of the formed adhesive layer may be lowered.

According to the study of the present inventor, when a curing agent other than an epoxy compound is used, the remarkable effect of the present invention cannot be obtained. For example, it was confirmed that when an isocyanate curing agent, which is often used as a curing agent, is used, the viscosity is severe due to its high reactivity, and it is difficult to form a good adhesive layer.

[Other ingredients]
The adhesive composition of the present invention is a two-component curing type adhesive used by reacting a main agent and a curing agent at the time of use. A preferred embodiment of the adhesive composition of the present invention further includes a curing catalyst added together with a main agent and a curing agent. By further adding the curing catalyst, the formed adhesive layer exhibits good heat resistance. Examples of the curing catalyst used in the present invention include metal catalysts, acid and amine catalysts.

In addition to the above-mentioned components, the adhesive composition of the present invention has various kinds of reaction catalysts, acrylic resins, antifoaming agents, leveling agents, ultraviolet absorbers, antioxidants and the like used at the time of urethanization extension, if necessary. Known additives can be appropriately added and used as long as the object of the present invention is not impaired.

Next, the present invention will be described in more detail with reference to Production Examples, Synthesis Examples, Examples and Comparative Examples. In addition, "part" in the text is based on mass.

<Production example of compound I>
[Production Example 1: Synthesis of cyclic carbonate compound (I)]
100 parts of bisphenol A type epoxy resin with epoxy equivalent of 187 (trade name "Epototo YD-128", manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.), 20 parts of sodium iodide (manufactured by Wako Pure Chemical Industries, Ltd.), and N-methyl-2- 150 parts of pyrrolidone was placed in a reaction vessel equipped with a stirrer and a recirculator with an air release port. Then, carbon dioxide was continuously blown with stirring, and the reaction was carried out at 100 ° C. for 10 hours. Then, 300 parts of water was added to the solution after completion of the reaction to precipitate the product, and the mixture was filtered off. The obtained white powder was recrystallized from toluene to obtain 52 parts (yield 42%) of the white powder.

When the obtained compound was analyzed by IR (the trade name "FT / IR-350" manufactured by JASCO Corporation was used. The same device was used in other examples), the raw material epoxy around ^{910 cm -1 was used.} The peak derived from the carbonyl disappeared, and a peak derived from the carbonyl of the carbonate group, which is not present in the raw material, was confirmed around ^{1800 cm -1.} In addition, as a result of analysis by HPLC (manufactured by JASCO Corporation, trade name "LC-2000"; trade name of column "FinePakSIL C18-T5"; mobile phase acetonitrile + water), the peak of the raw material disappeared and it became highly polar. A new peak appeared, the purity of which was 98%. As a result of DSC measurement (differential scanning calorimetry), the melting point was 178 ° C, and the melting point range was ± 5 ° C.

From the above, it was confirmed that this powder was a compound having a structure represented by the following formula, in which a cyclic carbonate structure was introduced by a reaction between an epoxy group and carbon dioxide. This was abbreviated as compound (I). The proportion of carbon dioxide-derived components in the chemical structure of this compound (I) was 20.5% (calculated value).

[Production Example 2: Synthesis of cyclic carbonate compound (II)]
As the epoxy resin, a hydroquinone type epoxy resin having an epoxy equivalent of 115 (trade name: Denacol EX-203, manufactured by Nagase ChemteX Corporation) was used, but the same method as in Production Example 1 was used, and the structure represented by the following formula 5 A member ring cyclic carbonate compound (II) was synthesized. The obtained compound (II) was a white crystal and had a melting point of 141 ° C. The yield was 55%, the result of IR analysis was similar to that of compound (I), and the purity by HPLC analysis was 97%. The proportion of carbon dioxide-derived components in the chemical structure of the obtained compound (II) was 28.0% (calculated value).

<Calculation of the content of carbon dioxide, which is a reaction raw material, in polyhydroxyurethane resin>
The content of carbon dioxide in the resin as the reaction product is a value obtained by calculating the mass% of the carbon dioxide-derived segment used as the reaction raw material in the chemical structure of the target polyhydroxyurethane resin. Specifically, when synthesizing the polyhydroxyurethane resin constituting the present invention, it is used as a raw material monomer (epoxy compound) used in the synthesis for obtaining a cyclic carbonate-containing compound used for a reaction with a diamine compound. It was calculated from the theoretical amount of carbon dioxide that reacts with it, and the obtained calculated value was taken as the carbon dioxide content.

[Synthesis Example 1]
The cyclic carbonate compound (I) obtained in Production Example 1 was placed in a reaction vessel equipped with a stirrer with a torque meter and a reflux device with an air opening, and hexamethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the compound. ) Was added so that the amine value of the resin after the reaction was about 44. Further, ethyl acetate was added as a reaction solvent, and the reaction was carried out for 24 hours while stirring at a temperature of 100 ° C. to obtain a solution A of a polyhydroxyurethane resin having a solid content of 50%. The resin constituting the obtained solution A is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the general formula (1) specified in the present invention. Table 1 shows the hydroxyl value and amine value of the polyhydroxyurethane resin constituting the solution A. The hydroxyl value and amine value shown in Table 1 are both calculated values. The same applies to the following examples.

[Synthesis Example 2]
The compound (I) obtained in Production Example 1 was placed in a reaction vessel equipped with a stirrer with a torque meter and a reflux device with an air opening, and the amine value of the resin after the reaction was designed to be about 42. Synthesis was carried out in the same manner as in Synthesis Example 1 except that a solution B of a polyhydroxyurethane resin having a solid content of 50% was obtained. The resin constituting the obtained solution B is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the general formula (1) specified in the present invention. Table 1 shows the hydroxyl value and amine value of the polyhydroxyurethane resin constituting the solution B.

[Synthesis Example 3]
The cyclic carbonate-containing compound (II) obtained in Production Example 2 is placed in a reaction vessel equipped with a stirrer with a torque meter and a reflux device with an air opening so that the amine value of the resin after the reaction is about 46. Synthesis was carried out in the same manner as in Synthesis Example 1 except that it was designed in 1 above, and synthesis was carried out in the same manner as in Synthesis Example 1 to obtain a solution C of a polyhydroxyurethane resin having a solid content of 50%. The resin constituting the obtained solution C is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the general formula (1) specified in the present invention. Table 1 shows the hydroxyl value and amine value of the polyhydroxyurethane resin constituting the solution C.

[Synthesis Example 4]
The compound (II) obtained in Production Example 2 was placed in a reaction vessel equipped with a stirrer with a torque meter and a reflux device with an air opening, and the design was made so that the amine value of the resin after the reaction was 180. Synthesis was carried out in the same manner as in Synthesis Example 1 except for the above, to obtain a solution D of a polyhydroxyurethane resin having a solid content of 50%. The resin constituting the obtained solution D is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the general formula (1) specified in the present invention. Table 1 shows the hydroxyl value and amine value of the polyhydroxyurethane resin constituting the solution D.

[Examples 1 to 3]
Compared to the polyhydroxyurethane resin A obtained in Synthesis Example 1, a commercially available bifunctional epoxy compound a having an epoxy equivalent of 210 (trade name "Denacol EX-252", manufactured by Nagase ChemteX Corporation) as an epoxy curing agent. To obtain two-component curable adhesive compositions A-1 to A-3. The ratio of the amine value of the resin A to the epoxy equivalent of the epoxy curing agent in these compositions is 0.21. Further, in the adhesive composition A-1, the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) to the epoxy group of the epoxy curing agent of the component (B) is 1. Formulated. Further, in the adhesive composition A-2, the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) to the epoxy group of the epoxy curing agent of the component (B) is 0.3. In the adhesive composition A-3, the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) to the epoxy group of the epoxy curing agent of the component (B) is 3. It was blended so as to be. Specifically, for example, in the adhesive composition A-1, the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin A to the epoxy group of the epoxy compound a having an epoxy equivalent of 210 is added to the polyhydroxyurethane resin A. The component (B) was added to the component (A) so as to have a value of 1, and the mixture was stirred well to obtain a two-component curable adhesive composition.

[Example 4]
Compared to the polyhydroxyurethane resin A obtained in Synthesis Example 1, a commercially available 3-4 functional epoxy compound f with an epoxy equivalent of 230 (trade name "Denacol EX-411", manufactured by Nagase ChemteX Corporation) was used as an epoxy curing agent. ) Was used to obtain a two-component curable adhesive composition A-4. The amine value of the resin A / the epoxy equivalent of the epoxy curing agent in this composition is 0.19. In the adhesive composition A-4, the ratio of the active hydrogen of the amino group of the polyhydroxyurethane resin of the component (A) to the epoxy group of the epoxy curing agent of the component (B) is 0.5. Formulated. Other than that, the composition of this example was obtained in the same manner as in Examples 1 to 3.

[Example 5]
Compared to the polyhydroxyurethane resin B obtained in Synthesis Example 2, a commercially available bifunctional epoxy compound b having an epoxy equivalent of 150 as an epoxy curing agent (trade name "Denacol EX-212", manufactured by Nagase ChemteX Corporation). Was used to obtain a two-component curable adhesive composition B. The amine value of the resin B / the epoxy equivalent of the epoxy curing agent in this composition is 0.28. Further, in this adhesive composition B, the active hydrogen of the amino group of the polyhydroxyurethane resin B and the epoxy group of the epoxy curing agent are blended so as to have a ratio of 1, and the others are blended in Examples 1 to 1. The composition of this example was obtained in the same manner as in 3.

[Example 6]
Compared to the polyhydroxyurethane resin C obtained in Synthesis Example 3, a commercially available bifunctional epoxy compound c having an epoxy equivalent of 150 as an epoxy curing agent (trade name "Denacol EX-851", manufactured by Nagase ChemteX Corporation). To obtain a two-component curable adhesive composition C-1. The amine value of the resin C / the epoxy equivalent of the epoxy curing agent in this composition is 0.29. Further, in this adhesive composition C-1, the active hydrogen of the amino group of the polyhydroxyurethane resin C and the epoxy group of the epoxy curing agent are blended so as to have a ratio of 1, and the others are described in Examples. The composition of this example was obtained in the same manner as in 1-3.

[Example 7]
Compared to the polyhydroxyurethane resin C obtained in Synthesis Example 3, as an epoxy curing agent, a commercially available bifunctional type aromatic epoxy compound d having an epoxy equivalent of 110 (trade name "Denacol EX-201", Nagase ChemteX Corporation) A two-component curable adhesive composition C-2 was obtained. The amine value of the resin C / the epoxy equivalent of the epoxy curing agent in this composition is 0.42. Further, in this adhesive composition C-2, the active hydrogen of the amino group of the polyhydroxyurethane resin C is blended so that the ratio of the epoxy group of the epoxy curing agent is 1, and the others are described in Examples. The composition of this example was obtained in the same manner as in 1-3.

[Example 8]
For the polyhydroxyurethane resin D obtained in Synthesis Example 8, a commercially available bifunctional epoxy compound e (trade name "Denacol EX-911", manufactured by Nagase ChemteX Corporation) having an epoxy equivalent of 160 was used as an epoxy curing agent. To obtain a two-component curable adhesive composition D. The amine value of the resin D / the epoxy equivalent of the epoxy curing agent in this composition is 1.13. Further, in this adhesive composition D, the active hydrogen of the amino group of the polyhydroxyurethane resin D and the epoxy group of the epoxy curing agent are blended so as to have a ratio of 1, and the others are blended in Examples 1 to 1. The composition of this example was obtained in the same manner as in 3.

[Comparative Example 1]
A comparative adhesive composition was prepared using a commercially available adhesive that is a two-component epoxy curable type. Specifically, FL240 (trade name, manufactured by Mitsubishi Chemical Co., Ltd.), an epoxy resin curing agent having an amine value of 195 to 225, and epoxy resin a (trade name "Denacol EX-252", manufactured by Nagase ChemteX Corporation) having an epoxy equivalent of 210. The adhesive composition E of this comparative example was prepared by adjusting the solution to which ethyl acetate was added to have the same solid content of 50% as in Example 1 and stirring well.

[Comparative Example 2]
In this comparative example, in order to compare the gas barrier properties of the formed adhesive layer, PVA having excellent gas barrier properties was used as an adhesive composition for comparison. Specifically, a solution prepared by adding ethyl acetate to 100 parts of PVA JP-03 (trade name, manufactured by Japan Vam & Poval) was adjusted so that the solid content was 50%, which was the same as in Example 1, and the solid content was adjusted well. The stirred product was used as the adhesive composition F of this comparative example. The adhesive composition F is a one-component curable adhesive.

[Comparative Example 3]
When the isocyanate curing agent Duranate TPA-100 (trade name, manufactured by Asahi Kasei Chemicals Co., Ltd.) was added to the polyhydroxyurethane resin A obtained in Synthesis Example 1 as a curing agent, gelation occurred rapidly. Therefore, no further evaluation was performed.

[Comparative Examples 4 and 5]
Compared to the polyhydroxyurethane resin A obtained in Synthesis Example 1, a commercially available bifunctional epoxy compound a having an epoxy equivalent of 210 (trade name "Denacol EX-252", manufactured by Nagase ChemteX Corporation) as an epoxy curing agent. To obtain two-component curable adhesive compositions A-5 and A-6, respectively. The amine value of the resin A / the epoxy equivalent of the epoxy curing agent in these compositions is 0.22. Further, in the adhesive compositions A-5 and A-6, the ratios of the active hydrogen of the amino group of the polyhydroxyurethane resin A and the epoxy group of the epoxy curing agent are 0.2 and 3.5, respectively. The composition of this example was obtained in the same manner as in Examples 1 to 3 except for the above.

<Evaluation>
Using the adhesive compositions of Examples and Comparative Examples obtained above, they were applied and cured on each substrate specified by the evaluation method to obtain a coating film (adhesive layer), which was used as an evaluation sample. And said. Then, the adhesive strength and oxygen permeability (described as OTR in the table) of each coating film were measured and evaluated by the following evaluation methods. Table 2 summarizes the evaluation results.

[Oxygen permeability (OTR)]
Using the adhesive compositions of Examples and Comparative Examples, they were coated on a PET film as a base material so that the film thickness after drying was 10 μm, and then dried at 100 ° C. for 30 minutes to form a coating film ( An adhesive layer) was formed, and this laminate was used as an evaluation sample. For each evaluation sample, the oxygen permeability was measured in accordance with JIS K7126, and this was used as the evaluation of gas barrier property. It can be judged that the lower this value is, the better the gas barrier property is. Specifically, using an oxygen transmission rate measuring device (manufactured by MOCON, trade name: OX-TRAN2 / 21ML), the oxygen transmission rate of each evaluation sample and PET film used as a base material is relative to 23 ° C. The measurement was performed under the condition of humidity of 65% (23 ° C. oxygen permeability), and the oxygen permeability of the coating film (adhesive layer) was measured. The oxygen permeability of the coating film (adhesive layer) is a value calculated from the measured value in consideration of the amount corresponding to the oxygen permeability of the base material. The unit is ml · 20 μm / m ² · day · atm, and a ^{value exceeding 2000 ml · 20 μm / m 2} · day · atm is described as> 2000. The smaller the value described, the more it can be evaluated that the coating film (adhesive layer) has excellent gas barrier properties. The evaluation results are shown in Table 2.

[Adhesive strength test]
Using the adhesive compositions of Examples and Comparative Examples, they were applied onto an unstretched pet film (corona-treated 25 μm) so that the ^{amount of each applied was 3.0 g / m 2 as a solid resin content.} Next, the diluting solvent was dried using a dryer, passed through a nip roll (nip temperature 25 ° C., roll pressure: 0.1 MPa) while being layered on an unstretched polypropylene film (corona-treated 30 μm), and then at a temperature of 40 ° C. for 3 days. , Aging was performed to prepare a laminated film. Next, a test piece having a width of 15 mm was cut out from the obtained laminated film, and a tensile tester (manufactured by Shimadzu Corporation, model name: EZ-S) was used to pull the test piece in an environment of 25 ° C. and 65% RH. The test was carried out at 300 mm / min, and the T-shaped peel strength (N / 15 mm) was measured. The evaluation results are shown in Table 2.

As shown in Table 2 (Table 2-1 to Table 2-3), according to the present invention, a polyhydroxyurethane resin, which is a resin capable of using carbon dioxide as a raw material, is used, and an epoxy is used as a curing agent. By using the compound in an amount that is a peculiar ratio to the resin, the formed adhesive layer has sufficient adhesive strength and exhibits high gas barrier property, so that its practicality is further improved. It is expected to be used from the aspect of protecting the global environment.

Claims (5)

A two-component curable, polyhydroxyurethane resin adhesive composition having at least a component (A) as a main agent and a component (B) as a curing agent.
The main agent (A) is a polyhydroxyurethane resin having at least a hydroxyl group and a terminal amino group and having a repeating unit represented by the following general formula (1).
The component (B), which is a curing agent, is an epoxy compound having one or more functional groups.
Wherein the amine value of the total polyhydroxy urethane resin has a ratio [amine value / epoxy equivalent] of the epoxy equivalent of having the said epoxy compound is 0.05 or more 3.50 or less, and, the polyhydroxy urethane resin The ratio of the active hydrogen of the amino group to the epoxy group of the epoxy compound [active hydrogen of the amino group / epoxy group] is configured to be in the range of 0.3 to 3.0. Epoxy composition.

[In the general formula (1), X is a direct bond, an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 4 to 40 carbon atoms, or an aromatic hydrocarbon having 6 to 40 carbon atoms. Any of the groups, the structure may include an ether bond, an amino bond, a sulfonyl bond, an ester bond, a hydroxyl group, a halogen atom and a polyalkylene glycol chain consisting of 2 to 6 carbon atoms of repeating units 1 to 30. good. Further, in the general formula (1), Y is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 15 carbon atoms. the said structure, an ether bond, a sulfonyl bond, may contain a hydroxyl group and a halogen atom, and wherein between the repeating units, to Y of different configurations may be mixed, as Y, the following general formula (2) It may have the structure shown by . Further, in the general formula (1), Z represents any of the following general formulas (3) to (6), and both within the repeating unit and between the repeating units, from the group of these general formulas. One or more selected species may be mixed. ]

[In the general formulas (3) to (6), R independently represents a hydrogen atom or a methyl group, and the bond on the right side is bonded to the oxygen atom of the main chain in the general formula (1) and is on the left side. The bonder binds to X in the general formula (1), or if the X is a direct bond, it binds to the other Z. ]

[In the general formula (2), Y ₁ and Y ₂ may be the same or different, and may be an aliphatic hydrocarbon group having 1 to 15 carbon atoms, an alicyclic hydrocarbon group having 4 to 15 carbon atoms, or a carbon number of carbon atoms. It is a 6 to 15 aromatic hydrocarbon group, and the structure may contain an ether bond, a sulfonyl bond, a hydroxyl group and a halogen atom. ] The adhesive composition according to claim 1, wherein the polyhydroxyurethane resin has a hydroxyl value of 100 mgKOH / g or more and 350 mgKOH / g or less, and an amine value of 10 mgKOH / g or more and 300 mgKOH / g or less. The polyhydroxyurethane resin is a polyaddition reaction product of a compound having two or more 5-membered cyclic carbonate structures synthesized by using carbon dioxide as a raw material in at least a part thereof, and a compound having two or more amino groups. The adhesive composition according to claim 1 or 2 , wherein 0.1% by mass or more and 30% by mass or less of the total mass is composed of -O-CO- bonds derived from carbon dioxide. Forming the thickness 20μm of the coating film, the temperature 23 ° C., an oxygen permeability under constant temperature and humidity ^65%, or less ^{400ml / m 2 · 24h · atm} , claim 1 having the adhesive property and gas barrier property The adhesive composition according to any one of 3 to 3. A laminate in which two or more layers of the same or different materials selected from the group consisting of plastic film, polyolefin sealant, fiber cloth, paper, vapor-deposited plastic film, metal foil, metal and concrete are bonded via an adhesive layer. The laminate is characterized in that the adhesive layer is formed of the adhesive composition according to any one of claims 1 to 4.