JP7125871B2 - Two-component curing adhesive composition, laminate film and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a two-component curable adhesive composition, a laminate film and a method for producing the same, and more specifically, a two-component curable adhesive composition, a laminate film using the two-component curable adhesive composition, and The present invention relates to a method for producing a laminate film.

BACKGROUND ART Conventionally, laminated composite films, which are obtained by laminating various substrates with adhesives for lamination, have been widely used in various industrial fields such as food, medical care, home appliances, and electronic members. Also, as a lamination adhesive, for example, a two-component curing type polyurethane adhesive containing a main agent made of polyol and a curing agent made of isocyanate is known.

The base material of the laminate composite film is appropriately selected according to its use. For example, in the application of a vacuum insulation material for vacuum packaging a core material, a gas barrier film having gas barrier properties is selected as the packaging material, and when a high level of gas barrier properties is required, multiple gas barrier films are laminated A laminated composite film is used.

In addition, it is known that polyurethane adhesives exhibit excellent adhesive performance because they have functional groups (urethane bonds) exhibiting strong hydrogen bonding ability.

However, when multiple gas barrier films are adhered with a two-component curing type polyurethane adhesive, the isocyanate group (-NCO) reacts with moisture on the surface of the gas barrier film, moisture in the atmosphere, and moisture in the adhesive (blended liquid). , a carbamic acid group (--NHCOOH) to become an amino group (--NH ₂ ) and may generate carbon dioxide (CO ₂ ). When the carbon dioxide gas is sealed between the gas barrier films, there is a problem that the laminated composite film causes a bubble-like appearance defect.

Therefore, gas barrier laminated composite films with excellent appearance have been investigated. For example, multiple substrates with gas barrier properties are cured by the reaction of a compound having an amino group protected with a ketone group and a compound having an epoxy group. A gas barrier film laminate has been proposed that is adhered using an adhesive that does the same (see, for example, Patent Document 1).

JP 2006-051751 A

However, for adhesives that cure through the reaction of a compound (main agent) in which an amino group is protected with a ketone group (blocking agent) and a compound (curing agent) that has an epoxy group, the ketone group (blocking agent) becomes an amino group during curing. and free ketone groups (blocking agent) remain in the cured product of the adhesive.

Therefore, when a laminate composite film using the above-mentioned adhesive is used as a packaging material for a vacuum insulation material, the blocking agent is gradually released into the vacuum, causing a decrease in the degree of vacuum, resulting in a decrease in heat insulation. be.

Therefore, an adhesive that does not contain a blocking agent is required. , and a carbodiimide compound (for example, a carbodiimide-modified polyisocyanate).

Such a two-part curable adhesive composition has excellent adhesive strength, and since it does not contain a blocking agent, it can suppress a decrease in the degree of vacuum when used for a vacuum heat insulating material.

On the other hand, the two-component curing adhesive composition is sometimes required to have heat resistance and pot life after mixing the main agent and the curing agent depending on the application. If the pot life is short, the viscosity of the two-component curing adhesive composition increases during processing, which may cause problems such as variation in the coating amount and deterioration of leveling properties.

The present invention provides a two-component curable adhesive composition capable of obtaining excellent heat resistance and pot life, a laminate film having excellent gas barrier properties obtained by using the two-component curable adhesive composition, and a laminate. A film manufacturing method.

Furthermore, the present invention provides a two-component curable adhesive composition for obtaining a laminate film capable of suppressing a decrease in the degree of vacuum when used as a vacuum insulation material, and a two-component curable adhesive composition obtained by using the two-component curable adhesive composition. and a method for producing the laminated film.

The present invention [1] is a two-component curable adhesive composition for bonding between a plurality of gas barrier films, comprising a carboxy-containing component having a carboxy group and a carbodiimide-containing component containing a carbodiimide compound, The carboxy-containing component comprises an acid anhydride adduct of a polyester polyol, wherein the acid anhydride comprises a non-carbocyclic anhydride having no cyclic hydrocarbon skeleton and a carbocyclic anhydride having a cyclic hydrocarbon skeleton. It contains a two-component curable adhesive composition.

In the present invention [2], the carbocyclic anhydride is 65% by mass or less relative to the total amount of the carbocyclic anhydride and the carbocyclic anhydride, and the carbocyclic anhydride is , 35% by mass or more, the two-component curable adhesive composition according to [1] above.

In the present invention [3], the carbocyclic anhydride is 10% by mass or more relative to the total amount of the carbocyclic anhydride and the carbocyclic anhydride, and the carbocyclic anhydride is , 90% by mass or less, the two-component curable adhesive composition according to the above [1] or [2].

The present invention [4] is according to any one of the above [1] to [3], wherein the carbocyclic anhydride contains maleic anhydride, and the carbocyclic anhydride contains phthalic anhydride. It contains a two-part curable adhesive composition.

The present invention [5] provides a plurality of gas barrier films, and a curing of the two-component curable adhesive composition according to any one of the above [1] to [4], which is interposed between the plurality of gas barrier films. a laminate film with an adhesive layer that is an object.

The present invention [6] comprises a preparation step of preparing a plurality of gas barrier films, and a plurality of gas barrier films via the two-component curable adhesive composition according to any one of [1] to [4] above. are laminated to obtain a laminate.

The present invention [7] includes the method for producing a laminate film according to [6] above, comprising a curing step of heating and curing the laminate after the laminating step.

The two-part curable adhesive composition of the present invention contains a carboxy-containing component having a carboxy group and a carbodiimide-containing component containing a carbodiimide compound, and the carboxy-containing component is attached to the terminal hydroxyl group of the polyol. Acid anhydrides include non-carbocyclic anhydrides having no cyclic hydrocarbon backbone and carbocyclic anhydrides having a cyclic hydrocarbon backbone.

In such a two-component curing adhesive composition, gas generation can be suppressed without using a blocking agent. Thus, if no blocking agent is used, the blocking agent will not be liberated during curing, and no free blocking agent will remain in the cured product. Therefore, when it is used for a vacuum heat insulating material, it is possible to suppress a decrease in the degree of vacuum.

In addition, according to such a two-component curable adhesive composition, a laminate film using the two-component curable adhesive composition, and a method for producing the same, excellent heat resistance is obtained due to the carbocyclic anhydride. Moreover, the pot life after mixing of the main agent and the curing agent can be extended due to the carbocyclic anhydride.

FIG. 1 is a schematic diagram showing one embodiment of the laminate film of the present invention.

The two-component curable adhesive composition of the present invention is a two-component curable adhesive composition for bonding between a plurality of gas barrier films (described later), and is a carboxy-containing component having a carboxy group (in the present application, the main agent and and a carbodiimide-containing component (which may be referred to as a curing agent in the present application) containing a carbodiimide compound.

The carboxy-containing component (main ingredient) contains a compound having a carboxy group as a main component.

Examples of the compound having a carboxy group include compounds having a carboxy group at the end of the molecule, and specific examples thereof include anhydride acid adducts of polyester polyols.

An acid anhydride adduct of polyester polyol is obtained by adding an acid anhydride to a terminal hydroxyl group of polyester polyol.

The polyester polyol is a high molecular weight polyol having two or more hydroxyl groups and a number average molecular weight of 400 or more, preferably 500 or more and 20,000 or less, preferably 10,000 or less.

As the polyester polyol, more specifically, for example, a low-molecular-weight polyol (preferably a dihydric alcohol) and a polybasic acid (preferably a dibasic acid) are mixed under known conditions so that the low-molecular-weight polyol has many hydroxyl groups. A polycondensate obtained by esterification reaction at a molar excess ratio with respect to the carboxy group of the basic acid may be mentioned.

The low-molecular-weight polyol is a compound having a number average molecular weight of 60 or more, preferably 100 or more and less than 500, preferably less than 400, having two or more hydroxyl groups, such as ethylene glycol, propylene glycol, 1,3-propane. Diol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanediol Methanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8 diols, dihydric alcohols such as bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, e.g. tetramethylolmethane (pentaerythritol), diglycerin tetrahydric alcohols such as, for example, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, heptahydric alcohols such as perseitol, Examples include octahydric alcohols such as sucrose, preferably dihydric alcohols and trihydric alcohols, and more preferably dihydric alcohols.

These low-molecular-weight polyols can be used alone or in combination of two or more.

Examples of polybasic acids include oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl-3-ethylglutaric acid. , azelaic acid, saturated aliphatic dicarboxylic acids such as sebacic acid, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as acids, cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, and derived from these carboxylic acids Acid anhydrides such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone Tetracarboxylic dianhydrides, acid halides derived from these carboxylic acids, such as oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, etc., and acid (di)methyl esters (e.g., terephthalic acid dimethyl ester, etc.).

The polyester polyol may also contain castor oil or hydrogenated castor oil as raw materials in addition to the low-molecular-weight polyol and polybasic acid described above.

As the polyester polyol, for example, a low molecular weight polyol and a hydroxycarboxylic acid such as a hydroxyl group-containing vegetable oil fatty acid (eg, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) , and vegetable oil-based polyester polyols obtained by condensation reaction under known conditions.

As the polyester polyol, for example, polycaprolactone polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using a low molecular weight polyol (preferably a dihydric alcohol) as an initiator. , polyvalerolactone polyols, and lactone-based polyester polyols such as those obtained by copolymerizing them with dihydric alcohols.

Polyester polyols also include polyesteramide polyols.

Examples of polyesteramide polyols include polyesteramide polyols obtained by using low-molecular-weight polyamines (e.g., ethylenediamine, propylenediamine, hexamethylenediamine, etc.) as starting materials in the esterification reaction of the polyester polyols described above. .

These polyester polyols can be used alone or in combination of two or more.

The viscosity of the polyester polyol is, for example, 1000 mPa s or more, preferably 2000 mPa s or more, under 25°C conditions, and is, for example, 50,000 mPa s or less, preferably 20,000 mPa s, under 150°C conditions. It is below.

The viscosity is measured using a rotational viscometer or cone-plate viscometer according to JIS K 7117-1 (1999) or JIS K 5600-2-3 (2014).

An anhydride is a compound (also referred to as an acid anhydride) having at least one acid anhydride group.

Acid anhydrides include non-carbocyclic anhydrides having no cyclic hydrocarbon backbone and carbocyclic anhydrides having a cyclic hydrocarbon backbone. That is, the acid anhydride consists of a non-carbocyclic anhydride and a carbocyclic anhydride.

A cyclic hydrocarbon skeleton is a cyclic skeleton made of hydrocarbon, and specifically includes an aromatic ring skeleton, a saturated alicyclic skeleton, an unsaturated alicyclic skeleton, and the like.

These cyclic hydrocarbon skeletons may be monocyclic, condensed, or bridged.

Further, the number of ring members of the cyclic hydrocarbon skeleton is not particularly limited, and examples thereof include 3- to 20-membered rings, specifically 3-, 4-, 5-, 6-, and 8-membered rings, A 10-membered ring, a 12-membered ring, and the like are included.

The cyclic hydrocarbon skeleton does not contain an acid anhydride skeleton. That is, an anhydride skeleton (heterocyclic skeleton) formed by dehydration condensation of an organic acid during production of an acid anhydride is not included in the cyclic hydrocarbon skeleton.

Non-carbocyclic anhydrides are acid anhydrides that do not have a cyclic hydrocarbon backbone in their molecular structure, such as oxalic anhydride, succinic anhydride, 2-alkyl (C12-C18) succinic anhydride, maleic anhydride. etc.

These carbocyclic anhydrides can be used alone or in combination of two or more.

By using the non-carbocyclic anhydride, it is possible to improve the heat resistance of the cured product of the two-component curing adhesive composition.

From the viewpoint of improving heat resistance, the non-carbocyclic anhydride includes preferably succinic anhydride and maleic anhydride, more preferably maleic anhydride.

The carbocyclic anhydride is an acid anhydride having one or more (preferably, singular) cyclic hydrocarbon skeletons in its molecular structure, such as phthalic anhydride, tetrahydrophthalic anhydride (1, 2, 3, 6 -tetrahydrophthalic anhydride), trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and the like.

These carbocyclic anhydrides may be used alone or in combination of two or more.

By using the carbocyclic anhydride, the pot life of the two-pack curing adhesive composition can be improved.

From the viewpoint of improving the pot life, the carbocyclic anhydride preferably includes phthalic anhydride and tetrahydrophthalic anhydride, and more preferably includes phthalic anhydride.

And both these carbocyclic anhydrides and carbocyclic anhydrides are used in the preparation of the anhydride adducts of polyester polyols. As a result, the two-part curable adhesive composition can have both excellent heat resistance derived from the non-carbocyclic anhydride and excellent pot life derived from the non-carbocyclic anhydride.

Such polyester polyol anhydride adducts, more specifically, for example, polyester polyol anhydride adducts (i.e., polyester acid anhydride adducts of polyols).

The method for producing both anhydride adducts of polyester polyols will be described in detail below.

In the production of both anhydride adducts of polyester polyols, for example, a carbocyclic anhydride and a carbocyclic anhydride (hereinafter collectively referred to as an acid anhydride) are added simultaneously or sequentially to a polyester polyol. and heat to react.

In such a case, the proportion of the carbocyclic anhydride and the carbocyclic anhydride used in combination is appropriately selected from the viewpoint of achieving both heat resistance and pot life.

More specifically, the ratio of the carbocyclic anhydride and the carbocyclic anhydride used in combination depends on the equivalent ratio of the main agent and the curing agent to be described later, but the ratio of the carbocyclic anhydride and the carbocyclic anhydride is With respect to the total amount, the non-carbocyclic anhydride is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, further preferably 20% by mass or more, more preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, for example, 99% by mass or less, preferably 95% by mass or less, or more Preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, still more preferably 70% by mass or less, still more preferably 65% by mass or less, still more preferably 60% by mass % or less.

Further, the carbocyclic anhydride is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, relative to the total amount of the carbocyclic anhydride and the carbocyclic anhydride. , more preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass or more, for example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, even more preferably 80% by mass or less, further preferably 70% by mass or less, and further It is preferably 65% by mass or less, more preferably 60% by mass or less.

If the proportion of the carbocyclic anhydride is above the above lower limit and the proportion of the carbocyclic anhydride is below the above upper limit, the excellent heat resistance derived from the carbocyclic anhydride can be obtained more favorably. can be done.

Further, when the proportion of the carbocyclic anhydride is less than the above upper limit and the proportion of the carbocyclic anhydride is above the above lower limit, the excellent pot life derived from the carbocyclic anhydride can be obtained more satisfactorily. be able to.

In addition, from the viewpoint of improving heat resistance, the amount of non-carbocyclic anhydride is adjusted to be greater than that of carbocyclic anhydride. Specifically, the non-carbocyclic anhydride, for example, exceeds 50% by mass, preferably 55% by mass or more, more preferably more than the total amount of the non-carbocyclic anhydride and the non-carbocyclic anhydride. is 60% by mass or more, for example, 70% by mass or less, preferably 65% by mass or less.

In addition, the carbocyclic anhydride is, for example, 30% by mass or more, preferably 35% by mass or more, for example, less than 50% by mass, based on the total amount of the carbocyclic anhydride and the carbocyclic anhydride. , preferably 45% by mass or less, more preferably 40% by mass or less.

On the other hand, especially from the viewpoint of improving the pot life, the non-carbocyclic anhydride is adjusted to be less than the carbocyclic anhydride. Specifically, the carbocyclic anhydride is, for example, 30% by mass or more, preferably 35% by mass or more, relative to the total amount of the carbocyclic anhydride and the carbocyclic anhydride. It is less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less.

In addition, the carbocyclic anhydride exceeds, for example, 50% by mass, preferably 55% by mass or more, more preferably 60% by mass, based on the total amount of the carbocyclic anhydride and the carbocyclic anhydride. % or more, for example, 70% by mass or less, preferably 65% by mass or less.

These carbocyclic anhydrides and carbocyclic anhydrides may be mixed in advance and used, or may be used simultaneously or sequentially without being mixed.

Preferably, the non-carbocyclic anhydride and the carbocyclic anhydride are premixed and used as the anhydride composition.

In addition, in the blending of the anhydride with the polyester polyol, the anhydride group (total amount) of the anhydride and the hydroxyl group of the polyester polyol may be equal, or one of them may be excessive or insufficient. You may have

More specifically, for example, with respect to 1 mol of hydroxyl groups in the polyester polyol, the anhydride group (total amount) in the anhydride is, for example, 0.3 or more, preferably 0.5 mol or more, more preferably 0 0.7 mol or more, for example, 3 or less, preferably 2 mol or less, more preferably 1.5 mol or less.

If the blending ratio of the acid anhydride is within the above range, a laminate having both excellent appearance and excellent adhesiveness can be obtained.

In the above reaction, the reaction temperature is, for example, 100° C. or higher, preferably 130° C. or higher, and for example, 200° C. or lower, preferably 180° C. or lower.

Also, the reaction time is, for example, 60 minutes or longer, preferably 120 minutes or longer, and for example, 600 minutes or shorter, preferably 300 minutes or shorter.

In the above reaction, if the proportion of the anhydride group (total amount) is less than 1 mol with respect to 1 mol of the hydroxyl group of the polyester polyol (that is, the acid anhydride deficiency ratio), some of the hydroxyl groups of the polyol are acid-modified. , the remaining hydroxyl groups remain without acid modification.

In addition, when the ratio of the anhydride groups (total amount) to 1 mol of the hydroxyl groups of the polyester polyol exceeds 1 mol (i.e., the excess ratio of acid anhydride), the anhydride adduct of the polyester polyol contains unreacted anhydride groups. obtained as a composition containing

Moreover, the above reaction may be carried out in the absence of a solvent or in the presence of an organic solvent that is blended as necessary. Preferably, the polyester polyol and the acid anhydride are reacted in the absence of solvent.

Examples of organic solvents include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; nitriles such as acetonitrile; alkyl esters such as methyl acetate, ethyl acetate, butyl acetate and isobutyl acetate; Aliphatic hydrocarbons such as hexane, n-heptane and octane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, and methyl cellosolve acetate. , ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PMA), 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc. Glycol ether esters, e.g. ethers such as diethyl ether, tetrahydrofuran, dioxane Halogenated aliphatic hydrocarbons such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloroethane , for example, polar aprotons such as N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide and hexamethylphosphonylamide.

These organic solvents can be used alone or in combination of two or more.

After completion of the reaction, all or part of the unreacted acid anhydride and organic solvent can be removed by a known method such as a distillation method or an extraction method, if necessary. Also, after the reaction is completed, the above organic solvent can be added to adjust the concentration of the acid anhydride adduct of the polyester polyol.

Thereby, the carbon ring-free acid anhydride and the carbocyclic ring-containing acid anhydride can be added to the polyester polyol, and both anhydride acid adducts of the polyester polyol can be obtained. That is, an anhydride adduct of polyester polyol can be obtained as a bianhydride adduct of polyester polyol.

And the carboxy-containing component (main agent) can contain both anhydride acid adducts of polyester polyols.

Further, as the polyester polyol anhydride addition product, in addition to the above-mentioned polyester polyol anhydride addition product, for example, a polyester polyol anhydride addition product obtained by using a carbocyclic anhydride alone (i.e., Non-carbocyclic anhydride acid adduct of polyester polyol) and an anhydride adduct of polyester polyol obtained by using a carbocyclic anhydride alone (i.e., carbocyclic anhydride acid adduct of polyester polyol) in combination You can also

Non-carbocyclic anhydride adducts of polyester polyols can be obtained by using only non-carbocyclic anhydrides in the above process.

The reaction conditions are the same as above, and if necessary, the concentration of the carbon ring-free acid anhydride adduct of the polyester polyol can be adjusted by the above method.

Also, the carbon ring-containing anhydride adduct of the polyester polyol can be obtained by using only the carbocyclic anhydride alone in the above-described method.

The reaction conditions are the same as above, and if necessary, the concentration of the carbon ring-containing anhydride adduct of the polyester polyol can be adjusted by the above method.

In this method, a carbon ring-free acid anhydride adduct of polyester polyol and a carbon ring-containing acid anhydride adduct of polyester polyol are used in combination.

More specifically, the carboxy-containing component (base ingredient) contains both a carbocyclic anhydride acid adduct of a polyester polyol and a carbocyclic anhydride acid adduct of a polyester polyol.

When used in combination in this way, the carbocyclic anhydride acid adduct of the polyester polyol and the carbocyclic anhydride acid adduct of the polyester polyol are mixed in advance, and the polyester polyol anhydride acid adduct is added to the polyester polyol. It can also be obtained as a mixture of a carbocyclic anhydride acid adduct of and a carbocyclic anhydride acid adduct of a polyester polyol, and when using a two-component curable adhesive composition described later, the carbon of the polyester polyol The ring-free anhydride adduct and the carbocyclic anhydride adduct of the polyester polyol can also be mixed with the carbodiimide-containing component (curing agent) without prior mixing with each other.

In addition, the combined ratio of the non-carbocyclic anhydride adduct of the polyester polyol and the non-carbocyclic anhydride adduct of the polyester polyol is the ratio of the non-carbocyclic anhydride and the above-described carbocyclic anhydride. are the same.

That is, the ratio of the carbon ring-free acid anhydride adduct of the polyester polyol and the carbon ring-containing acid anhydride adduct of the polyester polyol used in combination depends on the equivalent ratio of the main agent and the curing agent described later, but the carbon ring-free polyester polyol Based on the total amount of the anhydride adduct and the carbocyclic anhydride adduct of the polyester polyol, the carbocyclic anhydride adduct of the polyester polyol is, for example, 1% by mass or more, preferably 5% by mass or more, or more. Preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass or more, still more preferably 40% by mass % or more, for example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less, further preferably 80% by mass or less, further preferably , 70% by mass or less, more preferably 65% by mass or less, more preferably 60% by mass or less.

Further, the carbon ring-containing anhydride acid adduct of the polyester polyol is preferably, for example, 1% by mass or more with respect to the total amount of the carbocyclic anhydride acid adduct of the polyester polyol and the carbocyclic anhydride acid adduct of the polyester polyol. is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, still more preferably 35% by mass Above, more preferably 40% by mass or more, for example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass or less, further preferably, 80% by mass or less, more preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.

Moreover, from the viewpoint of improving heat resistance in particular, the carbon ring-free acid anhydride adduct of the polyester polyol is adjusted to be larger than the carbon ring-containing acid anhydride adduct of the polyester polyol. Specifically, with respect to the total amount of the carbocyclic anhydride adduct of the polyester polyol and the carbocyclic anhydride acid adduct of the polyester polyol, the carbocyclic anhydride adduct of the polyester polyol is, for example, 50 mass %, preferably 55% by mass or more, more preferably 60% by mass or more, for example, 70% by mass or less, preferably 65% by mass or less.

Further, the carbon ring-containing anhydride acid adduct of the polyester polyol is preferably, for example, 30% by mass or more with respect to the total amount of the carbocyclic anhydride acid adduct of the polyester polyol and the carbocyclic anhydride acid adduct of the polyester polyol. is 35% by mass or more, for example, less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less.

On the other hand, especially from the viewpoint of improving the pot life, the carbon ring-free acid anhydride adduct of the polyester polyol is adjusted to be less than the carbon ring-containing acid anhydride adduct of the polyester polyol. Specifically, with respect to the total amount of the carbocyclic anhydride adduct of the polyester polyol and the carbocyclic anhydride adduct of the polyester polyol, the carbocyclic anhydride adduct of the polyester polyol is, for example, 30 mass % or more, preferably 35 mass % or more, for example, less than 50 mass %, preferably 45 mass % or less, more preferably 40 mass % or less.

In addition, the carbon ring-containing anhydride acid adduct of the polyester polyol exceeds, for example, 50% by mass with respect to the total amount of the carbocyclic anhydride acid adduct of the polyester polyol and the carbocyclic anhydride acid adduct of the polyester polyol. , preferably 55% by mass or more, more preferably 60% by mass or more, for example, 70% by mass or less, preferably 65% by mass or less.

If the carbocyclic anhydride adduct of the polyester polyol and the carbocyclic anhydride adduct of the polyester polyol are used in combination in the above ratio, the ratio of the carbocyclic anhydride and the carbocyclic anhydride used in combination is within the above range. , and both heat resistance and pot life can be achieved.

Examples of the polyester polyol anhydride adduct include, for example, both anhydride acid adducts of polyester polyols, carbocyclic anhydride acid adducts of polyester polyols, and/or carbocyclic anhydride acid adducts of polyester polyols. and can be used together.

Also in such a case, the ratio of both anhydride acid adducts of polyester polyols, carbocyclic anhydride acid adducts of polyester polyols, and/or carbocyclic anhydride acid adducts of polyester polyols is carbocyclic The combined ratio of the non-containing anhydride and the carbocyclic anhydride is appropriately adjusted so as to fall within the above range.

The polyester polyol anhydride adduct preferably includes a combination of a carbocyclic anhydride acid adduct of a polyester polyol and a carbocyclic anhydride acid adduct of a polyester polyol.

The number average molecular weight (molecular weight in terms of polystyrene in terms of GPC) Mn of the acid anhydride adduct of polyester polyol is, for example, 2000 or more, preferably 3000 or more, and for example, 20000 or less, preferably 10000 or less.

As long as the carboxy-containing component (main component) contains the acid anhydride adduct of the above polyester polyol as a main component, it may optionally contain additives described later, and may be diluted with the above organic solvent. may have been

The content of the acid anhydride addition product of the polyester polyol is, for example, 50% by mass or more, preferably 80% by mass or more, and for example, 100% by mass or less, preferably 100% by mass or less, based on the total amount of the carboxy-containing component (main agent). , 99% by mass or less.

Further, the solid content concentration of the carboxy-containing component (main agent) is, for example, 30% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, and for example, 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less.

In addition, the acid value (based on JIS K 1557-5 (2007)) of the carboxy-containing component (solid content) is, for example, 1 mgKOH/g or more, preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more. , for example, 100 mgKOH/g or less, preferably 70 mgKOH/g or less, more preferably 50 mgKOH/g or less.

In addition, the carboxy group equivalent (56100/acid value (mgKOH/g)) of the carboxy-containing component (solid content) is, for example, 561 or more, preferably 801 or more, more preferably 1122 or more, and for example 56100 or less. , preferably 11220 or less, more preferably 5610 or less.

The carbodiimide compound contained in the carbodiimide-containing component (curing agent) can be obtained, for example, as a carbodiimide-modified polyisocyanate.

A carbodiimide-modified polyisocyanate is a modified polyisocyanate (derivative) having at least one carbodiimide group in one molecule.

A carbodiimide-modified polyisocyanate can be obtained, for example, by heating a polyisocyanate in the presence of a carbodiimidation catalyst to cause a carbodiimidation reaction.

Examples of polyisocyanates include polyisocyanate monomers such as aliphatic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates.

Examples of aliphatic polyisocyanates include linear (linear or branched: acyclic) aliphatic polyisocyanates, and specific examples include ethylene diisocyanate, trimethylene diisocyanate, 1,2- Propylene diisocyanate, butane diisocyanate (tetramethylene diisocyanate, 1,2-butane diisocyanate, 2,3-butane diisocyanate, 1,3-butane diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate, dodecamethylene diisocyanate and other chain aliphatic diisocyanates.

Moreover, an alicyclic polyisocyanate is also mentioned as an aliphatic polyisocyanate.

Examples of alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexylmethane diisocyanate or mixtures thereof (hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, Alicyclic diisocyanates such as 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof (hydrogenated XDI), norbornane diisocyanate (NBDI), and the like are included.

Aromatic polyisocyanates include, for example, m- or p-phenylene diisocyanate or mixtures thereof, 2,4- or 2,6-tolylene diisocyanate or mixtures thereof (TDI), 4,4′-, 2,4′- or 2,2'-diphenylmethane diisocyanate or mixtures thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate (NDI) ) and other aromatic diisocyanates.

As araliphatic polyisocyanates, for example, 1,3- or 1,4-xylylene diisocyanate or mixtures thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof (TMXDI), Araraliphatic diisocyanates such as ω,ω'-diisocyanate-1,4-diethylbenzene and the like are included.

These polyisocyanates can be used alone or in combination of two or more.

Polyisocyanates preferably include chain aliphatic polyisocyanates and araliphatic polyisocyanates.

Examples of the carbodiimidation catalyst include, but are not limited to, trialkyl phosphate compounds, phosphorene oxide compounds, phosphorene sulfide compounds, phosphine oxide compounds, and phosphine compounds.

Examples of trialkyl phosphates include trialkyl phosphate compounds having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate and trioctyl phosphate.

Examples of phosphorene oxide compounds include 3-methyl-1-phenyl-2-phosphorene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phosphorene-1-oxide (EMPO), 1 , 3-dimethyl-2-phospholene-1-oxide, 1-phenyl-2-phospholene-1-oxide, 1-methyl-2-phospholene-1-oxide, 1-ethyl-2-phospholene-1-oxide and these and phosphorene oxide compounds having 4 to 18 carbon atoms such as double bond isomers of.

Examples of phosphorene sulfide compounds include phosphorene sulfide compounds having 4 to 18 carbon atoms such as 1-phenyl-2-phosphorene-1-sulfide.

Examples of phosphine oxide compounds include phosphine oxide compounds having 3 to 21 carbon atoms such as triphenylphosphine oxide and tritolylphosphine oxide.

Phosphine compounds include, for example, phosphine compounds having 3 to 30 carbon atoms such as bis(oxadiphenylphosphino)ethane.

These carbodiimidation catalysts can be used alone or in combination of two or more.

The blending ratio of the carbodiimidation catalyst is not particularly limited, and is appropriately set according to the purpose and application.

As the heating conditions, the heating temperature is, for example, 30° C. or higher, preferably 60° C. or higher, and, for example, 200° C. or lower, preferably 180° C., under normal pressure and an inert gas (such as nitrogen gas) atmosphere. It is below. Also, the heating time is, for example, 1 hour or more, preferably 3 hours or more, and is, for example, 50 hours or less, preferably 40 hours or less.

As a result, the polyisocyanate undergoes decarboxylation condensation to obtain a carbodiimide compound (that is, a carbodiimide-modified polyisocyanate).

In addition, in the carbodiimidation reaction, if necessary, the above-described organic solvent can be blended, and after the completion of the reaction, if necessary, by a known method such as distillation method or extraction method, unreacted polyisocyanate or , all or part of the organic solvent can be removed. Further, the concentration of the solution of the carbodiimide compound can be adjusted by adding the above organic solvent after the completion of the reaction.

Also, prior to the carbodiimidation reaction, the polyisocyanate can be alcohol-modified with a known alcohol (polyoxyethylene monomethyl ether, 1-methoxy-2-propanol, etc.). In the alcohol modification, for example, the urethanization reaction is performed at a ratio of less than 1 (OH/NCO) of the hydroxyl group of the alcohol to the isocyanate group of the polyisocyanate. In addition, if necessary, the above-described organic solvent and a known urethanization catalyst can be blended, and after the completion of the reaction, if necessary, the unreacted polyisocyanate is removed by a known method such as distillation or extraction. Alternatively, all or part of the organic solvent can be removed.

In the carbodiimide compound solution, the solid content concentration is, for example, 50% by mass or more, preferably 60% by mass or more, and is, for example, 100% by mass or less, preferably 90% by mass or less, more preferably 80% by mass. % or less.

The carbodiimide group equivalent of the carbodiimide compound (solid content) is, for example, 150 or more, preferably 200 or more, and for example, 500 or less, preferably 400 or less.

The above carbodiimide compound can also be obtained as a commercial product. concentration 50 mass%, carbodiimide group equivalent 404 (solid content equivalent 202), manufactured by Nisshinbo Co., Ltd.), Carbodilite V09GB (solid content concentration 70 mass%, carbodiimide group equivalent 298 (solid content equivalent 209), manufactured by Nisshinbo Co., Ltd. ) and the like.

The carbodiimide-containing component (curing agent) may contain the above carbodiimide compound alone, or may contain two or more of them. Moreover, the additive mentioned later can also be contained.

The content of the carbodiimide compound is, for example, 50% by mass or more, preferably 80% by mass or more, and for example, 100% by mass or less, preferably 99% by mass, relative to the total amount of the carbodiimide-containing component (curing agent). It is below.

In addition, the two-component curing adhesive composition may optionally contain either one or both of the carboxy-containing component (main agent) and the carbodiimide-containing component (curing agent), for example, phosphoric acid or Its derivatives, silane coupling agents, epoxy resins, catalysts, coatability improvers, leveling agents, antifoaming agents, stabilizers such as antioxidants and UV absorbers, plasticizers, surfactants, pigments, Additives such as fillers, organic or inorganic fine particles, and antifungal agents can be added as appropriate. The amount of the additive to be added is appropriately determined according to its purpose and application.

When such a two-component curing adhesive composition is used, a carboxy-containing component as a main component and a carbodiimide-containing component as a curing agent are blended to prepare a mixed solution, and if necessary, mixed. The liquid is diluted with an organic solvent and applied to the substrate (adherend).

The mixing ratio of the carboxy-containing component (main agent) and the carbodiimide-containing component (curing agent) (hereinafter sometimes referred to as equivalent ratio) is, for example, the carboxy group in the carboxy-containing component (the carboxy group contained in the carboxy-containing component). The carbodiimide group in the carbodiimide-containing component (the carbodiimide group of the carbodiimide compound contained in the carbodiimide-containing component) is, for example, 0.85 mol or more, preferably 0.90 mol or more, more preferably 0, per 1 mol. 0.93 mol or more, for example, 5.0 mol or less, preferably 4.5 mol or less, more preferably 4.0 mol or less.

If the blending ratio (equivalence ratio) of the carboxy-containing component (main agent) and the carbodiimide-containing component (curing agent) is within the above range, the two-component curing adhesive composition will have excellent adhesiveness, and the resulting laminate will be excellent. It is possible to combine a good appearance with excellent adhesiveness.

Moreover, when the equivalent ratio is relatively high (1.3 or more, preferably 2.0 or more), the two-component curing adhesive composition can obtain excellent heat resistance. That is, in such a case, excellent heat resistance can be obtained even when the amount of the non-carbocyclic anhydride that ensures heat resistance is relatively small.

Therefore, when the equivalence ratio is relatively high, the non-carbocyclic anhydride can be adjusted to be less than the carbocyclic anhydride, specifically, the non-carbocyclic anhydride is For example, it can be less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less, and even in such a case, excellent heat resistance and pot life can be obtained.

Such a two-component curing adhesive composition contains a carboxy-containing component having a carboxy group and a carbodiimide-containing component containing a carbodiimide compound. In such a two-part curing adhesive composition, the carboxy group of the carboxy-containing component and the carbodiimide group of the carbodiimide-containing component undergo an acyl urea reaction, so that no carbon dioxide gas is generated during curing, and due to its structure, curing does not occur. Even after (adhesion), the possibility of carbon dioxide gas generation due to moisture in the atmosphere is extremely low even after a certain period of time has passed. can be obtained.

In particular, in a laminate film in which the base film has a gas barrier property, if gas is generated in the adhesive layer, the escape of the gas is limited, which may lead to a fatal appearance defect. On the other hand, the two-component curing adhesive composition of the present invention hardly generates gas over time, and is therefore suitable for lamination of gas barrier films.

In addition, this two-component curing adhesive composition contains an acyl urea group exhibiting strong hydrogen-bonding ability, like a urethane bond, and therefore exhibits excellent adhesive performance.

Furthermore, in such a two-component curing adhesive composition, the carboxy-containing component contains a compound in which an acid anhydride is added to the terminal hydroxyl group of a polyol, and the acid anhydride has no carbocyclic hydrocarbon skeleton and does not have a cyclic hydrocarbon skeleton. It contains an acid anhydride and a carbocyclic anhydride having a cyclic hydrocarbon skeleton.

In such a two-component curing adhesive composition, gas generation can be suppressed without using a blocking agent. Thus, if no blocking agent is used, the blocking agent will not be liberated during curing, and no free blocking agent will remain in the cured product. Therefore, when it is used for a vacuum heat insulating material, it is possible to suppress a decrease in the degree of vacuum.

In addition, according to such a two-component curable adhesive composition, a laminate film using the two-component curable adhesive composition, and a method for producing the same, excellent heat resistance is obtained due to the carbocyclic anhydride. Moreover, the pot life after mixing of the main agent and the curing agent can be extended due to the carbocyclic anhydride.

A gas-barrier laminate film (laminate) obtained using a two-component curing adhesive composition and a method for producing the same will be described in detail below.

In FIG. 1 , a gas barrier laminate film 1 includes a plurality (two) of gas barrier films 2 and an adhesive layer 3 interposed between the gas barrier films 2 .

The gas barrier film 2 is a film having gas barrier properties, and has an oxygen permeability (25° C., 80% RH (JIS K 7126-2 (2006)) of 100 mL/m ² 24 hr MPa or less, preferably , is defined as a film of 50 mL/m ² ·24 hr·MPa or less.

The oxygen permeability can also be measured with an oxygen permeability measuring device manufactured by Modern Control.

Specific examples of the gas barrier film 2 include metal foil (such as aluminum foil). Further, for example, a plastic film provided with a metal film (e.g., an aluminum film, etc.), a plastic film provided with a metal vapor deposition film (aluminum vapor deposition film, silica vapor deposition film, alumina vapor deposition film, silica/alumina binary vapor deposition film, etc.) can also be mentioned. be done. Examples of plastic films include polyethylene terephthalate (PET) film, nylon (NY) film, cellulose acetate (TAC) film, ethylene-vinyl alcohol copolymer (EVOH) film, and the like, preferably PET film. , cellulose acetate (TAC) film, ethylene-vinyl alcohol copolymer (EVOH) film. The thickness of the metal film, the thickness of the vapor-deposited metal film, and the thickness of the plastic film are not particularly limited, and are appropriately set according to the purpose and application.

These gas barrier films 2 can be used alone or in combination of two or more.

As the gas barrier film 2, preferably, a plastic film having a metal deposition film is used. More preferably, a plastic film provided with an aluminum deposition film, a plastic film provided with a silica deposition film, a plastic film provided with an alumina deposition film, and a plastic film provided with a silica/alumina binary deposition film are mentioned. Moreover, as a plastic film provided with such a metal deposition film, preferably, a PET film, a cellulose acetate (TAC) film, and an ethylene-vinyl alcohol copolymer (EVOH) film can be mentioned.

More preferably, the gas barrier film 2 includes a PET film with an aluminum vapor deposition film, a PET film with a silica vapor deposition film, a PET film with an alumina vapor deposition film, and a PET film with a silica/alumina binary vapor deposition film.

FIG. 1 shows a plastic film 5 provided with a metal deposition film 4 as the gas barrier film 2 .

Further, although not shown in FIG. 1, the gas barrier film 2 may include, for example, an anchor coat layer between the metal deposition film 4 and the plastic film 5, and the surface of the metal deposition film 3 (plastic film 4) may be provided with an overcoat layer.

The thickness of the gas barrier film 2 is, for example, 5 μm or more, preferably 10 μm or more, and for example, 30 μm or less, preferably 20 μm or less.

The adhesive layer 3 is a cured product of the two-component curing adhesive composition described above, and is laminated between a plurality of (two) gas barrier films 2 . In other words, the adhesive layer 3 is formed between the gas barrier films 2 when a plurality (two) of the gas barrier films 2 are pasted together with the two-component curing adhesive composition.

In the production of the laminate film 1, for example, a plurality (two) of gas barrier films 2 can be pasted together with the adhesive layer 3 interposed therebetween so that the respective metal deposition films 4 face each other.

Alternatively, for example, a plurality of (two) gas barrier films 2 may be attached such that the plastic films 5 face each other with the adhesive layer 3 interposed therebetween.

Further, for example, a plurality of (two) gas barrier films 2 are arranged such that the metal deposition layer 4 of one gas barrier film 2 and the plastic film 5 of the other gas barrier film 2 face each other with the adhesive layer 3 interposed therebetween. It can also be pasted together.

Preferably, as shown in FIG. 1 , a plurality (two) of gas barrier films 2 are pasted together with an adhesive layer 3 interposed therebetween such that the metal deposition films 4 face each other.

The thickness of the adhesive layer 3 is, for example, 1 μm or more, preferably 2 μm or more, and for example, 10 μm or less, preferably 5 μm or less.

Although FIG. 1 shows a laminate film 1 in which two gas barrier films 2 are laminated together, the number of gas barrier films 2 is not limited to the above. It can also be pasted together.

Also, the laminate film 1 can be provided with a heat seal layer 6 on one side or both sides thereof, as indicated by the dashed line in FIG.

The heat-sealing layer 6 is a layer that imparts heat-sealing properties to the laminate film 1, and examples thereof include thermoplastic polyolefin films such as polyethylene films and unstretched polypropylene films.

The thickness of the heat seal layer 6 is, for example, 10 μm or more, preferably 20 μm or more, and for example, 200 μm or less, preferably 150 μm or less.

Specifically, the heat seal layer 6 is laminated on the surface of the gas barrier film 2 (the other side to the one side on which the adhesive layer 3 is formed) via the heat seal adhesive layer 7 .

The heat-sealing adhesive layer 7 may be, for example, a cured product of the above two-component curing adhesive composition, or a cured product of other known adhesives (polyurethane adhesives, etc.). good too.

The thickness of the heat seal adhesive layer 7 is, for example, 1 μm or more, preferably 2 μm or more, and for example, 10 μm or less, preferably 5 μm or less.

If necessary, the surface of the gas barrier film 2 may be coated with an anchoring agent, and then a resin such as polyethylene may be extruded to laminate the heat seal layer 6 . In such a case, the coating amount of the coating layer of the anchoring agent is, for example, 0.1 g/m ² or more, preferably 0.2 g/m ² or more, and for example, 2.0 g/m ² or less, preferably 1.0 g/m ² or less.

In order to manufacture such a laminate film 1, for example, first, a plurality (for example, two) of gas barrier films 2 are prepared (preparation step).

Next, in this method, a plurality of gas barrier films 2 are laminated together via the two-component curing adhesive composition to obtain a laminate (laminating step).

Specifically, in the lamination process, for example, after the carboxy-containing component and the carbodiimide-containing component are diluted with the above organic solvent and blended, the resulting mixture is applied to the surface of each gas barrier film by a solvent-type laminator, and the solvent is After volatilizing, the coated surfaces are bonded together, and then cured and cured at normal temperature or at elevated temperature, or the blended viscosity of the carboxy-containing component and the carbodiimide-containing component is normal temperature to 100 ° C., for example, In the case of about 100 to 10,000 mPa·s, preferably about 100 to 5,000 mPa·s, for example, the carboxy-containing component and the carbodiimide-containing component are blended as they are, and the resulting mixture is applied to each gas barrier film by a solvent-free laminator. A method of coating the surface and bonding the coated surfaces together is adopted.

The coating amount of the two-component curing adhesive composition is, for example, in the case of a solvent type, the basis weight (solid content) after solvent volatilization is 2.0 to 8.0 g / m ² , and the non-solvent type. In total, it is 1.0 to 4.0 g/m ² .

As a result, the carboxy group in the carboxy-containing component and the carbodiimide group in the carbodiimide-containing component undergo an acyl urea reaction to cure the two-component curing adhesive composition. As a result, the laminate film 1 is obtained as a laminate of the gas barrier film 2 .

Moreover, in this method, the obtained laminate is heated and cured (curing step), if necessary.

The curing temperature in the curing step is, for example, 20° C. or higher, preferably 40° C. or higher, and for example, 80° C. or lower, preferably 70° C. or lower.

The curing time is, for example, 24 hours or longer, preferably 48 hours or longer, and for example, 240 hours or shorter, preferably 120 hours or shorter.

Thereby, the improvement of the adhesiveness between the gas barrier films 2 can be aimed at.

Furthermore, if necessary, the heat-seal layer 6 can be adhered to the surface of the gas barrier film 2 via the heat-seal adhesive layer 7 in the same manner as in the above lamination step (see broken line in FIG. 1). Thereby, the laminate film 1 can be provided with heat-sealing properties.

The obtained laminate film 1 has excellent gas barrier properties against oxygen, water vapor, etc., and is used in the field of gas barrier films, specifically in the field of heat insulation such as vacuum insulation materials, packaging films for foods and pharmaceuticals, It is suitably used in food packaging containers (including bottles), optical films, industrial films, etc., and is particularly suitably used in the heat insulation field such as vacuum insulation materials.

In addition, in the present invention, components (sometimes referred to as other components) other than the above-described main agent and curing agent may be contained within a range that does not impair the purpose and effect. The content of these other components is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, relative to the total amount of the adhesive composition.

EXAMPLES Next, the present invention will be described based on Production Examples, Examples and Comparative Examples, but the present invention is not limited by the following Examples. "Parts" and "%" are based on mass unless otherwise specified. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.

Moreover, various measuring methods are shown below.

<Acid value (solid content)>
An appropriate amount of the sample was weighed and dissolved in a mixed solvent of toluene/methanol=7/3 (weight ratio), a few drops of phenolphthalein indicator were added, and titration was performed with a 0.1 mol/L ethanolic potassium hydroxide solution. I asked.

<Carboxy group equivalent (solid content)>
Using the acid value determined above, it was determined by the following formula.

Carboxy group equivalent = 56100/acid value <Amount of terminal hydroxyl groups>
An appropriate amount of the sample was weighed, and 20 mL of a mixed solution of acetic anhydride/pyridine (30 mL/400 mL) and 2 mL of a pyridine solution of 4-dimethylaminopyridine (concentration: 1 g/100 mL) were added, and dissolved with stirring at room temperature for 30 minutes to remove terminal hydroxyl groups. was added with acetic anhydride. Then, after diluting with 50 mL of pyridine, excess acid was back-titrated with a 1 mol/L sodium hydroxide aqueous solution to obtain an acetyl value (mgKOH/g). Based on this result (value) and the separately measured acid value, the amount of terminal hydroxyl groups (hydroxyl value) was calculated according to the following formula.

Hydroxyl value = Acetyl value + Acid value <Main agent (component containing carboxyl)>
Production Example 1 (Preparation of anhydride adduct A)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged into a reactor and esterified at 180 to 220°C. reacted. When the acid value became 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added and the esterification reaction was continued. This produced a polyester polyol.

After that, when the viscosity at 150 ° C. reaches 9640 mPa s (measured with a cone plate viscometer; compliant with JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups is determined by titration, and its equal equivalent Maleic anhydride was added so as to obtain (1 mol of anhydride groups: 1 mol of hydroxyl groups), and the mixture was stirred at 150° C. for 90 minutes to add to the hydroxyl groups. This gave a non-carbocyclic acid anhydride adduct of a polyester polyol.

1100 g of ethyl acetate was then added to dissolve the carbocyclic anhydride adduct of the polyester polyol. As a result, an anhydride acid adduct A was obtained as 60% by mass.

The acid value (solid content) of the acid anhydride adduct A was 10.8 mgKOH/g, and the carboxy group equivalent (solid content) was 3,117.

Production Example 2 (Preparation of anhydride adduct B)
A polyester polyol was produced in the same manner as in Production Example 1.

After that, when the viscosity at 150° C. reaches 9640 mPa s, the amount of terminal hydroxyl groups is determined by titration, and phthalic anhydride is added so that the equivalent amount (1 mol of anhydride group: 1 mol of hydroxyl group) is added to 150. C. for 90 minutes to allow addition to hydroxyl groups. As a result, a carbon ring-containing anhydride adduct of polyester polyol was obtained.

Thereafter, 1100 g of ethyl acetate was added to dissolve the carbon ring-containing anhydride adduct of the polyester polyol. As a result, an anhydride acid adduct B was obtained as a 60% by mass solution.

The acid value (solid content) of the anhydride adduct B was 11.4 mgKOH/g, and the carboxy group equivalent (solid content) was 2,913.

Production Example 3 (Preparation of anhydride adduct C)
A polyester polyol was produced in the same manner as in Production Example 1.

After that, when the viscosity at 150° C. reaches 9640 mPa·s, the amount of terminal hydroxyl groups is determined by titration, and tetrahydrophthalic anhydride is added so as to have an equivalent amount (1 mol of anhydride group: 1 mol of hydroxyl group). The mixture was stirred at 150° C. for 90 minutes to add hydroxyl groups. As a result, a carbon ring-containing anhydride adduct of polyester polyol was obtained.

Thereafter, 1100 g of ethyl acetate was added to dissolve the carbon ring-containing anhydride adduct of the polyester polyol. As a result, an anhydride acid adduct C was obtained as 60% by mass.

The acid value (solid content) of the anhydride adduct C was 11.0 mgKOH/g, and the carboxy group equivalent (solid content) was 3,060.

Production Example 4 (Preparation of anhydride adduct D)
A polyester polyol was produced in the same manner as in Production Example 1.

After that, when the viscosity at 150 ° C. reached 9640 mPa s, the amount of terminal hydroxyl groups was determined by titration, and succinic anhydride was added so that the equivalent amount (1 mol of anhydride group: 1 mol of hydroxyl group) was added to 150. C. for 90 minutes to allow addition to hydroxyl groups. This gave a non-carbocyclic acid anhydride adduct of a polyester polyol.

1100 g of ethyl acetate was then added to dissolve the carbocyclic anhydride adduct of the polyester polyol. As a result, an anhydride acid adduct D was obtained as a 60% by mass solution.

The acid value (solid content) of the acid anhydride adduct D was 10.6 mgKOH/g, and the carboxy group equivalent (solid content) was 3,170.

Production Example 5 (Preparation of anhydride adduct E)
A polyester polyol was produced in the same manner as in Production Example 1.

After that, when the viscosity at 150° C. reaches 9640 mPa·s, the amount of terminal hydroxyl groups is determined by titration, and maleic anhydride and phthalic anhydride are added so as to have an equivalent amount (1 mol of anhydride group: 1 mol of hydroxyl group). (maleic anhydride: phthalic anhydride = 50:50 (mass ratio)) was added and stirred at 150°C for 90 minutes to add to the hydroxyl group. As a result, a double anhydride adduct of polyester polyol was obtained.

After that, 1100 g of ethyl acetate was added to dissolve the both anhydride acid adducts of the polyester polyol. As a result, the acid anhydride adduct E was obtained as a 60 mass % solution.

The acid value (solid content) of the acid anhydride adduct E was 11.6 mgKOH/g, and the carboxy group equivalent (solid content) was 2,902.

Production Example 6 (Preparation of anhydride adduct F)
A polyester polyol was produced in the same manner as in Production Example 1.

After that, when the viscosity at 150° C. reaches 9640 mPa·s, the amount of terminal hydroxyl groups is determined by titration, and maleic anhydride and phthalic anhydride are added so as to have an equivalent amount (1 mol of anhydride group: 1 mol of hydroxyl group). (maleic anhydride:tetrahydrophthalic anhydride=50:50 (mass ratio)) was added and stirred at 150° C. for 90 minutes to add to the hydroxyl group. As a result, a double anhydride adduct of polyester polyol was obtained.

After that, 1100 g of ethyl acetate was added to dissolve the both anhydride acid adducts of the polyester polyol. As a result, the acid anhydride adduct E was obtained as a 60 mass % solution.

The acid value (solid content) of the anhydride adduct F was 12.3 mgKOH/g, and the carboxy group equivalent (solid content) was 2,737.

<Curing agent (carbodiimide-containing component)>
As curing agent A, the following products were used.
Curing agent A: Nisshinbo Corp. Carbodilite V09GB (solid content concentration 70% by mass, carbodiimide group equivalent 298 (solid content equivalent 209)
<Two-component curing adhesive composition>
Reference Examples 1-5, 8-9, 11, Examples 6-7, 10, 12-17 and Comparative Examples 1-7
A main agent (carboxy-containing component) and a curing agent (carbodiimide-containing component) are mixed at an equivalent ratio R (carbodiimide group/carboxy group (molar ratio)) shown in Tables 1 to 3, and then a solvent (ethyl acetate) is added. A mixture was prepared by dilution. Next, the resulting mixture was applied to Techbarrier TX as a gas barrier film (manufactured by Mitsubishi Plastics, PET film with silica vapor deposition film, 12 μm, 5.0 mL/m ² 24 hr MPa) at a coating amount of 3.3 g/ It was applied so as to be m ² (dry film thickness), and the silica deposited layers of the gas barrier film were bonded together. After that, the obtained laminate was cured at 60° C. for 3 days.

When using a plurality of polyester polyol anhydride adducts as the main agent (carboxy-containing component), the polyester polyol anhydride adducts are mixed in advance before mixing with the curing agent (carbodiimide-containing component). board.

<Evaluation>
(Hot peel strength of laminate film)
It was measured at 120° C., 15 mm width, and tensile speed of 300 mm/min according to JIS K 6854-3 (1999).

(pot life)
In each reference example, each example and each comparative example, after mixing the main agent and the curing agent, the mixed liquid was stored at 25 ° C., and the viscosity after 2 minutes (immediately) and 24 hours was measured at 25 ° C. It was measured. In addition, when the liquid mixture solidified, it was set as "impossible to measure." The results are shown in Tables 1-3.

1 laminate film 2 gas barrier film 3 adhesive layer

Claims (6)

A two-component curing adhesive composition for bonding between a plurality of gas barrier films,
a carboxy-containing component having a carboxy group;
a carbodiimide-containing component containing a carbodiimide compound;
the carboxy-containing component comprises an acid anhydride adduct of a polyester polyol;
The acid anhydride is
containing a non-carbocyclic anhydride having no cyclic hydrocarbon skeleton and a carbocyclic anhydride having a cyclic hydrocarbon skeleton ;
With respect to the total amount of the carbocyclic anhydride and the carbocyclic anhydride,
The non-carbocyclic anhydride is 45% by mass or less,
The carbocyclic anhydride is 55% by mass or more
A two-component curing adhesive composition characterized by: With respect to the total amount of the carbocyclic anhydride and the carbocyclic anhydride,
The non-carbocyclic anhydride is 10% by mass or more,
2. The two-part curable adhesive composition according to claim 1 , wherein the carbocyclic anhydride is 90% by mass or less. the non-carbocyclic anhydride comprises maleic anhydride;
3. The two-part curable adhesive composition according to claim 1 , wherein the carbocyclic anhydride contains phthalic anhydride. a plurality of gas barrier films;
A laminate film comprising an adhesive layer interposed between a plurality of said gas barrier films and being a cured product of the two-part curable adhesive composition according to any one of claims 1 to 3 . . A preparation step of preparing a plurality of gas barrier films;
and a lamination step of obtaining a laminate by laminating a plurality of gas barrier films via the two-component curing adhesive composition according to any one of claims 1 to 3 . manufacturing method. 6. The method for producing a laminated film according to claim 5 , further comprising a curing step of heating and curing the laminate after the laminating step.

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