JP2020007480A - Two-part curable adhesive composition, laminate film and method for producing the same - Google Patents

Abstract

A two-component curable adhesive composition capable of obtaining excellent heat resistance and pot life, a laminated film excellent in gas barrier properties obtained using the two-component curable adhesive composition, and a laminated film To provide a method for manufacturing the same. Furthermore, a two-part curable adhesive composition for obtaining a laminate film capable of suppressing a decrease in the degree of vacuum when used for a vacuum heat insulating material, a laminate film obtained using the two-part curable adhesive composition, And to provide a method for producing a laminated film. A two-part curable adhesive composition used for bonding a gas barrier film contains a carboxy-containing component having a carboxy group and a carbodiimide-containing component containing a carbodiimide compound, wherein the carboxy-containing component is a polyester polyol. The anhydride contains a carbon ring-free anhydride having no cyclic hydrocarbon skeleton and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton. [Selection diagram] Fig. 1

Description

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

  2. Description of the Related Art Conventionally, laminated composite films in which various substrates are bonded with a laminating adhesive have been widely used in various industrial fields such as food, medical care, home appliances, and electronic members. Further, as a laminating adhesive, for example, a two-component curable polyurethane adhesive containing a main agent composed of a polyol and a curing agent composed of an isocyanate is known.

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

  Further, it is known that a polyurethane adhesive has excellent adhesive performance because it has a functional group (urethane bond) exhibiting strong hydrogen bonding ability.

However, when a plurality of gas barrier films are bonded with a two-component curable polyurethane adhesive, the isocyanate groups (-NCO) react with the surface moisture of the gas barrier film, the moisture in the atmosphere, the moisture in the adhesive (composition liquid), and the like. sometimes with made to an amino group through a carbamate group (-NHCOOH) (-NH _2), causing the carbon dioxide (CO _2). When the carbon dioxide gas is sealed between the gas barrier films, there is a problem in that a bubble-like appearance defect is caused in the laminated composite film.

  Therefore, a gas barrier laminate composite film having excellent appearance is being studied.For example, a plurality of substrates having gas barrier properties are cured by a reaction between a compound in which an amino group is protected by a ketone group and a compound having an epoxy group. There has been proposed a gas barrier film laminate bonded using an adhesive (see, for example, Patent Document 1).

JP 2006-051751 A

  However, an adhesive which cures by the reaction of a compound (main agent) in which an amino group is protected with a ketone group (blocking agent) and a compound having an epoxy group (curing agent) has a ketone group (blocking agent) when cured. And free ketone groups (blocking agents) remain in the cured product of the adhesive.

  Therefore, when a laminate composite film using the above adhesive is used as a wrapping material for a vacuum heat insulating material, the blocking agent is gradually released in a vacuum, causing a decrease in the degree of vacuum and causing a problem that heat insulating properties are reduced. is there.

  Therefore, an adhesive that does not contain a blocking agent is required. As such an adhesive, for example, a compound having a carboxy group (for example, a maleic anhydride adduct of a polyol or a phthalic anhydride adduct of a polyol) is used. And a carbodiimide compound (for example, a carbodiimide-modified polyisocyanate).

  Such a two-part curable adhesive composition has excellent adhesive strength and further does not contain a blocking agent, so that when used as a vacuum heat insulating material, a decrease in the degree of vacuum can be suppressed.

  On the other hand, the two-component curable adhesive composition may be required to have heat resistance and a pot life after mixing the main agent and the curing agent, depending on the application. If the pot life is short, the two-component curable adhesive composition will increase in viscosity during processing, which may cause problems such as occurrence of variation in coating amount and reduction in leveling property.

  The present invention provides a two-part curable adhesive composition capable of obtaining excellent heat resistance and pot life, a laminate film excellent in gas barrier properties obtained using the two-part curable adhesive composition, and a laminate. This is a method for producing a film.

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

  The present invention [1] is a two-part 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 contains an anhydride adduct of a polyester polyol, wherein the anhydride is a carbon ring-free anhydride having no cyclic hydrocarbon skeleton and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton. Containing two-part curable adhesive composition.

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

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

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

  The present invention [5] is interposed between a plurality of gas barrier films and the plurality of gas barrier films, and cures the two-part curable adhesive composition according to any one of [1] to [4]. And an adhesive layer which is an object.

  The present invention [6] provides a plurality of gas barrier films via a preparation step of preparing a plurality of gas barrier films and the two-part curable adhesive composition according to any one of the above [1] to [4]. And a laminating step of obtaining a laminated body.

  The present invention [7] includes the method for producing a laminate film according to the above [6], further 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 has an anhydride at the terminal hydroxyl group of the polyol. The acid anhydride contains a compound to which an acid is added, and the acid anhydride contains a carbon ring-free anhydride having no cyclic hydrocarbon skeleton and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton.

  In such a two-part curable adhesive composition, gas generation can be suppressed without using a blocking agent. As described above, when the blocking agent is not used, the blocking agent is not released at the time of curing, so that no free blocking agent remains in the cured product. Therefore, when used as a vacuum heat insulating material, a decrease in the degree of vacuum can be suppressed.

  According to such a two-part curable adhesive composition, a laminate film using the two-part curable adhesive composition and a method for producing the same, excellent heat resistance derived from the carbon ring-containing anhydride is obtained. In addition, the pot life after mixing the main agent and the curing agent can be prolonged due to the carbon-ring-containing anhydride.

FIG. 1 is a schematic view 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 a carboxy-containing component having a carboxy group (in the present application, And a carbodiimide-containing component containing a carbodiimide compound (which may be referred to as a curing agent in the present application).

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

  Examples of the compound having a carboxy group include a compound having a carboxy group at a molecular terminal, and specifically include an acid anhydride adduct of a polyester polyol.

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

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

  More specifically, as the polyester polyol, for example, a low molecular weight polyol (preferably a dihydric alcohol) and a polybasic acid (preferably a dibasic acid) are mixed under known conditions with a low molecular weight polyol having a large number of hydroxyl groups. A polycondensate obtained by performing an esterification reaction at a ratio of an excess molar amount to the carboxy group of the basic acid is exemplified.

  The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more, preferably 100 or more, less than 500, and preferably less than 400, and includes, for example, ethylene glycol, propylene glycol, and 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-cyclohexanedi Methanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and its Mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol and the like. Polyhydric alcohols, for example, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, for example, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol) and diglycerin, for example, pentahydric alcohols such as xylitol, for example, sorbitol Hexahydric alcohols such as mannitol, allitol, iditol, daritol, alditol, inositol, dipentaerythritol, for example, 7-valent alcohols such as perseitol, for example, sucrose, etc. Such as polyhydric alcohols and the like, preferably dihydric alcohols, include trihydric alcohols, more preferably include 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, for example, maleic acid, fumaric acid, unsaturated aliphatic dicarboxylic acids such as itaconic acid, for example, orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, naphthalenedicarboxylic acid Aromatic dicarboxylic acids such as acids, for example, cycloaliphatic dicarboxylic acids such as hexahydrophthalic acid, for example, dimer acids, hydrogenated dimer acids, other carboxylic acids such as heptic acid, and derived from these carboxylic acids Acid anhydrides, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride 2-alkyl anhydride (C12-C18) succinic acid, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and acid halides derived from these carboxylic acids and the like, For example, oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride and the like, and, for example, acid (di) methyl ester (for example, terephthalic acid dimethyl ester and the like) can be mentioned.

  As the polyester polyol, a castor oil or a hydrogenated castor oil can be contained as a raw material in addition to the low-molecular-weight polyol and the polybasic acid.

  Further, 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 (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, and the like). And vegetable oil-based polyester polyols obtained by a condensation reaction under known conditions.

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

  Further, the polyester polyol includes a polyesteramide polyol.

  Examples of the polyesteramide polyol include, for example, a polyesteramide polyol obtained by using a low molecular weight polyamine (eg, ethylenediamine, propylenediamine, hexamethylenediamine, etc.) as a raw material in the esterification reaction of the polyesterpolyol 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 under 25 ° C. conditions, preferably 2000 mPa · s or more, and under 150 ° C. conditions, for example, 50,000 mPa · s or less, preferably 20,000 mPa · s. It is as follows.

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

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

  The anhydride contains a carbon ring-free anhydride having no cyclic hydrocarbon skeleton and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton. That is, the acid anhydride comprises a carbon ring-free anhydride and a carbon ring-containing anhydride.

  The cyclic hydrocarbon skeleton is a cyclic skeleton composed of a hydrocarbon, and specific examples thereof include an aromatic ring skeleton, a saturated alicyclic skeleton, and an unsaturated alicyclic skeleton.

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

  The number of ring members of the cyclic hydrocarbon skeleton is not particularly limited, and is, for example, a 3 to 20-membered ring, specifically, a 3-, 4-, 5-, 6-, or 8-membered ring, 10-membered rings, 12-membered rings and the like can be mentioned.

  Note that the cyclic hydrocarbon skeleton does not include an anhydride skeleton. That is, the anhydride skeleton (heterocyclic skeleton) formed by dehydrating and condensing the organic acid during the production of the anhydride is not included in the cyclic hydrocarbon skeleton.

  The carbocyclic-free anhydride is an anhydride having no cyclic hydrocarbon skeleton in the molecular structure, such as oxalic anhydride, succinic anhydride, 2-alkyl (C12 to C18) succinic anhydride, and maleic anhydride. And the like.

  These anhydrides containing no carbon ring can be used alone or in combination of two or more.

  By using an anhydride containing no carbon ring, the heat resistance of the cured product of the two-component curable adhesive composition can be improved.

  Further, from the viewpoint of improving the heat resistance, the acid containing no carbon ring preferably includes succinic anhydride and maleic anhydride, and more preferably maleic anhydride.

  The carbocycle-containing anhydride is an anhydride having one or more (preferably one) cyclic hydrocarbon skeleton in the molecular structure, and examples thereof include phthalic anhydride and tetrahydrophthalic anhydride (1,2,3,6). -Tetrahydrophthalic anhydride), trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride and the like.

  These carbon ring-containing anhydrides can be used alone or in combination of two or more.

  By using the carbon ring-containing anhydride, the pot life of the two-part curable adhesive composition can be improved.

  From the viewpoint of improving the pot life, the carbon ring-containing anhydride preferably includes phthalic anhydride and tetrahydrophthalic anhydride, and more preferably includes phthalic anhydride.

  Then, both the carbon-ring-free anhydride and the carbon-ring-containing anhydride are used in the production of an anhydride adduct of the polyester polyol. Thereby, the two-part curable adhesive composition can have both excellent heat resistance derived from a non-carbon-ring-containing anhydride and excellent pot life derived from a carbon-containing anhydride.

  More specifically, as an acid anhydride adduct of such a polyester polyol, for example, an acid adduct of a polyester polyol obtained by using a non-carbon-ring-containing anhydride and a carbon-ring-containing anhydride together (ie, polyester And dianhydride adducts of polyols).

  Hereinafter, a method for producing a bifunctional anhydride adduct of a polyester polyol will be described in detail.

  In the production of a dianhydride adduct of a polyester polyol, for example, a carbon ring-free anhydride and a carbon ring-containing anhydride (hereinafter sometimes collectively referred to as an anhydride) are simultaneously or sequentially added to a polyester polyol. And heat to react.

  In such a case, the combined ratio of the carbon-ring-free anhydride and the carbon-ring-containing anhydride is appropriately selected from the viewpoint of achieving both heat resistance and pot life.

  More specifically, the combination ratio of the carbocyclic-free anhydride and the carbocyclic-containing anhydride depends on the equivalent ratio of the base agent and the curing agent, which will be described later. For example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, more preferably 1% by mass or more, based on the total amount. 20% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, further preferably 40% by mass or more, for example, 99% by mass or less, preferably 95% by mass or less, Preferably, it is 90% by mass or less, more preferably, 85% by mass or less, further preferably, 80% by mass or less, more preferably, 70% by mass or less, further preferably, 65% by mass or less. More preferably 60 mass% or less.

  In addition, the carbon ring-containing anhydride is, for example, 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total amount of the carbon ring-free anhydride and the carbon ring-containing anhydride. More preferably, it is 15% by mass or more, further preferably, 20% by mass or more, further preferably, 30% by mass or more, further preferably, 35% by mass or more, more preferably 40% by mass or more. 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, further preferably 70% by mass or less, It is preferably at most 65% by mass, more preferably at most 60% by mass.

  If the proportion of the carbocyclic-free anhydride exceeds the above lower limit and the proportion of the carbocyclic-containing anhydride is below the above upper limit, excellent heat resistance derived from the carbocyclic-free anhydride can be better obtained. Can be.

  In addition, if the proportion of the carbocyclic-free anhydride is below the upper limit and the proportion of the carbocyclic anhydride is above the lower limit, an excellent pot life derived from the carbocyclic anhydride is more preferably obtained. be able to.

  In addition, from the viewpoint of improving heat resistance, the amount of the anhydride containing no carbon ring is adjusted to be greater than that of the anhydride containing a carbon ring. Specifically, based on the total amount of the carbocyclic-free anhydride and the carbocyclic-containing anhydride, the amount of the carbocyclic-free anhydride exceeds, for example, 50% by mass, preferably 55% by mass or more, more preferably Is 60% by mass or more, for example, 70% by mass or less, preferably 65% by mass or less.

  Further, the amount of the carbon ring-containing anhydride is, for example, 30% by mass or more, preferably 35% by mass or more, and for example, less than 50% by mass, based on the total amount of the non-carbon ring-containing anhydride and the carbon ring-containing anhydride. , Preferably 45% by mass or less, more preferably 40% by mass or less.

  On the other hand, particularly from the viewpoint of improving the pot life, the amount of the anhydride containing no carbon ring is adjusted to be smaller than that of the anhydride containing a carbon ring. Specifically, the amount of the carbocyclic-free anhydride is, for example, 30% by mass or more, preferably 35% by mass or more, based on the total amount of the carbocyclic-free anhydride and the carbocyclic-containing anhydride. It is less than 50% by mass, preferably 45% by mass or less, more preferably 40% by mass or less.

  Further, the amount of the carbon ring-containing anhydride exceeds, for example, 50% by mass, preferably 55% by mass or more, and more preferably 60% by mass, based on the total amount of the non-carbon-ring-containing anhydride and the carbocyclic-containing anhydride. %, For example, 70% by mass or less, preferably 65% by mass or less.

  These carbon-ring-free anhydrides and carbon-ring-containing anhydrides may be mixed in advance and used, or may be used simultaneously or sequentially without being mixed.

  Preferably, the anhydride containing no carbon ring and the anhydride containing carbon ring are mixed in advance and used as an acid anhydride composition.

  In addition, in the blending of the acid anhydride with the polyester polyol, the acid anhydride group (total amount) of the acid anhydride and the hydroxyl group of the polyester polyol may be equivalent, one of them may be excessive, and the other may be insufficient. It may be.

  More specifically, for example, the number of acid anhydride groups (total amount) in the acid anhydride is, for example, 0.3 or more, preferably 0.5 or more, more preferably 0 to 1 mol of the hydroxyl group of the polyester polyol. It is at least 0.7 mol, for example, at most 3, preferably at most 2 mol, more preferably at most 1.5 mol.

  When the mixing ratio of the anhydride is in 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, for example, 200 ° C. or lower, preferably 180 ° C. or lower.

  The reaction time is, for example, 60 minutes or more, preferably 120 minutes or more, and for example, 600 minutes or less, preferably 300 minutes or less.

  In the above reaction, when the ratio of the acid anhydride group (total amount) is less than 1 mol per 1 mol of the hydroxyl group of the polyester polyol (that is, the ratio of the acid anhydride deficiency), a part of the hydroxyl groups of the polyol is acid-modified. The remaining hydroxyl groups remain without acid modification.

  When the amount of the anhydride group (total amount) exceeds 1 mole per 1 mole of the hydroxyl group of the polyester polyol (that is, the excess amount of the anhydride), the anhydride adduct of the polyester polyol is converted into the unreacted anhydride group. Is obtained as a composition containing

  In addition, the above reaction may be performed in the absence of a solvent or in the presence of an organic solvent blended as necessary. Preferably, the polyester polyol and the acid anhydride are reacted without solvent.

  As the organic solvent, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, nitriles such as acetonitrile, methyl acetate, ethyl acetate, butyl acetate, alkyl esters such as isobutyl acetate, for example, n- Aliphatic hydrocarbons such as hexane, n-heptane and octane, for example, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, for example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, for example, 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- Glycol ether esters such as -methoxybutyl acetate and ethyl-3-ethoxypropionate; for example, ethers such as diethyl ether, tetrahydrofuran and dioxane; for example, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide And halogenated aliphatic hydrocarbons such as methylene iodide and dichloroethane, and polar aprotons such as N-methylpyrrolidone, dimethylformamide, N, N'-dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide and the like. No.

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

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

  Thereby, a carbon-ring-free anhydride and a carbon-ring-containing anhydride can be added to the polyester polyol, and a bi-anhydride adduct of the polyester polyol can be obtained. That is, an anhydride adduct of the polyester polyol can be obtained as a double anhydride adduct of the polyester polyol.

  And the carboxy-containing component (base agent) can contain both anhydride adducts of the polyester polyol.

  In addition, as the acid anhydride adduct of the polyester polyol, in addition to the both acid anhydride adduct of the polyester polyol, for example, an acid adduct of a polyester polyol obtained by using a carbon ring-free acid anhydride alone (that is, A polyester polyol having no carbon ring-containing acid anhydride) and an acid adduct of polyester polyol obtained by using the carbon ring-containing anhydride alone (that is, a carbon ring-containing acid anhydride adduct of polyester polyol). You can also.

  The carbon-ring-free anhydride adduct of the polyester polyol can be obtained by using only the carbon-ring-free anhydride alone in the above-mentioned method.

  The reaction conditions are the same as described above, and if necessary, the concentration of the carbocyclic-free anhydride-added product of the polyester polyol can be adjusted by the above-described method.

  Further, the carbocycle-containing anhydride adduct of the polyester polyol can be obtained by using only the carbocycle-containing anhydride alone in the method described above.

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

  Then, in this method, a carbocycle-free anhydride adduct of the polyester polyol and a carbocycle-containing anhydride adduct of the polyester polyol are used in combination.

  More specifically, the carboxy-containing component (base agent) contains both a carbon-ring-free anhydride adduct of a polyester polyol and a carbon-ring-containing anhydride adduct of a polyester polyol.

  In this case, when used in combination, a carbocycle-free anhydride adduct of the polyester polyol and a carbocycle-containing anhydride adduct of the polyester polyol are mixed in advance, and the anhydride adduct of the polyester polyol is mixed with the polyester polyol. Can be obtained as a mixture of a carbon-ring-free anhydride adduct of a polyester polyol and a carbon-ring-containing anhydride adduct of a polyester polyol. The non-ring-containing anhydride adduct and the carbon-ring-containing anhydride adduct of the polyester polyol can be mixed together with the carbodiimide-containing component (curing agent) without previously mixing with each other.

  Further, the combination ratio of the carbon-ring-free anhydride adduct of the polyester polyol and the carbon-ring-containing anhydride of the polyester polyol is the combination ratio of the above-described carbon-ring-free anhydride and the carbon-ring-containing anhydride. Is the same.

  That is, the combined ratio of the carbocycle-free anhydride adduct of the polyester polyol and the carbocycle-containing anhydride adduct of the polyester polyol depends on the equivalent ratio of the base agent and the curing agent, which will be described later. Based on the total amount of the acid anhydride adduct and the carbocycle-containing anhydride adduct of the polyester polyol, the carbocycle-free anhydride adduct of the polyester polyol is, for example, 1% by mass or more, preferably 5% by mass or more, Preferably, it is at least 10% by mass, more preferably at least 15% by mass, further preferably at least 20% by mass, further preferably at least 30% by mass, further preferably at least 35% by mass, further preferably at least 40% by mass. %, For example, 99% by mass or less, preferably 95% by mass or less, more preferably 90% by mass. % Or less, more preferably 85 wt% or less, more preferably 80 wt% or less, more preferably 70 wt% or less, more preferably, 65 mass% or less, more preferably 60 mass% or less.

  Further, based on the total amount of the carbocyclic-free anhydride adduct of the polyester polyol and the carbocycle-containing anhydride of the polyester polyol, the carbocycle-containing anhydride of the polyester polyol is, for example, 1% by mass or more, preferably Is at least 5% by mass, more preferably at least 10% by mass, still more preferably at least 15% by mass, further preferably at least 20% by mass, further preferably at least 30% by mass, further preferably at least 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, further preferably 65% by mass or less, more preferably Is 0 mass% or less.

  From the viewpoint of improving the heat resistance, in particular, the amount is adjusted such that the carbon-ring-free anhydride adduct of the polyester polyol is larger than the carbon-ring-containing anhydride adduct of the polyester polyol. Specifically, based on the total amount of the carbocyclic-free anhydride adduct of the polyester polyol and the carbocycle-containing anhydride of the polyester polyol, the carbocyclic-free anhydride adduct of the polyester polyol is, for example, 50% by 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, based on the total amount of the carbon-ring-free acid anhydride of the polyester polyol and the carbon-ring-containing anhydride of the polyester polyol, the carbon-ring-containing anhydride of the polyester polyol is, for example, preferably at least 30% by mass, more preferably 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, particularly from the viewpoint of improving the pot life, the amount is adjusted so that the carbon ring-free anhydride adduct of the polyester polyol is smaller than the carbon ring-containing anhydride adduct of the polyester polyol. Specifically, based on the total amount of the carbocyclic-free anhydride adduct of the polyester polyol and the carbocyclic anhydride anhydride of the polyester polyol, the carbocyclic-free anhydride adduct of the polyester polyol is, for example, 30% by mass. %, Preferably 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.

  In addition, the carbon-ring-containing anhydride adduct of the polyester polyol exceeds 50% by mass, for example, based on the total amount of the carbon-ring-free anhydride adduct of the polyester polyol and the carbon-ring-containing anhydride adduct of the polyester polyol. Preferably, it is 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 above-mentioned ratio is used in combination with the carbocyclic-free anhydride adduct of the polyester polyol and the carbocyclic-containing anhydride adduct of the polyester polyol, the combined ratio of the carbocyclic-free anhydride and the carbocyclic-containing anhydride is in the above range. And it is possible to achieve both heat resistance and pot life.

  Examples of the acid anhydride adducts of polyester polyols include, for example, both acid anhydride adducts of polyester polyols and carbon ring-free acid anhydride adducts of polyester polyols and / or carbon ring-containing acid adducts of polyester polyols. Can also be used in combination.

  Even in such a case, the ratio of the bicarboxylic acid anhydride adduct of the polyester polyol to the carbocycle-free anhydride adduct of the polyester polyol and / or the carbocycle-containing anhydride adduct of the polyester polyol is such that It is appropriately adjusted so that the combined ratio of the non-containing anhydride and the carbon ring-containing anhydride is within the above range.

  As the acid anhydride adduct of the polyester polyol, preferably, a combination of a carbon ring-free anhydride adduct of the polyester polyol and a carbon ring-containing anhydride adduct of the polyester polyol is used.

  The number average molecular weight (molecular weight in terms of polystyrene by GPC) Mn of the anhydride adduct of the polyester polyol is, for example, 2,000 or more, preferably 3,000 or more, for example, 20,000 or less, preferably 10,000 or less.

  If necessary, the carboxy-containing component (main component) may contain the additives described below as long as it contains the above-mentioned acid anhydride adduct of the polyester polyol, and may be diluted with the above-mentioned organic solvent. It may be.

  The content ratio of the acid adduct of the polyester polyol to the total amount of the carboxy-containing component (main component) is, for example, 50% by mass or more, preferably 80% by mass or more, for example, 100% by mass or less, preferably 100% by mass or less. , 99% by mass or less.

  Further, the solid 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, for example, 100% by mass or less, preferably, 90 mass% or less, more preferably 80 mass% or less.

  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, it is 100 mgKOH / g or less, preferably 70 mgKOH / g or less, more preferably 50 mgKOH / g or less.

  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.

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

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

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

  Examples of the aliphatic polyisocyanate include linear (linear or branched: acyclic) aliphatic polyisocyanates, and specifically, for example, 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), chain aliphatic diisocyanates such as 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caprate, dodecamethylene diisocyanate, and the like. It is.

  In addition, examples of the aliphatic polyisocyanate include alicyclic polyisocyanate.

  Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, and 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate; IPDI), 4,4′-, 2,4′- or 2,2′-dicyclohexylmethane diisocyanate or a mixture thereof (hydrogenated MDI), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, Examples thereof include 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof (hydrogenated XDI), and an alicyclic diisocyanate such as norbornane diisocyanate (NBDI).

  Examples of the aromatic polyisocyanate include m- or p-phenylene diisocyanate or a mixture thereof, 2,4- or 2,6-tolylene diisocyanate or a mixture thereof (TDI), 4,4′-, 2,4′- Or 2,2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalenediisocyanate (NDI ) And the like.

  Examples of the araliphatic polyisocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof (TMXDI), and araliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene.

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

  As the polyisocyanate, preferably, a chain aliphatic polyisocyanate and an araliphatic polyisocyanate are used.

  The carbodiimidization catalyst is not particularly limited, and examples thereof include a trialkyl phosphate ester compound, a phosphorene oxide compound, a phosphorene sulfide compound, a phosphine oxide compound, and a phosphine compound.

  Examples of the trialkyl phosphate include a trialkyl phosphate ester-based compound having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate, and trioctyl phosphate.

  Examples of the phospholene oxide-based compound include 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO), 1-ethyl-3-methyl-2-phospholene-1-oxide (EMPO), , 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 a phosphorene oxide compound having 4 to 18 carbon atoms, such as a double bond isomer.

  Examples of the phosphorene sulfide-based compound include a phosphorene sulfide-based compound having 4 to 18 carbon atoms such as 1-phenyl-2-phospholene-1-sulfide.

  Examples of the phosphine oxide compound include a phosphine oxide compound having 3 to 21 carbon atoms such as triphenylphosphine oxide and tolylphosphine oxide.

  Examples of the phosphine-based compound include a phosphine-based compound having 3 to 30 carbon atoms, such as bis (oxadiphenylphosphino) ethane.

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

  The mixing ratio of the carbodiimidization catalyst is not particularly limited, and is appropriately set according to the purpose and use.

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

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

  In the carbodiimidization reaction, if necessary, the above-described organic solvent can be blended.After the reaction is completed, if necessary, by a known method such as a distillation method or an extraction method, unreacted polyisocyanate or In addition, all or a part of the organic solvent can be removed. After the reaction is completed, the concentration of the solution of the carbodiimide compound can be adjusted by adding the above organic solvent.

  Further, before the carbodiimidization reaction, the polyisocyanate can be alcohol-modified with a known alcohol (eg, polyoxyethylene monomethyl ether, 1-methoxy-2-propanol). In the alcohol modification, for example, the urethanization reaction is performed at a ratio of an equivalent of the hydroxyl group of the alcohol to the isocyanate group of the polyisocyanate (OH / NCO) of less than 1. Further, if necessary, the above-mentioned organic solvent and a known urethanization catalyst can be blended.After the reaction is completed, if necessary, unreacted polyisocyanate is obtained by a known method such as a distillation method or an extraction method. Alternatively, all or a part of the organic solvent can be removed.

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

  Further, 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, for example, carbodilite V05S (solid content concentration 90% by mass, carbodiimide group equivalent 291 (solid equivalent 262), manufactured by Nisshinbo Industries, Inc.), carbodilite V07 (solid 50% by mass, carbodiimide group equivalent 404 (solid equivalent 202), Nisshinbo Industries, Ltd.), carbodilite V09GB (solids concentration 70% by mass, carbodiimide group equivalent 298 (solids equivalent 209), Nisshinbo Industries, Ltd.) ).

  The carbodiimide-containing component (curing agent) may contain the carbodiimide compound alone, or may contain two or more carbodiimide compounds. Further, additives described below can be contained.

  The content ratio 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 based on the total amount of the carbodiimide-containing component (curing agent). It is as follows.

  In addition, the two-part curable adhesive composition may contain, if necessary, one or both of a carboxy-containing component (main component) and a carbodiimide-containing component (curing agent), for example, phosphoric acid or Its derivatives, silane coupling agents, furthermore, epoxy resins, catalysts, coatability improvers, leveling agents, defoamers, stabilizers such as antioxidants and ultraviolet absorbers, plasticizers, surfactants, pigments, Additives such as fillers, organic or inorganic fine particles, and fungicides can be appropriately compounded. The amount of the additive is appropriately determined depending on the purpose and use.

  Then, such a two-part curable adhesive composition, when used, has a carboxy-containing component as a main component and a carbodiimide-containing component as a curing agent, blends them to prepare a mixed solution, and mixes if necessary. The liquid is diluted with an organic solvent and applied to a substrate (adherend).

  The mixing ratio of the carboxy-containing component (main component) and the carbodiimide-containing component (curing agent) (hereinafter, sometimes referred to as an equivalent ratio) is, for example, a carboxy group in the carboxy-containing component (a 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 mol per mol. It is at least 0.93 mol, for example, at most 5.0 mol, preferably at most 4.5 mol, more preferably at most 4.0 mol.

  When the mixing ratio (equivalent ratio) of the carboxy-containing component (main component) and the carbodiimide-containing component (curing agent) is within the above range, the two-part curable adhesive composition has excellent adhesiveness, and the obtained laminate is excellent. Appearance and excellent adhesiveness.

  When the equivalent ratio is relatively high (1.3 or more, preferably 2.0 or more), the two-part curable adhesive composition can obtain excellent heat resistance. That is, in such a case, excellent heat resistance can be obtained even when the amount of carbon-ring-free anhydride that ensures heat resistance is relatively small.

  Therefore, when the equivalent ratio is relatively high, the carbocyclic-free anhydride can be adjusted to be less than the carbocyclic-containing anhydride.Specifically, the carbocyclic-free 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. Even in such a case, excellent heat resistance and pot life can be obtained.

  Then, such a two-part curable 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 curable adhesive composition, since the carboxy group of the carboxy-containing component and the carbodiimide group of the carbodiimide-containing component undergo an acylurea reaction, they do not generate carbon dioxide gas at the time of curing. Even after a lapse of time after (adhesion), since the possibility of carbon dioxide gas generation due to moisture in the atmosphere is extremely low, it is possible to suppress the generation of bubbles between the films of the laminate film, and to provide an excellent appearance. Can be obtained.

  In particular, in the case of a laminated film in which the base film has gas barrier properties, when gas is generated in the adhesive layer, the escape area of the gas is limited, which may lead to a fatal appearance defect. On the other hand, the two-part curable adhesive composition of the present invention is suitable for lamination of a gas barrier film because it hardly generates gas over time.

  In addition, this two-part curable adhesive composition contains an acylurea group exhibiting strong hydrogen bonding ability as well as a urethane bond, and thus exhibits excellent adhesive performance.

  Further, in such a two-part curable adhesive composition, the carboxy-containing component contains a compound in which an anhydride is added to a terminal hydroxyl group of a polyol, and the anhydride contains no carbon ring having no cyclic hydrocarbon skeleton. It contains an anhydride and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton.

  In such a two-part curable adhesive composition, gas generation can be suppressed without using a blocking agent. As described above, when the blocking agent is not used, the blocking agent is not released at the time of curing, so that no free blocking agent remains in the cured product. Therefore, when used as a vacuum heat insulating material, a decrease in the degree of vacuum can be suppressed.

  According to such a two-part curable adhesive composition, a laminate film using the two-part curable adhesive composition and a method for producing the same, excellent heat resistance derived from the carbon ring-containing anhydride is obtained. In addition, the pot life after mixing the main agent and the curing agent can be prolonged due to the carbon-ring-containing anhydride.

  Hereinafter, a gas barrier laminate film (laminate) obtained by using the two-part curable adhesive composition and a method for producing the laminate film will be described in detail.

  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 It is defined as the following film ^{50mL / m 2 · 24hr · MPa} .

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

  Specific examples of the gas barrier film 2 include a metal foil (for example, an aluminum foil). Further, for example, a plastic film provided with a metal film (eg, an aluminum film), a plastic film provided with a metal vapor-deposited film (eg, an aluminum vapor-deposited film, a silica vapor-deposited film, an alumina vapor-deposited film, a silica / alumina binary vapor-deposited film), and the like are also included. Can be Examples of the plastic film include a polyethylene terephthalate (PET) film, a nylon (NY) film, a cellulose acetate (TAC) film, an ethylene-vinyl alcohol copolymer (EVOH) film, and the like, preferably a PET film. , A cellulose acetate (TAC) film and an ethylene-vinyl alcohol copolymer (EVOH) film. In addition, the thickness of the metal film, the thickness of the metal deposition film, and the thickness of the plastic film are not particularly limited, and are appropriately set according to the purpose and use.

  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 vapor-deposited film, a plastic film provided with a silica-deposited film, a plastic film provided with an alumina-deposited film, and a plastic film provided with a silica-alumina binary vapor-deposited film are given. Further, as a plastic film provided with such a metal vapor-deposited film, preferably, a PET film, a cellulose acetate (TAC) film, and an ethylene-vinyl alcohol copolymer (EVOH) film are used.

  More preferably, the gas barrier film 2 includes a PET film having an aluminum evaporated film, a PET film having a silica evaporated film, a PET film having an alumina evaporated film, and a PET film having a silica-alumina binary evaporated film.

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

  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. 4 may be provided with an overcoat layer on the other surface with respect to one surface.

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

  The adhesive layer 3 is a cured product of the two-part curable adhesive composition described above, and is laminated between a plurality (two) of 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 bonded with the two-component curable adhesive composition.

  In the production of the laminated film 1, for example, a plurality of (two) gas barrier films 2 can be bonded via the adhesive layer 3 such that the metal deposition films 4 face each other.

  Further, for example, a plurality of (two) gas barrier films 2 can be bonded together 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 via the adhesive layer 3 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. It can be attached.

  Preferably, as shown in FIG. 1, a plurality (two) of gas barrier films 2 are bonded via an adhesive layer 3 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 or more, for example, 10 μm or less, preferably 5 μm or less.

  Although FIG. 1 shows a laminated film 1 in which two gas barrier films 2 are bonded together, the number of gas barrier films 2 is not limited to the above, and three or more gas barrier films 2 may be formed by the above-described method. Can also be attached.

  Further, the laminate film 1 can be provided with a heat seal layer 6 on one or both sides thereof, as shown by a broken line in FIG.

  The heat seal layer 6 is a layer that imparts heat sealability to the laminate film 1 and includes, for example, a thermoplastic polyolefin film such as a polyethylene film and an unstretched polypropylene film.

  The thickness of the heat seal layer 6 is, for example, 10 μm or more, preferably 20 μm or more, 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 surface with respect to the one surface on which the adhesive layer 3 is formed) via the heat seal adhesive layer 7.

  The heat seal adhesive layer 7 may be, for example, a cured product of the above-described two-component curable adhesive composition, or a cured product of another known adhesive (such as a polyurethane adhesive). Is also good.

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

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

  In order to manufacture such a laminated 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 bonded via the two-part curable adhesive composition to obtain a laminate (lamination step).

  Specifically, in the laminating step, for example, after diluting and blending the carboxy-containing component and the carbodiimide-containing component with the above organic solvent, the resulting mixture is applied to each gas barrier film surface by a solvent type laminator, After volatilizing, the coated surfaces are bonded together, and then cured and cured at room temperature or under heating, or the compounding viscosity of the carboxy-containing component and the carbodiimide-containing component is from room temperature to 100 ° C., for example, In the case of about 100 to 10000 mPa · s, preferably about 100 to 5000 mPa · s, for example, after blending the carboxy-containing component and the carbodiimide-containing component as they are, the obtained mixture is mixed with each gas barrier film using a solventless laminator. Applying to the surface and bonding the applied surface It is.

The amount of the two-component curable adhesive composition to be applied is, for example, in the case of a solvent type, the basis weight (solid content) after volatilization of the solvent, 2.0 to 8.0 g / m ² , and a solvent-free type if, it is a 1.0~4.0g / ^{m 2.}

  As a result, the carboxy group in the carboxy-containing component and the carbodiimide group in the carbodiimide-containing component undergo an acylurea reaction, and the two-part curable adhesive composition is cured. As a result, a laminate film 1 is obtained as a laminate of the gas barrier film 2.

  In this method, the obtained laminate is cured by heating as needed (curing step).

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

  The curing time is, for example, 24 hours or more, preferably 48 hours or more, for example, 240 hours or less, preferably 120 hours or less.

  Thereby, the adhesiveness between the gas barrier films 2 can be improved.

  Further, if necessary, the heat seal layer 6 can be bonded to the surface of the gas barrier film 2 via the heat seal adhesive layer 7 in the same manner as in the above laminating step (see the broken line in FIG. 1). Thereby, the heat sealing property can be provided to the laminated film 1.

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

  In the present invention, components other than the above-mentioned main agent and curing agent (sometimes referred to as other components) may be contained within a range not to impair the purpose and effect thereof. The content of the other components is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less, based on the total amount of the adhesive composition.

  Next, the present invention will be described based on Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. Note that “parts” and “%” are based on mass unless otherwise specified. Specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the mixing ratios (corresponding to them) described in the above-mentioned “Embodiments of the Invention”. Substitute the upper limit value (value defined as “less than” or “less than”) or the lower limit value (value defined as “over” or “exceed”) such as content ratio, physical property value, and parameter be able to.

  Various measurement methods are described below.

<Acid value (solid content)>
An appropriate amount of the sample is weighed, dissolved in a mixed solvent of toluene / methanol = 7/3 (weight ratio), a few drops of a phenolphthalein indicator is added, and titrated 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 equation.

Carboxy group equivalent = 56100 / acid value <terminal hydroxyl group amount>
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 by stirring at room temperature for 30 minutes. Acetic anhydride was added to. Next, after diluting with 50 mL of pyridine, excess acid was back titrated with a 1 mol / L aqueous sodium hydroxide solution to determine an acetyl value (mgKOH / g). From the result (value) and the acid value separately measured, the amount of terminal hydroxyl group (hydroxyl value) was determined by the following formula.

Hydroxyl value = acetyl value + acid value <Main agent (carboxy-containing component)>
Production Example 1 (Preparation of acid 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 each charged into a reaction vessel, 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 further continued. Thus, a polyester polyol was produced.

  Thereafter, when the viscosity at 150 ° C. becomes 9640 mPa · s (measured by a cone-plate viscometer; in accordance with JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent (1 mol of acid anhydride group: 1 mol of hydroxyl group), and maleic anhydride was added thereto, followed by stirring at 150 ° C. for 90 minutes to add to the hydroxyl group. As a result, a carbon-ring-free anhydride adduct of the polyester polyol was obtained.

  Thereafter, 1100 g of ethyl acetate was added to dissolve the carbon ring-free anhydride adduct of the polyester polyol. Thereby, the acid anhydride adduct A was obtained at 60% by mass.

  The acid value (solid content) of the anhydride adduct A was 10.8 mgKOH / g, and the carboxy group equivalent (solid content) was 3117.

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

  Thereafter, when the viscosity at 150 ° C. becomes 9640 mPa · s, the amount of terminal hydroxyl groups is determined by titration, and phthalic anhydride is added to give an equivalent equivalent (1 mol of anhydride group: 1 mol of hydroxyl group) to 150 equivalents. The mixture was stirred at 90 ° C for 90 minutes to be added to a hydroxyl group. As a result, a carbon polyol-containing acid anhydride adduct of the polyester polyol was obtained.

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

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

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

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

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

  The acid value (solid content) of the acid anhydride adduct C was 11.0 mgKOH / g, and the carboxy group equivalent (solid content) was 3060.

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

  Thereafter, when the viscosity at 150 ° C. became 9640 mPa · s, the amount of terminal hydroxyl groups was determined by titration, and succinic anhydride was added to give an equivalent equivalent (1 mol of an acid group: 1 mol of a hydroxyl group). The mixture was stirred at 90 ° C for 90 minutes to be added to a hydroxyl group. As a result, a carbon-ring-free anhydride adduct of the polyester polyol was obtained.

  Thereafter, 1100 g of ethyl acetate was added to dissolve the carbon ring-free anhydride adduct of the polyester polyol. Thus, an acid anhydride 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 3170.

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

  Thereafter, when the viscosity at 150 ° C. became 9640 mPa · s, the amount of terminal hydroxyl groups was determined by titration, and maleic anhydride and phthalic anhydride were adjusted so as to have an equivalent equivalent (1 mol of acid anhydride: 1 mol of hydroxyl). (Maleic anhydride: phthalic anhydride = 50: 50 (mass ratio)), and the mixture was stirred at 150 ° C. for 90 minutes to be added to a hydroxyl group. Thus, an adduct of both anhydrides of the polyester polyol was obtained.

  Thereafter, 1100 g of ethyl acetate was added to dissolve both anhydrides of the polyester polyol. Thus, an acid anhydride adduct E was obtained as a 60% by 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 2902.

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

  Thereafter, when the viscosity at 150 ° C. became 9640 mPa · s, the amount of terminal hydroxyl groups was determined by titration, and maleic anhydride and phthalic anhydride were adjusted so as to have an equivalent equivalent (1 mol of acid anhydride: 1 mol of hydroxyl). (Maleic anhydride: tetrahydrophthalic anhydride = 50: 50 (mass ratio)), and the mixture was stirred at 150 ° C. for 90 minutes to be added to a hydroxyl group. Thus, an adduct of both anhydrides of the polyester polyol was obtained.

  Thereafter, 1100 g of ethyl acetate was added to dissolve both anhydrides of the polyester polyol. Thus, an acid anhydride adduct E was obtained as a 60% by mass solution.

  The acid value (solid content) of the acid anhydride adduct F was 12.3 mgKOH / g, and the carboxy group equivalent (solid content) was 2737.

<Curing agent (carbodiimide-containing component)>
The following products were used as the curing agent A.
Curing agent A: Carbodilite V09GB manufactured by Nisshinbo Co. (solid content concentration 70% by mass, carbodiimide group equivalent 298 (solid equivalent 209)
<Two-component curable adhesive composition>
Examples 1 to 17 and Comparative Examples 1 to 7
The main agent (carboxy-containing component) and the 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 further mixed with a solvent (ethyl acetate). After dilution, a mixture was prepared. Then, the resulting mixture, Tech barrier TX as a gas barrier film (Mitsubishi Plastics, Inc., PET film with silica-deposited ^{film, 12μm, 5.0mL / m 2 ·} 24hr · MPa) in coating amount 3.3 g / m ² (dry film thickness), and the silica vapor-deposited layers of the gas barrier film were bonded together. Thereafter, the obtained laminate was cured at 60 ° C. for 3 days.

  When an acid adduct of a plurality of polyester polyols is used as the main agent (carboxy-containing component), the acid adduct of the polyester polyol is mixed in advance before mixing with the curing agent (carbodiimide-containing component). Was.

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

(Pot life)
In each of Examples and Comparative Examples, after mixing the main agent and the curing agent, the mixed solution was stored at 25 ° C., and the viscosities after 2 minutes (immediately) and after 24 hours were measured at 25 ° C. In addition, when the liquid mixture was solidified, it was set as "measurable". The results are shown in Tables 1 to 3.

1 Laminated film 2 Gas barrier film 3 Adhesive layer

Claims (7)

A two-part curable 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 contains an anhydride adduct of a polyester polyol,
The anhydride is
A two-part curable adhesive composition comprising: a carbon ring-free anhydride having no cyclic hydrocarbon skeleton; and a carbon ring-containing anhydride having a cyclic hydrocarbon skeleton. With respect to the total amount of the carbon ring-free anhydride and the carbon ring-containing anhydride,
The carbocyclic-free anhydride is 65% by mass or less;
2. The two-part curable adhesive composition according to claim 1, wherein the amount of the carbon ring-containing anhydride is 35% by mass or more. With respect to the total amount of the carbon ring-free anhydride and the carbon ring-containing anhydride,
The carbocyclic-free anhydride is 10% by mass or more;
3. The two-part curable adhesive composition according to claim 1, wherein the carbon ring-containing anhydride is 90% by mass or less. 4. The carbocyclic-free anhydride comprises maleic anhydride,
The two-part curable adhesive composition according to any one of claims 1 to 3, wherein the carbon ring-containing anhydride contains phthalic anhydride. A plurality of gas barrier films,
A laminate film interposed between a plurality of the gas barrier films and comprising an adhesive layer that is a cured product of the two-component curable adhesive composition according to any one of claims 1 to 4. . A preparation step of preparing a plurality of gas barrier films,
A laminating step of laminating a plurality of gas barrier films via the two-part curable adhesive composition according to any one of claims 1 to 4 to obtain a laminate. Manufacturing method. The method for producing a laminated film according to claim 6, further comprising a curing step of heating and curing the laminate after the laminating step.

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