TW201835277A - Two-component curable adhesive composition, laminate film, and method for producing laminate film - Google Patents

Abstract

Provided is a two-component curable adhesive composition used to adhere a gas barrier film, the composition containing: a carboxy-containing component having a carboxy group; and a carbodiimide-containing component which contains a carbodiimide compound.

Description

 Two-liquid hardening type adhesive composition, laminated film and manufacturing method thereof  

The present invention relates to a two-liquid curing type adhesive composition, a laminated film, and a method for producing the same, and more particularly to a two-liquid curing type adhesive composition, a laminated film using the two-liquid curing type adhesive composition, And a method of manufacturing a laminated film.

It is widely used in various industrial fields such as foods, medical care, home appliances, and electronic components, for example, a laminated composite film in which various substrates are bonded by a laminating adhesive. Further, for the laminating adhesive, a two-liquid-curing polyurethane adhesive containing a main component composed of a polyhydric alcohol and a curing agent composed of an isocyanate is known.

The base material of the laminated composite film is appropriately selected in accordance with the use. For example, in the case of a vacuum insulation material in which a core material is vacuum-packed, when a packaging material is selected as a gas barrier film having a gas barrier property and a high gas barrier property is required, a laminated composite film laminated with a plurality of gas barrier films is used.

Further, it is known that since the polyurethane adhesive has a functional group (amine ester bond) having a strong hydrogen bond energy, it exhibits excellent adhesion properties.

However, when a plurality of gas barrier films are followed by a two-liquid curing type polyurethane adhesive, the surface moisture of the isocyanate group (-NCO) and the gas barrier film, the moisture in the atmosphere, and the binder (blending liquid) may be present. A reaction occurs in which water or the like reacts to form an amine group (-NH ₂ ) via an aminocarboxylic acid group (-NHCOOH), and a carbonic acid gas (CO ₂ ) is formed. On the other hand, if the carbon dioxide gas is sealed between the gas barrier films, there is a problem that the laminated composite film is inferior in bubble appearance.

Therefore, a gas barrier laminated composite film excellent in appearance is examined. For example, a gas barrier laminate is proposed, and a plurality of substrates having gas barrier properties are used, and a compound which protects an amine group by a ketone group and a ring are used. The compound of the oxy group is reacted, and the hardened adhesive is carried out (for example, refer to Patent Document 1).

 [Previous Technical Literature]    [Patent Literature]  

Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-051751

However, with a compound which is protected by a ketone group (blocker) and which is hardened by reaction with an epoxy group-containing compound, the ketone group (blocker) is deblocked from the amine group upon hardening. This causes a free ketone group (blocker) to remain in the hardened substance of the adhesive.

Therefore, when a laminated composite film using the above-mentioned adhesive is used, and a packaging material which is a vacuum heat insulating material is used, the blocking agent is gradually released in a vacuum, and the degree of vacuum is lowered, which may cause a problem that the heat insulating property is lowered.

An object of the present invention is to provide a two-liquid-curing adhesive composition having excellent appearance and excellent adhesion, a laminated film having excellent gas barrier properties obtained by using the two-liquid-curable adhesive composition, and a laminated film. Production method. Further, an object of the present invention is to provide a two-liquid-curing adhesive composition for obtaining a laminated film capable of suppressing a decrease in vacuum when used in a vacuum heat insulating material, and obtaining the composition using the two-liquid curing type adhesive A laminated film and a method of producing a laminated film.

The present invention [1] comprises a two-liquid hardening type adhesive composition which is a two-liquid hardening type adhesive composition which is followed by a plurality of gas barrier films, comprising: a carboxyl group-containing carboxyl group; and a carbon dioxide A carbon-containing diimine component of an imine compound.

The two-liquid-curing adhesive composition according to the above [1], wherein the carboxyl group-containing component contains an acid anhydride adduct of a polyester polyol.

The two-liquid-curing adhesive composition according to the above [2], wherein the acid anhydride group in the acid anhydride is 0.7 mol or more with respect to the hydroxyl group of the polyester polyol. proportion.

The two-liquid-curing adhesive composition according to any one of the above-mentioned [1], wherein the carbon-containing two is the same as the carboxyl group in the carboxyl-containing component. The carbodiimide group in the quinone imine component contains a ratio of 1.3 mol or more and 4 mol or less.

The present invention [5] includes a laminated film comprising: a plurality of gas barrier films and an adhesive layer; the adhesive layer is interposed between the plurality of gas barrier films, and is the above [1] to [4] A cured product of a two-liquid-curing adhesive composition as described.

The present invention [6] includes a method for producing a laminated film, comprising: a preparation step of preparing a plurality of gas barrier films; and the two-liquid curing type adhesive agent according to any one of the above [1] to [4] The composition is a lamination step in which a plurality of gas barrier films are bonded to each other to obtain a laminate.

The method of producing a laminated film according to the above [6], wherein after the laminating step, a aging step of heating and aging the layered body is included.

The two-liquid-curing adhesive composition of the present invention contains a carboxyl group-containing component having a carboxyl group and a carbon-containing diinimide component containing a carbodiimide compound.

The two-liquid hardening type adhesive composition is subjected to a guanidinium reaction with a carboxyl group containing a carboxyl component and a carbodiimide group of a carbon-containing bisinimide component, so that carbonic acid gas is not generated upon hardening, and After the structure is hardened (subsequently), even if it passes over time, the possibility of generating carbonic acid gas due to moisture or the like in the atmosphere is extremely low, so that generation of bubbles between the films of the laminated film can be suppressed, and an excellent appearance can be obtained. In particular, if the film which is a base material has a gas barrier laminated film, if a gas is generated in the adhesive layer, the gas escape is restricted, and a fatal appearance defect is implicated. On the other hand, the two-liquid hardening type adhesive composition of the present invention is suitable for lamination of a gas barrier film because gas is hardly generated with time.

Further, the two-liquid-curing adhesive composition has an excellent hydrazine-urea group having a strong hydrogen bond energy as well as an amine ester bond, and thus exhibits excellent adhesion properties.

Further, since the two-liquid hardening type adhesive composition does not use a blocking agent, gas generation can be suppressed. According to this, if the blocking agent is not used, the blocking agent is not released during the curing, so that no free blocking agent remains in the cured product. Therefore, when used in a vacuum insulation material, the degree of vacuum can be suppressed from being lowered.

1‧‧‧Laminated film

2‧‧‧ gas barrier film

3‧‧‧Next layer

4‧‧‧Metal evaporation film

5‧‧‧Plastic film

6‧‧‧Heat seal

7‧‧‧Heat seal layer

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing an embodiment of a laminated film of the present invention.

The two-liquid-curing adhesive composition of the present invention is a two-liquid hardening type adhesive composition in which a plurality of gas barrier films (described later) are followed, and contains a carboxyl group-containing carboxyl group component (also referred to as "main in this case". In the case of the agent, and the carbon-containing diimine component containing a carbodiimide compound (in the present case, it is also referred to as a "hardener").

The carboxyl group-containing component is, for example, a compound having a carboxyl group. The compound having a carboxyl group is, for example, a compound having a carboxyl group at the terminal of the molecule.

The compound having a carboxyl group at the terminal of the molecule may, for example, be a compound in which an acid anhydride is added to a terminal hydroxyl group of a polyhydric alcohol (hereinafter also referred to as "an acid anhydride adduct of a polyhydric alcohol").

The polyol may be, for example, a high molecular weight polyol and a low molecular weight polyol.

The high molecular weight polyol has a compound 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, and may be, for example, a polyether polyol, a polyester polyol, or a polyester decylamine. Polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, vinyl monomer modified polyol.

Examples of the polyether polyol include a polyalkylene polyol, a polytetramethylene glycol diol, and a polytrimethylene ether glycol.

The polyalkylene polyol may be an addition polymer of an alkylene oxide such as ethylene oxide or propylene oxide as a starting agent of a low molecular weight polyol or an aromatic/aliphatic polyamine as described later (including two or more types) The random and/or block copolymer of the alkylene oxide).

The polyether polyol may specifically be, for example, a polyethylene polyol, a polypropylene polyol, a polyethylene ‧ polypropylene copolymer (a random copolymer, a block copolymer), or the like.

The polytetramethyl ether glycol can be, for example, a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran or an amorphous polytetramethylene glycol glycol of a glycol described later in a polymerization unit of tetrahydrofuran.

Further, for example, a plant-derived polytetramethyl ether glycol derived from tetrahydrofuran produced from a plant raw material base such as furfural may be used.

The polytrimethylene ether glycol can be, for example, a polyol produced by polycondensation of 1,3-propanediol derived from plants.

The polyester polyol may, for example, be a low molecular weight polyol (preferably a glycol) to be described later and a polybasic acid (preferably a dibasic acid) under a known condition depending on the hydroxyl group of the low molecular weight polyol relative to the polybasic acid. The carboxyl group is a polycondensate obtained by performing an esterification reaction in a ratio of excess mole.

Examples of the polybasic acid include oxalic acid, malonic acid, succinic acid, methyl succinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, and 3-methyl- a saturated aliphatic dicarboxylic acid such as 3-ethylglutaric acid, sebacic acid or sebacic acid; an unsaturated aliphatic dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid; An aromatic dicarboxylic acid such as citric acid, isophthalic acid, p-citric acid, toluene dicarboxylic acid or naphthalene dicarboxylic acid; an alicyclic dicarboxylic acid such as hexahydrophthalic acid; for example, a dimer acid, a hydrogenated dimer acid, Other carboxylic acids such as chlorendic acid; and anhydrides derived from such carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, Tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride; and cerium halide derived from such carboxylic acid or the like, such as dichlorooxalic acid, adipic acid dichloride Further, azelaic acid dichloride or the like; in addition, for example, an acid (di)methyl ester (for example, dimethyl phthalate or the like) can be used.

Further, the polyester polyol may, for example, be a low molecular weight polyol described later, a fatty acid-containing vegetable oil fatty acid (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) A vegetable oil-based polyester polyol obtained by subjecting a hydroxycarboxylic acid to a condensation reaction under known conditions.

Further, the polyester polyol is, for example, a low molecular weight polyol (preferably a glycol) to be described later as a starter, and is subjected to ring-opening polymerization with a lactone such as ε-caprolactone or γ-valerolactone. The obtained polycaprolactone polyol, polyvalerolactone polyol, and a lactone polyester polyol which is copolymerized with the diol described later, and the like.

The polyester decylamine polyol can be used, for example, in the esterification reaction of the above polyester polyol by using a low molecular weight polyamine (for example, ethylenediamine, propylenediamine, hexamethylenediamine, etc.) as a raw material. A polyester decylamine polyol or the like obtained.

The polycarbonate polyol can be, for example, a ring-opening polymer of ethyl carbonate which is a low molecular weight polyol (preferably a glycol) as a starting agent; or, for example, 1,4-butanediol, 1 a diol such as 5-pentanediol, 3-methyl-1,5-pentanediol or 1,6-hexanediol, or an amorphous polycarbonate polyol copolymerized with a ring-opening polymer .

Further, the polyurethane polyol may be a ratio of the equivalent ratio (OH/NCO) of the hydroxyl group to the isocyanate group of the polyether polyol, the polyester polyol, and/or the polycarbonate polyol obtained as described above, in excess of one. A polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol obtained by reacting with a polyisocyanate described later.

The epoxy polyol can be, for example, an epoxy polyol obtained by reacting a low molecular weight polyol described later with a polyfunctional halogen alcohol such as epichlorohydrin or β-methylepichlorohydrin.

The vegetable oil polyol may be, for example, a hydroxyl-containing vegetable oil such as castor oil or coconut oil. For example, a castor oil polyol or an ester-modified castor oil polyol obtained by reacting a castor oil polyol with a polypropylene polyol.

The polyolefin polyol (polyhydroxyalkane) may be, for example, a polybutadiene polyol, a partially saponified ethylene-vinyl acetate copolymer, or the like.

The acrylic polyol can be, for example, a copolymer obtained by copolymerizing a hydroxyl group-containing (meth) acrylate with a copolymerizable vinyl monomer copolymerizable with a hydroxyl group-containing (meth) acrylate.

Further, the "(meth)acryl group" is defined as a propylene group and/or a methacryl group, and the "(meth) acrylate" is defined as an acrylate and/or a methacrylate.

The hydroxyl group-containing (meth) acrylate may be, for example, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, or (meth)acrylic acid-6. - Hydroxyhexyl ester, 2,2-dimethylolbutyl (meth)acrylate, polyhydroxymaleate, hydroxyalkyl methacrylate, and the like.

Examples of the copolymerizable vinyl single system include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, second butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, Methyl)hexyl acrylate, isodecyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, (meth)acrylic acid An alkyl (meth)acrylate such as an ester (carbon number 1 to 12); an aromatic vinyl monomer such as styrene, vinyl toluene or α-methylstyrene; for example, a vinyl cyanide such as (meth)acrylonitrile For example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trishydroxyl Alkane polyol poly(meth)acrylates such as propane di(meth)acrylate, trimethylolpropane tri(meth)acrylate; for example 3-(2-isocyanate-2-propyl)-α- An isocyanate group-containing vinyl monomer such as methyl styrene.

The copolymerizable vinyl monomer is preferably, for example, an alkyl (meth)acrylate having 2 to 12 carbon atoms.

That is, the acrylic polyol is preferably a copolymer of, for example, a hydroxyl group-containing (meth) acrylate and a carbon number of 2 to 12 alkyl (meth) acrylate.

Further, the acrylic polyol can be obtained by copolymerizing the hydroxyl group-containing (meth) acrylate and the copolymerizable vinyl monomer in the presence of a suitable solvent and a polymerization initiator.

Further, the acrylic polyol also covers, for example, a polyoxyl polyol, a fluorine polyol.

The polyoxyl polyol can be, for example, a vinyl-containing polyfluorene such as γ-methylpropenyloxypropyltrimethoxydecane blended into a copolymerizable vinyl monomer during the copolymerization of the above acrylic polyol. An acrylic polyol of an oxygen compound.

The fluoropolyol is, for example, an acrylic polyol containing a vinyl fluoride compound such as tetrafluoroethylene or chlorotrifluoroethylene which is blended with a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.

The vinyl monomer-modified polyol can be obtained by using the above high molecular weight polyol and reacting with a vinyl monomer. The high molecular weight polyol is preferably a high molecular weight polyol selected from, for example, a polyether polyol, a polyester polyol, and a polycarbonate polyol.

Further, the vinyl single system may, for example, be the above-mentioned alkyl (meth)acrylate, vinyl cyanide or dicyanethyleneethylene. These vinyl single systems may be used alone or in combination of two or more. Further, among these, it is preferred to use, for example, an alkyl (meth)acrylate.

Further, the vinyl monomer-modified polyol is such that the high molecular weight polyol and the vinyl monomer are, for example, a radical polymerization initiator (for example, a persulfate, an organic peroxide, an azo compound, etc.) It can be obtained by reacting in the next step.

These high molecular weight polyols may be used alone or in combination of two or more.

The high molecular weight polyol is preferably, for example, a polyester polyol.

The viscosity (25 ° C) of the high molecular weight polyol is, for example, 1000 mPa ‧ or more, preferably 2,000 mPa ‧ s or more, and is, for example, 1,000,000 mPa ‧ s or less, preferably 300,000 mPa ‧ s or less.

Further, the viscosity was measured by a cone-and-plate viscometer according to JIS K 5600-2-3 (2014).

The low molecular weight polyol is a compound having two or more hydroxyl groups, a number average molecular weight of 60 or more, preferably 100 or more, and less than 400, preferably less than 500, and examples thereof include ethylene glycol, propylene glycol, and 1,3-propanediol. , 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl -1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolpentane, alkane (C7-20) glycol, 1,3- or 1,4 - cyclohexanedimethanol and mixtures thereof; 1,3- or 1,4-cyclohexanediol and mixtures thereof; hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2, a diol such as 6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol or dipropylene glycol; for example, glycerin, trimethylolpropane, triiso a trihydric alcohol such as propanolamine; for example, a tetrahydric alcohol such as tetramethylolmethane (pentaerythritol) or diglycerin; a pentavalent alcohol such as xylitol; for example, sorbitol, hexahexaol, allitol, Ethyl alcohols such as iditol, dulcitol, altritol, inositol, dipentaerythritol, etc.; for example, perseitol Heptahydric alcohol; an octavalent alcohol such as sucrose, and the like.

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

The polyols may be used alone or in combination of two or more.

The polyol is preferably, for example, a high molecular weight polyol, more preferably a polyester polyol.

The acid anhydride is a compound having at least one acid anhydride group (also referred to as "anhydride"), and may be, for example, an acid anhydride used in the production of the above polyester polyol, and specific examples thereof include oxalic anhydride, succinic anhydride, and maleic anhydride. And phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, diphenyl ketone tetracarboxylic dianhydride, and the like.

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

The acid anhydride is preferably, for example, maleic anhydride, decanoic anhydride or trimellitic anhydride, and more preferably, for example, phthalic anhydride or maleic anhydride.

A method of adding such an acid anhydride to a terminal hydroxyl group of a polyol is, for example, adding an acid anhydride to a polyol and heating to carry out a reaction.

When the acid anhydride is blended, the acid anhydride group and the hydroxyl group of the polyol may be equal to each other, or may be excessive or insufficient.

More specifically, for example, the acid anhydride group in the acid anhydride is, for example, 0.3 or more, preferably 0.5 mol or more, more preferably 0.7 mol or more, and more preferably 3 or less, preferably 2 mol or less, or more, based on the hydroxyl group of the polyol. Good 1.5 moles below.

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

Further, 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.

Further, 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.

Thereby, an acid anhydride adduct of a polyhydric alcohol can be obtained.

Further, in the above reaction, when the ratio of the acid anhydride group to less than 1 mole (i.e., the ratio of the anhydride deficiency) is relative to the hydroxyl group of the polyol, the hydroxyl group of the partial polyol is acid-modified, and the rest. The hydroxyl group is not modified by the acid and remains.

Further, when the acid anhydride group is in a ratio of more than 1 mol (i.e., an excess ratio of an acid anhydride) with respect to the hydroxyl group of the polyol, the anhydride adduct of the polyhydric alcohol can obtain a composition containing an unreacted acid anhydride group. .

Further, the above reaction may be carried out in the absence of a solvent or in the presence of an organic solvent which is optionally blended.

Examples of the organic solvent 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; An aliphatic hydrocarbon such as n-hexane, n-heptane or octane; an alicyclic hydrocarbon such as cyclohexane or methylcyclohexane; an aromatic hydrocarbon such as toluene, xylene or ethylbenzene; for example Methyl cyanoacetate, ethyl cyproterone acetate, methyl carbitol acetate, ethyl carbitol acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PMA), acetic acid - a glycol ether ester such as 3-methyl-3-methoxybutyl ester or ethyl-3-ethoxypropionate; for example, diethyl ether, tetrahydrofuran, and An ether such as alkane; for example, a halogenated aliphatic hydrocarbon such as methyl chloride, dichloromethane, chloroform, carbon tetrachloride, methyl bromide, diiodomethane or dichloroethane; for example, N-methylpyrrolidone, dimethyl Polar aprotic such as formamide, N, N'-dimethylacetamide, dimethyl hydrazine, hexamethylphosphoniumamine and the like.

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

Further, after the completion of the reaction, all or a part of the unreacted acid anhydride or the organic solvent may be removed by a known method such as distillation or extraction. Further, after the completion of the reaction, the organic solvent may be added to adjust the concentration of the anhydride adduct of the polyol.

Further, the compound having a carboxyl group at the terminal of the molecule is not limited to the acid anhydride addition product of the above polyol, and for example, a low molecular weight polyol (preferably diol) and a polybasic acid are preferably produced in the production of the above polyester polyol. The dibasic acid can be obtained by subjecting the carboxyl group of the polybasic acid to the hydroxyl group of the low molecular weight polyol in excess of the molar ratio under known conditions.

The compound having a carboxyl group at the terminal of the molecule may be used singly or in combination of two or more.

The compound having a carboxyl group at the terminal of the molecule is preferably an anhydride adduct of, for example, a polyhydric alcohol, more preferably an anhydride adduct of, for example, a polyester polyol.

Further, the compound having a carboxyl group may be, for example, a compound having a carboxyl group in the middle of the molecular chain, in addition to the compound having a carboxyl group at the terminal of the molecule.

Examples of the compound having a carboxyl group in the middle of the molecular chain include a low molecular weight polyol having a branched carboxyl group, a high molecular weight polyol having a branched carboxyl group, and the like.

The low molecular weight polyol having a branched carboxyl group has one or more carboxyl groups in the middle of the molecular chain, two or more hydroxyl groups at the molecular terminal, and a number average molecular weight of 60 or more, preferably 100 or more, and less than 400, preferably less than 500. For the compound, for example, 2,2-dimethylol acetate, 2,2-dimethylol lactate, 2,2-dimethylolpropionic acid (alias: dimethylolpropionic acid (DMPA)), a polyhydroxyalkanic acid such as 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutanoic acid or 2,2-dihydroxymethylpentanoic acid, etc., preferably, for example, 2,2-dihydroxy Methyl propionic acid.

The high molecular weight polyol-containing molecular chain having a branched carboxyl group has one or more carboxyl groups in the middle, two or more hydroxyl groups at the molecular terminal, and a compound having a number average molecular weight of 400 or more, preferably 500 or more, and 20,000 or less, preferably 10,000 or less. For example, a polyether polyol having a branched carboxyl group, a polyester polyol having a branched carboxyl group, a polyester phthalamide polyol having a branched carboxyl group, a polycarbonate polyol having a branched carboxyl group, a polyurethane polyol having a branched carboxyl group, Branched carboxyl group-containing epoxy polyol, branched carboxyl group-containing vegetable oil polyol, branched carboxyl group-containing polyolefin polyol, branched carboxyl group-containing acrylic polyol, branched carboxyl group-containing vinyl monomer modified polyol. Preferably, for example, a branched carboxyl group-containing polyether polyol, a branched carboxyl group-containing polyester polyol, and a branched carboxyl group-containing polyurethane polyol may be used.

The polyether polyol containing a branched carboxyl group can be obtained, for example, by using a branched carboxyl group-containing low molecular weight polyol as a starter in the production of the above polyether polyol.

The polyester polyol having a branched carboxyl group can be obtained, for example, by using a branched carboxyl group-containing low molecular weight polyol as a raw material (low molecular weight polyol) in the production of the above polyester polyol.

The polyurethane-containing polyol having a branched carboxyl group is, for example, a low-molecular-weight polyol having a branched carboxyl group, a polyether polyol having a branched carboxyl group, and a polyester polyol having a branched carboxyl group, in the production of the above-mentioned polyurethane polyol. Available.

These compounds having a carboxyl group in the middle of the molecular chain may be used singly or in combination of two or more. The compound having a carboxyl group in the middle of the molecular chain is preferably, for example, a high molecular weight polyol having a branched carboxyl group.

Further, a terminal hydroxyl group having a carboxyl group in the middle of the molecular chain (a compound having a carboxyl group in the middle of the molecular chain and having a hydroxyl group at the molecular terminal) may be further added with an acid anhydride by the above method. Thereby, a compound having a carboxyl group at the molecular terminal and the middle of the molecular chain can be obtained.

Further, a compound having a carboxyl group at the molecular terminal and the molecular chain is, for example, a polyester polyol having a branched carboxyl group, and a low molecular weight polyol having a branched carboxyl group and a polybasic acid, depending on the carboxyl group of the polybasic acid. The hydroxyl group of the low molecular weight polyol having a branched carboxyl group is obtained by esterification reaction in a ratio of excess mole.

As described above, the carboxyl group-containing compound may, for example, be a compound obtained by adding a hydroxyl group to a hydroxyl group at the molecular terminal, and having no carboxyl group in the middle of the molecular chain (molecular terminal addition acid anhydride - a compound having no carboxyl group in the middle of the molecular chain); for example; a compound obtained by reacting a raw material (polybasic acid and a low molecular weight polyol) according to a blending ratio of a terminal of a molecule, and having no carboxyl group in the middle of the molecular chain (a compound having a carboxyl group at the molecular terminal and a carboxyl group in the middle of the molecular chain); For example, a compound having a carboxyl group in the middle of the molecular chain and having no carboxyl group at the terminal of the molecule (a compound having no carboxyl group at the molecular terminal and a carboxyl group in the middle of the molecular chain); for example, an acid anhydride is added to the hydroxyl group at the terminal of the molecule, and the carboxyl group is obtained in the middle of the molecular chain. a compound (a molecular terminal addition anhydride - a compound having a carboxyl group in the middle of a molecular chain); for example, a raw material (a polybasic acid, a low molecular weight polyol, and a branched molecular carboxyl group-containing low molecular weight polyol) is reacted according to a blending ratio of a molecular terminal to a carboxyl group. And a compound having a carboxyl group in the middle of the molecular chain (a compound having a carboxyl group at the molecular terminal and a carboxyl group in the middle of the molecular chain) is obtained.

These carboxyl group-containing compounds may be used alone or in combination of two or more.

The compound having a carboxyl group is preferably a compound which may have, for example, a carboxyl group at the molecular terminal. In other words, for example, a molecular terminal addition acid anhydride-a compound having no carboxyl group in the middle of the molecular chain, a compound having a carboxyl group at the molecular terminal and a carboxyl group in the middle of the molecular chain, and a terminal acid addition anhydride-molecule chain having a carboxyl group in the middle of the molecular chain are preferable. The compound or the terminal of the molecule contains a compound having a carboxyl group in the middle of the carboxyl group, and more preferably, for example, a terminal terminal addition acid anhydride-a compound having no carboxyl group in the middle of the molecular chain. Particularly preferred are, for example, anhydride adducts of polyhydric alcohols and anhydride adducts of preferred polyester polyols.

The number average molecular weight (polystyrene-equivalent molecular weight in terms of GPC) of the carboxyl group-containing compound is, for example, 2,000 or more, preferably 3,000 or more, and for example, 20,000 or less, preferably 10,000 or less.

The solid content concentration of the carboxy component is, for example, 30% by mass or more, preferably 50% by mass or more, and is, for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.

The acid value of the carboxyl group-containing component (according to JIS K 1557-5 (2007)) is, for example, 1 mgKOH/g or more, preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and for example, 100 mgKOH/g or less, preferably 70 mgKOH/ Below g, more preferably 50 mgKOH/g or less.

Further, the carboxyl group-containing (solid content) carboxyl group equivalent (56100/acid value (mgKOH/g)) 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, or more. Good below 5610.

The carboxyl group-containing component may contain the above-mentioned compound having a carboxyl group alone or in combination of two or more. Further, it may contain an additive described later.

The content ratio of the carboxyl group-containing compound is, for example, 50% by mass or more, preferably 80% by mass or more, and preferably 100% by mass or less, preferably 99% by mass or less, based on the total amount of the carboxyl group-containing component.

The carbodiimide compound contained in the carbodiimide-containing component is, for example, a carbodiimide modified body obtained by obtaining a polyisocyanate.

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

The carbodiimide upgrading system of polyisocyanate is obtained, for example, by heating a polyisocyanate in the presence of a carbodiimide catalyst, by subjecting to a carbon dihydrazide reaction.

The polyisocyanate may, for example, be a polyisocyanate monomer such as an aliphatic polyisocyanate, an aromatic polyisocyanate or an aromatic aliphatic polyisocyanate.

The aliphatic polyisocyanate may be, for example, a chain (linear or branched: acyclic) aliphatic polyisocyanate, and specific examples thereof include ethylene diisocyanate, trimethylene diisocyanate, and 1,2-extension. Propylene diisocyanate, butyl diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-five Methyl diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6- A chain aliphatic diisocyanate such as isocyanate methyl hexanoate or dodecyl diisocyanate.

Further, the aliphatic polyisocyanate may also be, for example, an alicyclic polyisocyanate.

Examples of the alicyclic polyisocyanate include 1,3-cyclopentene diisocyanate, 1,4-diisocyanate cyclohexyl ester, 1,3-diisocyanate cyclohexyl ester, and isocyanic acid-3- Isocyanatomethyl-3,5,5-trimethylcyclohexyl ester (isophorone diisocyanate; IPDI), 4,4'-, 2,4'- or 2,2'-dicyclohexyl Methane diisocyanate or a mixture thereof (hydrogenated MDI), methyl-2,4-diisocyanate cyclohexyl ester, methyl-2,6-diisocyanate cyclohexyl ester, 1,3- or 1,4- Bis(isocyanatomethyl)cyclohexane or a mixture thereof (hydrogenated XDI), reduced An alicyclic diisocyanate such as an alkyl diisocyanate (NBDI) or the like.

The aromatic polyisocyanate may, for example, be m- or p-phenylene diisocyanate or a mixture thereof, 2,4- or 2,6-toluene 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 An aromatic diisocyanate such as bis-isocyanate or 1,5-naphthalene diisocyanate (NDI).

The aromatic aliphatic polyisocyanate may, for example, be 1,3- or 1,4-terethanyl diisocyanate or a mixture thereof (XDI), 1,3- or 1,4-tetramethyl benzene dimethylene An aromatic aliphatic diisocyanate such as diisocyanate or a mixture thereof (TMXDI), ω, ω'-diisocyanate-1,4-diethylbenzene or the like.

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

The polyisocyanate is preferably, for example, a chain aliphatic polyisocyanate or an aromatic aliphatic polyisocyanate, and more preferably, for example, pentamethylene diisocyanate (PDI).

The carbodiimide-forming catalyst is not particularly limited, and examples thereof include a trialkyl phosphate-based compound, a phosphine oxide-based compound, a phosphene sulfide-based compound, a phosphine oxide-based compound, and a phosphine-based compound.

The trialkyl phosphate may, for example, be a trialkyl phosphate compound having 3 to 24 carbon atoms such as trimethyl phosphate, triethyl phosphate or trioctyl phosphate.

The phosphorus oxide-based compound may, for example, be 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO) or 1-ethyl-3-methyl-2-phosphene-1- Oxide (EMPO), 1,3-dimethyl-2-phosphene-1-oxide, 1-phenyl-2-phosphene-1-oxide, 1-methyl-2-phosphene-1 - an oxide, a 1-ethyl-2-phosphene-1-oxide, and a phosphonene compound having 4 to 18 carbon atoms such as these double bond isomers.

The phosphonene sulfide-based compound may, for example, be a phosphonene sulfide compound having 4 to 18 carbon atoms such as 1-phenyl-2-phosphene-1-thioether.

The phosphine oxide-based compound may, for example, be a phosphine oxide compound having 3 to 21 carbon atoms such as triphenylphosphine oxide or trimethylphosphine oxide.

The phosphine-based compound may, for example, be a phosphine-based compound having 3 to 30 carbon atoms such as bis(diphenylphosphine oxide) ethane.

These carbodiimide catalysts may be used singly or in combination of two or more.

The blending ratio of the carbodiimide catalyst is not particularly limited, and can be appropriately set in accordance with the purpose and use.

The heating conditions are in a normal pressure and an inert gas (such as nitrogen), and 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 or lower. Further, the heating time is, for example, 1 hour or longer, preferably 3 hours or longer, and for example, 50 hours or shorter, preferably 40 hours or shorter.

Thereby, the polyisocyanate is subjected to decarbonation condensation to obtain a carbodiimide compound (i.e., a carbodiimide modified body of a polyisocyanate).

Further, the carbon dioxime imidization reaction may be blended with the above organic solvent as needed, and after the reaction is completed, unreacted polyisocyanate or organic solvent may be removed by a known method such as distillation or extraction as needed. All or part of it. Further, after the reaction is completed, the above organic solvent may be added to adjust the solution concentration of the carbodiimide compound.

Further, the polyisocyanate may be subjected to alcohol modification using a known alcohol (polyoxyethylene monomethyl ether, 1-methoxy-2-propanol or the like) before the carbohydrazide imidization reaction. In the case of alcohol modification, for example, an amine esterification reaction is carried out at a ratio of an equivalent ratio (OH/NCO) of a hydroxyl group of an alcohol to an isocyanate group of a polyisocyanate of less than 1. Further, the organic solvent and the known amine esterification catalyst may be blended as needed, and after the reaction is completed, unreacted polyisocyanate or organic solvent may be removed by a known method such as distillation or extraction as needed. All or part of it.

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, and for example, 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less.

Further, the carbodiimide compound (solid portion) has a carbodiimide group equivalent of, for example, 150 or more, preferably 200 or more, and for example, 500 or less, preferably 400 or less.

Further, the carbodiimide group equivalent can be determined from ¹³ C-NMR mass spectrum according to the examples described later.

In addition, the number average molecular weight (polystyrene-equivalent molecular weight in terms of GPC) Mn of the carbodiimide compound is, for example, 1,000 or more, preferably 2000 or more, from the viewpoint of the appearance and adhesion of the obtained laminate. From the viewpoint of the lamination strength, for example, 5,000 or less, preferably 4,000 or less.

In addition, the weight average molecular weight (polystyrene-equivalent molecular weight in terms of GPC) Mw of the carbodiimide compound is, for example, 1,500 or more, preferably 2,000 or more, from the viewpoint of the appearance of the obtained laminated body. The viewpoint of the strength is, for example, 15,000 or less, preferably 10,000 or less.

In addition, the molecular weight distribution (dispersion degree) Mw/Mn is, for example, 1 or more, preferably 2 or more, and is preferably 10 or less, preferably 5 or less, from the viewpoint of achieving both the appearance of the laminated body and the bonding strength.

Further, the above carbodiimide compound can be obtained in the form of a commercially available product, for example, Carbodilite V05S [solid content concentration: 90% by mass, carbodiimide equivalent 291 (solid equivalent: 262), Nisshinbo Co., Ltd. System], Carbodilite V07 [solid content concentration 50% by mass, carbodiimide equivalent 404 (solid content equivalent 202), Nisshin Textile Co., Ltd.], Carbodilite V09GB [solid content concentration 70% by mass, carbon dioxide The amine group equivalent is 298 (solid content equivalent: 209), manufactured by Nisshinbo Co., Ltd., and the like.

The carbodiimide component may contain the above carbodiimide compound alone or in combination of two or more. Further, it may contain an additive described later.

The content ratio of the carbodiimide compound is, for example, 50% by mass or more, preferably 80% by mass or more, and preferably 100% by mass or less, preferably 99% by mass or less, based on the total amount of the carbodiimide component.

Further, the two-liquid-curing adhesive composition may be appropriately blended as needed, for example, in either or both of the carboxy-containing component (main component) and the carbon-containing bis-imine component (hardener), as needed. : phosphoric acid or its derivative, decane coupling agent, and even stabilizers such as epoxy resin, catalyst, coating improver, leveling agent, antifoaming agent, antioxidant, ultraviolet absorber, etc.; plasticizer, interface Additives such as active agents, pigments, fillers, organic or inorganic microparticles, and mildew inhibitors. The blending amount of the additive can be appropriately determined in accordance with the purpose and use.

Further, the two-liquid-curing adhesive composition is prepared by mixing a carboxy-containing component as a main component and a carbodiimide-containing component as a curing agent, and mixing the mixture to prepare a mixed solution. The mixture is diluted with an organic solvent as needed, and then applied to a substrate (adhesive).

The blending ratio of the carboxy-containing component to the carbodiimide-containing component is, for example, 1 mol with respect to the carboxyl group in the carboxyl group-containing component (carboxy group having a carboxyl compound contained in the carboxy component), and the carbodiimide component The carbodiimide group (carbodiimide group of the carbodiimide compound contained in the carbodiimide component) is, for example, 1 mol or more, preferably 1.3 mol or more, more preferably 1.5 moles or more, and for example, 5 moles or less, preferably 4 moles or less, more preferably 3 moles or less.

When the blending ratio of the carboxyl group-containing component and the carbon-containing imide component is within the above range, the obtained laminate can have both an excellent appearance and excellent adhesion.

Further, the two-liquid curing type adhesive composition contains a carboxyl group-containing component having a carboxyl group and a carbon-containing diinimide component containing a carbodiimide compound. The two-liquid hardening type adhesive composition is subjected to a guanidinium reaction of a carboxyl group-containing carboxyl group and a carbodiimide group-containing carbodiimide group, so that carbonic acid gas is not generated during hardening, and In the structure, even after passing through the curing (following), the possibility of generating carbonic acid gas due to moisture or the like in the atmosphere is extremely low, so that generation of bubbles between the films of the laminated film can be suppressed, and an excellent appearance can be obtained.

In particular, when a film which is a substrate is a gas barrier layered film, if a gas is generated in the subsequent layer, the escape of the gas is limited, which may be implicated in fatal appearance defects. On the other hand, the two-liquid hardening type adhesive composition of the present invention is suitable for lamination of a gas barrier film because gas is hardly generated with time.

Further, the two-liquid-curing adhesive composition has an excellent hydrazine-urea group having a strong hydrogen bond energy as well as an amine ester bond, and thus exhibits excellent adhesion properties.

Further, since the two-liquid hardening type adhesive composition does not use a blocking agent, gas generation can be suppressed. According to this, if the blocking agent is not used, the blocking agent is not released during the curing, so that no free blocking agent remains in the cured product. Therefore, when used in a vacuum insulation material, the degree of vacuum can be suppressed from being lowered.

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

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

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

Further, the oxygen permeability can also be measured by an oxygen permeability measuring device manufactured by Modern Controls.

The gas barrier film 2 may specifically be, for example, a metal foil (for example, aluminum foil or the like). Further, for example, a plastic film provided with a metal film (for example, an aluminum film) or a metal deposition film (aluminum vapor deposition film, a ruthenium dioxide vapor deposition film, an alumina vapor deposition film, a cerium oxide, and an aluminum oxide binary vapor) may be provided. Plastic film, etc. for coating. Further, the plastic film may be, for example, a polyethylene terephthalate (PET) film, a nylon (NY) film, a cellulose acetate (TAC) film, or the like, and is preferably, for example, a PET film or a cellulose acetate (TAC). )film. Further, 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 can be appropriately set in accordance with the purpose and use.

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

The gas barrier film 2 is preferably a plastic film having a metal deposition film, for example. More preferably, it may be a plastic film having a ruthenium dioxide vapor deposition film, a plastic film having an alumina vapor deposition film, or a plastic film having a ruthenium dioxide/alumina binary vapor deposition film. Further, such a plastic film having a metal deposition film may preferably be, for example, a PET film or a cellulose acetate (TAC) film.

More preferably, the gas barrier film 2 is a PET film having a ruthenium dioxide vapor deposition film, a PET film having an alumina vapor deposition film, and a PET film having a ruthenium dioxide/alumina binary vapor deposition film.

In FIG. 1, the gas barrier film 2 is a plastic film 5 provided with a metal deposition film 4.

Further, although not shown in FIG. 1, the gas barrier film 2 may be provided with an anchor coating between the metal deposition film 4 and the plastic film 5, for example, or on the surface of the metal deposition film 4 (the plastic may be formed). A protective layer is provided on the other side of one side of the film 5.

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

Next, the layer 3 is a cured product of the above two-liquid-curing type adhesive composition, 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 the plurality of (two) gas barrier films 2 are bonded together by the two-liquid curing type adhesive composition.

In the production of the laminated film 1, for example, the plurality of (two) gas barrier films 2 can be bonded together via the adhesive layer 4 in a state in which the respective metal deposition films 4 are opposed to each other.

Further, for example, the plurality of (two) gas barrier films 2 may be bonded together via the adhesive layer 3 in a state in which the respective plastic films 5 are opposed to each other.

Further, for example, via the adhesive layer 3, the metal vapor-deposited layer 4 of one of the gas barrier films 2 and the plastic film 5 of the other gas barrier film 2 may be opposed to each other to form a plurality of (two) gas barrier films 2 Make a fit.

Preferably, as shown in FIG. 1, the plurality of (two) gas barrier films 2 are bonded to each other via the adhesive layer 4 in a state in which the respective metal deposition films 4 are opposed to each other.

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

1 is a laminated film 1 in which two gas barrier films 2 are bonded together, but the number of the gas barrier films 2 is not limited to the above, and three or more gas barrier films 2 may be used. The method is to fit.

Further, the laminated film 1 is provided with a heat seal layer 6 on one or both sides 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 may be, for example, a thermoplastic film such as a polyethylene film or an unstretched polypropylene film.

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.

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

Further, the heat seal adhesive layer 7 may be, for example, a cured product of the above-described two-liquid curing type adhesive composition, or a cured product of another known adhesive (polyurethane adhesive or the like).

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

Further, if an anchor agent is applied to the surface of the gas barrier film 2 as needed, a resin such as polyethylene is extruded to laminate the heat seal layer 6. In this case, the coating amount of the anchor coating layer 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.

Further, in the production of such a laminated film 1, for example, a plurality of (for example, two) gas barrier films 2 are first prepared (preparation step).

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

Specifically, the laminating step is carried out, for example, after the carboxy-containing component and the carbodiimide-containing component are blended by dilution with the above organic solvent, and then the obtained mixture is applied to each resist by a solvent-type laminator. The surface of the gas film, after the solvent is volatilized, the coated surface is pasted, and then cured at room temperature or under heating to cure; or when the carboxylate component and the carbon-containing diterpene component are blended In the case of a normal temperature of -100 ° C, for example, about 100 to 10000 mPa ‧ s, preferably about 100 to 5,000 mPa ‧ s, for example, directly blending the carboxy-containing component with the carbodiimide-containing component, and then obtaining the obtained mixture A method of applying a solvent-free laminator to the surfaces of the respective gas barrier films to bond the coated surfaces.

Further, the coating amount of the two-liquid curing type adhesive composition, for example, in the case of a solvent type, is 2.0 to 8.0 g/m ² in terms of basis weight (solid content) after solvent evaporation, and 1.0 in the case of solventless type. ~4.0g/m ² .

Thereby, the carboxyl group in the carboxyl group-containing component is subjected to a guanidinium reaction with the carbodiimide group in the carbodiimide component to cure the two-liquid-curable adhesive composition. As a result, the laminated film 1 of the laminate of the gas barrier film 2 can be obtained.

Further, in this method, the obtained laminate is subjected to heat curing (aging step) as needed.

The aging temperature in the aging 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.

Further, the aging 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 adhesion between the gas barrier films 2 can be improved.

Further, as in the above-described lamination step, the layer 6 may be thermally sealed on the surface of the gas barrier film 2 via the heat seal bonding layer 7 (see the broken line in Fig. 1). Thereby, the laminated film 1 can be provided with heat sealability.

Further, the obtained laminated film 1 is excellent in gas barrier properties against oxygen and water vapor, and is suitable for use in the field of gas barrier films, specifically, for example, in the field of heat insulation such as vacuum insulation materials, and foods. Packaging films such as pharmaceuticals, food packaging containers (including bottles), optical films, industrial films, etc., are particularly suitable for use in insulation fields such as vacuum insulation.

Further, in the present invention, components other than the main agent and the curing agent (also referred to as "other components") may be contained within a range that does not impair the purpose and effect. The content of the other components is preferably 40% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less based on the total amount of the adhesive composition.

 [Examples]  

Next, the present invention will be described based on the production examples, examples, and comparative examples, but the present invention is not limited by the following examples. In addition, "parts" and "%" are quality benchmarks unless otherwise stated. Further, the specific numerical values such as the blending ratio (content ratio), the physical property value, and the parameters used in the following descriptions may be replaced by the blending ratios (content ratios) described in the above-mentioned "embodiments", The upper limit value (the value defined by "below" or "not full") or the lower limit (the value defined by "above" or "exceed") for physical property values and parameters.

Further, various measurement methods are shown below.

 <acid value>  

The sample was weighed in an appropriate amount, and dissolved in a mixed solvent of toluene/methanol = 7/3 (weight ratio), and a few drops of the phenolphthalein indicator were dropped, and titrated with a 0.1 mol/L ethanol potassium hydroxide solution.

 <carboxy equivalent (solids)>  

Using the acid value determined as described above, it is determined according to the following formula.

Carboxyl equivalent = 56100 / acid value

 <Carbodiamine equivalent (solids)>  

Using the polycarbodiimide composition described later, ¹³ C-NMR was measured according to the following apparatus and conditions, and the carbodiimide group equivalent (solid content) was calculated from the functional group integral value and the loading amount described later. In addition, the chemical shift ppm basis used tetramethyl decane (0 ppm) in a CDCL ₃ solvent.

Device: ECA-500 (made by JEOL)

Conditions: Measurement frequency: 125 MHz, solvent: CDCL ₃ , solute concentration: 50% by mass

Measuring temperature: room temperature, number of scans 8500 times

Repeat time: 3.0 seconds, pulse width: 30 ° (3.70 μsec)

Carbon-dependent peak of carbodiimide group (N=C=N group in carbodiimide group): 139 ppm

Carbon-dependent peak of the amine ester group (C=O group in the amine ester group): 156 ppm

Further, the carbodiimide equivalent is calculated according to the results of the above NMR measurement according to a usual method.

 <Amount of terminal hydroxyl group>  

Weigh the sample in an appropriate amount, add 20 mL of a mixed solution of anhydrous acetic acid/pyridine (30 mL/400 mL), and 2 mL of a pyridine solution (concentration 1 g/100 mL) of 4-dimethylaminopyridine, and stir at room temperature for 30 minutes to dissolve. The end is added with anhydrous acetic acid. Subsequently, after diluting with 50 mL of pyridine, the remaining acid was back-titrated with a 1 mol/L sodium hydroxide aqueous solution to obtain an acetylation value (mgKOH/g). From the result (value) and the acid value measured separately, the amount of terminal hydroxyl groups (hydroxyl value) was determined according to the following formula.

Hydroxyl value = acetamidine value + acid value

 <Main agent (containing carboxy component)>    Production Example 1 (Preparation of Main Agent A)  

184.8 g of citric acid, 246.4 g of isononanoic acid, 216.6 g of adipic acid, 131.2 g of ethylene glycol, 168.2 g of diethylene glycol, and 165.1 g of neopentyl glycol were placed in a reaction vessel at 180-220. The esterification reaction is carried out at °C. When the acid value was 8 mgKOH/g or less, 0.07 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C is 1930 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014) (the same applies hereinafter)), the amount of terminal hydroxyl groups is determined by titration, and the like Maleic anhydride was added in the form of a multiple equivalent (anhydride group 1 mole: hydroxyl group 1 mole), and the mixture was stirred at 150 ° C for 90 minutes to be added to a hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 374.1 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the terminal of the molecule. Further, KB5403 (manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent (hereinafter the same)) 1.75 g, KBM603 (manufactured by Shin-Etsu Chemical Co., Ltd., decane coupling agent (hereinafter the same)), 0.87 g, and 0.44 g of phosphoric acid were added to obtain a solid content. 73.2% of the main agent A. The acid value was 25.2 mgKOH/g, and the carboxyl equivalent (solids) was 1629.

 Production Example 2 (Preparation of Main Agent B)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, at a temperature of 150 ° C, the viscosity became 5040 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K), and the amount of terminal hydroxyl groups was determined by titration to obtain an equivalent weight (anhydride group 1 mol: hydroxyl 1 mol) The maleic anhydride was added in the same manner and stirred at 150 ° C for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 628.5 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component B of 72.0% of a solid content. The acid value was 16.3 mgKOH/g, and the carboxyl equivalent (solids) was 2478.

 Production Example 3 (Preparation of Main Agent C)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C became 9640 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, and was equivalently equivalent (anhydride group Maleic anhydride was added in the form of 1 molar: hydroxyl group 1 molar, and the mixture was stirred at 150 ° C for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1100 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component C of 60.6% of a solid content. The acid value was 11.3 mgKOH/g, and the carboxyl equivalent (solids) was 2994.

 Production Example 4 (Preparation of Main Agent D)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C was 9230 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, and the amount was changed to 2 equivalents (anhydride group Maleic anhydride was added in the form of 2 molar (hydroxyl 1 molar), and the mixture was stirred at 150 ° C for 120 minutes to be added to a hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1146 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the terminal of the molecule. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component D of 57.1% of a solid content. The acid value was 23.4 mgKOH/g, and the carboxyl equivalent (solids) was 1369.

 Production Example 5 (Preparation of Main Agent E)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C was 9360 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, which was 0.5 equivalents (anhydride group Maleic anhydride was added in a manner of 0.5 mol: hydroxyl group 1 molar, and the mixture was stirred at 150 ° C for 120 minutes to be added to a hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1100 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component E of 60.5% of a solid content. The acid value was 5.95 mgKOH/g, and the carboxyl equivalent (solids) was 5705.

 Production Example 6 (Preparation of Main Agent F)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C was 9100 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, and was equivalently equivalent (anhydride group In the manner of 1 mol: hydroxyl 1 mol), benzene trimellitic anhydride was added, and the mixture was stirred at 150 ° C for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1100 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component F of 60.5% of a solid content. The acid value was 23.8 mgKOH/g, and the carboxyl equivalent (solids) was 1428.

 Production Example 7 (Preparation of Main Agent G)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C is 7400 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups is determined by titration, and is equivalently equivalent (anhydride group In 1 molar (hydroxyl 1 molar), phthalic anhydride was added, and the mixture was stirred at 150 ° C for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1100 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal. Further, KBM403: 2.93 g, KBM603: 1.47 g, and phosphoric acid 0.73 g were added to obtain a main component G of 64.9% of a solid content. The acid value was 17.0 mgKOH/g, and the carboxyl equivalent (solids) was 2142.

 Production Example 8 (Preparation of Main Agent H)  

274.3 g of citric acid, 240 g of isophthalic acid, 117 g of ethylene glycol, 163.4 g of neopentyl glycol, 216.3 g of 1,6-hexanediol, and 0.14 g of zinc acetate were placed in a reaction vessel at 180-220 ° C. The esterification reaction is carried out. When the acid value was 20 mgKOH/g or less, 150.8 g of adipic acid was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C was 5160 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups was determined by titration, and was equivalently equivalent (anhydride group Maleic anhydride was added in the form of 1 molar: hydroxyl group 1 molar, and the mixture was stirred at 150 ° C for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 667 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the terminal of the molecule. Further, KBM403: 1.65 g, KBM603: 0.82 g, and 0.41 g of phosphoric acid were added to obtain a main component H of 64.7% of a solid content. The acid value was 30.7 mgKOH/g, and the carboxyl equivalent (solids) was 1184.

 Production Example 9 (Main Agent I)  

Takelac A-620 (manufactured by Mitsui Chemicals Co., Ltd.) was used as the main agent I.

 Production Example 10 (Preparation of Main Agent J)  

310.5 g of citric acid, 414 g of isononanoic 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 in a reaction vessel at 180-220 ° C, respectively. The esterification reaction is carried out. When the acid value was 8 mgKOH/g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was further continued.

Then, the viscosity at 150 ° C is 9820 mPa ‧ (measured by a cone-and-plate viscometer; according to JIS K 5600-2-3 (2014)), the amount of terminal hydroxyl groups is determined by titration, and is equivalently equivalent (anhydride group Maleic anhydride was added in the form of 1 molar: hydroxyl group 1 molar, and the mixture was stirred at 150 ° C for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxyl group at the molecular end is obtained.

Then, 1100 g of ethyl acetate was added to dissolve a compound having a carboxyl group at the molecular terminal to obtain a main component C of 59.3% of a solid content. The acid value was 10.4 mgKOH/g, and the carboxyl equivalent (solids) was 3199.

 <hardener (carbon-containing diazide component)>  

The following products were used for the hardeners A to C and the hardener E.

Further, the curing agents D, F and G were produced in the following manner.

Hardener A: Carbodilite V05S manufactured by Nisshinbo Co., Ltd., solid content concentration 90% by mass, carbodiimide equivalent 291 (solid equivalent 262)

Hardener B: Carbodilite V07 manufactured by Nisshinbo Co., Ltd., solid content concentration 50% by mass, carbodiimide equivalent 404 (solid content equivalent 202)

Hardener C: Carbodilite V09GB manufactured by Nisshinbo Co., Ltd., solid content concentration 70% by mass, and carbon dimercapto group equivalent 298 (solid content equivalent 209)

Hardener E: TAKENATE A-50 (terminal isocyanate group containing amine ester resin, manufactured by Mitsui Chemicals, Inc.)

Hardener D: Hardener D was produced in the following manner.

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of pentamethylene diisocyanate and Uniox M400 (polyoxyethylene monomethyl ether (manufactured by Nippon Oil Co., Ltd.) were charged at room temperature. 44.2 parts by mass and 13.4 parts by mass of 1-methoxy-2-propanol, while introducing nitrogen, the mixture was heated to 80 ° C under normal pressure, and stirred for 6 hours to carry out an amine esterification reaction.

Next, 330.5 parts by mass of xylene in an organic solvent and 2.0 parts by mass of 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO) of a carbodiimide catalyst were placed in reflux. The reaction was terminated by stirring at 141 ° C for 8 hours.

After completion of the reaction, the mixture was cooled to 80 ° C, and xylene was distilled off under reduced pressure to obtain a hardener D belonging to the composition of the polycarbodiimide. The solid concentration was 98.8%, and the carbodiimide equivalent (solids) was 299.

Hardener F: The hardener F was produced in the following manner.

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of 1,3-bis(isocyanatomethyl)cyclohexane and 9.54 mass of isobutanol were charged at room temperature. Share. While introducing nitrogen, the mixture was heated to 80 ° C under normal pressure, and stirred for 6 hours to carry out an amine esterification reaction. Next, 231.0 parts by mass of propylene glycol monomethyl ether acetate (PMA) charged with an organic solvent, and 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO) of a carbodiimide catalyst. 2.0 parts by mass, and the mixture was stirred under reflux (150 ° C) for 8 hours to terminate the reaction.

After completion of the reaction, the mixture was cooled to 80 ° C, and a part of the PMA was distilled off under reduced pressure to obtain a hardener F belonging to the composition of the polycarbodiimide. The solid concentration was 88.4%, and the carbodiimide equivalent (solids) was 265.

Hardener G: Hardener G is produced by the following method.

In a four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube, 100.0 parts by mass of isophorone diisocyanate and 8.34 parts by mass of isobutyl alcohol were charged at room temperature. While introducing nitrogen, the mixture was heated to 80 ° C under normal pressure, and stirred for 6 hours to carry out an amine esterification reaction.

Next, 228.5 parts by mass of propylene glycol monomethyl ether acetate (PMA) charged with an organic solvent, and 3-methyl-1-phenyl-2-phosphene-1-oxide (MPPO) of a carbodiimide catalyst. 2.0 parts by mass, and the mixture was stirred under reflux (150 ° C) for 8 hours to terminate the reaction.

After completion of the reaction, the mixture was cooled to 80 ° C, and a part of the PMA was distilled off under reduced pressure to obtain a hardener G belonging to the composition of the polycarbodiimide. The solids concentration was 74.5%, and the carbodiimide equivalent (solids) was 310.

 [Examples 1 to 25 and Comparative Example 1]  

According to the blend ratio R (carbodiimide group / carboxyl group (mole ratio)) described in Tables 1 to 5, the main component (containing a carboxyl component) and a hardener (carbon-containing diazide component) are mixed. Further, a mixture obtained by diluting with a solvent (ethyl acetate) is used as a gas barrier film TECHBARRIER TX (PET film made of Mitsubishi Resin Co., Ltd., having a ruthenium dioxide vapor deposition film, 12 μm, 5.0 mL/m ² ‧24 hr ‧ MPa) was applied in a state where the coating amount was 3.3 g/m ² (dry film thickness), and the cerium oxide vapor-deposited layers of the gas barrier film were bonded to each other. Then, the obtained laminate was aged at 60 ° C for 3 days.

 <evaluation>    (observation of the appearance of laminate)  

For the appearance of the laminate after aging at 60 ° C for 3 days, the evaluation was carried out according to the following criteria.

○: no foaming

△: slightly foamed

×: foaming

 (peel strength of laminated film)  

The measurement was carried out at 24 ° C according to JIS K 6854-3 (1999) at a width of 15 mm and a tensile speed of 300 mm/min.

 (thermal peel strength of laminated film)  

The measurement was carried out at 120 ° C according to JIS K 6854-3 (1999) at a width of 15 mm and a tensile speed of 300 mm/min.

 (heat-resistant creep of laminated film)  

The test piece was cut into a thin square shape having a width of 15 mm, and peeled off, and a 100 g hammer was placed on the single-sided film, and the offset width of 3 minutes was measured at 120 ° C, and the value was converted to the offset width per minute.

In addition, the above-described embodiments of the present invention are provided by way of illustration and not limitation. Variations of the invention that are readily apparent to those skilled in the art are intended to be included within the scope of the appended claims.

 (industrial availability)  

The two-liquid-curing adhesive composition, the laminated film, and the method for producing the same according to the present invention are suitable for use in a heat insulating field such as a vacuum insulation material, and even a packaging film for foods, medicinal products, and food packaging containers (including bottles). ), the field of gas barriers such as optical films and industrial films.

Claims (7)

 A two-liquid hardening type adhesive composition comprising a two-liquid hardening type adhesive composition which is followed by a plurality of gas barrier films, comprising: a carboxyl group-containing component having a carboxyl group; and a carbon-containing compound containing a carbodiimide compound Diimine component.    The liquid-hardening type adhesive composition according to claim 1, wherein the carboxyl group-containing component contains an acid anhydride adduct of a polyester polyol.    The liquid-curable adhesive composition according to claim 2, wherein the acid anhydride group in the acid anhydride is 0.7 mol or more in relation to the hydroxyl group of the polyester polyol.    The liquid-hardening type adhesive composition according to claim 1, wherein the carbodiimide group in the carbodiimide-containing component contains 1.3 mole relative to the carboxyl group 1 mol in the carboxy-containing component. Above and below 4 moles.    A laminated film comprising: a plurality of gas barrier films; and an adhesive layer which is interposed between the plurality of gas barrier films and is a cured product of the two-liquid hardening type adhesive composition of claim 1.    A method for producing a laminated film, comprising: a preparation step of preparing a plurality of gas barrier films; and a laminating step of attaching a plurality of gas barrier films via the two liquid hardening type adhesive composition of claim 1 Get a laminate.    The method for producing a laminated film according to claim 6, wherein after the laminating step, a aging step of heating and aging the laminate is included.