WO2018128032A1 - 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-component curable adhesive composition, laminate film and method for producing the same

The present invention relates to a two-component curable adhesive composition, a laminate film, and a method for producing the same. Specifically, the two-component curable adhesive composition, a laminate film in which the two-component curable adhesive composition is used, and The present invention relates to a method for producing a laminate film.

Conventionally, a laminated composite film in which various base materials are bonded together with an adhesive for laminating has been widely used in various industrial fields such as food, medical care, home appliances, and electronic materials. Further, as a laminating adhesive, for example, a two-component curable polyurethane adhesive containing a main agent made of polyol and a curing agent made of isocyanate is known.

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

Also, polyurethane adhesives are known to exhibit excellent adhesive performance because they have functional groups (urethane bonds) that exhibit strong hydrogen bonding ability.

However, when two or more gas barrier films are bonded with a two-component curable polyurethane adhesive, the isocyanate group (-NCO) reacts with the surface moisture of the gas barrier film, moisture in the atmosphere, moisture in the adhesive (mixed solution), etc. In some cases, a carbamate group (—NHCOOH) is converted into an amino group (—NH ₂ ) and carbon dioxide gas (CO ₂ ) is generated. When the carbon dioxide gas is sealed between the gas barrier films, there is a problem that a bubble-like appearance defect is caused in the laminated composite film.

Therefore, a gas barrier laminate composite film having an excellent appearance has been studied. For example, a plurality of base materials having gas barrier properties are cured by a reaction between a compound having an amino group protected with 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 that cures by a reaction between a compound in which an amino group is protected with a ketone group (blocking agent) and a compound having an epoxy group causes the ketone group (blocking agent) to deblock from the amino group at the time of curing. Free ketone groups (blocking agents) remain in the cured product.

Therefore, when the laminated composite film in which the adhesive is used is used as a packaging material for a vacuum heat insulating material, the blocking agent is gradually released into the vacuum, causing a decrease in the degree of vacuum, and the heat insulating property is reduced. is there.

An object of the present invention is a two-part curable adhesive composition having excellent appearance and an excellent adhesive force, a laminate film excellent in gas barrier properties obtained using the two-part curable adhesive composition, and It is providing the manufacturing method of a laminate film. Furthermore, the object of the present invention is to use a two-component curable adhesive composition for obtaining a laminate film that can suppress a decrease in the degree of vacuum when used in a vacuum heat insulating material, and the two-component curable adhesive composition. Another object of the present invention is to provide a laminate film obtained by the above method and a method for producing the laminate film.

The present invention [1] is a two-component curable adhesive composition that bonds between a plurality of gas barrier films, and includes a carboxy-containing component having a carboxy group and a carbodiimide-containing component containing a carbodiimide compound. A two-component curable adhesive composition is included.

[2] The present invention [2] includes the two-component curable adhesive composition according to the above [1], wherein the carboxy-containing component contains an acid anhydride adduct of polyester polyol.

The invention [3] is a two-component curable adhesive according to the above [2], wherein the hydroxyl group-free in the acid anhydride is a ratio of 0.7 mol or more with respect to 1 mol of the hydroxyl group of the polyester polyol. Contains the composition.

In the present invention [4], the carbodiimide group in the carbodiimide-containing component is contained in a ratio of 1.3 mol to 4 mol with respect to 1 mol of the carboxy group in the carboxy-containing component. The two-component curable adhesive composition according to any one of [3] to [3].

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

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

This invention [7] contains the manufacturing method of the laminate film as described in said [6] provided with the curing process which heat-cures the said laminated body after the said lamination process.

The two-component 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.

In such a two-component curable adhesive composition, the carboxy group of the carboxy-containing component and the carbodiimide group of the carbodiimide-containing component undergo an acylureaization reaction, so that no carbon dioxide gas is generated during curing, and the structure is cured. (Adhesion) Even if time passes, the possibility of carbon dioxide generation due to moisture in the atmosphere is extremely low, so it is possible to suppress the generation of bubbles between the films of the laminate film, and an excellent appearance Obtainable. In particular, in a laminated film having a gas barrier property as a base film, when gas is generated in the adhesive layer, the gas escape space is limited, which may lead to a fatal appearance defect. On the other hand, the two-component curable adhesive composition of the present invention is suitable for laminating a gas barrier film because it hardly generates gas over time.

Moreover, since this two-component curable adhesive composition contains an acylurea group exhibiting a strong hydrogen bonding ability in the same manner as a urethane bond, it exhibits excellent adhesive performance.

Moreover, in such a two-component curable adhesive composition, gas generation can be suppressed without using a blocking agent. As described above, if 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 it uses for a vacuum heat insulating material, the fall of a vacuum degree can be suppressed.

FIG. 1 is a schematic view showing an 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 that adheres between a plurality of gas barrier films (described later), and includes a carboxy-containing component having a carboxy group (in this application, the main agent and And a carbodiimide-containing component (sometimes referred to as a curing agent in the present application) containing a carbodiimide compound.

The carboxy-containing component contains, for example, a compound having a carboxy group. Examples of the compound having a carboxy group include a compound having a carboxy group at the molecular end.

Specific examples of the compound having a carboxy group at the molecular terminal include a compound in which an acid anhydride is added to the terminal hydroxyl group of a polyol (hereinafter, sometimes referred to as an acid anhydride adduct of a polyol).

Examples of the polyol include a high molecular weight polyol and a low molecular weight polyol.

The high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, preferably 500 or more and 20000 or less, preferably 10,000 or less. For example, polyether polyol, polyester polyol, polyesteramide polyol, Examples include polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, and vinyl monomer-modified polyol.

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

Examples of the polyalkylene polyol include addition polymers of alkylene oxides such as ethylene oxide and propylene oxide, which are initiated with a low molecular weight polyol or an aromatic / aliphatic polyamine described later (random and / or two or more alkylene oxides). Or a block copolymer).

Specific examples of the polyether polyol include polyethylene polyol, polypropylene polyol, polyethylene / polypropylene copolymer (random copolymer, block copolymer), and the like.

Examples of the polytetramethylene ether glycol include a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, and amorphous polytetramethylene ether glycol obtained by copolymerizing a dihydric alcohol described later with a polymerization unit of tetrahydrofuran.

Also, plant-derived polytetramethylene ether glycols starting from tetrahydrofuran produced based on plant-based materials such as furfural can be mentioned.

Examples of the polytrimethylene ether glycol include a polyol produced by condensation polymerization of plant-derived 1,3-propanediol.

Examples of the polyester polyol include a low molecular weight polyol (preferably a dihydric alcohol) and a polybasic acid (preferably a dibasic acid) described below, and the hydroxyl group of the low molecular weight polyol is a polybasic acid under known conditions. Examples thereof include polycondensates obtained by esterification at a ratio of an excess mole relative to a carboxy group.

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, 3-methyl-3-ethylglutaric acid Saturated aliphatic dicarboxylic acids such as azelaic acid and sebacic acid, for example, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, such as orthophthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalenedicarboxylic acid Derived from aromatic dicarboxylic acids such as acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, for example, other carboxylic acids such as dimer acid, hydrogenated dimer acid, het acid, and the like Acid anhydrides such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, and acid halides derived from these carboxylic acids For example, oxalic acid dichloride, adipic acid dichloride, sebacic acid dichloride, and the like, and acid (di) methyl ester (for example, terephthalic acid dimethyl ester and the like) can be mentioned.

Further, examples of polyester polyols include hydroxycarboxylic acids such as low molecular weight polyols described later and hydroxyl group-containing vegetable oil fatty acids (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid). And vegetable oil-based polyester polyols obtained by a condensation reaction under known conditions.

Polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone, for example, using a low molecular weight polyol (preferably a dihydric alcohol) described below as an initiator, for example, Examples include caprolactone polyol, polyvalerolactone polyol, and lactone polyester polyol obtained by copolymerizing a dihydric alcohol described later.

Examples of the polyesteramide polyol include a polyesteramide polyol obtained by using a low molecular weight polyamine (for example, ethylenediamine, propylenediamine, hexamethylenediamine, etc.) together as a raw material in the esterification reaction of the polyester polyol described above. .

Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using a low molecular weight polyol (preferably a dihydric alcohol) described later as an initiator, for example, 1,4-butanediol, 1,5-pentanediol, Examples thereof include amorphous polycarbonate polyols obtained by copolymerizing a dihydric alcohol such as 3-methyl-1,5-pentanediol and 1,6-hexanediol with a ring-opening polymer.

The polyurethane polyol reacts with the polyisocyanate to be described later at a ratio in which the equivalent ratio of hydroxyl groups to isocyanate groups (OH / NCO) exceeds 1 with the polyether polyol, polyester polyol and / or polycarbonate polyol obtained as described above. By making it, it can be obtained as a polyester polyurethane polyol, a polyether polyurethane polyol, a polycarbonate polyurethane polyol, or a polyester polyether polyurethane polyol.

Examples of the epoxy polyol include an epoxy polyol obtained by a reaction between a low molecular weight polyol described later and a polyfunctional halohydrin such as epichlorohydrin or β-methylepichlorohydrin.

Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and palm oil. For example, castor oil polyol, or ester-modified castor oil polyol obtained by reaction of castor oil polyol and polypropylene polyol can be used.

Examples of the polyolefin polyol (polyhydroxyalkane) include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

Examples of the acrylic polyol include a copolymer obtained by copolymerizing a hydroxyl group-containing (meth) acrylate and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing (meth) acrylate.

In addition, (meth) acryl is defined as acryl and / or methacryl, and (meth) acrylate is defined as acrylate and / or methacrylate.

Examples of hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, and 2,2-dihydroxymethyl. Examples thereof include butyl (meth) acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate.

Examples of the copolymerizable vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl acrylate, isobornyl (meth) ) Alkyl (meth) acrylates such as acrylate (1 to 12 carbon atoms), for example, aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, Vinyl cyanides such as ronitrile, for example, ethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate And alkane polyol poly (meth) acrylates such as trimethylolpropane tri (meth) acrylate, and vinyl monomers containing an isocyanate group such as 3- (2-isocyanato-2-propyl) -α-methylstyrene.

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

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

The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing (meth) acrylates and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

The acrylic polyol includes, for example, silicone polyol and fluorine polyol.

Examples of the silicone polyol include an acrylic polyol in which a silicone compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane is blended as the copolymerizable vinyl monomer in the copolymerization of the acrylic polyol described above. .

As the fluorine polyol, for example, in the copolymerization of the acrylic polyol described above, as the copolymerizable vinyl monomer, for example, an acrylic polyol in which a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene is blended may be mentioned. .

The vinyl monomer-modified polyol can be obtained by a reaction between the above-described high molecular weight polyol and a vinyl monomer. The high molecular weight polyol is preferably a high molecular weight polyol selected from polyether polyol, polyester polyol and polycarbonate polyol.

Further, examples of the vinyl monomer include the above-described alkyl (meth) acrylate, vinyl cyanide, vinylidene cyanide, and the like. These vinyl monomers can be used alone or in combination of two or more. Of these, alkyl (meth) acrylate is preferable.

The vinyl monomer-modified polyol is obtained by reacting these high molecular weight polyol and vinyl monomer in the presence of a radical polymerization initiator (for example, persulfate, organic peroxide, azo compound, etc.), for example. Can be obtained.

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

As the high molecular weight polyol, polyester polyol is preferable.

The viscosity (25 ° C.) of the high molecular weight polyol is, for example, 1000 mPa · s or more, preferably 2000 mPa · s or more, for example, 1000000 mPa · s or less, preferably 300000 mPa · s or less.

The viscosity is measured with a cone plate viscometer according to JIS K 5600-2-3 (2014).

The low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more, preferably 100 or more and less than 400, preferably less than 500, such as ethylene glycol, propylene glycol, 1,3-propane. Diol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentane Diol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol and mixtures thereof, hydrogenated bis Dihydric alcohols such as enols A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, such as glycerin , Trimethylolpropane, triisopropanolamine and other trihydric alcohols, for example, tetramethylolmethane (pentaerythritol), diglycerin and other tetrahydric alcohols, for example, xylitol and other pentahydric alcohols, such as sorbitol, mannitol, allitol, iditol , Hexavalent alcohols such as dulcitol, altritol, inositol, dipentaerythritol, etc., for example, 7-valent alcohols such as perseitol, for example, 8-valent alcohols such as sucrose, etc. It is.

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

Polyols can be used alone or in combination of two or more.

As the polyol, a high molecular weight polyol is preferable, and a polyester polyol is more preferable.

Anhydric acid is a compound having at least one hydroxyl group (also referred to as an acid anhydride), and examples thereof include acid anhydrides used in the production of the above-described polyester polyols. Oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride Etc.

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

Preferred examples of the anhydride include maleic anhydride, phthalic anhydride, and trimellitic anhydride, and more preferred examples include phthalic anhydride and maleic anhydride.

As a method for adding these anhydrides to the terminal hydroxyl group of the polyol, for example, an anhydride is added to the polyol and heated to react.

In the blending of the anhydride, the hydroxyl-free groups and the hydroxyl groups of the polyol may be in equal amounts, either one of which may be excessive or insufficient.

More specifically, for example, the hydroxyl group in the anhydride is 0.3 or more, preferably 0.5 mol or more, more preferably 0.7 mol or more with respect to 1 mol of the hydroxyl group of the polyol. For example, it is 3 or less, preferably 2 mol or less, more preferably 1.5 mol or less.

If 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 longer, preferably 120 minutes or longer, for example, 600 minutes or shorter, preferably 300 minutes or shorter.

Thereby, an acid anhydride adduct of polyol is obtained.

In the above reaction, when the hydroxyl group-free ratio is less than 1 mole per mole of the hydroxyl group of the polyol (that is, the acid-deficient ratio), part of the hydroxyl group of the polyol is acid-modified and the remaining hydroxyl group Remains unmodified with acid.

Further, in the case where the ratio of hydroxyl-free hydroxyl group exceeds 1 mole per mole of polyol (ie, excess acid anhydride ratio), the anhydride anhydride adduct is a composition containing unreacted hydroxyl-free groups. As obtained.

In addition, the above reaction may be in the absence of a solvent or in the presence of an organic solvent to be blended as necessary.

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, such as 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, such as 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 3-methoxybutyl acetate and ethyl-3-ethoxypropionate, for example, ethers such as diethyl ether, tetrahydrofuran and dioxane, such as methyl chloride, methylene chloride, chloroform, carbon tetrachloride, bromide Halogenated aliphatic hydrocarbons such as methyl, methylene iodide and dichloroethane, for example, polar aprotics such as N-methylpyrrolidone, dimethylformamide, N, N′-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonamide, etc. Is mentioned.

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

Further, after completion of the reaction, the unreacted acid anhydride or 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. Moreover, after completion | finish of reaction, said organic solvent can be added and the density | concentration of the anhydride acid addition product of a polyol can also be adjusted.

Further, the compound having a carboxy group at the molecular end is not limited to the acid anhydride adduct of the above-mentioned polyol. For example, in the production of the polyester polyol described above, a low molecular weight polyol (preferably a dihydric alcohol) and a polybasic acid are used. (Preferably, a dibasic acid) can also be obtained by subjecting it to an esterification reaction under a known condition at a ratio where the carboxy group of the polybasic acid is in an excess mole relative to the hydroxyl group of the low molecular weight polyol.

These compounds having a carboxy group at the molecular end can be used alone or in combination of two or more.

Preferred examples of the compound having a carboxy group at the molecular terminal include an acid anhydride adduct of polyol, and more preferably an acid anhydride adduct of polyester polyol.

Further, examples of the compound having a carboxy group include compounds having a carboxy group in the middle of the molecular chain in addition to the compound having a carboxy group at the molecular end.

Examples of the compound having a carboxy group in the middle of the molecular chain include a branched carboxy group-containing low molecular weight polyol and a branched carboxy group-containing high molecular weight polyol.

The branched carboxy group-containing low molecular weight polyol has a number average molecular weight of 60 or more, preferably 100 or more and less than 400, preferably 500 having one or more carboxy groups in the middle of the molecular chain and two or more hydroxyl groups at the molecular ends. For example, 2,2-dimethylolacetic acid, 2,2-dimethylollactic acid, 2,2-dimethylolpropionic acid (also known as dimethylolpropionic acid (DMPA)), 2,2-dimethylolbutane Examples thereof include polyhydroxyalkanoic acids such as acid, 2,2-dimethylolbutyric acid and 2,2-dimethylolvaleric acid, and preferably 2,2-dimethylolpropionic acid.

The branched carboxyl group-containing high molecular weight polyol has a number average molecular weight of 400 or more, preferably 500 or more and 20000 or less, preferably 10,000 having one or more carboxy groups in the middle of the molecular chain and two or more hydroxyl groups at the molecular ends. The following compounds, for example, branched carboxy group-containing polyether polyol, branched carboxy group-containing polyester polyol, branched carboxy group-containing polyester amide polyol, branched carboxy group-containing polycarbonate polyol, branched carboxy group-containing polyurethane polyol, branched carboxy group-containing Epoxy polyol, branched carboxy group-containing vegetable oil polyol, branched carboxy group-containing polyolefin polyol, branched carboxy group-containing acrylic polyol, branched carboxy group-containing vinyl monomer modified polymer Ol. Preferably, branched carboxy group-containing polyether polyol, branched carboxy group-containing polyester polyol, and branched carboxy group-containing polyurethane polyol are used.

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

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

The branched carboxy group-containing polyurethane polyol can be obtained, for example, by using a branched carboxy group-containing low molecular weight polyol, a branched carboxy group-containing polyether polyol, a branched carboxy group-containing polyester polyol in the production of the above-described polyurethane polyol. .

These compounds having a carboxy group in the middle of the molecular chain can be used alone or in combination of two or more. The compound having a carboxy group in the middle of the molecular chain is preferably a branched carboxy group-containing high molecular weight polyol.

In addition, an acid anhydride may be further added to the hydroxyl group at the molecular end of a compound having a carboxy group in the middle of the molecular chain (a compound having a carboxy group in the middle of the molecular chain and a hydroxyl group at the molecular end) by the above method. it can. Thereby, a compound having a carboxy group at the molecular end and in the middle of the molecular chain is obtained.

In addition, the compound having a carboxy group at the molecular end and in the middle of the molecular chain may be obtained by, for example, branching a branched carboxy group-containing low molecular weight polyol and a polybasic acid, and branching the carboxy group of the polybasic acid when producing a branched carboxy group-containing polyester polyol. It can also be obtained by carrying out an esterification reaction at a ratio of an excess mole relative to the hydroxyl group of the carboxy group-containing low molecular weight polyol.

As described above, the compound having a carboxy group is, for example, a compound obtained by adding an acid anhydride to a hydroxyl group at the molecular end, having no carboxy group in the middle of the molecular chain (molecular end anhydride addition-carboxyl in the middle of the molecular chain). Group-free compound), for example, a compound having no carboxy group in the middle of the molecular chain (molecular terminal carboxy) obtained by reacting raw materials (polybasic acid and low molecular weight polyol) at a blending ratio in which the molecular terminal is a carboxy group Group-containing compound containing no carboxy group in the middle of the molecular chain), for example, a compound having a carboxy group in the middle of the molecular chain and not having a carboxy group at the molecular end (compound containing no carboxy group at the molecular end-containing carboxy group in the middle of the molecular chain) For example, a compound having a carboxy group in the middle of a molecular chain (molecular End-anhydride addition-compound containing a carboxy group in the middle of the molecular chain), for example, by reacting raw materials (polybasic acid, low molecular weight polyol and branched carboxy group-containing low molecular weight polyol) at a blending ratio in which the molecular terminal is a carboxy group And compounds having a carboxy group in the middle of the molecular chain (comprising molecular terminal carboxy group-containing compound in the middle of the molecular chain).

These compounds having a carboxy group can be used alone or in combination of two or more.

The compound having a carboxy group is preferably a compound having a carboxy group at least at the molecular end. That is, preferably, molecular terminal anhydride addition-molecular chain intermediate carboxy group-free compound, molecular terminal carboxy group-containing molecular chain intermediate carboxy group-free compound, molecular terminal acid addition-molecular chain intermediate carboxy group-containing compound, molecule A compound containing a terminal carboxy group-containing a carboxy group in the middle of a molecular chain may be mentioned, and a compound containing an acid anhydride added in a molecular terminal-a compound containing no carboxy group in the middle of a molecular chain is more preferred. More preferably, an anhydride acid addition product of a polyol is mentioned, Especially preferably, an anhydride acid addition product of a polyester polyol is mentioned.

The number average molecular weight (polystyrene equivalent molecular weight in terms of GPC) Mn of the compound having a carboxy group is, for example, 2000 or more, preferably 3000 or more, for example, 20000 or less, preferably 10,000 or less.

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

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

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, for example, 56100 or less. Preferably, it is 11220 or less, More preferably, it is 5610 or less.

The carboxy-containing component may contain the above-mentioned compound having a carboxy group alone, or may contain two or more kinds. Moreover, the additive mentioned later can also be contained.

The content ratio of the compound having a carboxy group with respect to the total amount of the carboxy-containing component is, for example, 50% by mass or more, preferably 80% by mass or more, for example, 100% by mass or less, preferably 99% by mass or less. It is.

The carbodiimide compound contained in the carbodiimide-containing component can be obtained, for example, as a carbodiimide-modified product of polyisocyanate.

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

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

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

Examples of the aliphatic polyisocyanate include a linear (straight or branched chain: acyclic) aliphatic polyisocyanate, and specific examples include ethylene diisocyanate, trimethylene diisocyanate, 1,2- Propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene 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-diisocyanate methylcapate, dodecamethylene diisocyanate Etc., and the like.

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

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

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-naphthalene diisocyanate (NDI) And aromatic diisocyanates.

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, a chain aliphatic polyisocyanate and an araliphatic polyisocyanate are preferable, and pentamethylene diisocyanate (PDI) is more preferable.

The carbodiimidization catalyst is not particularly limited, and examples thereof include trialkyl phosphate compounds, phospholene oxide compounds, phospholene sulfide compounds, phosphine oxide compounds, and phosphine compounds.

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

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

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

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

Examples of the phosphine compound include phosphine compounds 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 application.

As heating conditions, the heating temperature is, for example, 30 ° C. or more, preferably 60 ° C. or more, for example, 200 ° C. or less, preferably 180 ° C. in an atmosphere of normal pressure and inert gas (such as nitrogen gas). 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.

Thereby, the polyisocyanate is decarboxylated and condensed to obtain a carbodiimide compound (that is, a carbodiimide-modified product of polyisocyanate).

In the carbodiimidization reaction, the above-mentioned organic solvent can be blended if necessary, and after completion of the reaction, if necessary, by a known method such as a distillation method or an extraction method, unreacted polyisocyanate or All or part of the organic solvent can be removed. Moreover, after completion | finish of reaction, said organic solvent can be added and the density | concentration of the solution of a carbodiimide compound can also be adjusted.

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

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

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

The carbodiimide group equivalent can be determined from a ¹³ C-NMR 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, 1000 or more, preferably 2000 or more, from the viewpoint of the appearance and adhesiveness of the obtained laminate, and the laminate strength. From the viewpoint, for example, it is 5000 or less, preferably 4000 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, 1500 or more, preferably 2000 or more from the viewpoint of the appearance of the obtained laminate, and from the viewpoint of laminate strength. For example, it is 15000 or less, preferably 10,000 or less.

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

In addition, said carbodiimide compound can also be obtained as a commercial item, for example, carbodilite V05S (solid content concentration 90 mass%, carbodiimide group equivalent 291 (solid content equivalent 262), Nisshinbo Co., Ltd. make), carbodilite V07 (solid). 50% by weight concentration, carbodiimide group equivalent 404 (solid content equivalent 202), manufactured by Nisshinbo Industries, Inc., Carbodilite V09GB (solid content concentration 70% by weight, carbodiimide group equivalent 298 (solid content equivalent 209), manufactured by Nisshinbo Industries, Ltd.) ) And the like.

The carbodiimide-containing component may contain the above-mentioned carbodiimide compound alone, or may contain two or more kinds. Moreover, the additive mentioned later can also be contained.

The content ratio of the carbodiimide compound with respect to the total amount of the carbodiimide-containing component is, for example, 50% by mass or more, preferably 80% by mass or more, for example, 100% by mass or less, preferably 99% by mass or less.

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

Such a two-component curable adhesive composition is prepared by using a carboxy-containing component as a main component and a carbodiimide-containing component as a curing agent to prepare a mixed solution at the time of use. The liquid is diluted with an organic solvent and applied to a substrate (adhered body).

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

If the blending ratio of the carboxy-containing component and the carbodiimide-containing component is in the above range, the obtained laminate can have both excellent appearance and excellent adhesiveness.

And such a two-component 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-component curable adhesive composition, the carboxy group of the carboxy-containing component and the carbodiimide group of the carbodiimide-containing component undergo an acylureaization reaction, so that no carbon dioxide gas is generated during curing, and the structure is cured. (Adhesion) Even if time passes, the possibility of carbon dioxide generation due to moisture in the atmosphere is extremely low, so it is possible to suppress the generation of bubbles between the films of the laminate film, and an excellent appearance Can be obtained.

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

Moreover, since this two-component curable adhesive composition contains an acylurea group exhibiting a strong hydrogen bonding ability in the same manner as a urethane bond, it exhibits excellent adhesive performance.

Moreover, in such a two-component curable adhesive composition, gas generation can be suppressed without using a blocking agent. As described above, if 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 it uses for a vacuum heat insulating material, the fall of a vacuum degree can be suppressed.

Hereinafter, the gas barrier laminate film (laminate) obtained using the two-component curable adhesive composition and the production method thereof will be described in detail.

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 a gas barrier property and has an oxygen permeability (25 ° C., 80% RH (JIS K 716-2 (2006)) of 100 mL / m ² · 24 hr · MPa or less, preferably , 50 mL / m ² · 24 hr · MPa or less.

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

Specific examples of the gas barrier film 2 include metal foil (for example, aluminum foil). Also, for example, a plastic film provided with a metal film (for example, an aluminum film), a plastic film provided with a metal vapor-deposited film (aluminum vapor-deposited film, silica vapor-deposited film, alumina vapor-deposited film, silica / alumina binary vapor-deposited film, etc.), etc. It is done. Moreover, as a plastic film, a polyethylene terephthalate (PET) film, a nylon (NY) film, a cellulose acetate (TAC) film etc. are mentioned, for example, Preferably, a PET film and a cellulose acetate (TAC) film are mentioned. In addition, the thickness of a metal film, the thickness of a metal vapor deposition film, and the thickness of a plastic film are not specifically limited, It sets suitably according to the objective and a use.

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

The gas barrier film 2 is preferably a plastic film provided with a metal vapor deposition film. More preferably, a plastic film provided with a silica vapor deposition film, a plastic film provided with an alumina vapor deposition film, and a plastic film provided with a silica / alumina binary vapor deposition film may be mentioned. Moreover, as a plastic film provided with such a metal vapor deposition film, Preferably, a PET film and a cellulose acetate (TAC) film are mentioned.

More preferably, the gas barrier film 2 includes a PET film having a silica deposited film, a PET film having an alumina deposited film, and a PET film having a silica / alumina binary deposited film.

FIG. 1 shows a plastic film 5 having a metal vapor deposition film 4 as a 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 vapor deposition film 4 and the plastic film 5, and the surface of the metal vapor deposition film 3 (plastic film). 4 may be provided with an overcoat layer.

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

The adhesive layer 3 is a cured product of the above-described two-component curable adhesive composition, 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 together with the two-component curable adhesive composition.

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

Also, for example, a plurality (two) of gas barrier films 2 can be bonded so that the plastic films 5 face each other through the adhesive layer 3.

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

Preferably, as shown in FIG. 1, a plurality (two) of gas barrier films 2 are bonded together so that the metal vapor deposition films 4 face each other through the adhesive layer 3.

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 laminate 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 can be combined with the method described above. You can also paste together.

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

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

The thickness of the heat seal layer 6 is, for example, 10 μm or more, preferably 20 μm or more, 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 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 two-component curable adhesive composition, or may be a cured product of other known adhesives (such as polyurethane adhesives). 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.

Moreover, after applying an anchor agent to the surface of the gas barrier film 2 as needed, resin, such as polyethylene, can be extruded and the heat seal layer 6 can also be laminated | stacked. In such a case, the coating amount of the anchor agent coating layer 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 laminate film 1, for example, first, a plurality (for example, two) of gas barrier films 2 are prepared (preparation step).

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

Specifically, in the laminating step, for example, after the carboxy-containing component and the carbodiimide-containing component are diluted with the above organic solvent and blended, the resulting mixture is applied to the surface of each gas barrier film with a solvent-type laminator, After volatilization, the coated surfaces are bonded together, and then cured by curing at room temperature or under heating, or the blending 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 the carboxy-containing component and the carbodiimide-containing component are blended as they are, the resulting mixture is mixed with each gas barrier film by a solventless laminator. Applying to the surface and pasting the coated surface It is.

The application amount of the two-part curable adhesive composition is, for example, 2.0 to 8.0 g / m ² in the basis weight (solid content) after solvent evaporation, 1.0 to 4.0 g / m ² .

Thereby, the carboxy group in the carboxy-containing component and the carbodiimide group in the carbodiimide-containing component undergo an acylureaization reaction, and the two-component 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 heated and cured as necessary (curing process).

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.

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

Furthermore, if necessary, the heat seal layer 6 can be adhered to the surface of the gas barrier film 2 via the heat seal adhesive layer 7 in the same manner as in the above-described laminating process (see the broken line in FIG. 1). Thereby, the heat sealing property can be imparted to the laminate film 1.

The resulting laminate film 1 is excellent in gas barrier properties against oxygen, water vapor, and the like, and is in the field of gas barrier films, specifically, heat insulating fields such as vacuum heat insulating materials, and further packaging films such as foods and pharmaceuticals, It is suitably used in food packaging containers (including bottles), optical films, industrial films and the like, and particularly preferably in the heat insulation field 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 included within a range that does not impede its purpose and effect. The content of this other component is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to 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. “Part” and “%” are based on mass unless otherwise specified. In addition, specific numerical values such as a blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and a blending ratio corresponding to them ( Substituting the upper limit value (numerical value defined as “less than” or “less than”) or the lower limit value (number defined as “greater than” or “exceeded”) such as content ratio), physical property values, parameters, etc. be able to.

Various measurement methods are shown below.

<Acid value>
Weigh an appropriate amount of the sample, dissolve it in a mixed solvent of toluene / methanol = 7/3 (weight ratio), add a few drops of phenolphthalein indicator, and titrate with 0.1 mol / L ethanolic potassium hydroxide solution. Asked.

<Carboxy group equivalent (solid content)>
It calculated | required by the following formula using the acid value calculated | required above.

Carboxy group equivalent = 56100 / acid value <Carbodiimide group equivalent (solid content)>
Using a polycarbodiimide composition described later, ¹³ C-NMR was measured under the following apparatus and conditions, and a carbodiimide group equivalent (solid content) was calculated from an integrated value and a charged amount of a functional group described later. In addition, tetramethylsilane (0 ppm) in CDCL ₃ solvent was used as a reference for chemical shift ppm.
Equipment; ECA-500 type (manufactured by JEOL)
Conditions; Measurement frequency: 125 MHz, solvent: CDCL ₃ , solute concentration: 50% by mass
Measurement temperature: room temperature, number of scans 8500, repetition time: 3.0 seconds, pulse width: 30 ° (3.70 μsec)
Carbon assignment peak of carbodiimide group (N = C = N group in carbodiimide group): 139 ppm
Carbon attribute peak of urethane group (C = O group in urethane group): 156 ppm
In addition, a carbodiimide equivalent is computed by a conventional method based on said NMR measurement result.

<Terminal hydroxyl group content>
Weigh an appropriate amount of the sample, add 20 mL of a mixed solution of acetic anhydride / pyridine (30 mL / 400 mL) and 2 mL of pyridine solution of 4-dimethylaminopyridine (concentration 1 g / 100 mL), stir and dissolve at room temperature for 30 minutes. Acetic anhydride was added to the. Next, after diluting with 50 mL of pyridine, the excess acid was back titrated with a 1 mol / L aqueous sodium hydroxide solution to determine the acetyl value (mgKOH / g). From this result (value) and the separately measured acid value, the terminal hydroxyl group amount (hydroxyl value) was determined by the following formula.

Hydroxyl value = acetyl value + acid value <main agent (carboxy-containing component)>
Production Example 1 (Preparation of main agent A)
184.8 g of terephthalic acid, 246.4 g of isophthalic 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 charged into a reaction vessel, respectively, and the ester was added at 180 to 220 ° C. It was made to react. When the acid value became 8 mgKOH / g or less, 0.07 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. reached 1930 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant (hereinafter the same)), the amount of terminal hydroxyl groups was determined by titration. Maleic anhydride was added so as to have the same equivalent (1 mol of hydroxyl group: 1 mol of hydroxyl group), and the mixture was stirred at 150 ° C. for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 374.1 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end. Further, KBM403 (manufactured by Shin-Etsu Silicone, silane coupling agent (hereinafter the same)) 1.75 g, KBM603 (manufactured by Shin-Etsu Silicone, silane coupling agent (hereinafter the same)) 0.87 g, 0.44 g of phosphoric acid, and solid content 73.2% of main agent A was obtained. The acid value was 25.2 mgKOH / g, and the carboxy group equivalent (solid content) was 1629.

Production Example 2 (Preparation of main agent B)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged into a reaction vessel, respectively, and esterified at 180 to 220 ° C. I let you. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. reached 5040 mPa · s (measured with a cone plate viscometer; JIS K compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent (hydroxyl-free 1 mol: hydroxyl group 1 mol) ) And maleic anhydride was added so that the resulting mixture was stirred at 150 ° C. for 90 minutes to add to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

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

Production Example 3 (Preparation of main agent C)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. was 9640 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent Maleic anhydride was added so as to be (hydroxyl-free 1 mol: hydroxyl group 1 mol), and the mixture was stirred at 150 ° C. for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

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

Production Example 4 (Preparation of main agent D)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. was 9230 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and twice the equivalent Maleic anhydride was added so as to be (hydroxyl-free 2 mol: hydroxyl group 1 mol), and the mixture was stirred at 150 ° C. for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 1146 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end. Further, 2.93 g of KBM403, 1.47 g of KBM603 and 0.73 g of phosphoric acid were added to obtain a base D having a solid content of 57.1%. The acid value was 23.4 mgKOH / g, and the carboxy group equivalent (solid content) was 1369.

Production Example 5 (Preparation of main agent E)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. was 9360 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration. Maleic anhydride was added so that it might become a double equivalent (hydroxyl-free 0.5 mol: hydroxyl group 1 mol), and it stirred at 150 degreeC for 120 minutes, and was added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 1100 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end. Further, 2.93 g of KBM403, 1.47 g of KBM603, and 0.73 g of phosphoric acid were added to obtain a base E having a solid content of 60.5%. The acid value was 5.95 mgKOH / g, and the carboxy group equivalent (solid content) was 5705.

Production Example 6 (Preparation of main agent F)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. became 9100 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent The trimellitic anhydride was added so that it might become (1 mol of hydroxyl groups: 1 mol of hydroxyl groups), and it stirred at 150 degreeC for 120 minutes, and was added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 1100 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end. Further, 2.93 g of KBM403, 1.47 g of KBM603 and 0.73 g of phosphoric acid were added to obtain a base F having a solid content of 60.5%. The acid value was 23.8 mgKOH / g, and the carboxy group equivalent (solid content) was 1428.

Production Example 7 (Preparation of main agent G)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. became 7400 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent Phthalic anhydride was added so as to be (hydroxyl-free 1 mol: hydroxyl group 1 mol), and the mixture was stirred at 150 ° C. for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

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

Production Example 8 (Preparation of main agent H)
274.3 g of terephthalic 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 charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. It was made to react. When the acid value became 20 or less, 150.8 g of adipic acid was added, and the esterification reaction was further continued.

Thereafter, when the viscosity at 150 ° C. reached 5160 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent Maleic anhydride was added so as to be (hydroxyl-free 1 mol: hydroxyl group 1 mol), and the mixture was stirred at 150 ° C. for 120 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 667 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end. Further, 1.65 g of KBM403, 0.82 g of KBM603, and 0.41 g of phosphoric acid were added to obtain a main agent H having a solid content of 64.7%. The acid value was 30.7 mgKOH / g, and the carboxy group equivalent (solid content) was 1184.

Production Example 9 (Main agent I)
Takelac A-620 (polyester polyol, Mitsui Chemicals) was used as the main agent I.

Production Example 10 (Preparation of main agent J)
310.5 g of terephthalic acid, 414 g of isophthalic acid, 363.9 g of adipic acid, 220.4 g of ethylene glycol, 282.6 g of diethylene glycol, and 277.3 g of neopentyl glycol were charged in a reaction vessel, respectively, and esterified at 180 to 220 ° C. Reacted. When the acid value became 8 mgKOH / g or less, 0.15 g of titanium tetrabutoxide (TTB) was added, and the esterification reaction was continued.

Thereafter, when the viscosity at 150 ° C. became 9820 mPa · s (measured with a cone plate viscometer; JIS K 5600-2-3 (2014) compliant), the amount of terminal hydroxyl groups was determined by titration, and its equivalent equivalent Maleic anhydride was added so as to be (hydroxyl-free 1 mol: hydroxyl group 1 mol), and the mixture was stirred at 150 ° C. for 90 minutes to be added to the hydroxyl group. Thereby, a compound having a carboxy group at the molecular end was obtained.

Thereafter, 1100 g of ethyl acetate was added to dissolve the compound having a carboxy group at the molecular end to obtain a base C having a solid content of 59.3%. The acid value was 10.4 mg KOH / g, and the carboxy group equivalent (solid content) was 3199.

<Curing agent (carbodiimide-containing component)>
The following products were used as curing agents A to C and curing agent E.

Moreover, the hardening | curing agents D, F, and G were manufactured with the following method.
Curing agent A: Nisshinbo Carbodilite V05S, solid content concentration 90% by mass, carbodiimide group equivalent 291 (solid content equivalent 262)
Curing agent B: Carbodilite V07 manufactured by Nisshinbo Co., Ltd., solid content concentration 50 mass%, carbodiimide group equivalent 404 (solid content equivalent 202)
Curing agent C: Carbodilite V09GB manufactured by Nisshinbo Co., Ltd., solid content concentration 70% by mass, carbodiimide group equivalent 298 (solid content equivalent 209)
Curing agent E: Takenate A-50 (terminal isocyanate group-containing urethane resin, manufactured by Mitsui Chemicals)
Curing agent D: Curing agent D was 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 pentamethylene diisocyanate at room temperature, UNIOX M400 (polyoxyethylene monomethyl ether (manufactured by NOF)) Was charged at 44.2 parts by mass and 13.4 parts by mass of 1-methoxy-2-propanol, heated to 80 ° C. under normal pressure while introducing nitrogen, and stirred for 6 hours for urethanization reaction. .

Subsequently, 330.5 parts by mass of xylene as an organic solvent and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) as a carbodiimidization catalyst were charged, and the mixture was refluxed. The reaction was terminated by stirring for 8 hours at (141 ° C.).

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

Curing agent F: Curing agent F was 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 1,3-bis (isocyanatomethyl) cyclohexane and 9.54 isobutanol were added at room temperature. The mass part was charged. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 6 hours to cause urethanization reaction.
Subsequently, 231.0 parts by mass of propylene glycol monomethyl ether acetate (PMA) as an organic solvent and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) as a carbodiimidization catalyst A portion of the mixture was charged and stirred under reflux (150 ° C.) for 8 hours to complete the reaction.

After completion of the reaction, the mixture was cooled to 80 ° C., and PMA was partially distilled off under reduced pressure to obtain a curing agent F as a polycarbodiimide composition. The solid content concentration was 88.4%, and the carbodiimide group equivalent (solid content) was 265.

Curing agent G: Curing agent G was produced by the following method.

A four-necked flask equipped with a stirrer, a thermometer, a reflux tube, and a nitrogen introduction tube was charged with 100.0 parts by mass of isophorone diisocyanate and 8.34 parts by mass of isobutanol at room temperature. While introducing nitrogen, the mixture was heated to 80 ° C. under normal pressure and stirred for 6 hours to cause urethanization reaction.

Subsequently, 228.5 parts by mass of propylene glycol monomethyl ether acetate (PMA) as an organic solvent and 2.0 parts by mass of 3-methyl-1-phenyl-2-phospholene-1-oxide (MPPO) as a carbodiimidization catalyst A portion of the mixture was charged and stirred under reflux (150 ° C.) for 8 hours to complete the reaction.

After completion of the reaction, the mixture was cooled to 80 ° C., and PMA was partially distilled off under reduced pressure to obtain a curing agent G as a polycarbodiimide composition. The solid content concentration was 74.5%, and the carbodiimide group equivalent (solid content) was 310.

Examples 1 to 25 and Comparative Example 1
The main component (carboxy-containing component) and curing agent (carbodiimide-containing component) are mixed at the mixing ratio R (carbodiimide group / carboxy group (molar ratio)) shown in Tables 1 to 5, and further diluted with a solvent (ethyl acetate). The coating solution obtained was applied to Tech Barrier TX (Mitsubishi Resin, PET film with a silica vapor deposition film, 12 μm, 5.0 mL / m ² · 24 hr · MPa) as a gas barrier film. m 2 was coated to a ^(dry film thickness) was bonded to silica-deposited layer between the gas barrier film. Thereafter, the obtained laminate was cured at 60 ° C. for 3 days.

<Evaluation>
(Appearance observation of laminated products)
The appearance of the laminate after curing at 60 ° C. for 3 days was evaluated according to the following criteria: ○: No foaming △: Slightly foamed X: Foamed (peeling strength of the laminate film)
In accordance with JIS K 6854-3 (1999), measurement was performed at 24 ° C., 15 mm width, and tensile speed 300 mm / min.

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

(Heat-resistant creep of laminate film)
The test piece was cut into a strip shape with a width of 15 mm, peeled off, a 100 g weight was attached to the film on one side, the deviation width was measured at 120 ° C. for 3 minutes, and the value was converted to the deviation width per minute.

Although the above invention has been provided as an exemplary embodiment of the present invention, this is merely an example and should not be interpreted in a limited manner. Variations of the present invention that are apparent to one of ordinary skill in the art are within the scope of the following claims.

The two-component curable adhesive composition, the laminate film, and the method for producing the same of the present invention are used in the heat insulation field such as a vacuum heat insulating material, and further, packaging films such as foods and pharmaceuticals, food packaging containers (including bottles), and optics. It is suitably used in the gas barrier field such as films and industrial films.

1 Laminate film 2 Gas barrier film 3 Adhesive layer

Claims (7)

1. A two-component curable adhesive composition for bonding between a plurality of gas barrier films,
   A carboxy-containing component having a carboxy group;
   A two-component curable adhesive composition comprising a carbodiimide-containing component containing a carbodiimide compound.
2. The two-component curable adhesive composition according to claim 1, wherein the carboxy-containing component contains an acid anhydride adduct of polyester polyol.
3. 3. The two-component curable adhesive composition according to claim 2, wherein the non-hydroxyl group in the anhydride is in a ratio of 0.7 mol or more with respect to 1 mol of the hydroxyl group of the polyester polyol.
4. For 1 mol of carboxy group in the carboxy-containing component,
   The two-component curable adhesive composition according to claim 1, wherein the carbodiimide group in the carbodiimide-containing component is contained in a proportion of 1.3 mol or more and 4 mol or less.
5. A plurality of gas barrier films;
   A laminate film comprising: an adhesive layer which is interposed between the plurality of gas barrier films and is a cured product of the two-component curable adhesive composition according to claim 1.
6. A preparation step of preparing a plurality of gas barrier films;
   A laminate film manufacturing method comprising: a laminate step of bonding a plurality of gas barrier films through the two-component curable adhesive composition according to claim 1 to obtain a laminate.
7. The method for producing a laminate film according to claim 6, further comprising a curing step for heating and curing the laminate after the laminating step.

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