JP7137937B2 - Laminating adhesives and packaging materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to a lamination adhesive and a packaging material, and more particularly to a lamination adhesive used for lamination of composite films and a packaging material obtained using the lamination adhesive.

Laminated films are known as wrapping materials used in various industrial fields. Such laminate films are prepared by laminating various films with an adhesive.

As such an adhesive, for example, a polyurethane adhesive composition containing an organic polyisocyanate, an organic polyol, an oxyacid of phosphorus or a derivative thereof, an amine compound and an epoxy resin has been proposed. , a reaction product of 100 g of polyester polyol and 6.2 g of isophorone diisocyanate, phosphoric acid, dibutylamine, Epicoat 1002 (epoxy resin) and the like are added to the main component D, 174.2 g of tolylene diisocyanate and 44 g of trimethylolpropane. An adhesive combined with 0.7 g of the reaction product curing agent C has been proposed (see, for example, Patent Document 1 (Example Adhesive No. 7)).

JP-A-7-11225

On the other hand, adhesives used for laminate films are required to further improve various properties depending on the application of the laminate film.

For example, in the field of packaging materials for pharmaceuticals and quasi-drugs, in addition to adhesive strength for laminating various films, drawability for molding while suppressing damage to various films is required. There is also a demand for heat and humidity resistance that does not cause peeling even in a high humidity and heat environment.

INDUSTRIAL APPLICABILITY The present invention provides a lamination adhesive capable of obtaining excellent adhesive strength, drawability and resistance to moist heat, and a packaging material obtained using the lamination adhesive.

The present invention [1] contains a polyisocyanate component, a polyol component and an epoxy component, the polyol component contains a polyurethane polyol modified with an aromatic polyisocyanate, and the polyol component has a weight average molecular weight of 30000 or more. 50000 or less, the epoxy equivalent of the epoxy component is 440 g/eq or more and 700 g/eq or less, and the content ratio of the epoxy component is 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyol component. , including laminating adhesives.

The present invention [2] is the above [1], wherein the total content of the polyol component and the epoxy component is 5 parts by mass or more and 8 parts by mass or less with respect to 1 part by mass of the polyisocyanate component. Contains laminating adhesive.

The present invention [3] includes the laminate adhesive according to the above [1] or [2], wherein the polyisocyanate component is a polyol-modified tolylene diisocyanate.

The present invention [4] includes the laminate adhesive according to any one of [1] to [3] above, wherein the epoxy component has an epoxy equivalent of 600 g/eq or more and 700 g/eq or less.

The present invention [5] is according to any one of the above [1] to [4], wherein the content of the epoxy component is 20 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyol component. of laminating adhesive.

The present invention [6] is the above [1] to [5], wherein the total content of the polyol component and the epoxy component is 6 parts by mass or more and 8 parts by mass or less with respect to 1 part by mass of the polyisocyanate component. ] comprising the laminating adhesive according to any one of the above.

The present invention [7] includes the laminate adhesive according to any one of the above [1] to [6], wherein the epoxy component has a weight average molecular weight of 4000 or less.

The present invention [8] is a composite film comprising the lamination adhesive according to any one of [1] to [7] above, and a first film and a second film adhered to each other by the lamination adhesive. and wherein the composite film includes a packaging material characterized by having a recess recessed to accommodate an object to be packaged.

The lamination adhesive of the present invention can improve drawability while ensuring adhesive strength, and is also excellent in moist heat resistance.

Therefore, according to the lamination adhesive of the present invention, a composite film having excellent adhesive strength can be obtained, and even when the composite film is molded, cracks in the composite film can be suppressed. Delamination can be suppressed even when the composite film is placed under high temperature and high humidity conditions.

Moreover, since the packaging material of the present invention comprises the first film and the second film adhered by the lamination adhesive, it is excellent in adhesive strength, drawability and resistance to moist heat.

Furthermore, since the laminating adhesive described above can improve the resistance to moist heat of the composite film, the composite film can be molded so as to form a concave portion for accommodating the object to be packaged. It is possible to suppress the occurrence of cracks in the film.

FIG. 1 is a schematic configuration diagram of a packaging bag provided with one embodiment of the packaging material of the present invention.

The laminate adhesive of the present invention contains a polyisocyanate component, a polyol component and an epoxy component.

Examples of polyisocyanate components include polyisocyanate monomers and modified polyisocyanates.

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

Examples of aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof), 4, 4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-, 2,4′- or 2,2′-diphenylmethane diisocyanate or mixtures thereof) (MDI), aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI) and 4,4'-diphenylether diisocyanate;

Examples of araliphatic polyisocyanates include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra araliphatic diisocyanates such as methylxylylene diisocyanate (or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4-diethylbenzene, and the like.

Examples of aliphatic polyisocyanates include 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), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc. and aliphatic diisocyanates.

Aliphatic polyisocyanates also include alicyclic polyisocyanates. Alicyclic polyisocyanates include, for example, 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3 ,5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis(cyclohexylisocyanate) (4,4′-, 2,4′- or 2,2′-methylenebis(cyclohexylisocyanate), these Trans, Trans -, Trans, Cis-, Cis, Cis-, or mixtures thereof)) (H ₁₂ MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane Alicyclics such as diisocyanates (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or mixtures thereof) (H ₆ XDI) group diisocyanates.

These polyisocyanate monomers can be used singly or in combination of two or more.

Examples of modified polyisocyanates include the above polyisocyanate monomers, for example, oligomers (e.g., trimers (isocyanurate modified, iminooxadiazinetrione modified), etc.), biuret modified, allophanate modified. , modified oxadiazinetrione, modified polyol (alcohol adduct), and the like.

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

Among such polyisocyanate-modified products, polyol-modified products (alcohol adducts) are preferred.

The polyol modified product is obtained by combining the above-described polyisocyanate monomer and a low-molecular-weight polyol (described later) so that the equivalent ratio (isocyanate group/hydroxyl group) of the isocyanate group of the polyisocyanate monomer to the hydroxyl group of the low-molecular-weight polyol is 1. obtained by reacting at a rate exceeding Therefore, the polyol-modified product contains urethane bonds generated by the reaction between isocyanate groups and hydroxyl groups and isocyanate groups remaining after the reaction.

The low-molecular-weight polyol used in the modified polyol is preferably trihydric alcohol (triol), more preferably trimethylolpropane (TMP).

The polyisocyanate component is preferably a modified polyisocyanate, more preferably a modified aromatic diisocyanate, a modified alicyclic diisocyanate, and from the viewpoint of the heat and humidity resistance of a laminate film (described later), more preferably an aromatic Examples include polyol-modified diisocyanates (preferably triol-modified aromatic diisocyanates), and particularly preferably, the polyisocyanate component is polyol-modified tolylene diisocyanate (preferably triol-modified tolylene diisocyanate). mentioned.

Moreover, as a polyisocyanate component, for example, the above-described polyisocyanate monomer and a modified polyisocyanate can be used in combination. When a polyisocyanate monomer and a modified polyisocyanate are used in combination, the mixing ratio thereof is appropriately set according to the purpose and application.

The polyisocyanate component preferably consists of a polyol-modified product, more preferably a polyol-modified aromatic diisocyanate (preferably a triol-modified aromatic diisocyanate), particularly preferably a polyol-modified tolylene diisocyanate. (preferably a triol-modified aromatic diisocyanate).

In addition, the isocyanate group content (NCO mass%) of the polyisocyanate component is, for example, 1% by mass or more, preferably 5% by mass or more, based on the solid content, and more preferably from the viewpoint of the adhesive strength of the laminate adhesive. , 14.5% by mass or more, for example, 50% by mass or less, preferably 30% by mass or less, and more preferably less than 20% by mass from the viewpoint of moist heat resistance of the laminate film (described later). The isocyanate group content can be determined by the isocyanate group content test described in JIS K7301 (the same applies hereinafter).

Moreover, the polyisocyanate component can be used by diluting it with an organic solvent.

Examples of organic solvents include ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), nitriles (e.g., acetonitrile, etc.), alkyl esters (e.g., methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, etc.), fats, family hydrocarbons (e.g. n-hexane, n-heptane, octane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, methylcyclohexane, etc.), aromatic hydrocarbons (e.g., toluene, xylene, ethylbenzene, etc.) , glycol ether esters (e.g., methyl cellosolve acetate, ethyl cellosolve acetate, methyl carbitol acetate, etc.), ethers (e.g., diethyl ether, tetrahydrofuran, dioxane, etc.), halogenated aliphatic hydrocarbons (e.g., methyl chloride, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, etc.), polar aprotons (eg, N-methylpyrrolidone, dimethylformamide, N,N'-dimethylacetamide, dimethylsulfoxide, etc.).

These organic solvents can be used alone or in combination of two or more. The organic solvent preferably includes alkyl esters, more preferably ethyl acetate.

Further, when the polyisocyanate component is diluted with an organic solvent, the solid content concentration of the polyisocyanate component is, for example, 10% by mass or more, preferably 30% by mass or more, for example, 95% by mass or less, preferably 90% by mass or more. % by mass or less. The polyisocyanate component can also be used without being diluted with an organic solvent, that is, at a solid content concentration of 100% by mass.

The polyol component contains a polyurethane polyol modified with an aromatic polyisocyanate. A polyurethane polyol modified with an aromatic polyisocyanate is hereinafter referred to as an aromatic polyurethane polyol.

If the polyol component contains an aromatic polyurethane polyol, it is possible to improve adhesive strength, drawability, and resistance to moist heat.

Aromatic polyurethane polyol is a reaction product of aromatic polyisocyanate and high molecular weight polyol, and has two or more hydroxyl groups in the molecule.

Aromatic polyisocyanates include the above-described aromatic polyisocyanate monomers and modified products.

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

The aromatic polyisocyanate preferably includes an aromatic polyisocyanate monomer, and more preferably includes a tolylene diisocyanate monomer.

High-molecular-weight polyols include high-molecular-weight compounds (preferably polymers) having two or more hydroxyl groups in the molecule and a number average molecular weight of 400 or more, preferably 500 or more, for example, 5000 or less.

Specific examples of high-molecular-weight polyols include polyether polyols, polyester polyols, and polycarbonate polyols, preferably polyester polyols.

A polyester polyol is prepared, for example, by reacting a polybasic acid with a low molecular weight polyol.

Examples of polybasic acids include saturated aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, etc.), unsaturated aliphatic dicarboxylic acids (eg, , maleic acid, fumaric acid, itaconic acid, etc.), aromatic dicarboxylic acids (e.g., orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, etc.), alicyclic dicarboxylic acids (e.g., hexahydrophthalic acid, etc.), etc. (eg, dimer acid, hydrogenated dimer acid, etc.), acid anhydrides derived from these carboxylic acids, and the like. These polybasic acids can be used alone or in combination of two or more.

Among such polybasic acids, preferred are saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, more preferred are mixtures containing saturated aliphatic dicarboxylic acids and aromatic dicarboxylic acids, and particularly preferred are include mixtures containing isophthalic acid and sebacic acid. In addition, when polybasic acid contains aromatic dicarboxylic acid, polyester polyol contains an aromatic ring.

The low-molecular-weight polyol is a compound having a number average molecular weight of 40 or more and less than 400 and having two or more hydroxyl groups. glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, hydrogenated bisphenol A, bisphenol A, diethylene glycol, triethylene glycol, etc.), trihydric alcohols (e.g., glycerin, trimethylolpropane) , triisopropanolamine, etc.), tetrahydric alcohols (e.g., tetramethylolmethane (pentaerythritol), diglycerin, etc.), pentahydric alcohols (e.g., xylitol, etc.), hexahydric alcohols (e.g., sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, etc.), heptahydric alcohols (eg, perseitol, etc.), octahydric alcohols (eg, sucrose, etc.), and the like. These low-molecular-weight polyols can be used alone or in combination of two or more.

Among such low-molecular-weight polyols, preferred are dihydric alcohols (low-molecular-weight diols), more preferred are mixtures containing two or more dihydric alcohols (low-molecular-weight diols), and particularly preferred are includes a mixture containing a linear dihydric alcohol having 2 to 4 carbon atoms (preferably ethylene glycol) and a branched dihydric alcohol having 4 to 6 carbon atoms (preferably neopentyl glycol).

Then, in order to react the polybasic acid and the low-molecular-weight polyol, the equivalent ratio of the hydroxyl group of the low-molecular-weight polyol to the carboxyl group of the polybasic acid (hydroxyl group/carboxyl group) is, for example, a ratio exceeding 1 and 2 or less. If necessary, an esterification catalyst is added to cause an esterification reaction between the polybasic acid and the low-molecular-weight polyol.

Esterification catalysts include, for example, organic titanium compounds (e.g., tetramethyl titanate, tetrabutyl titanate, etc.), organic tin compounds (e.g., tin octoate, dibutyltin oxide, etc.), metal acetate salts (e.g., zinc acetate, manganese acetate , calcium acetate, etc.). These esterification catalysts can be used alone or in combination of two or more.

Among such esterification catalysts, tin octoate and zinc acetate are preferred. The addition ratio of the esterification catalyst is, for example, 0.001 parts by mass or more, preferably 0.01 parts by mass or more, for example, 0.5 parts by mass or less, preferably , 0.06 parts by mass or less. That is, in the esterification reaction, when an esterification catalyst is added, the polyol component contains the esterification catalyst.

As reaction conditions for the esterification reaction, the temperature is, for example, 150° C. or more and 250° C. or less, and the time is, for example, 8 hours or more and 96 hours or less. The esterification reaction is preferably carried out under an inert gas atmosphere (eg nitrogen, argon, etc.).

Thereby, the polybasic acid and the low-molecular-weight polyol undergo an esterification reaction to prepare a polyester polyol. The polyester polyol can also be prepared by a known transesterification reaction between the alkyl ester of polybasic acid and the low-molecular-weight polyol.

The high molecular weight polyol is preferably dissolved in the above organic solvent and used as a high molecular weight polyol solution. The organic solvent preferably includes alkyl esters, more preferably ethyl acetate.

The solid content concentration of the high-molecular-weight polyol solution is, for example, 30% by mass or more, preferably 50% by mass or more, and for example, 90% by mass or less, preferably 70% by mass or less.

The hydroxyl value of the high-molecular-weight polyol solution is, on a solid basis, for example, 3 mgKOH/g or more, preferably 10 mgKOH/g or more, more preferably 35 mgKOH/g or more, for example 60 mgKOH/g or less, preferably 40 mgKOH/g. g or less.

Incidentally, the hydroxyl value can be determined by an acetylation method or a phthalation method conforming to the A method or B method of JIS K 1557-1 (2007).

The number average molecular weight (Mn) of the high molecular weight polyol is, for example, 400 or more, preferably 500 or more, and for example, 5,000 or less, preferably 4,000 or less.

Further, the weight average molecular weight (Mw) of the high molecular weight polyol is, for example, 6000 or more, preferably 7000 or more, and for example, 100000 or less, preferably 80000 or less.

The number average molecular weight (Mn) and weight average molecular weight (Mw) are polystyrene equivalent molecular weights measured by GPC. The method for measuring the number average molecular weight (Mn) and the weight average molecular weight (Mw) conforms to the examples described later (same below).

In order to react the high-molecular-weight polyol with the aromatic polyisocyanate, the equivalent ratio of the hydroxyl groups of the high-molecular-weight polyol to the isocyanate groups of the aromatic polyisocyanate is, for example, more than 1, preferably 1.1 or more. , For example, blending at a ratio of 5 or less, preferably 3 or less, and if necessary, adding a urethanization catalyst and the above organic solvent to cause a urethanization reaction between the high molecular weight polyol and the aromatic polyisocyanate. .

Examples of the urethanization catalyst include known urethanization catalysts such as amines and organometallic compounds.

Examples of amines include tertiary amines (e.g., triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, etc.), quaternary ammonium salts (e.g., tetraethylhydroxylammonium, etc.), imidazoles (e.g., imidazole, 2-ethyl-4-methylimidazole, etc.).

Examples of organometallic compounds include organotin compounds (tin acetate, tin octylate, tin oleate, tin laurate, etc.), organolead compounds (e.g., lead octanoate, lead naphthenate, etc.), organonickel compounds ( nickel naphthenate, etc.), organic cobalt compounds (e.g., cobalt naphthenate, etc.), organic copper compounds (e.g., copper octoate, etc.), organic bismuth compounds, organic zirconium compounds, organic titanium compounds, organic zinc compounds, and the like. be done. These urethanization catalysts can be used alone or in combination of two or more.

Among such urethanization catalysts, organic tin compounds are preferred, and tin octylate is more preferred. The addition ratio of the urethanization catalyst is, for example, 0.001 parts by mass or more, preferably 0.05 parts by mass or more, for example, 1 part by mass or less, with respect to 100 parts by mass of the aromatic polyisocyanate. It is 0.8 parts by mass or less. That is, in the urethanization reaction, when a urethanization catalyst is added, the polyol component contains the urethanization catalyst.

As the reaction conditions for the urethanization reaction, the temperature is, for example, 40° C. or higher and 100° C. or lower, and the time is, for example, 2 hours or longer and 24 hours or shorter.

Then, in the urethanization reaction, preferably, the disappearance of the isocyanate group is confirmed by a known method such as a titration method with di-n-butylamine or Fourier transform infrared spectroscopy (FT-IR) analysis, and the end point of the reaction. to decide.

As described above, the high molecular weight polyol (preferably polyester polyol) and the aromatic polyisocyanate undergo a urethanization reaction to prepare an aromatic polyurethane polyol (aromatic polyurethane polyester polyol).

Further, in the preparation of the aromatic polyurethane polyol, for example, in the method described above, an appropriate ratio of low-molecular-weight polyol can be used together with the high-molecular-weight polyol. Moreover, after reacting a high-molecular-weight polyol and an aromatic polyisocyanate, the obtained reaction product can be further reacted with a low-molecular-weight polyol.

From the viewpoint of reactivity, preferably, after the high-molecular-weight polyol and the aromatic polyisocyanate are reacted, the obtained reaction product is further reacted with the low-molecular-weight polyol.

More specifically, for example, first, the equivalent ratio of the hydroxyl groups of the high molecular weight polyol to the isocyanate groups of the aromatic polyisocyanate is, for example, less than 1, preferably 0.9 or less, for example, 0.2 or more. If necessary, the above urethanization catalyst and the above organic solvent are added to cause a urethanization reaction between the high-molecular-weight polyol and the aromatic polyisocyanate. As the reaction conditions for the urethanization reaction, the temperature is, for example, 40° C. or higher and 100° C. or lower, and the time is, for example, 2 hours or longer and 24 hours or shorter.

As a result, a urethane prepolymer having an isocyanate group at the molecular end (an isocyanate group-terminated prepolymer) is obtained.

Next, in this method, the resulting isocyanate group-terminated prepolymer is reacted with the low-molecular-weight polyol described above.

Low-molecular-weight polyols can be used alone or in combination of two or more. As the low-molecular-weight polyol, the dihydric alcohols described above (e.g., ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexanediol, hydrogenated bisphenol A, bisphenol A, diethylene glycol, triethylene glycol, etc.), more preferably diethylene glycol.

In this method, the equivalent ratio of the hydroxyl groups of the low-molecular-weight polyol to the isocyanate groups of the isocyanate-terminated prepolymer is, for example, more than 1, preferably 1.1 or more, for example, 5 or less, preferably 3 or less. If necessary, a urethanization catalyst and the above organic solvent are added to cause a urethanization reaction between the isocyanate group-terminated prepolymer and the low-molecular-weight polyol. As the reaction conditions for the urethanization reaction, the temperature is, for example, 40° C. or more and 100° C. or less, and the time is, for example, 0.2 hours or more and 2 hours or less.

As described above, the isocyanate group-terminated prepolymer (that is, the reaction product of the high-molecular-weight polyol and the aromatic polyisocyanate) and the low-molecular-weight polyol undergo a urethanization reaction to form an aromatic polyurethane polyol (aromatic polyurethane polyester polyol). is prepared.

The number average molecular weight (Mn) of the aromatic polyurethane polyol is, for example, 800 or more, preferably 1,000 or more, and for example, 10,000 or less, preferably 9,000 or less.

Also, the weight average molecular weight (Mw) of the aromatic polyurethane polyol is, for example, 30,000 or more, preferably 35,000 or more, and for example, 50,000 or less, preferably 45,000 or less.

If the weight average molecular weight (Mw) of the aromatic polyurethane polyol is within the above range, it is possible to improve adhesive strength, drawability, and resistance to moist heat.

In addition, the polyol component can contain other polyols (polyols other than aromatic polyurethane polyols).

Other polyols include, for example, known high molecular weight polyols such as polyurethane polyols, polyether polyols, polyester polyols, and polycarbonate polyols modified with non-aromatic polyisocyanates (the above aliphatic polyisocyanates, the above araliphatic polyisocyanates, etc.). Molecular weight polyols, such as the low molecular weight polyols mentioned above, may be mentioned.

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

When other polyols are contained in the polyol component, the content ratio is within a range that does not impair the excellent effects of the present invention, and for example, 50% by mass or less, preferably 30% by mass, relative to the total amount of the polyol components. % by mass or less, more preferably 10% by mass or less.

The polyol component preferably contains an aromatic polyurethane polyol alone without containing other polyols. In other words, the polyol component preferably consists of an aromatic polyurethane polyol.

Moreover, the polyol component can be used by diluting it with the above-described organic solvent.

When the polyol component is diluted with an organic solvent, the solid content concentration of the polyol component is, for example, 10% by mass or more, preferably 30% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less. . The polyol component can also be used without being diluted with an organic solvent, that is, at a solid concentration of 100% by mass.

The solid content of the polyol component has a number average molecular weight (Mn) of, for example, 800 or more, preferably 1,000 or more, and for example, 10,000 or less, preferably 9,000 or less.

Moreover, in the solid content of the polyol component, the weight average molecular weight (Mw) is 30,000 or more, preferably 35,000 or more, and 50,000 or less, preferably 45,000 or less.

If the weight average molecular weight (Mw) of the polyol component is within the above range, it is possible to improve adhesive strength, drawability and resistance to moist heat.

Epoxy components include, for example, epoxy resins.

Epoxy resins are high-molecular-weight compounds having epoxy groups, and are reaction products of polyhydric phenols such as bisphenol A and tetrahydroxydiphenylethane with polyfunctional halohydrins such as epichlorohydrin and β-methylepichlorohydrin. ,Obtainable. Epoxy resins also include epoxidized polybutadiene.

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

Epoxy resins preferably include reaction products of polyhydric phenols and polyfunctional halohydrins, more preferably reaction products of bisphenol A and epichlorohydrin.

In addition, the epoxy component can be used by diluting it with the above-described organic solvent.

When the epoxy component is diluted with an organic solvent, the solid content concentration of the epoxy component is, for example, 10% by mass or more, preferably 30% by mass or more, for example, 95% by mass or less, preferably 90% by mass or less. . The epoxy component can also be used without being diluted with an organic solvent, that is, at a solid concentration of 100% by mass.

The solid content of the epoxy component has a number average molecular weight (Mn) of, for example, 1,000 or more, preferably 1,500 or more, and, for example, 3,500 or less, preferably 1,700 or less.

Moreover, in the solid content of the epoxy component, the weight average molecular weight (Mw) is, for example, 3,000 or more, preferably 3,500 or more, and, for example, 5,000 or less, preferably 4,000 or less.

If the weight average molecular weight (Mw) of the epoxy component is within the above range, it is possible to improve adhesive strength, drawability, and resistance to moist heat.

In the solid content of the epoxy component, the epoxy equivalent is 440 g/eq or more, preferably 550 g/eq or more, more preferably 600 g/eq or more, and 700 g/eq or less, preferably 680 g/eq or less. be.

If the epoxy equivalent exceeds the above lower limit, it is possible to improve adhesive strength, drawability, and resistance to moist heat. Moreover, if the epoxy equivalent is less than the above upper limit, it is possible to improve the adhesive strength and drawability.

Moreover, the polyisocyanate component, the polyol component and the epoxy component can contain a silane coupling agent as needed.

Preferably, the polyol component contains a silane coupling agent.

The silane coupling agent has, for example, the structural formula R—Si≡(X) ₃ or R—Si≡(R′)(X) ₂ (wherein R is a vinyl group, an epoxy group, an amino group, an imino group, represents an organic group having an isocyanate group or a mercapto group, R' represents a lower alkyl group having 1 to 4 carbon atoms, and X represents a methoxy group, an ethoxy group or a chlorine atom.).

Specific examples of silane coupling agents include chlorosilanes (eg, vinyltrichlorosilane), epoxysilanes (eg, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3 ,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.), aminosilanes (e.g., N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc.), vinylsilanes (e.g., vinyltriethoxysilane). ethoxysilane, etc.), isocyanatosilane (eg, γ-isocyanatopropyltrimethoxysilane, etc.), and the like. These silane coupling agents can be used alone or in combination of two or more.

Among such silane coupling agents, epoxysilane is preferred, and γ-glycidoxypropyltrimethoxysilane is more preferred.

The content of the silane coupling agent is appropriately set according to the purpose and application.

The polyisocyanate component, polyol component and epoxy component may further contain stabilizers such as phosphoric acid, curing catalysts, coating modifiers, leveling agents, antifoaming agents, antioxidants, and UV absorbers as necessary. Additives such as agents, plasticizers, surfactants, pigments, fillers, organic or inorganic fine particles, anti-mold agents may be added. The addition ratio of these additives is appropriately determined depending on the purpose and application.

Such a laminate adhesive is used as a two-component polyurethane adhesive containing a polyisocyanate component as a curing agent and a polyol component and an epoxy component as main ingredients.

Specifically, in using the laminate adhesive, first, the polyisocyanate component, the polyol component and the epoxy component are separately prepared. Next, the polyol component and the epoxy component are mixed to prepare a main agent. After that, at the time of use (at the time of lamination), a polyisocyanate component (curing agent) and a mixture of a polyol component and an epoxy component (main agent) are blended.

The content ratio of the epoxy component is 10 parts by mass or more, preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and 40 parts by mass or less, preferably 35 parts by mass, relative to 100 parts by mass of the polyol component. It is not more than 30 parts by mass, more preferably not more than 30 parts by mass.

If the content of the epoxy component is within the above range, excellent adhesive strength can be obtained, excellent drawability can be obtained, and excellent moist heat resistance can be obtained.

In addition, in the laminate adhesive, the blending ratio of the polyisocyanate component (curing agent), the polyol component and the epoxy component (main agent) is determined by the equivalent ratio of the isocyanate group in the curing agent to the hydroxyl group in the main agent (isocyanate group/hydroxyl group ) is, for example, 1 or more, preferably 1.6 or more, more preferably 2 or more, for example, 10 or less, preferably 5.8 or less, more preferably 3.5 or less. be.

If the equivalent ratio between the main agent and the curing agent is within the above range, excellent adhesive strength can be obtained, excellent drawability can be obtained, and excellent moist heat resistance can be obtained.

Further, on a mass basis, the total amount of the main agent (polyol component and epoxy component) is, for example, 3 parts by mass or more, preferably 5 parts by mass or more, more preferably 1 part by mass of the curing agent (polyisocyanate component). , 6 parts by mass or more, for example, 10 parts by mass or less, preferably 8 parts by mass or less.

If the mass ratio of the main agent and the curing agent is within the above range, excellent adhesive strength can be obtained, excellent drawability can be obtained, and excellent moist heat resistance can be obtained.

Such a lamination adhesive can improve drawability while ensuring adhesive strength, and is also excellent in heat and humidity resistance.

Therefore, according to the laminating adhesive described above, a composite film having excellent adhesive strength can be obtained, and cracking of the composite film can be suppressed even when the composite film is molded. Delamination (peeling) can be suppressed even when the film is placed under high temperature and high humidity conditions.

More specifically, the lamination adhesive is prepared as a solvent type or non-solvent type, and is used, for example, for laminating a laminate film as an example of a composite film.

When the lamination adhesive is prepared as a solvent type, the polyisocyanate component, the polyol component and the epoxy component are diluted with a known organic solvent and blended to prepare the lamination adhesive. A lamination adhesive is applied to the surface of one film to form an adhesive layer. Thereafter, the organic solvent is volatilized from the adhesive layer, the adhesive layer is attached to the other film, and then cured and cured at room temperature or under heat. The coating amount is about 2.0 to 8.0 g/m ² in basis weight (solid content) after volatilization of the organic solvent.

In addition, when the viscosity of the polyisocyanate component, the polyol component and the epoxy component blended at room temperature to 100° C. is, for example, about 100 to 10,000 mPa s, preferably about 100 to 5,000 mPa s, the laminate adhesive can be prepared as a solventless type.

When the laminate adhesive is prepared as a non-solvent type, the polyisocyanate component, the polyol component and the epoxy component are blended as they are to prepare the laminate adhesive, and then this laminate adhesive is applied to one side by a solvent-free laminator. It is applied to the surface of the film to form an adhesive layer. After that, the adhesive layer is attached to the other film and cured by curing at room temperature or under heat. The coating amount is, for example, about 0.5 to 5.0 g/m ² in basis weight (solid content).

With these, two films are adhered to each other by an adhesive layer (laminating adhesive) to prepare a laminated film.

The adhesive strength (T-type peel test) of such a laminate film is, for example, 8.0 N/15 mm or more, preferably 8.5 N/15 mm or more, more preferably 9.0 N/15 mm or more, usually 20 N/ 15 mm or less.

A method for measuring the adhesive strength of the laminate film will be described in detail later in Examples.

Such laminated films are used as packaging materials in various industrial fields. It is used as an exterior material for batteries.

In addition, since the laminate film is excellent in drawability and resistance to heat and humidity, it is particularly suitable for applications requiring drawability and resistance to heat and humidity. Specifically, as shown in FIG. is preferably used for

The pharmaceutical packaging bag 10 is a PTP (Press Through Pack) packaging sheet, and includes a laminate film 1 as an example of a packaging material and a cover film 6 .

The laminate film 1 has a laminated structure, and includes an outer layer film 2 as an example of a first film, an outer layer adhesive layer 4, a support film 3 as an example of a second film, and an inner layer adhesive layer 7. , and an inner layer film 5 in this order.

The outer layer film 2 is positioned as the outermost layer of the laminate film 1 . Examples of the outer layer film 2 include plastic films made of polyethylene terephthalate, nylon (registered trademark), polyethylene, polypropylene (e.g., unstretched polypropylene or stretched polypropylene), polyvinyl chloride, polyvinylidene chloride, etc., preferably A plastic film made of nylon (registered trademark) can be mentioned. Further, the surface (inner side) of the outer layer film 2 can be subjected to known activation treatment such as corona treatment, UV treatment, plasma treatment, etc., if necessary. The thickness of the outer layer film 2 is, for example, 5 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 50 μm or less.

The outer layer adhesive layer 4 is an adhesive cured film (hardened product) made of the laminate adhesive described above and cured by reaction of a polyisocyanate component, a polyol component, and an epoxy component. Further, the outer layer adhesive layer 4 is formed by applying the lamination adhesive to the surface of the outer layer film 2 or the support film 3 as described above.

The thickness of the outer adhesive layer 4 is, for example, 2 μm or more, preferably 3 μm or more, and for example, 10 μm or less, preferably 8 μm or less.

The support film 3 is arranged so as to sandwich the outer layer adhesive layer 4 with the outer layer film 2 . Thereby, the support film 3 and the outer layer film 2 are adhered to each other by the outer layer adhesive layer 4 . Examples of the support film 3 include metal foils made of aluminum, stainless steel, iron, copper, lead, and the like, and preferably metal foils made of aluminum. The thickness of the support film 3 is, for example, 5 μm or more, preferably 20 μm or more, for example, 200 μm or less, preferably 60 μm or less.

The inner layer adhesive layer 7 is made of an adhesive, and the adhesive is not particularly limited, and may be the lamination adhesive described above or a known adhesive. The inner layer adhesive layer 7 is formed by applying an adhesive to the surface of the support film 3 or the inner layer film 5 . The thickness range of the inner adhesive layer 7 is the same as the thickness range of the outer adhesive layer 4 .

The inner layer film 5 is arranged so as to sandwich the inner layer adhesive layer 7 with the support film 3 . Thereby, the inner layer film 5 and the support film 3 are adhered to each other by the inner layer adhesive layer 7 . Examples of the inner layer film 5 include the plastic films described above, preferably plastic films made of polypropylene, polyethylene, or polyvinyl chloride. The thickness range of the inner layer film 5 is the same as the thickness range of the support film 3 .

The laminate film 1 has a concave portion 9 for accommodating a medicine 8 as an example of a wrapper object. The recessed portion 9 has a concave shape that is open toward one side, and is recessed from the inner layer film 5 side toward the outer layer film 2 side. The concave portion 9 is formed by a known molding process.

Such a packaging bag 10 is manufactured by closing the concave portion 9 with the cover film 6 while the medicine 8 is contained in the concave portion 9 of the laminate film 1 .

Since the laminate film 1 includes the outer layer film 2 and the support film 3 that are adhered together by the laminate adhesive, the laminate film 1 is excellent in adhesive strength, drawability, and resistance to moist heat.

Furthermore, since the lamination adhesive described above can improve the resistance to moist heat of the laminate film 1, the laminate film 1 can be molded so as to form a concave portion for accommodating the object to be packaged. , the occurrence of cracks in the laminate film 1 can be suppressed.

EXAMPLES The present invention will be explained more specifically by showing Examples below, but the present invention is not limited to them. Specific numerical values such as the mixing ratio (content ratio), physical property values, parameters, etc. used in the following description are described in the above "Mode for Carrying Out the Invention", the corresponding mixing ratio (content ratio ), physical property values, parameters, etc. can. "Parts" and "%" are based on mass unless otherwise specified.

Also, the number average molecular weight and weight average molecular weight described below were measured as follows.
Determination of number average molecular weight and weight average molecular weight:
After dissolving 40 mg of the sample in 4 mL of tetrahydrofuran to prepare a 1 w/v% solution, the solution was measured by gel permeation chromatography (GPC) under the following conditions, and the number average molecular weight (Mn) was calculated by standard polystyrene conversion. and weight average molecular weight (Mw) were measured.
Data processing device: Product number EMPOWER2 (manufactured by Waters)
Differential refractive index detector: 2414 type differential refractive index detector Column: PLgel 5 μm Mixed-C Product No. 1110-6500 (manufactured by Polymer Laboratories) 3 Mobile phase: Tetrahydrofuran Column flow rate: 1 mL/min
Injection volume: 100 μL
Measurement temperature: 40°C
Molecular weight calibration: TSK standard Polystyrene manufactured by TOSOH
<Polyisocyanate component>
Preparation Example 1 (Polyisocyanate component A)
Aromatic polyisocyanate modified product (“Takenate A-3”, trimethylolpropane modified product of TDI, isocyanate group content 12.6% by mass (solid content conversion: 16.8% by mass), solid content concentration 75% by mass ( Ethyl acetate solvent), manufactured by Mitsui Chemicals) was used as polyisocyanate component A.

Preparation Example 2 (Polyisocyanate Component B)
Aromatic polyisocyanate modified product (“Takenate A-12”, a mixture of TDI trimethylolpropane modified product and MDI trimethylolpropane modified product, isocyanate group content 10.6% by mass (in terms of solid content: 15. 1% by mass) and a solid concentration of 70% by mass (ethyl acetate solvent), manufactured by Mitsui Chemicals, Inc.) was used as the polyisocyanate component B.

Preparation Example 3 (Polyisocyanate Component C)
Aromatic polyisocyanate modified product ("Coronate L", trimethylolpropane modified product of TDI, isocyanate group content 11.8% by mass (solid content conversion: 16.8% by mass), solid content concentration 70% by mass (ethyl acetate Solvent), manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as polyisocyanate component C.

Preparation Example 4 (Polyisocyanate Component D)
An alicyclic polyisocyanate modified product (“Takenate D-170N”, HDI trimer, isocyanate group content 20.7% by mass, solid concentration 100% by mass, manufactured by Mitsui Chemicals, Inc.) was used as polyisocyanate component D.

<Polyol component>
Synthesis Example 1 (Aromatic Polyurethane Polyol A)
(Esterification reaction)
Mix 330.6 g of isophthalic acid (IPA) and 402.5 g of sebacic acid (SbA) as polybasic acids, and 72.8 g of ethylene glycol (EG) and 376.5 g of neopentyl glycol (NPG) as low molecular weight polyols. did.

Then, 0.1 g of tin octylate (esterification catalyst) is added to the mixed solution, and the reaction temperature is adjusted to 180 to 220° C. under a nitrogen stream to cause an esterification reaction between the polybasic acid and the low-molecular-weight polyol. , predetermined amounts of water and glycol were distilled off to obtain a polyester polyol a.

Then, 700 g of polyester polyol a was dissolved in 300 g of ethyl acetate to prepare a polyester polyol solution a having a solid content concentration of 70% by mass.

In the polyester polyol solution a, the solid content had a hydroxyl value of 45.0 mgKOH/g, a number average molecular weight (Mn) of 2,419, and a weight average molecular weight (Mw) of 5,518.

(Urethane reaction)
A mixture of 499.7 g of polyester polyol solution a and 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (the weight ratio of 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate is 80/20 25.7 g of the mixture (hereinafter abbreviated as TDI-80) and 225.5 g of ethyl acetate (organic solvent) were mixed, and 0.008 g of tin octoate (urethanization catalyst) was added to the mixture. Under a nitrogen stream, the reaction temperature was adjusted to 60° C. and the reaction was carried out for 10 hours.

Thus, an aromatic polyurethane polyol A having a number average molecular weight (Mn) of 8,523 and a weight average molecular weight (Mw) of 40,682 was prepared.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of aromatic polyurethane polyol A. was added to prepare polyol component A.

Synthesis Example 2 (Aromatic Polyurethane Polyol B)
(Esterification reaction)
356.06 g of isophthalic acid (IPA) and 313.2 g of adipic acid (AA) as polybasic acids and 509.4 g of diethylene glycol (DEG) as low molecular weight polyol were mixed.

Then, 0.04 g of tin octylate (esterification catalyst) is added to the mixed solution, and the reaction temperature is adjusted to 180 to 220° C. under a nitrogen stream to cause an esterification reaction between the polybasic acid and the low-molecular-weight polyol. rice field. Then, predetermined amounts of water and glycol were distilled off to obtain polyester polyol b.

Then, 700 g of polyester polyol b was dissolved in 300 g of ethyl acetate to prepare a polyester polyol solution b having a solid content concentration of 70% by mass.

In the polyester polyol solution b, the solid content had a hydroxyl value of 32.1 mgKOH/g, a number average molecular weight (Mn) of 3,500, and a weight average molecular weight (Mw) of 7,980.

(Urethane reaction)
614.8 g of polyester polyol solution b, 24.4 g of TDI-80, and 273.9 g of ethyl acetate (organic solvent) are mixed, and 0.13 g of tin octylate (urethanization catalyst) is added to the mixture, Under a nitrogen stream, the reaction temperature was adjusted to 77 to 80° C., and polyester polyol b and TDI-80 were subjected to a urethanization reaction until the isocyanate group peak completely disappeared by FT-IR. Thus, an aromatic polyurethane polyol B having a number average molecular weight (Mn) of 4,028 and a weight average molecular weight (Mw) of 14,660 was prepared.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of aromatic polyurethane polyol B. was added to prepare polyol component B.

Synthesis Example 3 (Aromatic Polyurethane Polyol C)
(Esterification reaction)
186.8 g of isophthalic acid (IPA), 249.1 g of terephthalic acid (TPA) and 54.8 g of adipic acid (AA) as polybasic acids, and 104.8 g of ethylene glycol (EG) and neopentyl glycol as low molecular weight polyols. (NPG) 175.3 g. Then, 0.2 g of zinc acetate (esterification catalyst) is added to the mixed solution, the reaction temperature is adjusted to 180 to 220 ° C. under a nitrogen stream, and the polybasic acid and the low molecular weight polyol are esterified, Predetermined amounts of water and glycol were distilled off to obtain polyester polyol c.

Then, 700 g of polyester polyol c was dissolved in 300 g of ethyl acetate to prepare a polyester polyol solution c having a solid content concentration of 70% by mass.

In the polyester polyol solution c, the solid content had a hydroxyl value of 21.6 mgKOH/g, a number average molecular weight (Mn) of 5,282, and a weight average molecular weight (Mw) of 14,438.

(Urethane reaction)
875.1 g of polyester polyol solution, 25.1 g of Takenate 600 (1,3-bis(isocyanatomethyl)cyclohexane (1,3-H ₆ XDI), alicyclic polyisocyanate, manufactured by Mitsui Chemicals), and ethyl acetate (Organic solvent) 93.7 g was mixed, 0.06 g of tin octylate (urethanization catalyst) was added to the mixture, and the reaction temperature was adjusted to 77 to 80 ° C. under a nitrogen stream to obtain a polyester polyol. c and Takenate 600 were subjected to a urethanization reaction until the isocyanate group peak disappeared completely by FT-IR. Thus, an aromatic polyurethane polyol C having a number average molecular weight (Mn) of 5431 and a weight average molecular weight (Mw) of 19765 was prepared.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of aromatic polyurethane polyol C. was added to prepare polyol component C.

Synthesis Example 4 (polyester polyol D)
(Esterification reaction)
541.4 g of isophthalic acid (IPA) and 158.7 g of adipic acid (AA) as polybasic acids and 176.9 g of ethylene glycol (EG) and 190.1 g of neopentyl glycol (NPG) as low molecular weight polyols and 252.2 g of 6-hexanediol (1,6-HD) was mixed. Then, 0.2 g of zinc acetate (esterification catalyst) is added to the mixed solution, the reaction temperature is adjusted to 180 to 220 ° C. under a nitrogen stream, and the polybasic acid and the low molecular weight polyol are esterified, Predetermined amounts of water and glycol were distilled off to obtain polyester polyol D.

Polyester polyol D had a number average molecular weight (Mn) of 5,495 and a weight average molecular weight (Mw) of 14,871. Moreover, the hydroxyl value of the solid content was 21.6 mgKOH/g.

Then, the entire amount of polyester polyol D was dissolved in 350 g of ethyl acetate to prepare polyester polyol solution d having a solid content concentration of 65% by mass.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of polyester polyol D. to prepare a polyol component D.

Synthesis Example 5 (Aromatic Polyurethane Polyol E)
(Esterification reaction)
Mix 330.6 g of isophthalic acid (IPA) and 402.5 g of sebacic acid (SbA) as polybasic acids, and 72.8 g of ethylene glycol (EG) and 376.5 g of neopentyl glycol (NPG) as low molecular weight polyols. did.

Then, 0.1 g of tin octylate (esterification catalyst) is added to the mixed solution, and the reaction temperature is adjusted to 180 to 220° C. under a nitrogen stream to cause an esterification reaction between the polybasic acid and the low-molecular-weight polyol. , predetermined amounts of water and glycol were distilled off to obtain a polyester polyol e.

Then, 700 g of polyester polyol e was dissolved in 300 g of ethyl acetate to prepare a polyester polyol solution e having a solid content concentration of 70% by mass.

In the polyester polyol solution e, the solid content had a hydroxyl value of 45 mgKOH/g, a number average molecular weight (Mn) of 2,419, and a weight average molecular weight (Mw) of 5,518.

(Urethane reaction)
267.6 g of polyester polyol solution e, 25.2 g of TDI-80, and 142.9 g of ethyl acetate (organic solvent) are mixed, and 0.1 g of tin octylate (urethanization catalyst) is added to the mixture, Under a nitrogen stream, the reaction temperature was adjusted to 60° C. and the reaction was allowed to proceed for 10 hours.

Thus, an aromatic polyurethane polyol E having a number average molecular weight (Mn) of 8,113 and a weight average molecular weight (Mw) of 27,039 was prepared.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of aromatic polyurethane polyol E. was added to prepare polyol component E.

Synthesis Example 6 (IPDI-based polyurethane polyol F)
(Esterification reaction)
Mix 330.6 g of isophthalic acid (IPA) and 402.5 g of sebacic acid (SbA) as polybasic acids, and 72.8 g of ethylene glycol (EG) and 376.5 g of neopentyl glycol (NPG) as low molecular weight polyols. did.

Then, 0.1 g of tin octylate (esterification catalyst) is added to the mixed solution, and the reaction temperature is adjusted to 180 to 220° C. under a nitrogen stream to cause an esterification reaction between the polybasic acid and the low-molecular-weight polyol. , predetermined amounts of water and glycol were distilled off to obtain a polyester polyol f.

Then, 700 g of polyester polyol f was dissolved in 300 g of ethyl acetate to prepare a polyester polyol solution f having a solid content concentration of 70% by mass.

In the polyester polyol solution f, the solid content had a hydroxyl value of 45 mgKOH/g, a number average molecular weight (Mn) of 2,419, and a weight average molecular weight (Mw) of 5,518.

(Urethane reaction)
663.5 g of the polyester polyol solution, 33.1 g of isophorone diisocyanate (hereinafter abbreviated as IPDI), and 300.9 g of ethyl acetate (organic solvent) were mixed, and tin octylate (urethanization catalyst ) was added thereto, and the reaction temperature was adjusted to 60° C. under a nitrogen stream and reacted for 10 hours.

Thus, an IPDI-based polyurethane polyol F having a number average molecular weight (Mn) of 15,403 and a weight average molecular weight (Mw) of 38,339 was prepared.

Next, 5.0 g of a silane coupling agent (“KBM-403”, 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) and 124.56 g of ethyl acetate were added to the total amount of IPDI-based polyurethane polyol F. In addition, polyol component F was prepared.

<Epoxy component>
Preparation example 1 (epoxy component A)
Trade name Epotato YD-901 (reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 440 to 500 g / eq, number average molecular weight 1070, weight average molecular weight 2547, solid content concentration 50% by mass, manufactured by Nippon Steel & Sumikin Chemical), epoxy It was designated as component A.

Preparation example 2 (epoxy component B)
Trade name Epototo YD-902LK (reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 600 to 700 g / eq, number average molecular weight 1667, weight average molecular weight 3527, solid content concentration 50% by mass, manufactured by Nippon Steel & Sumikin Chemical), epoxy It was designated as component B.

Preparation example 3 (epoxy component C)
Trade name Epotato YD-902 (reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 600 to 700 g/eq, number average molecular weight 1804, weight average molecular weight 4672, manufactured by Nippon Steel & Sumikin Chemical) was used as epoxy component C.

Preparation example 4 (epoxy component D)
Epotote YD-903N (trade name) (reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 780 to 840 g/eq, number average molecular weight 2319, weight average molecular weight 5963, manufactured by Nippon Steel & Sumikin Chemical) was used as epoxy component D.

Preparation Example 5 (Epoxy Component E)
Trade name Epotato YD-904 (reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 900 to 1000 g/eq, number average molecular weight 2864, weight average molecular weight 7884, manufactured by Nippon Steel & Sumikin Chemical) was used as epoxy component E.

Preparation Example 6 (Epoxy Component F)
The epoxy component C was AER-6052 (product name: bisphenol A type epoxy resin, epoxy equivalent: 620 to 660 g/eq, manufactured by ADEKA).

Examples 1-9 and Comparative Examples 1-11
<Preparation of laminate adhesive>
A laminate adhesive was obtained with the formulation shown in Tables 1 and 2.

Specifically, first, a polyol component and an epoxy component were mixed according to the formulations shown in Tables 1 and 2 to prepare a main agent.

Next, the resulting main agent and a polyisocyanate component as a curing agent were mixed at the compounding ratios (solution basis and solid content basis) shown in Tables 1 and 2 to obtain a laminate adhesive. Table 1 shows the solid content concentration (NV) of the main agent and the solid content concentration (NV) of the curing agent.

<Production of composite film>
A laminating adhesive was diluted with ethyl acetate, and a bar coater was used to coat a 25 μm thick nylon (registered trademark) film (“ ^Bonyl RX”, one-sided corona-treated , KOHJIN FILM & CHEMICALS CO., LTD.) was applied onto the corona-treated surface at room temperature to volatilize the organic solvent. Then, the laminate adhesive coated surface of the nylon (registered trademark) film and the matte surface (non-glossy surface) of 40 μm thick aluminum foil (“Aluminum Haku CE (8079)” manufactured by Toyo Aluminum Co., Ltd.) were pasted together. .

Next, a two-liquid curable polyurethane adhesive [main agent ("Takelac A-525S", manufactured by Mitsui Chemicals, Inc.) and a curing agent ("Takelac A-52", manufactured by Mitsui Chemicals, Inc.) are combined at a mass ratio of 9:1. [mixed with]] is diluted with ethyl acetate, and applied on the surface of the aluminum foil opposite to the nylon (registered trademark) film using a bar coater so that the basis weight is 4 g / m ² (solid content). , the organic solvent was volatilized. Then, the surface of the aluminum foil coated with the two-liquid curing type polyurethane adhesive and the corona-treated surface of a 40 μm-thick unstretched polypropylene film (“RXC-3”, single-sided corona treatment, manufactured by Mitsui Chemicals Tohcello Co., Ltd.) were pasted together. rice field.

After that, by curing at 60 ° C. for 3 days, the laminate adhesive is cured to bond between the aluminum foil and the nylon (registered trademark) film, and the two-component curing polyurethane adhesive is cured to remove the aluminum. A composite film was obtained by bonding between the foil and the polypropylene film.

(evaluation)
(1) Adhesive strength A long test sample (width: 15 mm, length: 150 mm) was cut out from each of the composite films prepared in each example and each comparative example. Then, in accordance with JIS K 6854-3 (1999), the test sample was subjected to a T-type peel test at a crosshead speed of 300 mm / min using a universal tensile measurement device, and the composite film. Adhesion strength was measured. The results are shown in Tables 1 and 2.
(2) Drawability A square test sample (one piece: 6 cm) was cut out from each of the composite films prepared in each example and each comparative example. Then, the test sample was molded from the non-stretched polypropylene film side with a 1t servo press machine (punch size: 30×30 mm, manufactured by Yamaoka Seisakusho) so as to have a concave depth of 5 mm.

Seven such test samples were molded, each of which was quantified according to the following criteria by demerit points out of 10 points, and the average value of the five test samples excluding one point each above and below was obtained.
Corner pinhole: -1 point Corner crack: -2 points Corner breakage: -3 point side breakage: -4 points The average value was evaluated according to the following evaluation criteria.
○: 8 points or more △: 5 to less than 8 points ×: Less than 5 points (3) Heat and humidity resistance test From each of the composite films prepared in each example and each comparative example, a long shape (width: 15 mm, length : 50 mm) were cut out in triplicate. Then, each of the three test samples was stretched by 30% in the length direction using a universal tension measuring device under the conditions of a distance between chucks of 50 mm and a tensile speed of 100 mm/min.

Then, the stretched test samples (three) were housed in a thermo-hygrostat and left at 70° C. and 90% RH for 3 days. After that, the condition of the test sample was visually confirmed.

The evaluation criteria for resistance to moist heat are shown below.
○: Good. No delamination is observed on all three test samples.
△: Within the allowable range. Partial delamination in the width direction is observed in at least one of the three test samples.
×: Defective. Delamination across the entire width (15 mm) is observed in all three test samples.

The details of the abbreviations in the table are described below.
<Polyisocyanate component>
Polyisocyanate A: Polyisocyanate component A of Preparation Example 1, "Takenate A-3", trimethylolpropane-modified TDI, isocyanate group content 12.6% by mass (solid content conversion: 16.8% by mass, Mitsui Chemicals Polyisocyanate B manufactured by Co., Ltd.: Polyisocyanate component B of Preparation Example 2, "Takenate A-12", trimethylolpropane-modified aromatic diisocyanate, isocyanate group content 10.6% by mass (in terms of solid content: 15.1 mass %), solid content concentration 70% by mass (ethyl acetate solvent), Polyisocyanate C manufactured by Mitsui Chemicals: Polyisocyanate component C of Preparation Example 3, "Coronate L", modified TDI trimethylolpropane, isocyanate group content 11. 8% by mass (solid content conversion: 16.8% by mass), solid content concentration 70% by mass (ethyl acetate solvent), Polyisocyanate D manufactured by Nippon Polyurethane Industry Co., Ltd.: Polyisocyanate component D of Preparation Example 4, “Takenate D-170N ”, HDI trimer, isocyanate group content 20.7% by mass, solid content concentration 100% by mass, manufactured by Mitsui Chemicals <Polyol component>
Polyol A: aromatic polyurethane polyol A obtained in Synthesis Example 1
Polyol B: Aromatic polyurethane polyol B obtained in Synthesis Example 2
Polyol C: aromatic polyurethane polyol C obtained in Synthesis Example 3
Polyol D: Polyester polyol D obtained in Synthesis Example 4
Polyol E: Aromatic polyurethane polyol E obtained in Synthesis Example 5
Polyol F: IPDI-based polyurethane polyol F obtained in Synthesis Example 6
<Epoxy component>
Epoxy A: Epoxy component A of Preparation Example 1, trade name Epototh YD-901, reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 440 to 500 g/eq, solid content concentration 50% by mass, Nippon Steel & Sumikin Chemical Epoxy B: Epoxy component B of Preparation Example 2, trade name Epototh YD-902LK, reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 600 to 700 g/eq, number average molecular weight 1667, weight average molecular weight 3527, solid content concentration 50% by mass, Nippon Steel & Sumikin Chemical Epoxy C: Epoxy component C of Preparation Example 3, trade name Epototh YD-902, reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 600 to 700 g/eq, number average molecular weight 1804, weight average molecular weight 4672, Nippon Steel & Sumikin Chemical Epoxy D: Epoxy component D of Preparation Example 4, trade name Epototh YD-903N, reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 780 to 840 g/eq, number average molecular weight 2319, weight average molecular weight 5963, Nippon Steel & Sumikin Chemical Epoxy E: Epoxy component E of Preparation Example 5, trade name Epototh YD-904, reaction product of bisphenol A and epichlorohydrin, epoxy equivalent 900 to 1000 g/eq, number average molecular weight 2864, weight average molecular weight 7884, Nippon Steel & Sumikin Chemical Epoxy F: Epoxy component F of Preparation Example 6, trade name AER-6052, bisphenol A type epoxy resin, epoxy equivalent 620 to 660 g/eq, manufactured by ADEKA

REFERENCE SIGNS LIST 1 laminate film 2 outer layer film 3 support film 4 outer layer adhesive layer 8 drug 9 concave portion 10 packaging bag

Claims (8)

containing a polyisocyanate component, a polyol component and an epoxy component,
The polyisocyanate component contains a polyol-modified aromatic diisocyanate,
The polyol component contains a polyurethane polyester polyol modified with an aromatic polyisocyanate,
The weight average molecular weight of the polyol component is 30000 or more and 50000 or less,
The epoxy equivalent of the epoxy component is 440 g/eq or more and 700 g/eq or less,
A laminate adhesive, wherein the content of the epoxy component is 10 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polyol component. The laminate adhesive according to claim 1, wherein the total content of the polyol component and the epoxy component is 5 parts by mass or more and 8 parts by mass or less with respect to 1 part by mass of the polyisocyanate component. . 3. The laminate adhesive according to claim 1, wherein the polyisocyanate component is a polyol-modified tolylene diisocyanate. The laminate adhesive according to any one of claims 1 to 3, wherein the epoxy component has an epoxy equivalent weight of 600 g/eq or more and 700 g/eq or less. The laminate adhesive according to any one of claims 1 to 4, wherein the content of the epoxy component is 20 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyol component. Any one of claims 1 to 5, wherein the total content of the polyol component and the epoxy component is 6 parts by mass or more and 8 parts by mass or less with respect to 1 part by mass of the polyisocyanate component. Laminating adhesive according to paragraph. The laminate adhesive according to any one of claims 1 to 6, wherein the epoxy component has a weight average molecular weight of 4000 or less. A laminate adhesive according to any one of claims 1 to 7,
a composite film comprising a first film and a second film adhered to each other by the lamination adhesive;
A packaging material, wherein the composite film has a recessed portion that is recessed so as to accommodate an object to be packaged.

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