TW202113021A - Two-pack type adhesive, multilayer body, molded body and packaging material - Google Patents

Abstract

The present invention provides a two-pack type adhesive which has excellent moldability, heat resistance and wet heat resistance. A two-pack type adhesive which is characterized by containing (A) a polyol composition that contains (A1) a polyester polyol and (B) a polyisocyanate composition that contains (B1) an isocyanate compound, and which is also characterized in that: the polyester polyol (A1) is a reaction product of (a1) a polybasic acid or a derivative thereof and (a2) a polyhydric alcohol; and the polyhydric alcohol (a2) contains (a2-1) a polyhydric alcohol wherein the number of carbon atoms in a methylene chain between two hydroxy groups is an odd number from 5 to 19.

Description

Two-component adhesives, laminates, molded products, packaging materials

The present invention relates to a two-component adhesive, a laminate, a molded body, and a packaging material obtained by using the two-component adhesive.

In packaging materials used for packaging various storage items such as food, daily necessities, and electronic components, in order to protect the contents from the impact during circulation, etc., deterioration caused by oxygen and moisture, strength, resistance to breakage, and gas barrier are required. Features such as sex. When heat sterilizing the contents, retort resistance, heat resistance, etc. are required, and transparency is also required in order to be able to confirm the contents. However, it is difficult to satisfy the necessary functions with one material. For example, a non-stretched polyolefin film used when sealing by heat sealing is excellent in hot workability, but on the other hand, oxygen barrier properties are insufficient. On the contrary, although the nylon film has excellent gas barrier properties, it has poor heat-sealability.

Therefore, different types of polymer materials or laminates formed by bonding polymer materials and metal substrates are widely used as packaging materials. In addition, a laminate in which a laminate is formed to form one or a plurality of accommodating parts may be used as a packaging material (Patent Documents 1 to 3). The laminated body formed with one or a plurality of accommodating portions seals the accommodating portion by joining with a laminated body in which a accommodating portion of the same shape is formed, or a laminated body that is not formed with a accommodating portion (without molding processing). As a joining method, thermal welding (heat sealing) is used. [Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. 2013-199283 Patent Document 2: Japanese Special Publication No. 2008-535746 Patent Document 3: Japanese Patent Application Publication No. 2015-082354

[The problem to be solved by the invention]

The object of the present invention is to provide a packaging material suitable for such use, that is, to provide a packaging material with excellent moldability, even after the heat fusion of the sealant layers for sealing the storage, the adhesive strength between the layers is not Packaging materials with poor appearance such as lowering and no bulging between layers. In addition, its object is to provide a two-component adhesive suitable for manufacturing such packaging materials with excellent moldability and heat resistance, a laminate and a molded body using the adhesive. [Means to solve the problem]

The present invention relates to a two-component adhesive, which is characterized by containing: a polyol composition (A) containing a polyester polyol (A1), and a polyisocyanate composition (B) containing an isocyanate compound (B1); poly Ester polyol (A1) is the reaction product of polyacid or its derivative (a1) and polyhydric alcohol (a2). Polyhydric alcohol (a2) contains the carbon atoms of the methylene chain between 2 hydroxyl groups. Polyhydric alcohols (a2-1) whose number is 5 or more and 19 or less and is an odd number. [Effects of Invention]

By using the two-component adhesive of the present invention, a packaging material can be obtained that has excellent moldability and does not reduce the adhesive strength between the sealant layers even after the heat fusion of the sealant layers for sealing the storage. , No appearance defects such as bulging between layers will occur.

＜Adhesive agent＞ The adhesive of the present invention is a two-component adhesive, which contains a polyol composition (A) containing a polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B1) as essential components , Polyester polyol (A1) is the reaction product of polybasic acid or its derivative (a1) and polyhydric alcohol (a2). Polyhydric alcohol (a2) contains the number of carbon atoms in the methylene chain between 2 hydroxyl groups. 5 or more and 19 or less and an odd number of polyhydric alcohols (a2-1).

(Polyol composition (A)) (Polyester polyol (A1)) Polyester polyol (A1) is a reaction product of polyacid or its derivative (a1) and polyhydric alcohol (a2).

Examples of the polybasic acid or its derivative (a1) used as the raw material of the polyester polyol (A1) include the following: malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2 ,2-Dimethylsuccinic acid, succinic anhydride, alkenyl succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid Aliphatic polybasic acids such as diacid, maleic anhydride and itaconic acid.

Dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, transbutane Alkyl ester products of aliphatic polybasic acids such as dimethyl acrylate, diethyl fumarate, dimethyl maleate, and diethyl maleate.

1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane Alkane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1, 2,4-Tricarboxylic acid-1,2-anhydride, himic anhydride, het anhydride and other alicyclic polybasic acids.

Phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2, 3-Naphthalenedicarboxylic acid anhydride, naphthalenedicarboxylic acid, 1,2,4- trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, biphenyl dicarboxylic acid, 1,2-bis (Phenoxy) ethane-p,p'-dicarboxylic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, isophthalic acid-5-sodium sulfonate, tetrachlorophthalic acid Aromatic polybasic acids such as dicarboxylic anhydride and tetrabromophthalic anhydride.

Methyl esters of aromatic polybasic acids such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate; one type or two or more types can be used in combination.

Among them, adipic acid, azelaic acid, sebacic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and its Anhydride or its methyl ester compound. In addition, from the viewpoint of improving moldability and heat resistance, the polybasic acid or its derivative (a1) preferably contains an aromatic ring-containing polybasic acid or its derivative (a1-1). Preferred are phthalic acid, isophthalic acid, terephthalic acid, 1,2,4- trimellitic acid and its anhydride or its methyl ester compound, more preferably isophthalic acid, terephthalic acid, 1 ,2,4-Mellitic acid and its anhydride or its methyl ester compound.

As the polyhydric alcohol (a2), it may be a diol or a polyhydric alcohol having a trifunctional or higher function. Examples of the above-mentioned diol include the following: ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1, 3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1, 3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,6-hexane Aliphatic diols such as diol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol.

Polyoxyethylene glycol, polyoxypropylene glycol and other ether glycols.

With the above aliphatic diols and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether , Allyl glycidyl ether and other modified polyether glycols obtained by ring-opening polymerization of various compounds containing cyclic ether bonds.

A lactone-based polyester polyol obtained by the polycondensation reaction of the aforementioned aliphatic diol with various lactones such as lactanoid and ε-caprolactone.

Bisphenols such as bisphenol A and bisphenol F.

An alkylene oxide adduct of bisphenol obtained by adding ethylene oxide and propylene oxide to bisphenols such as bisphenol A and bisphenol F.

Examples of the above-mentioned trifunctional or higher polyhydric alcohols include the following: aliphatic polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and neopentylerythritol.

With the above aliphatic polyols and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether , Allyl glycidyl ether and other various compounds containing cyclic ether bonds to obtain modified polyether polyols obtained by ring-opening polymerization.

A lactone-based polyester polyol obtained by the polycondensation reaction of the above-mentioned aliphatic polyol and various lactones such as ε-caprolactone.

In the present invention, the polyhydric alcohol (a2) contains an odd number of polyhydric alcohols (a2-1) with carbon atoms in the methylene chain between two hydroxyl groups of 5 or more and 19 or less as an essential component. The methylene chain may be linear or branched with side chains. When the methylene chain contains a side chain, the number of carbon atoms in the side chain is not included in the number of carbon atoms in the methylene chain. Hereinafter, this diol is also abbreviated as polyhydric alcohol (a2-1).

Examples of polyhydric alcohols (a2-1) with linear methylene chains include 1,5-pentanediol, 1,7-heptanediol, 1,9-nonanediol, and 1,11- Undecanediol, 1,13-tridecanediol, 1,15-pentadecanediol, 1,17-heptadecandiol, 1,19-nonadecanediol.

Examples of polyhydric alcohols (a2-1) whose methylene chain is branched include 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, and 3-methyl 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptane Alcohol, 4-methyl-1,7-heptanediol, 2-methyl-1,9-nonanediol, 3-methyl-1,9-nonanediol, 4-methyl-1,9- Nonanediol, 5-methyl-1,9-nonanediol, etc.

When the polyhydric alcohol (a2) contains the polyhydric alcohol (a2-1), the adhesive of the present invention can be formed to have excellent adhesiveness, moldability, and heat resistance. The reason is presumed as follows. In order to improve the heat resistance of the adhesive, it is preferable to combine ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and isosorbide , Succinic acid, 1,4-cyclohexane dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid and other components to improve the cohesive force of polyester polyols are added to the poly In the main skeleton of ester polyols. However, if such a component is added, the glass transition temperature of the polyester polyol increases, and the moldability or wettability of the adhesive decreases. The decrease in wettability will become an inducement for the decrease in adhesion. On the other hand, polyhydric alcohol (a2-1) has a higher effect of lowering the glass transition temperature of polyester polyol, so polyester polyol (A1) with polyhydric alcohol (a2-1) is used. Two-component adhesive) while maintaining moldability and wettability, adding high cohesive components to its skeleton can improve heat resistance. The blending amount of the component that improves the cohesive force of the polyester polyol is appropriately set depending on the balance with other components. As an example, it is 30 mol% or more and 90 mol% or less of the total amount of the polybasic acid or its derivative (a1) and the polyhydric alcohol (a2).

The blending amount of polyhydric alcohol (a2-1) can be adjusted appropriately in view of the necessary degree of moldability (molding temperature, molding depth, etc.). In terms of the balance of adhesion, moldability, and heat resistance, as an example, it is preferably 10 mol% or more of the polyhydric alcohol (a2), more preferably 30 mol% or more, and even more preferably 40 mol% %the above. There is no particular limitation on the upper limit, but it is preferably 90 mol% or less, more preferably 85 mol% or less, and still more preferably 80 mol% or less. Furthermore, when the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 5 or more and 11 or less, it is preferably 20 mol% or more of the polyhydric alcohol (a2), preferably 90 mol% % Or less, more preferably 40 mol% or more and 80 mol% or less. When the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 13 or more and 19 or less, it is preferably 10 mol% or more and 60 mol% or less, more preferably 15 mol% or more and Below 40 mol%.

From the point that it is more excellent in the balance between moldability and heat resistance, it is preferable that the methylene chain of the polyhydric alcohol (a2-1) is linear. Moreover, it is more preferable that the number of carbon atoms of the methylene chain is 7 or more and 15 or less, and more preferably 9 or more and 13 or less.

The polyhydric alcohol (a2) preferably further includes at least one selected from the group consisting of polyhydric alcohols having a branched alkylene structure (a2-2) and polyhydric alcohols having a cyclic structure (a2-3) . Hereinafter, the polyhydric alcohol (a2-2) with a branched alkylene structure is also referred to as polyhydric alcohol (a2-2), and the polyhydric alcohol (a2－3) with cyclic structure is also referred to as polyhydric alcohol. (A2－3).

Polyhydric alcohols (a2-2) are polyhydric alcohols with three-level or four-level carbon atoms in the molecular structure. Examples include: 1,2-propanediol, 2-methyl-1,3-propanediol, and neopentyl alcohol Alcohol, 2,2-Diethyl-1,3-Propanediol, 2-Methyl-2-Propyl-1,3-Propanediol, 2-Butyl-2-Ethyl-1,3-Propanediol, 2, 2-isobutyl-1,3-propanediol, 2,2-isopentyl-1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3 -Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl 1,3-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 2-methyl-1,8-octanediol and other branched chain alkyl diols; trimethylolethane, trimethylolpropane, neopentylerythritol and other tri-functional or more branched alkyl structures Functional alcohol; can be used alone or in combination of two or more. Among these, from the viewpoint that a polyester polyol (A1) having particularly excellent heat and humidity resistance can be obtained, neopentyl glycol is preferred.

Polyhydric alcohols (a2-3) are polyhydric alcohols with a cyclic structure in the molecular structure. The cyclic structure may be monocyclic, polycyclic, aromatic or alicyclic. It can also be a heterocyclic ring. Examples of such polyhydric alcohols (a2-3) include; 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol , 4-(hydroxymethyl)cyclohexanol, 4-(2-hydroxyethyl)cyclohexanol, 1,4-cyclohexanedimethanol, 4,4'-dicyclohexanol, 1,3-adamantane Diol, 1,3,5-adamantanol, 3-(hydroxymethyl)-1-adamantanol, tricyclo[5.2.1.0 ^2.6 ]-decane dimethanol, 1,2-benzenedimethanol, 1 ,4-Benzene dimethanol, 4,4-dihydroxy bisphenol, 4,4'-bisphenyl dimethanol, 2,2'-methylene diphenol, 2,4'-methylene diphenol, 4 ,4'-methylene diphenol, 4,4'-ethylene bisphenol A, bisphenol A, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, etc.

As the blending amount of the polyhydric alcohol (a2-1) increases, the solubility of the polyester polyol (A1) in organic solvents may decrease, or it may combine with the cured coating film of the polyisocyanate composition (B) described later (following The elastic modulus of the agent layer is reduced. If the solubility in organic solvents is reduced, the storage stability of the two-component adhesive of the present invention is reduced when it is made into a solvent type. If the elastic modulus of the cured coating film is reduced, it may cause the adhesive layer to change during the molding process. Damage, but because the polyhydric alcohol (a2) contains at least one selected from the group consisting of polyhydric alcohols (a2-2) and polyhydric alcohols (a2-3), that is, polyester polyol (A1) is derived from The structure of polyhydric alcohols (a2-2) and (a2-3) can prevent the decrease in storage stability and elasticity. Furthermore, polyhydric alcohols (a2-2) and (a2-3) can also be expected to improve the hydrolysis resistance of the cured coating film.

The total blending amount of the polyhydric alcohol (a2-2) and the polyhydric alcohol (a2-3) is appropriately adjusted depending on the balance with other components. As an example, it is preferably 10 mol% or more and 90 mol% or less. More preferably, it is 15 mol% or more and 70 mol% or less, and 20 mol% or more and 60 mol% or less.

The polyhydric alcohol (a2) may contain polyhydric alcohols (a-4) other than the polyhydric alcohols (a2-1) to (a2-3) within a range that does not impair the effects of the present invention.

In the present invention, the polyester polyol (A1) can be a polyester polyurethane polyol (polyester polyurethane polyol) using a polyacid or its derivative (a1), a polyhydric alcohol (a2), and a polyisocyanate as essential raw materials. As the polyisocyanate used in this case, a diisocyanate compound or a polyisocyanate compound with three or more functions can be mentioned. These polyisocyanates may be used individually, respectively, and may use 2 or more types together.

Examples of the diisocyanate compound include the following: butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-tri Aliphatic diisocyanates such as methyl hexamethylene diisocyanate, stubborn diisocyanate, m-tetramethyl stubborn diisocyanate, and lysine diisocyanate.

Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methyl ring Alicyclic diisocyanates such as hexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate.

1,5-Naphthalene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate Methylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate Aromatic diisocyanates such as phenyl diisocyanate and tolylene diisocyanate.

Examples of polyisocyanate compounds with more than three functions include diisocyanate oligomers, adduct type polyisocyanate compounds having urethane bond sites in the molecule, and uric acid having an isocyanurate ring structure in the molecule. Ester (nurate) type polyisocyanate compound.

The adduct type polyisocyanate compound having a amine ester bond site in the molecule can be obtained by, for example, reacting a diisocyanate compound with a polyhydric alcohol. Examples of the diisocyanate compound used in this reaction include the various diisocyanate compounds exemplified above as the diisocyanate compound, and these may be used alone, or two or more of them may be used in combination. In addition, the polyol compound used in the reaction may include various polyol compounds exemplified as the polyhydric alcohol (a2) above, or polyester polyols obtained by reacting a polyhydric alcohol with a polybasic acid, etc. These may They can be used alone, or two or more of them can be used in combination.

The urate-type polyisocyanate compound having an isocyanurate ring structure in the molecule can be obtained, for example, by reacting a diisocyanate compound with a monool and/or a diol. Examples of the diisocyanate compound used in this reaction include the various diisocyanate compounds exemplified above as the diisocyanate compound, and these may be used alone, or two or more of them may be used in combination. In addition, as the monoalcohol used in this reaction, hexanol, 2-ethylhexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecanol, n-tridecanol, n-tetradecyl alcohol, Alcohol, n-pentadecanol, n-heptadecanol, n-octadecyl alcohol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonanol, 2-hexyldecanol, 3, 9-diethyl-6-tridecanol, 2-isoheptylisoundecyl alcohol, 2-octyldodecanol, 2-decyltetradecyl alcohol, etc. As the diol, the above-mentioned polyhydric alcohols can be cited The aliphatic diols exemplified. These monoalcohols or diols may be used alone, or two or more of them may be used in combination.

The polyester polyol (A1) used in the present invention is a reaction product of a polybasic acid or its derivative (a1) and a polyhydric alcohol (a2), and the polybasic acid or its derivative (a1) has an aromatic ring The ratio of the polybasic acid or its derivative (a1-1) is preferably 30 mol% or more. Thereby, an adhesive agent with excellent storage stability can be made. Furthermore, in terms of improving moldability and heat resistance, the ratio of the polybasic acid or its derivative (a1) with the aromatic ring-containing polybasic acid or its derivative (a1-1) is more preferably 50 mol% Above, more preferably 70 mol% or more, and even more preferably 96 mol% or more. The polybasic acid or its derivative (a1) may all be a polybasic acid or its derivative (a1-1) having an aromatic ring.

Alternatively, the polyester polyol (A1) used in the present invention may also be a reaction product of a polyacid or its derivative (a1), a polyhydric alcohol (a2), and a polyisocyanate, and the polyacid or its derivative ( The ratio of the polybasic acid or its derivative (a1-1) with an aromatic ring in a1) is preferably 30 mol% or more. Thereby, an adhesive agent with excellent storage stability can be made. Furthermore, in terms of improving moldability and heat resistance, the ratio of the polybasic acid or its derivative (a1) with the aromatic ring-containing polybasic acid or its derivative (a1-1) is more preferably 50 mol% Above, more preferably 70 mol% or more, and even more preferably 96 mol% or more. The polybasic acid or its derivative (a1) may all be a polybasic acid or its derivative (a1-1) having an aromatic ring.

Regarding the hydroxyl value of the polyester polyol (A1) used in the present invention, it is preferably in the range of 1-40 mgKOH/g, more preferably 3 mgKOH/g or more, in terms of more excellent adhesive strength. Below 30 mgKOH/g.

Regarding the number average molecular weight (Mn) of the polyester polyol (A1) used in the present invention, it is preferably in the range of 2,000 to 100,000, more preferably 2,000～50,000. When the number average molecular weight is less than 2,000, the crosslinking density in the cured coating film may be too high, which may result in deterioration of the appearance and moldability of the laminate. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, more preferably in the range of 10,000 to 200,000.

Furthermore, in the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8320GPC manufactured by Tosoh Co., Ltd. Column: manufactured by Tosoh Co., Ltd. TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer) Data processing: Multi Station GPC-8020modelII manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40℃ Solvent Tetrahydrofuran Flow rate 0.35 ml/min Standard: Monodisperse Polystyrene Sample: 0.2% by mass of the tetrahydrofuran solution converted to the solid content of the resin is filtered with a microfilter (100 μl)

The solid component acid value of the polyester polyol (A1) used in the present invention is not particularly limited, but it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent, so it is preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more. It can also be 0 mgKOH/g.

The glass transition temperature of the polyester polyol (A1) used in the present invention is preferably -30°C or more and 20°C or less. By setting the glass transition temperature of the polyester polyol (A1) in this range, when used in combination with the following resin (A2), an adhesive with excellent bonding strength, moldability, heat resistance, and moisture and heat resistance can be made . The glass transition temperature of the polyester polyol (A1) is more preferably -20°C or higher, and more preferably 15°C or lower.

Furthermore, the glass transition temperature in the present invention refers to the value measured in the following manner. Using a differential scanning calorimetry device (DSC-7000 manufactured by SII NanoTechnology Co., Ltd., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature to 200°C at 10°C/min under a nitrogen flow of 30 mL/min. After that, it was cooled to -80°C at 10°C/min. Make it rise again at 10°C/min to 150°C and measure the DSC curve to extend the baseline on the low temperature side of the measurement result observed in the second heating step to the straight line on the high temperature side, and the step in the glass transition The intersection of the tangent line drawn by the point where the slope of the curve of the shape portion becomes the maximum is regarded as the glass transition point, and the temperature at this time is regarded as the glass transition temperature. In addition, although the temperature is raised to 200°C in the first temperature rise, it is sufficient as long as it is a temperature at which the polyester polyol (A1) is sufficiently melted. When 200°C is insufficient, it is appropriately adjusted. Similarly, about the cooling temperature, when it is insufficient at -80°C (when it is lower than the glass transition temperature, etc.), it is also adjusted appropriately.

In the synthesis of the polyester polyol (A1), the reaction of the polybasic acid or its derivative with the polyhydric alcohol, or the reaction of the polybasic acid or its derivative, the polyhydric alcohol, and the polyisocyanate may be performed by a known method.

For example, the reaction of a polybasic acid or its derivative with the above-mentioned polyhydric alcohol can be carried out by a condensation polymerization reaction. In addition, with regard to the reaction of the polybasic acid or its derivative, the polyhydric alcohol and the polyisocyanate, the polyester polyol obtained by reacting the polyhydric acid or its derivative with the polyhydric alcohol and the polyisocyanate can be If necessary, the polyisocyanate is reacted in the presence of a well-known and customary aminating catalyst to obtain the polyester polyol (A1) of the present invention.

The esterification reaction of polybasic acid or its derivatives and polyhydric alcohol is to add polybasic acid or its derivatives, polyhydric alcohol, and polymerization catalyst to a reaction vessel equipped with agitator and rectification equipment, stir and raise the temperature at normal pressure at the same time To about 130°C. Thereafter, the reaction temperature in the range of 130 to 260°C was increased in a ratio of 5 to 10°C for 1 hour while distilling off the generated water. After the esterification reaction is carried out for 4-12 hours, the pressure is gradually increased from normal pressure to the range of 1 to 300 torr and the residual polyhydric alcohol is distilled off at the same time to promote the reaction, thereby making it possible to produce polyester polyol (A1 ).

The polymerization catalyst used in the esterification reaction is preferably at least 1 selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14 and Group 15 of the periodic table A polymerization catalyst composed of a metal or a compound of the metal. Examples of the polymerization catalyst composed of the metal or its metal compound include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, Ge, and compounds of these metals, and more specifically, tetraisopropyl Titanium oxide, titanium tetrabutoxide, titanium oxyacetone acetonate, tin octoate, tin 2-ethylhexanoate, zinc acetone acetone, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, Hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, etc.

Commercially available polymerization catalysts that can be used in the esterification reaction include ORGATIX TA series, TC series, ZA series, ZC series, and AL series manufactured by Matsumoto Fine Chemica, and organotin manufactured by Nitto Chemical Co., Ltd. Department of catalysts, inorganic metal catalysts, inorganic tin compounds.

Regarding the amount of these polymerization catalysts used, as long as the esterification reaction can be controlled and a good quality polyester polyol (A1) can be obtained, there is no particular limitation. As an example, compared to the polybasic acid or its derivative and the polyhydric alcohol The total amount is 10-1000 ppm, preferably 20-800 ppm. In order to suppress the coloration of the polyester polyol (A1), it is more preferably 30 to 500 ppm.

In addition, the polyester polyurethane polyol used in the present invention can be obtained by chain extension of the polyester polyol obtained by the above method using polyisocyanate. As a specific manufacturing method, add polyester polyol, polyisocyanate, chain extension catalyst, and if necessary a good solvent of polyester polyol and polyisocyanate to the reaction vessel, and at a reaction temperature of 60-90°C Stir. The reaction is carried out until the isocyanate group derived from the polyisocyanate used does not substantially remain, and the polyester polyurethane polyol used in the present invention is obtained.

As the chain extension catalyst, well-known and commonly used catalysts generally used as amine esterification catalysts can be used. Specifically, organic tin compounds, organic tin carboxylates, lead carboxylates, bismuth carboxylates, titanium compounds, zirconium compounds, etc. can be cited, and they can be used alone or in combination. The use amount of the above-mentioned chain extension catalyst may be an amount that sufficiently promotes the reaction between the polyester polyol and the polyisocyanate. Specifically, it is preferably 5.0 relative to the total amount of the polyester polyol and the polyisocyanate. Less than mass%. In order to suppress the hydrolysis or coloring of the resin caused by the catalyst, it is more preferably 1.0% by mass or less. Furthermore, these chain extension catalysts can also be considered for use as a curing catalyst for the following polyol (A) and isocyanate composition (B).

As a method of confirming the remaining amount of isocyanate groups, the presence or absence of an absorption spectrum derived from isocyanate groups, that is, the absorption peak observed near ^{2260 cm -1, can be confirmed by infrared absorption spectrometry, or by titration} Method for quantification of isocyanate groups.

Good solvents used in the production of polyester polyurethane polyols include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, xylene, etc. . It can be used alone, or two or more of them can be used in combination.

(Resin (A2)) The polyol composition (A) of the present invention preferably contains a resin (A2) having a glass transition temperature of 50° C. or more and 110° C. or less in terms of being able to be formed into better adhesiveness, moldability, and heat resistance. It is believed that this resin (A2) is difficult to dissolve with the polyester polyol (A1), forming a sea-island structure in the cured coating film, and exerting the polyester polyol (A1)'s excellent wettability, adhesiveness, and adhesion to the substrate. Moldability, and even when the viscoelasticity of the polyester polyol (A1)-derived part of the hardened coating film is reduced under high temperature and high humidity, the resin (A2)-derived part will simulate the performance as The role of filler, so the adhesive layer is not easy to soften, showing good adhesiveness and heat resistance.

The resin (A2) can be used without particular limitation as long as the glass transition temperature is 50°C or higher and 110°C or lower. As an example, polyester resins, polyurethane resins, polyurea resins, acrylic resins, and polyamide resins can be mentioned. , Polyimide resin, epoxy resin, rosin modified epoxy resin, etc. In order to achieve good adhesion, moldability, and heat resistance, it is preferable that the resin (A2) and the polyester polyol (A1) are not completely compatible, and it is preferable to measure "to 50 parts by mass of the polyester polyol (A1) and The composition obtained by adding 30 parts by mass of the trimethylolpropane adduct of toluene diisocyanate to the resin (A2) by mass" shows that the loss tangent (tanδ) at the time of dynamic viscoelasticity is derived from polyester multi-component The peak of alcohol (A1) and the peak derived from resin (A2). The resin (A2) may or may not have functional groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, a thiol group, and a glycidyl group.

When the resin (A2) has a hydroxyl group, it is preferably a secondary or tertiary hydroxyl group. The hydroxyl value of the resin (A2) is preferably in the range of 1-40 mgKOH/g, and more preferably 3 mgKOH/g or more and 30 mgKOH/g or less in terms of more excellent adhesive strength. In addition, the hydroxyl value of the resin (A2) is preferably below the hydroxyl value of the polyester polyol (A1).

When the resin (A2) has a carboxyl group, the solid content acid value of the resin (A2) is not particularly limited, and it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent, which is preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more.

The glass transition temperature of the resin (A2) is 50°C or more and 110°C or less. By setting the glass transition temperature of the resin (A2) in this range, when used in combination with the polyester polyol (A1), it is possible to form an adhesive with excellent adhesive strength, moldability, heat resistance, and moisture and heat resistance. The glass transition temperature of the resin (A2) is more preferably 60°C or higher, and more preferably 65°C or higher. In addition, the glass transition temperature of the resin (A2) is more preferably 100°C or lower, and more preferably 90°C or lower.

The blending amount of the resin (A2) is appropriately adjusted depending on the degree of necessary heat resistance, so it is not particularly limited. It is preferably set to 90 mass parts relative to the total of 100 parts by mass of the polyester polyol (A1) and the resin (A2) Servings or less. It is more preferably 3 parts by mass or more and 65 parts by mass or less, and still more preferably 5 parts by mass or more and 50 parts by mass or less. Thereby, the adhesiveness, moldability, heat resistance, and humidity and heat resistance can be improved more reliably.

(Polyisocyanate composition (B)) The polyisocyanate composition (B) used in the present invention contains an isocyanate compound (B). The isocyanate compound (B) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule, and various compounds can be used. Specifically, various diisocyanate compounds, oligomers of diisocyanate compounds, various diisocyanate compounds and diol compounds described in the raw materials of the above-mentioned polyester polyol (A1) and polyester polyol (A2) can be used. The adducts obtained by the reaction are modified diisocyanate compounds, these biuret modified bodies, allophanate modified bodies, or various polyisocyanate compounds with three or more functions. These isocyanate compounds (B) may be used alone, respectively, or two or more of them may be used in combination.

(Adhesive and other ingredients) In the adhesive of the present invention, other components may be used in combination within a range that does not impair the effects of the present invention. For example, the polyol composition (A) may also contain a polyester polyol (A3) that is not equivalent to the polyester polyol (A1) and the resin (A2). Polyester polyol (A3) can be used as the "reaction product of polybasic acid or its derivatives and polyhydric alcohol", or as "polybasic acid or its derivatives, polyhydric alcohol, and polyisocyanate". The reaction product" is a polyester polyurethane polyol. In addition, the polybasic acid or its derivative, polyhydric alcohol, and polyisocyanate used in the synthesis of the polyester polyol (A3) can be the same as the polyester polyol (A1).

The polyester polyol (A3) is preferably a polyester polyol or a polyester polyurethane polyol in which the ratio of a polybasic acid or a polybasic acid or a derivative thereof having an aromatic ring in the polybasic acid or its derivatives is 30 mol% or more. Thereby, it can be formed as an adhesive agent excellent in storage stability. Furthermore, from the viewpoint of improving moldability and heat resistance, the ratio of the polybasic acid or its derivatives having an aromatic ring in the polybasic acid or its derivatives is more preferably 50 mol% or more, and more preferably 70 mol% % Or more, more preferably 96 mol%. All polybasic acids or derivatives thereof may be polybasic acids or derivatives thereof having an aromatic ring.

The hydroxyl value of the polyester polyol (A3) is preferably in the range of 1 to 40 mgKOH/g, more preferably 3 mgKOH/g or more, and 30 mgKOH/g or less from the viewpoint of more excellent adhesive strength.

The number average molecular weight (Mn) of the polyester polyol (A3) is preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, from the viewpoint of more excellent adhesive strength when used in adhesive applications. When the number average molecular weight is less than 2,000, the crosslink density in the cured coating film becomes too high, and the appearance and moldability of the laminate may deteriorate. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, more preferably in the range of 10,000 to 200,000.

The solid content acid value of the polyester polyol (A3) is not particularly limited, but it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent and preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more. It can also be 0 mgKOH/g. The glass transition temperature of the polyester polyol (A3) is preferably -30°C or higher and 20°C or lower, more preferably -20°C or higher, and more preferably 15°C or lower.

The blending amount of the polyester polyol (A3) is not particularly limited, but it is preferably 90 parts by mass or less with respect to 100 parts by mass of the total of the polyester polyol (A1) and the polyester polyol (A3). It is more preferably 3 parts by mass or more and 65 parts by mass or less, and still more preferably 3 parts by mass or more and 50 parts by mass or less. In addition, when the polyol composition contains polyester polyol (A1), resin (A2), and polyester polyol (A3), it is preferable to blend the resin (A2) with respect to 100 parts by mass in total. The amount is 3 parts by mass or more and 65 parts by mass or less.

The polyol composition (A) preferably contains a polycarbonate polyol compound. At this time, regarding the blending ratio of the total amount of polyester polyol (A1) and resin (A2) and the polycarbonate polyol compound, it becomes an adhesive with high adhesion to various substrates and excellent moisture and heat resistance. In terms of the agent, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably in the range of 60-99 mass%, relative to the total mass of the two. .

The number average molecular weight (Mn) of the polycarbonate polyol compound is preferably in the range of 300 to 2,000 in terms of high adhesion to various substrates and excellent moisture and heat resistance. The hydroxyl value is preferably in the range of 30 to 250 mgKOH/g, more preferably in the range of 40 to 200 mgKOH/g. Furthermore, the polycarbonate polyol compound is preferably a polycarbonate diol compound.

In addition, the polyol composition (A) preferably contains a polyoxyalkylene-modified polyol compound. At this time, the blending ratio of the total amount of the polyester polyol (A1) and the resin (A2) and the polyoxyalkylene modified polyol compound has high adhesion to various substrates and high humidity and heat resistance. In terms of an excellent adhesive, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably 60-99 relative to the total mass of the two. The range of mass%.

Regarding the number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound, it is preferably 300-2,000 in terms of high adhesion to various substrates and excellent moisture and heat resistance. The scope. The hydroxyl value is preferably in the range of 40 to 250 mgKOH/g, more preferably in the range of 50 to 200 mgKOH/g. In addition, the polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.

The polyol composition (A) may contain other resin components in addition to the polyester polyol (A1) and the resin (A2). When using other resin components, it is preferably used at 50% by mass or less with respect to the total mass of the main agent, and preferably used at 30% by mass or less. As a specific example of other resin components, epoxy resin is mentioned. Examples of the epoxy resin include: bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; and biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin. Epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These may be used alone, or two or more of them may be used in combination. Among these, it is preferable to use a bisphenol-type epoxy resin in terms of becoming an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.

Regarding the number average molecular weight (Mn) of the epoxy resin, it is preferably in the range of 300 to 2,000 in terms of high adhesion to various substrates and excellent moisture and heat resistance. In addition, the epoxy equivalent is preferably in the range of 150 to 1000 g/equivalent.

In the case of using epoxy resin, the blending ratio of the total amount of polyester polyol (A1) and resin (A2) and epoxy resin becomes higher adhesion to various substrates, and also has high moisture and heat resistance. In terms of an excellent adhesive, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably 60-99 mass relative to the total mass of the two % Range.

The polyol composition (A) used in the present invention may also contain an adhesion imparting agent. Examples of adhesion-imparting agents include rosin-based or rosin ester-based adhesion-imparting agents, terpene-based or terpene-phenol-based adhesion-imparting agents, saturated hydrocarbon resins, coumarone-based adhesion-imparting agents, coumarone-based adhesion-imparting agents, Styrene resin-based adhesive imparting agent, xylene resin-based adhesive imparting agent, phenol resin-based adhesive imparting agent, petroleum resin-based adhesive imparting agent, ketone resin-based adhesive imparting agent, etc. It is preferably a ketone resin-based adhesive imparting agent, a rosin-based or rosin ester-based adhesive imparting agent, and more preferably a ketone resin-based adhesive imparting agent. These may be used alone, or two or more of them may be used in combination. In the case of using an adhesion-imparting agent, the total mass of polyester polyol (A1) and resin (A2) is preferably relative to the total mass of polyester polyol (A1), resin (A2), and adhesion-imparting agent 80 to 99.99% by mass, more preferably 85 to 99.9% by mass.

Examples of rosin-based or rosin ester-based rosins include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarated rosin, and these glycerides, neopentyl erythritol esters, and methyl esters. Esters, ethyl esters, butyl esters, glycol esters, diethylene glycol esters, triethylene glycol esters, etc.

Examples of the terpene type or terpene phenol type include oligomerized terpene type, α-pinene polymer, β-pinene polymer, terpene phenol type, aromatic modified terpene type, hydrogenated terpene type, and the like.

Examples of petroleum resins include: petroleum resins obtained by polymerizing petroleum fractions with 5 carbon atoms obtained from pentene, pentadiene, isoprene, etc.; and petroleum resins derived from indene, methyl indene, and vinyl toluene , Styrene, α-methylstyrene, β-methylstyrene, etc., petroleum resins obtained by polymerization of petroleum fractions with 9 carbons; C5-C9 copolymerized petroleum resins obtained from the above-mentioned various monomers and used Hydrogenated petroleum resins; petroleum resins obtained from cyclopentadiene and dicyclopentadiene; and hydrogenated products of these petroleum resins; these petroleum resins use maleic anhydride and maleic acid Modified petroleum resin obtained by modification of diacid, fumaric acid, (meth)acrylic acid, phenol, etc.

As the phenol resin system, a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol, and the like. Examples of such phenols include the addition reaction of these phenols with formaldehyde using an alkali catalyst. Resol resin obtained, or novolac obtained by condensation reaction using acid catalyst, etc. In addition, rosin phenol resin obtained by adding phenol to rosin using an acid catalyst and thermally polymerizing it can also be exemplified.

As the ketone resin, known and commonly used ones can be cited, but formaldehyde resins, cyclohexanone-formaldehyde resins, and ketone-aldehyde condensation resins can be preferably used.

Regarding the adhesion imparting agent, those having various softening points can be obtained. In terms of compatibility, color tone, and thermal stability when mixed with other resins constituting the polyol composition (A), softening is preferred. A ketone resin-based adhesive imparting agent with a temperature of 70-160°C, preferably 80-100°C, or a rosin-based resin and its hydrogenated derivatives with a softening point of 80-160°C, preferably 90-110°C, more preferably It is a ketone resin-based adhesive agent having a softening point of 70 to 160°C, preferably 80 to 100°C. Also, a ketone resin-based adhesive imparting agent and a hydrogenated rosin-based adhesive imparting agent having an acid value of 2-20 mgKOH/g and a hydroxyl value of 10 mgKOH/g or less are preferable, and an acid value of 2-20 mgKOH/g is more preferable. 、A ketone resin adhesive agent with a hydroxyl value of 10 mgKOH/g or less.

In the adhesive of the present invention, as yet another good aspect, known phosphoric acids or derivatives thereof can be used in combination. In this way, the initial adhesion of the adhesive is further improved, and the troubles such as tunneling can be eliminated.

Examples of phosphoric acids or derivatives thereof used here include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and low phosphoric acid; for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and superphosphoric acid. ; For example, monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, Monoethyl phosphate, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate , Dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite and other mono- and diester compounds, from condensation Mono- and diester compounds of phosphoric acid and alcohols; for example, the addition of epoxy compounds such as ethylene oxide and propylene oxide to the above-mentioned phosphoric acid; for example, the addition of aliphatic or aromatic diglycidyl ether Epoxy phosphates etc. obtained from the above-mentioned phosphoric acid.

One kind or two or more kinds of the above-mentioned phosphoric acids or derivatives thereof may be used. As a method of containing the above-mentioned phosphoric acid or its derivatives, it is only necessary to mix them.

In addition, an adhesion promoter can also be used in the adhesive of the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins, and the like.

Examples of the silane coupling agent include: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethyl Aminosilanes such as oxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.; β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl triethoxy silane, etc. Oxysilane; vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-methacryloxy propyl trimethoxy silane and other vinyl groups Silane; hexamethyldisilazane, γ-mercaptopropyl trimethoxysilane, etc.

As the titanate coupling agent, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, Tetraoctanediol titanate, titanium lactate, titanium tetrastearyl oxide, etc.

In addition, as an aluminum-based coupling agent, for example, acetalkoxy aluminum diisopropoxide and the like can be cited.

As the adhesion promoter, a silane coupling agent is preferably used. In addition, the content of the accelerator (solid content) relative to 100 parts by mass of the solid content of the polyol composition (A) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass Parts or more, more preferably 0.7 parts by mass or more. In addition, the content of the accelerator (solid content) relative to 100 parts by mass of the solid content of the polyol composition (A) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 5 Parts by mass or less.

In the adhesive of the present invention, the blending ratio of the polyol composition (A) and the polyisocyanate composition (B) is preferably the total number of moles of hydroxyl groups contained in the polyol composition (A) [ The ratio [NCO]/[OH] of the molar number [NCO] of the isocyanate group contained in the OH] and the polyisocyanate composition (B) is set in the range of 1.5 to 15.0. Thereby, it becomes a two-component adhesive with excellent moldability, heat resistance, and moisture and heat resistance.

Excessive isocyanate compounds in the two-component adhesive will harden with moisture to become polymers and oligomers with urea bonds, which are believed to contribute to the improvement of heat resistance and moisture resistance of the cured coating film. Therefore, when the [NCO]/[OH] ratio is relatively small, for example, if it is about 1.5, the heat resistance and humidity resistance may be insufficient. In this case, for example, the polyol composition (A ) In the resin (A2) blending amount to deal with. In addition, when the [NCO]/[OH] ratio is relatively high, for example, if it is about 15.0, the coating film may become too hard due to the influence of the crosslinking density or the polymer or oligomer with urea bonds. The formability is reduced. In this case, it can be dealt with by increasing the blending amount of the polyester polyol (A1) in the polyol composition (A). In order to ensure the design freedom of the two-component adhesive and reliably improve the heat resistance and humidity resistance, the [NCO]/[OH] ratio is more preferably 2.0-10, and more preferably 2.5-8.0.

烷等醚類；甲苯、二甲苯等芳香族烴類；二氯甲烷、二氯乙烷等鹵代烴類；二甲亞碸、二甲基磺醯胺等。The adhesive of the present invention may be either a solvent type or a solventless type. Furthermore, the so-called "solvent type" adhesive in the present invention refers to the form used in the following method, the so-called dry lamination method: after the adhesive is applied to the substrate, it is heated in an oven or the like to make the coating film The organic solvent evaporates, and then it is bonded with other substrates. Either or both of the polyol composition (A) and the polyisocyanate composition (B) include a dissolution capable of dissolving the polyol composition (A) or the polyisocyanate composition (B) used in the present invention Organic solvents with higher performance. In the case of the solvent type, the organic solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or the polyisocyanate composition (B) may also be used as a diluent during coating. Examples of organic solvents with relatively high solubility include esters such as ethyl acetate, butyl acetate, and cellulose acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; and tetrahydrofuran ,two

Ethers such as alkanes; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and dichloroethane; dimethyl sulfide, dimethyl sulfonamide, etc.

In this specification, the "solvent-free" adhesive refers to the form of the following adhesive: the polyol composition (A) and the polyisocyanate composition (B) are substantially free of organic solvents with higher solubility as mentioned above , Especially ethyl acetate or methyl ethyl ketone, is used to apply the adhesive to the substrate without going through the step of heating the solvent to volatilize the solvent in an oven, etc., and the method of bonding with other substrates is so-called solvent-free Laminating method. The organic solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or polyisocyanate composition (B) or its raw materials is not completely removed, and the polyol composition (A) or polyisocyanate When a trace amount of organic solvent remains in the composition (B), it is understood that the organic solvent is not substantially contained. In addition, when the polyol composition (A) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (B) to become a part of the coating film, so there is no need to volatilize it after coating. Therefore, this form is also regarded as a solvent-free adhesive.

When the adhesive of the present invention is a solvent type, since the viscosity can be reduced by dilution with the solvent, even if the viscosity of the polyol composition (A) or polyisocyanate composition (B) used is slightly higher, can be used. On the other hand, in the case of the solvent-free type, low viscosity is valued in terms of the characteristics of reducing the viscosity by heating. As a means of reducing the viscosity, polyisocyanate composition (B) is mostly used as an inducement to increase the viscosity. The concentration of aromatics.

The adhesive of the present invention may also contain various additives such as ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoamers, antistatic agents, and antifogging agents.

The use of the adhesive of the present invention is not particularly limited, and since it is excellent in adhesive strength, moldability, moisture and heat resistance, and heat resistance, as an example, it can be preferably used as a battery packaging material.

＜Laminated body＞ The laminated system of the present invention uses the adhesive of the present invention and is obtained by laminating a plurality of substrates by a dry lamination method or a solvent-free lamination method. Examples of substrates include paper, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, fluorine resins, poly(meth)acrylic resins, and carbonates. Synthetic resin films, copper foils, aluminum foils and other metal foils obtained from synthetic resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins, or polyester resins .

The film thickness of the substrate is not particularly limited, and can be selected from 10 to 400 μm, for example. In order to improve the adhesion between the substrate and the adhesive, the surface of the substrate on which the adhesive is applied can also be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, ozone treatment, flame treatment, radiation treatment, and the like.

＜Packaging materials for batteries＞ Regarding the molded body obtained by molding the laminate of the present invention, as an example, it can be suitably used as a battery packaging material. As shown in FIG. 1, the battery packaging material is composed of a laminate in which at least the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, and the sealant layer 4 are laminated in this order. In the battery packaging material of the present invention, the outer layer side base material layer 1 becomes the outermost layer, and the sealant layer 4 becomes the innermost layer. That is, when assembling the battery, the battery element can be sealed by thermally fusing the sealant layers 4 located on the periphery of the battery element to each other. The adhesive of the present invention is used for the adhesive layer 2. In addition, as shown in FIG. 2, the battery packaging material of the present invention can also be provided with an adhesive layer 5 between the metal layer 3 and the sealant layer 4 as necessary to improve the adhesion.

(Outer layer side base material layer 1) In the battery packaging material of the present invention, the outer layer side base material layer 1 forms the outermost layer. There are no particular restrictions on the material forming the outer substrate layer 1 as long as it is insulating, and examples include polyester resins, polyamide resins, epoxy resins, acrylic resins, fluororesins, polyurethane resins, and silicone resins. , Phenolic resins, and resin films such as mixtures or copolymers of these. Among these, polyester resins and polyamide resins are preferred, and biaxially stretched polyester resins and biaxially stretched polyamide resins are more preferred. Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate, copolyester, Polycarbonate etc. In addition, as the polyamide resin, specifically, nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 6,10, polyhexamethylene diamide (MXD6 )Wait.

The outer base material layer 1 may be formed of a single resin film, but in order to improve pinhole resistance or insulation, it may be formed of two or more resin films. When the outer base material layer 1 is formed of multiple resin films, the resin films can be laminated via adhesive or adhesive resin and other components. The types and amounts of the components used are as follows: The situation of the bonding layer 2 or the bonding layer 5 is the same. In addition, the method of laminating two or more resin films is not particularly limited, and a known method can be used, for example, dry lamination, sandwich lamination, etc., preferably dry lamination. In the case of lamination by a dry lamination method, it is preferable to use an adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 0.5 to 10 μm.

The thickness of the outer layer-side base material layer 1 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 10-50 μm, preferably about 15-35 μm. When a polyester film is used, the thickness is preferably 9 μm-50 μm, and when a polyamide film is used, the thickness is preferably 10 μm-50 μm. As a packaging material, it can ensure sufficient strength, and can reduce the stress during stretch molding or extraction molding, and improve formability.

(Metal layer 3) In the battery packaging material, the metal layer 3 not only enhances the strength of the battery packaging material, but also functions as a barrier layer for preventing water vapor, oxygen, light, etc. from entering the battery. As the metal constituting the metal layer 3, specifically, aluminum, stainless steel, titanium, etc. can be cited, and aluminum is preferred. The metal layer 3 can be formed by metal foil or metal vapor deposition, etc., is preferably formed by metal foil, and more preferably is formed by aluminum foil. Furthermore, in order to stabilize the bonding, prevent dissolution or corrosion, etc., the metal layer 3 preferably has at least one side, and preferably both sides have been chemically treated. Here, the chemical treatment refers to the treatment of forming an acid-resistant film on the surface of the metal layer.

The thickness of the metal layer 3 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it can be about 10-50 μm, preferably about 25-45 μm.

(Sealant layer 4) In the battery packaging material of the present invention, the sealant layer 4 corresponds to the innermost layer, and is a layer for sealing the battery elements by thermally fusing the sealant layers to each other when the battery is assembled.

The resin component used in the sealant layer 4 is not particularly limited as long as it can be thermally welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

As the above-mentioned polyolefins, specifically, polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; homopolypropylene and block copolymers of polypropylene (for example, Block copolymers of propylene and ethylene), random copolymers of polypropylene (such as random copolymers of propylene and ethylene) and other polypropylenes; ethylene-butene-propylene terpolymers, etc. Among these polyolefins, polyethylene and polypropylene are preferable.

The above-mentioned cyclic polyolefin-based copolymer of an olefin and a cyclic monomer. Regarding the olefin as the constituent monomer of the above-mentioned cyclic polyolefin, for example, ethylene, propylene, 4-methyl-1-pentene, styrene, Butadiene, isoprene, etc. In addition, the cyclic monomers as the constituent monomers of the cyclic polyolefins include, for example, cyclic olefins such as norbornene; specifically, cyclopentadiene, dicyclopentadiene, and cyclohexadiene can be cited. Cyclic dienes such as alkenes, norbornadiene, etc. Among these polyolefins, cyclic olefins are preferred, and norbornene is more preferred.

The carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin using carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride.

The carboxylic acid-modified cyclic polyolefin is copolymerized by substituting α,β-unsaturated carboxylic acid or its anhydride for a part of the monomers constituting the cyclic polyolefin, or by making α,β-unsaturated carboxylic acid A polymer obtained by block polymerization or graft polymerization of an acid or its anhydride on a cyclic polyolefin. Regarding the cyclic polyolefin for carboxylic acid modification, it is the same as the above. In addition, the carboxylic acid used for the modification is the same as the one used for the modification of the acid-modified cycloolefin copolymer.

The sealant layer 4 may be formed by one type of resin component alone, or may be formed by a blended polymer obtained by combining two or more types of resin components. Furthermore, the sealant layer 4 may be formed of only one layer, or may be formed of two or more layers with the same or different resin components.

The thickness of the sealant layer 4 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 10 to 100 μm, preferably about 20 to 90 μm.

(Next to layer 5) In the battery packaging material of the present invention, the adhesive layer 5 is a layer provided as necessary between the metal layer 3 and the sealant layer 4 in order to firmly adhere them.

The adhesive layer 5 is formed by an adhesive capable of adhering the metal layer 3 and the sealant layer 4. As the adhesive layer used for the adhesive layer 5, for example, an adhesive composed of a combination of polyolefin resin and polyfunctional isocyanate, an adhesive composed of a combination of polyol and polyfunctional isocyanate, modified polyolefin resin, and heterogeneous Adhesive for cyclic compounds and hardeners. Alternatively, an adhesive such as acid-modified polypropylene can be melt-extruded onto the metal layer using a T-die extruder to form the adhesive layer 5. The sealant layer 4 is superimposed on the adhesive layer 5, and the metal layer 3 and the sealant Layer 4 is attached. When both the adhesive layer 2 and the adhesive layer 5 must be aged, they can be aged together. Furthermore, by setting the aging temperature to room temperature to 90°C, curing is completed in 2 days to 2 weeks, thereby exhibiting moldability.

The thickness of the adhesive layer 5 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 0.5-50 μm, preferably about 2-30 μm.

(Coating layer 6) In the battery packaging material of the present invention, in order to improve design, electrolyte resistance, abrasion resistance, moldability, etc., it can also be placed on the outer layer side substrate layer 1 (the outer layer side substrate layer 1 and the metal The side opposite to layer 3) is provided with a coating layer 6. The coating layer 6 is the outermost layer when the battery is assembled.

The coating layer 6 can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, etc., and is preferably formed of a two-component curing resin. Examples of the two-component curing resin for forming the coating layer 6 include two-component curing urethane resin, two-component curing polyester resin, and two-component curing epoxy resin. In addition, a matting agent may be blended in the coating layer 6.

As the matting agent, for example, fine particles having a particle diameter of about 0.5 nm to 5 μm can be cited. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. In addition, the shape of the matting agent is not particularly limited, and examples thereof include spherical, fibrous, plate-shaped, amorphous, and balloon-shaped. Specific examples of matting agents include talc, silica, graphite, kaolin, montmorilloide, montmorillonite, synthetic mica, magnesia, silica gel, zeolite, and hydroxide Aluminum, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, Magnesium stearate, carbon black, carbon nanotubes, high melting point nylon, cross-linked acrylic, cross-linked styrene, cross-linked polyethylene, benzoguanidine, gold, aluminum, copper, nickel, etc. These matting agents may be used alone or in combination of two or more kinds. Among these matting agents, from the viewpoint of dispersion stability and cost, silicon dioxide, barium sulfate, and titanium oxide are preferred. In addition, regarding the matting agent, various surface treatments such as insulation treatment and high-dispersibility treatment may be applied to the surface.

The method of forming the coating layer 6 is not particularly limited. For example, a method of applying the two-liquid hardening resin for forming the coating layer 6 to one surface of the outer layer side base material layer 1 can be cited. In the case of blending a matting agent, it is only necessary to add a matting agent to the two-component hardening resin and mix it and apply it.

(Method of manufacturing battery packaging materials) There are no particular limitations on the method of manufacturing the battery packaging material of the present invention as long as a laminate obtained by laminating each layer of a specific composition can be obtained, and the following methods are exemplified.

First, a laminate (hereinafter, sometimes referred to as "Laminate A") in which the outer layer side base material layer 1, the adhesive layer 2, and the metal layer 3 are sequentially laminated is formed. Regarding the formation of the laminate A, specifically, it can be carried out by the following dry lamination method: on the outer layer side base material layer 1 or on the metal layer 3 whose surface is chemically treated as necessary, using an extrusion method or a gravure After coating and drying the adhesive of the present invention by coating methods such as coating method and roll coating method and drying, the metal layer 3 or the outer layer side base material layer 1 is laminated and the adhesive layer 2 is cured.

Then, the sealant layer 4 is laminated on the metal layer 3 of the laminate A. When the sealant layer 4 is directly laminated on the metal layer 3, it is only necessary to coat the resin component constituting the sealant layer 4 on the metal layer 3 of the laminate A by a method such as a gravure coating method or a roll coating method. can. Moreover, when the adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4, for example, the following method can be cited: by co-extruding the adhesive layer 5 and the sealant layer 4 on the metal layer 3 of the laminate A Laminate (co-extrusion lamination method); in addition, a laminate of the laminate adhesive layer 5 and the sealant layer 4 is formed, and the laminate is laminated on the metal layer 3 of the laminate A by the thermal lamination method; in the laminate On the metal layer 3 of A, the adhesive used to form the adhesive layer 5 is laminated by an extrusion method or a method of drying at a high temperature of solution coating and then sintering, and prefabricated by a thermal lamination method The sheet-shaped sealant layer 4 is laminated on the adhesive layer 5; the melted adhesive layer 5 flows between the metal layer 3 of the laminate A and the sealant layer 4 previously formed into a sheet-like film, and passes through Next, in the layer 5, the laminated body A and the sealant layer 4 are bonded together (sandwich lamination method) and the like.

When the coating layer 6 is provided, the surface area layer coating layer 6 on the side opposite to the metal layer 3 of the outer layer side base material layer 1. The coating layer 6 is formed, for example, by coating the above-mentioned resin forming the coating layer 6 on the surface of the outer layer side base material layer 1. Furthermore, the order of the step of the surface area layer metal layer 3 of the outer layer side base material layer 1 and the step of the surface area layer coating layer 6 of the outer layer side base material layer 1 is not particularly limited. For example, after the coating layer 6 is formed on the surface of the outer substrate layer 1, the metal layer 3 may be formed on the surface of the outer substrate layer 1 opposite to the coating layer 6.

In the above manner, the coating layer 6/outer layer side base material layer 1/adhesive layer 2 provided as needed/metal layer with chemically treated surface as required 3/adhesive layer 5 provided as needed/sealant layer 4 In order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as needed, the laminated body constituted may be further subjected to heating treatments such as a heat roller contact type, a hot air type, a near or far infrared type, and the like. As a condition of such a heat treatment, 80-250 degreeC and 1 to 5 minutes are mentioned, for example.

In the battery packaging material of the present invention, regarding each layer constituting the laminate, in order to improve or stabilize the film-forming properties, layering processing, and the suitability of the final product for secondary processing (bagging, embossing), etc., it may be possible to improve or stabilize it. Perform surface activation treatments such as corona treatment, sandblasting treatment, oxidation treatment, and ozone treatment.

＜Battery container＞ The battery container of the present invention can be obtained by using the above-mentioned battery packaging material, and molding the outer layer side base material layer 1 to form a convex surface and the sealant layer 4 to form a concave surface. Furthermore, as a method of forming the recess, there are the following methods. ・Heat and air pressure molding method: A method in which battery packaging materials are sandwiched between a lower mold with holes for supplying high-temperature and high-pressure air and an upper mold with a pocket-shaped recess, which is heated and softened while supplying air to form a recess. ・Preheater plate-type compression molding method: After heating and softening the battery packaging material, it is clamped between the lower mold with a hole for supplying high-pressure air and the upper mold with a pocket-shaped concave portion, and the air is supplied to form the concave portion. method. ・Drum-type vacuum forming method: The battery packaging material is locally heated and softened by a heating roller, and then the recessed portion of the roller with a pocket-shaped recess is vacuumed to form the recessed portion. ・Pin molding method: A method in which the substrate sheet is heated and softened and then crimped by a bag-shaped concave-convex mold. ・Preheater plug assist (plug assist) compression molding method: This is a method of heating and softening the battery packaging material, and then sandwiching it between a lower mold with a hole for supplying high-pressure air and an upper mold with a pocket-shaped recess , The method of supplying air to form the concave part, and raising and lowering the convex plug during molding to assist the molding.

Among them, the preheater-assisted plug-in-air molding method as a heating vacuum molding method is preferable in terms of uniformly obtaining the thickness of the molded substrate.

(Use of packaging materials for batteries) The battery packaging material of the present invention is used as a battery container for sealing and accommodating battery elements such as positive electrodes, negative electrodes, and electrolytes.

Specifically, the battery packaging material of the present invention is used in a state where the metal terminals connected to each of the above-mentioned positive electrode and negative electrode protrude outward, and a flange portion (a region where the sealant layers contact each other) can be formed on the periphery of the battery element In the method of ), a battery element with at least a positive electrode, a negative electrode, and an electrolyte is covered, and the sealant layers of the flange portion are heat-sealed to seal each other, thereby providing a battery using a battery packaging material. Furthermore, when the battery packaging material of the present invention is used to house battery elements, it is used in such a way that the sealant part of the battery packaging material of the present invention becomes the inner side (the surface in contact with the battery element).

The battery packaging material of the present invention can be used for either primary batteries or secondary batteries, and is preferably used for secondary batteries. Regarding the type of secondary battery to which the battery packaging material of the present invention is applied, there is no particular limitation. Examples include: lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel-hydrogen storage batteries, nickel-cadmium storage batteries, and nickel- Iron batteries, nickel-zinc batteries, silver oxide-zinc batteries, metal-air batteries, multivalent cation batteries, condensers, capacitors, etc. Among these secondary batteries, as a preferable application target of the battery packaging material of the present invention, lithium ion batteries and lithium ion polymer batteries can be cited.

＜Other uses of laminated body and molded body＞ The use of the laminated body and the molded body of the laminated body of the present invention is not limited to battery packaging materials. The laminate of the present invention can also be used as a multilayer packaging material for the purpose of protecting food, medicines, and daily necessities. When used as a multilayer packaging material, its layer structure can be changed according to the content, use environment, and use form.

As one form of the packaging material, there may be mentioned a laminate obtained by laminating the sealant films of the laminate face to face, and then heat sealing the peripheral ends thereof. As a method of making a bag, the following method can be cited: bending or overlapping the laminate of the present invention so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral ends thereof are, for example, side-sealed or two-way sealed Type, three-sided sealing type, square sealing type, envelope attaching seal type, folding palm attaching seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, other heat seal types and other forms for heat sealing. The packaging material of the present invention can adopt various forms according to the content, use environment, and use form. It can also be self-supporting packaging materials (self-supporting bags), etc. As a method of heat sealing, it can be performed by known methods such as rod sealing, rotary roll sealing, belt sealing, pulse sealing, high frequency sealing, ultrasonic sealing, and the like.

As other forms of packaging materials, blister packaging (also known as squeeze packaging or PTP) can be cited. The blister package seals the storage portion by joining a laminate in which one or a plurality of storage portions are formed and a cover film. Since the laminated body of this invention is excellent in moldability, it can be used as a laminated body which forms a storage part, and can also be used as a cover film.

The present invention can also be used for applications other than packaging materials. As an example, a base material for decorative molding and sealing can be cited, but it is not limited to this. It can be suitably used for applications requiring any function or multiple functions of moldability, heat resistance, and moisture and heat resistance. [Example]

Hereinafter, specific synthesis examples and examples are given to explain the present invention in more detail, but the present invention is not limited to these examples. Furthermore, in the following examples, as for "parts" and "%", unless otherwise specified, they represent "parts by mass" and "% by mass", respectively.

＜Preparation of polyester polyol＞ (Synthesis example 1) Synthesis of polyester polyol (A1-1) Using 300.3 parts of isophthalic acid, 300.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 3000, the weight average molecular weight (Mw) is 16,000, and the resin hydroxyl value (calculated as solid content) is 19.2 mgKOH/g, resin acid value (conversion of solid content) of 0.55 mgKOH/g, glass transition temperature (Tg) of 10.7 ℃ polyester polyol (A1-1).

(Synthesis example 2) Synthesis of polyester polyol (A1-2) Used 424.8 parts of isophthalic acid, 182.0 parts of terephthalic acid, 57.1 parts of neopentyl glycol, 215.8 parts of 1,6-hexanediol, 34.0 parts of ethylene glycol, 3-methyl-1,5-pentanediol 86.3 parts, synthetic polyester polyol according to the usual method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 11,200, the weight average molecular weight (Mw) is 25,900, and the resin hydroxyl value (calculated as solid content) is 10.8 mgKOH/g, resin acid value (conversion of solid content) of 2.2 mgKOH/g, glass transition temperature (Tg) of 15.8 ℃ polyester polyol (A1-2).

(Synthesis example 3) Synthesis of polyester polyol (A1-3) Using 387.5 parts of isophthalic acid, 166.1 parts of terephthalic acid, 52.1 parts of neopentyl glycol, 167.4 parts of 1,6-hexanediol, and 227.0 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method . The obtained polyester polyol was diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) was 3,050, the weight average molecular weight (Mw) was 19,640, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A1-3) with 13.8 mgKOH/g, resin acid value (calculated as solid content) of 1.1 mgKOH/g, and glass transition temperature (Tg) of -3.6°C.

(Synthesis example 4) Synthesis of polyester polyol (A1-4) Using 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) was 1,980, the weight average molecular weight (Mw) was 19,920, and the resin hydroxyl value (calculated as solid content) was Polyester polyol (A1-4) with 13.8 mgKOH/g, resin acid value (calculated as solid content) of 0.46 mgKOH/g, and glass transition temperature (Tg) of 22.5°C.

(Synthesis example 5) Synthesis of polyester polyol (A1-5) Using 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) was 2,600, the weight average molecular weight (Mw) was 11,000, and the resin hydroxyl value (calculated as solid content) was Polyester polyol (A1-5) with 30.7 mgKOH/g, resin acid value (calculated as solid content) of 0.51 mgKOH/g, and glass transition temperature (Tg) of 7.3°C.

(Synthesis example 6) Synthesis of polyester polyol (A1-6) Using 365.7 parts of isophthalic acid, 156.7 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) was 2,300, the weight average molecular weight (Mw) was 18,220, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A1-6) with 16.8 mgKOH/g, resin acid value (calculated as solid content) of 0.71 mgKOH/g, and glass transition temperature (Tg) of -11.0°C.

(Synthesis example 7) Synthesis of polyester polyol (A1-7) Using 261.2 parts of isophthalic acid, 261.2 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 3,000, the weight average molecular weight (Mw) is 25,160, and the resin hydroxyl value (calculated as solid content) is Polyester polyol (A1-7) with 10.0 mgKOH/g, resin acid value (calculated as solid content) of 0.93 mgKOH/g, and glass transition temperature (Tg) of -9.1°C.

(Synthesis example 8) Synthesis of polyester polyol (A1-8) Using 273.9 parts of isophthalic acid, 273.9 parts of terephthalic acid, 51.5 parts of neopentyl glycol, 30.7 parts of ethylene glycol, and 370.0 parts of 1,9-nonanediol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 5,440, the weight average molecular weight (Mw) is 26,220, and the resin hydroxyl value (calculated as solid content) is Polyester polyol (A1-8) with 16.0 mgKOH/g, resin acid value (calculated as solid content) of 1.2 mgKOH/g, and glass transition temperature (Tg) of -3.0°C.

(Synthesis example 9) Synthesis of resin (A2) Using 697.2 parts of terephthalic acid, 72.9 parts of ethylene glycol, and 229.9 parts of 1,2-propylene glycol, polyester polyol was obtained according to a conventional method. Dilute the obtained polyester polyol with methyl ethyl ketone to 30% of the resin solid content to obtain a number average molecular weight (Mn) of 8,400, weight average molecular weight (Mw) of 61,300, and resin hydroxyl value (converted to solid content) ) Is a polyester polyol with 5.0 mgKOH/g, resin acid value (in terms of solid content) of 4.0 mgKOH/g, and glass transition temperature of 84°C. This polyester polyol is used as the resin (A2).

(Synthesis example 10) Synthesis of polyester polyol (A3-1) Using 170.2 parts of isophthalic acid, 407.8 parts of terephthalic acid, 11.1 parts of trimellitic anhydride, 47.8 parts of neopentyl glycol, and 363.1 parts of 1,6-hexanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 58% of the resin solid content, and the number average molecular weight (Mn) was 6,200, the weight average molecular weight (Mw) was 18,500, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A3-1) with 21.9 mgKOH/g, resin acid value (conversion of solid content) of 0.74 mgKOH/g, and glass transition temperature (Tg) of 7.3°C.

(Synthesis example 11) Synthesis of polyester polyol (A3-2) Using 900 parts of polyester polyol (A3-1) and 13.5 parts of cyclohexane diisocyanate, a chain extension reaction was carried out according to a conventional method to synthesize polyester polyurethane polyol. Dilute the obtained polyester polyurethane polyol with ethyl acetate to a resin solid content of 40%, and obtain a number average molecular weight (Mn) of 14,500, a weight average molecular weight (Mw) of 117,500, and a resin hydroxyl value (calculated as solid content) It is a polyester polyol (A3-2) of 5.2 mgKOH/g, resin acid value (calculated as solid content) of 1.8 mgKOH/g, and glass transition temperature (Tg) of 10.0°C.

(Comparative Synthesis Example 1) Synthesis of polyester polyol (AH-1) Using 316.4 parts of isophthalic acid, 316.4 parts of terephthalic acid, 59.5 parts of neopentyl glycol, 225.0 parts of 1,6-hexanediol, and 82.7 parts of ethylene glycol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) is 7,700, the weight average molecular weight (Mw) is 17,900, and the resin hydroxyl value (calculated as solid content) is 18.3 mgKOH/g, resin acid value (conversion of solid content) is 1.5 mgKOH/g, glass transition temperature (Tg) is 25.3 ℃ polyester polyol (AH-1).

(Comparative Synthesis Example 2) Synthesis of polyester polyol (AH-2) Using 395.4 parts of isophthalic acid, 179.7 parts of terephthalic acid, 29.2 parts of sebacic acid, 362.2 parts of 1,6-hexanediol, and 33.6 parts of ethylene glycol, polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 9,200, the weight average molecular weight (Mw) is 20,600, and the resin hydroxyl value (calculated as solid content) is 17.2 Polyester polyol (AH-2) with mgKOH/g, resin acid value (conversion of solid content) of 0.9 mgKOH/g, and glass transition temperature (Tg) of -0.7°C.

The physical properties of the polyester polyols obtained in Synthesis Examples 1-11 and Comparative Synthesis Examples 1 and 2 were measured as follows, and are summarized in Tables 1 and 2. Furthermore, the blending amount of polyhydric alcohol (a2-1), the blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) in the table are used in the synthesis of polyester polyol The proportion of individual polyhydric alcohols (a). In addition, 50 parts of polyester polyol (A1) and 50 parts of resin (A2) were measured for each of polyester polyol (A1-1), (A1-3), (A1-5) to (A1-8) , The dynamic viscoelasticity of the composition of 30 parts of the trimethylolpropane adduct of toluene diisocyanate has confirmed that there are peaks derived from polyester polyol (A1) and resin (A2) in the loss tangent (tanδ). ) Of the crest. (Molecular weight determination method) Measuring device: HLC-8320GPC manufactured by Tosoh Co., Ltd. Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: Multi Station GPC-8020modelII manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40℃ Solvent Tetrahydrofuran Flow rate 0.35 ml/min Standard: Monodisperse Polystyrene Sample: 0.2% by mass of the tetrahydrofuran solution converted to the solid content of the resin is filtered with a microfilter (100 μl)

(Acid value determination method) Accurately weigh 5.0 g of the sample, add 30 mL of neutral solvent to dissolve it, and titrate with 0.1 mol/L potassium hydroxide solution (methanol-based). The indicator system uses phenolphthalein. The measurement result is converted into the amount of potassium hydroxide required to neutralize 1 g sample, and the unit is mgKOH/g.

(Hydroxyl value determination method) Accurately weigh 4.0 g of the sample (calculated as solid content), add 25 mL of an acetylating agent composed of acetic anhydride/pyridine (volume ratio 1/19), seal it and heat it at 100°C for 1 hour. After acetylation, add 10 mL of ion-exchanged water and 100 mL of tetrahydrofuran, and use 0.5 mol/L potassium hydroxide solution (alcoholic) for titration. The indicator system uses phenolphthalein. The measurement result is converted to the amount of potassium hydroxide required to neutralize the acetic acid produced when 1 g of the sample is acetylated, and the unit is mgKOH/g.

(Glass transition temperature measurement method) Using DSC, heat 5 mg of the sample from room temperature at 10°C/min to 200°C under a nitrogen flow of 30 mL/min, then cool it down to -80°C at 10°C/min, and then heat it up again at 10°C/min To 150°C, and measure the DSC curve. In the measurement results observed in the second heating step, the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the stepped part of the glass transition becomes the largest The glass transition point is the temperature at this time as the glass transition temperature.

[Table 1] A1-1 A1-2 A1-3 A1-4 A1-5 A1－6 A1-7 Blending amount of polyhydric alcohol (a2－1) (mol%) 45 20 42.5 45 45 85 85 Blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) (mol%) 10 15 15 10 10 15 15 Glass transition temperature (℃) 10.7 15.8 -3.6 22.5 7.3 -11.0 －9.1 Acid value (mgKOH/g) 0.55 2.2 1.1 0.46 0.51 0.71 0.93 Hydroxyl value (mgKOH/g) 19.2 10.8 13.8 13.8 30.7 16.8 10.0 Number average molecular weight 3000 11200 3050 1980 2600 2300 3000 Weight average molecular weight 16000 25900 19640 19920 11000 18220 25160

[Table 2] A1-8 A2 A3-1 A3-2 AH-1 AH-2 Blending amount of polyhydric alcohol (a2－1) (mol%) 70 - - - 0 0 Blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) (mol%) 15 - - - 15 0 Glass transition temperature (℃) -3.0 84 7.3 10.0 25.3 －0.7 Acid value (mgKOH/g) 1.2 4.0 0.74 1.8 1.5 0.9 Hydroxyl value (mgKOH/g) 16.0 5.0 21.9 5.2 18.3 17.2 Number average molecular weight 5440 8400 6200 14,500 7700 9200 Weight average molecular weight 26220 61300 18500 117500 17,900 20600

＜Preparation of adhesive composition＞ (Example 1) Add 1.6 parts of KBM-403 (Non-volatile content of silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.: 100%) to a solution containing 100.0 parts of resin solid content of polyester polyol (A1-1), and stir well until KBM-403 completely dissolved. Add KW-75 (non-volatile isocyanate made by DIC company: 75% NCO%: 13.3) so that the non-volatile content becomes 30.3 parts, and then add ethyl acetate so that the non-volatile content becomes 25% and fully Stir to prepare the adhesive of Example 1.

(Example 2) ~ (Example 12) Except adjusting the materials and blending used in the preparation of the adhesive to the values described in Table 3 and Table 4, the adhesives of Examples 2 to 12 were produced in the same manner as in Example 1.

(Comparative example 1), (Comparative example 2) The adhesives of Comparative Example 1 and Comparative Example 2 were produced in the same manner as in Example 1, except that the materials and blending used in the preparation of the adhesive were adjusted to the values described in Table 5. In addition, the values described in Tables 3 to 5 are the amount of solid content (the amount of non-volatile content).

＜Production of laminated body Figure 2 constitution＞ (Example 1) On the matte surface of the 40 μm thick aluminum foil as the metal layer 3, the adhesive of Example 1 was applied in an amount of 4 g/m² with a dry laminator as the adhesive layer 2. After the solvent is volatilized, a 25 μm-thick stretched polyamide film is laminated as the outer base layer 1. Then, on the glossy surface of the aluminum foil of the metal layer 3 of the obtained laminated film, the adhesive used for the adhesive layer 5 was applied to a coating amount: 4 g/m² by a dry laminator to make After the solvent was evaporated, an unstretched polypropylene film with a thickness of 40 μm was laminated as the sealant layer 4, and then cured (aging) at 60° C. for 5 days to cure the adhesive to obtain the laminate of Example 1.

(Example 2) ~ (Example 12) In the same manner as in Example 1, the adhesives of Examples 2 to 12 were used as the adhesive layer 2 to obtain laminates of Examples 2 to 12.

(Comparative example 1), (Comparative example 2) In the same manner as in Example 1, the adhesives of Comparative Examples 1 and 2 were used as the adhesive layer 2 to obtain laminates of Comparative Examples 1 and 2.

The evaluation of the laminate was performed as follows. The results are shown in Table 3 to Table 5. ＜Adhesion strength＞ Using the "Autograph AGS-J" of Shimadzu Corporation, the peeling speed is 100 mm/min, the peeling width is 15 mm, and the peeling shape is peeled at 180°. The adhesion strength of the interface between 1 and the metal layer 3 was evaluated. The higher the value, the better as an adhesive.

＜Formability＞ Using Yamaoka Seisakusho Co., Ltd. "1 ton desktop servo press (SBN-1000)", the laminated body of the embodiment or the comparative example was cut into a size of 60×60 mm, and a blank sample (formed material, material). For the above blank samples, stretch the molding height from 4.5 mm to 6.5 mm by using a straight mold with no molding height at 23°C±5°C in such a way that the matte side of the aluminum foil becomes a convex side. , Evaluate the moldability by the maximum molding height that does not cause the fracture of the aluminum foil or the bulge between each layer.

Furthermore, the punch shape of the die used is a square with a side of 30 mm with an angle R of 2mm and a punch shoulder R of 1mm. The die hole shape of the die used is a 34 mm square with die hole angle R 2mm, die hole shoulder R: 1 mm, and the gap between the punch and the die hole is 0.3 mm on one side. Due to the above gap, a gradient corresponding to the molding height is generated. According to the height of the molding, the following 3 levels are evaluated. ◎: 5.5mm or more (excellent practically) 〇: 5.0mm or more (excellent practically) △: 4.5mm (practical area) ×: Break of aluminum foil or bulge between layers at 4.5mm

＜Heat resistance＞ Using Yamaoka Manufacturing Co., Ltd.’s "1 ton desktop servo press (SBN-1000)", the laminated body of the example or comparative example was cut into a size of 60×60 mm, and the matte surface of the aluminum foil became the outside. A straight mold with no molding height is used for stretch molding with a molding height of 5.0 mm. The flange part of the obtained 30 mm square pallet is connected to the side wall part, and the heat-sealing rod is closely adhered to the heat-sealing rod under the two conditions of 190°C for 3 seconds and 210°C for 3 seconds to confirm the boundary between the flange part and the side wall part. The appearance of 15 places near the part was evaluated whether swelling occurred between the stretched polyamide film and the aluminum foil. ◎: No swelling at 210°C for 3 seconds (excellent practically) 〇: No swelling at 190°C for 3 seconds (excellent for practical use) △: Swelling occurs at 190°C for 3 seconds, but less than 3 places (practical area) ×: Protrusion occurs in more than 4 places at 190℃ for 3 seconds

＜Damp and heat resistance＞ Using Yamaoka Manufacturing Co., Ltd.’s "1 ton desktop servo press (SBN-1000)", the laminated body of the example or comparative example was cut into a size of 60×60 mm, and the matte surface of the aluminum foil became the outside. A straight mold with no molding height is used for stretch molding with a molding height of 5.0 mm. Put the obtained 30 mm square tray into a constant temperature and humidity tank at 85°C and 85% RH and let it stand still. Take out the above-mentioned tray from the constant temperature and humidity tank, check the appearance of 15 places near the boundary between the flange part and the side wall part, and evaluate whether swelling occurs between the stretched polyamide film and the aluminum foil. ◎: No swelling after 168 hours of standing (excellent practically) 〇: No swelling when left for 72 hours (excellent for practical use) △: Uplift occurred when left for 72 hours, but less than 3 places (practical area) ×: Uplifts occurred in more than 4 places when left for 72 hours

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Polyester polyol (A1-1) 100 87.1 Polyester polyol (A1-2) 100 Polyester polyol (A1-3) 100 84.9 Polyester polyol (A1-4) 100 Polyester polyol (A1-5) Polyester polyol (A1－6) Polyester polyol (A1-7) Polyester polyol (A1-8) Resin (A2) 12.9 15.1 Polyester polyol (A3-1) Polyester polyol (A3－2) Polyester polyol (AH-1) Polyester polyol (AH-2) KBM-403 1.6 1.0 1.0 1.9 1.6 0.8 KW－75 30.3 20.2 19.2 19.5 27.7 19.2 Lupranate MI 3.4 NCO equivalent ratio [NCO]／[OH] 2.9 5.5 3.3 3.4 3.5 3.6 Adhesion strength (N/15 mm) 6.9 5.2 5.5 8.3 8.1 7.8 Formability 〇 △ 〇 ◎ ◎ 〇 Heat resistance 〇 〇 ◎ 〇 〇 ◎ Humidity and heat resistance 〇 〇 〇 △ 〇 ◎

[Table 4] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Polyester polyol (A1-1) Polyester polyol (A1-2) Polyester polyol (A1-3) Polyester polyol (A1-4) 51.4 Polyester polyol (A1-5) 91.5 33.9 Polyester polyol (A1－6) 85.1 Polyester polyol (A1-7) 85.1 Polyester polyol (A1-8) 84.9 Resin (A2) 8.5 14.9 14.9 15.1 9.4 Polyester polyol (A3-1) 56.7 Polyester polyol (A3－2) 48.6 Polyester polyol (AH-1) Polyester polyol (AH-2) KBM-403 1.6 0.8 0.8 0.8 1.9 1.8 KW－75 21.0 18.9 18.9 19.1 36.2 23.1 Lupranate MI 4.2 4.6 NCO equivalent ratio [NCO]／[OH] 2.4 3.0 4.8 3.2 8.9 3.4 Adhesion strength (N/15 mm) 4.6 8.6 7.6 7.8 7.1 4.6 Formability ◎ 〇 〇 〇 〇 〇 Heat resistance △ ◎ ◎ ◎ ◎ 〇 Humidity and heat resistance 〇 ◎ ◎ 〇 ◎ 〇

[table 5] Comparative example 1 Comparative example 2 Polyester polyol (A1-1) Polyester polyol (A1-2) Polyester polyol (A1-3) Polyester polyol (A1-4) Polyester polyol (A1-5) Polyester polyol (A1－6) Polyester polyol (A1-7) Polyester polyol (A1-8) Resin (A2) Polyester polyol (A3-1) Polyester polyol (A3－2) Polyester polyol (AH-1) 100 Polyester polyol (AH-2) 100 KBM-403 1.0 0.8 KW－75 20.3 18.9 Lupranate MI NCO equivalent ratio [NCO]／[OH] 2.6 2.6 Next strength (N/15mm) 6.3 7.2 Formability X 〇 Heat resistance 〇 〇 Humidity and heat resistance 〇 X

According to the results, it is clear that by using the adhesive of the present invention, a packaging material can be obtained that has excellent moldability even after the heat fusion of the sealant layers for sealing the storage, and then at high temperature In the long-term durability test under high humidity, there was no decrease in the adhesive strength between the layers, and the appearance defects such as bulging between the layers were suppressed.

1: Outer layer side substrate layer 2: Next layer 3: Metal layer 4: Sealant layer 5: Next layer

[FIG. 1] It is an example of the specific aspect of the laminated body which laminated|stacked the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, and the sealant layer 4 of this invention in order. [FIG. 2] It is an example of the specific aspect of the laminated body which laminated|stacked the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, the adhesive layer 5, and the sealant layer 4 of this invention in order.

1: Outer layer side substrate layer

2: Next layer

3: Metal layer

4: Sealant layer

Claims (15)

A two-component adhesive containing: Polyol composition (A) containing polyester polyol (A1), and Polyisocyanate composition (B) containing isocyanate compound (B1); The polyester polyol (A1) is a reaction product of a polyacid or its derivative (a1) and a polyhydric alcohol (a2). The polyhydric alcohol (a2) contains the number of carbon atoms in the methylene chain between the two hydroxyl groups. It is a polyhydric alcohol (a2-1) that is 5 or more and 19 or less and is an odd number. The two-component adhesive of claim 1, wherein the polyol composition (A) includes a resin (A2) having a glass transition temperature of 50° C. or more and 110° C. or less. The two-component adhesive of claim 1 or 2, wherein the resin (A2) is selected from polyester resins, polyurethane resins, polyurea resins, acrylic resins, polyamide resins, and polyimides At least one of the group consisting of resin, epoxy resin, and rosin-modified epoxy resin. The two-component adhesive according to any one of claims 1 to 3, wherein the resin (A2) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, a thiol group, and a glycidyl group At least one functional group. The two-component adhesive of claim 4, wherein the functional group is at least one selected from the group consisting of a secondary hydroxyl group and a tertiary hydroxyl group. The two-component adhesive of any one of claims 2 to 5, wherein the blending amount of the resin (A2) with respect to 100 parts by mass of the polyester polyol (A1) and the resin (A2) in total is 90 parts by mass or less. The two-component adhesive of claim 1 or 2, wherein the above-mentioned polyhydric alcohol (a2) comprises polyhydric alcohols (a2-2) having a branched alkylene structure and polyhydric alcohols having a cyclic structure (A2-3) At least one of the group consisting of. The two-component adhesive of any one of claims 1 to 7, wherein the blending amount of the polyhydric alcohol (a2-1) in the polyhydric alcohol (a2) is 10 mol% or more and 90 mol% Ear% or less. The two-component adhesive of claim 7 or 8, wherein the above-mentioned polyhydric alcohol (a2-2) having a branched alkylene structure in the above-mentioned polyhydric alcohol (a2) and the above-mentioned polyhydric alcohol having a cyclic structure The total blending amount of alcohol (a2-3) is 10 mol% or more and 90 mol% or less. The two-component adhesive of any one of claims 1 to 9, wherein the polybasic acid or its derivative (a1) comprises a polybasic acid or its derivative (a1-1) having an aromatic ring, and the polybasic acid The blending amount of the above-mentioned aromatic ring-containing polybasic acid or its derivative (a1-1) in its derivative (a1) is 30 mol% or more. The two-component adhesive of any one of claims 1 to 10, wherein the ratio of the isocyanate group of the polyisocyanate composition (B) to the hydroxyl group of the polyol composition (A) [NCO]/[ OH] is 1.5 or more and 15.0 or less. Such as the two-component adhesive of any one of claims 1 to 11, which is used as a packaging material for batteries. A packaging material for a battery comprising at least an outer layer side base material layer 1, an adhesive layer 2, a metal layer 3, and a sealant layer 4 laminated in this order, and the adhesive layer 2 is any one of claims 1 to 12 The hardened substance of the two-component adhesive. A battery container formed by molding the battery packaging material of claim 13. A battery using the battery container of claim 14.

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