WO2020246243A1

WO2020246243A1 - Adhesive, adhesive for packaging material for battery, laminate, packaging material for battery, container for battery, and battery

Info

Publication number: WO2020246243A1
Application number: PCT/JP2020/019957
Authority: WO
Inventors: 裕季小林; 勉菅野; 英美中村; 神山　達哉
Original assignee: Dic株式会社
Priority date: 2019-06-03
Filing date: 2020-05-20
Publication date: 2020-12-10
Also published as: CN113825817A; CN113825817B; JP6809658B1; JPWO2020246243A1

Abstract

Provided are: a two-component-type adhesive having excellent moldability, heat resistance, and resistance to moist heat; and a laminate, a molded body; and a packaging material which are obtained by using the two-component-type adhesive.　A two-component-type adhesive is characterized by comprising: a polyol composition (A) containing a crystalline polyester polyol (A1); and a polyisocyanate composition (B) containing an isocyanate compound (B), wherein the crystalline polyester polyol (A1) has a glass transition temperature of -20°C to 10°C, a melting point of 80°C to 160°C, and a number average molecular weight of 2,000 to 30,000.

Description

Adhesives, battery packaging adhesives, laminates, battery packaging, battery containers and batteries

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

Packaging materials used for packaging various stored items such as foods, daily necessities, and electronic elements are resistant to strength and cracking in order to protect the contents from impacts received during distribution and deterioration due to oxygen and moisture. , Gas barrier properties, etc. are required. When the contents are heat sterilized, retort resistance, heat resistance, etc. are required, and transparency may be required so that the contents can be confirmed. However, it is difficult to satisfy the required functions with one kind of material. For example, the non-stretched polyolefin film used when sealing by heat sealing is excellent in heat processability, but has insufficient oxygen barrier property. Nylon film, on the other hand, has excellent gas barrier properties, but is inferior in heat seal properties.

For this reason, different types of polymer materials and laminates of polymer materials and metal substrates are widely used as packaging materials. In addition, a laminate in which one or more storage portions are formed by molding the laminate may be used as a packaging material (Patent Document 1-3). A laminate in which one or more storage portions are formed is joined to a laminate in which storage portions having the same shape are formed or a laminate in which no storage portion is formed (not molded). Seal the compartment. Heat fusion (heat sealing) is used as the joining method.

Japanese Unexamined Patent Publication No. 2013-199283 Special Table 2008-535746 Japanese Unexamined Patent Publication No. 2015-082354

The present invention is a packaging material suitable for such applications, that is, it has excellent moldability, and even after heat fusion between the sealant layers performed for sealing the stored material, the adhesive strength between the layers does not decrease, and the layers do not deteriorate. It is an object of the present invention to provide a packaging material having no appearance defects such as floating. Another object of the present invention is to provide a two-component adhesive having excellent moldability and heat resistance, which is suitable for producing such a packaging material, and a laminate or a molded product using the same.

The present inventors include a polyol composition (A) containing a crystalline polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B), which comprises a crystalline polyester polyol (A1). By using a two-component adhesive having a glass transition temperature of -20 ° C or higher and 10 ° C or lower, a melting point of 80 ° C or higher and 160 ° C or lower, and a number average molecular weight of 2,000 or higher and 30,000 or lower. The above problem has been solved.

That is, the present invention contains a polyol composition (A) containing a crystalline polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B), and is a glass of the crystalline polyester polyol (A1). The present invention relates to a two-component adhesive having a transition temperature of −20 ° C. or higher and 10 ° C. or lower, a melting point of 80 ° C. or higher and 160 ° C. or lower, and a number average molecular weight of 2,000 or higher and 30,000.

By using the two-component adhesive of the present invention, it has excellent moldability, and even after heat fusion between the sealant layers performed to seal the stored material, the adhesive strength between the layers does not decrease, and the layers do not deteriorate. It is possible to obtain a packaging material that does not have an appearance defect such as floating.

This is an example of a specific embodiment of the laminated body in which the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, and the sealant layer 4 are sequentially laminated. This is an example of a specific embodiment of the laminated body in which 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 are sequentially laminated.

<Adhesive>
The adhesive of the present invention contains a polyol composition (A) and a polyisocyanate composition (B) containing an isocyanate compound (B), and the polyol composition (A) has a glass transition temperature of −20 ° C. or higher. It is a two-component adhesive containing a crystalline polyester polyol (A1) having a temperature of 10 ° C. or lower, a melting point of 80 ° C. or higher and 160 ° C. or lower, and a number average molecular weight of 2,000 or higher and 30,000 or lower.

(Polyform composition (A))
(Crystally polyester polyol (A1))
The polyol composition (A) used in the adhesive of the present invention contains a crystalline polyester polyol (A1). The crystalline polyester polyol (A1) is a polyester polyol obtained by using a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials and having crystallinity.

Examples of the polybasic acid or a derivative thereof used as a raw material for the crystalline polyester polyol (A1) include malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, succinic acid anhydride, and alkenyl succinic acid anhydride. An aliphatic polybasic acid such as acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, malonic acid, malonic acid anhydride, and itaconic acid;

An aliphatic polybasic acid such as dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelic acid, diethyl sebacate, dimethyl fumarate, diethyl fumarate, dimethyl maleate, diethyl maleate, etc. Alkyl esterified product;

1,1-Cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid , Tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, hymic anhydride, hetic anhydride, etc. Group polybasic acid;

Orthophthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, naphthalic acid, Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, biphenyldicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p'-dicarboxylic acid, benzophenonetetracarboxylic acid, benzophenonetetracarboxylic acid di Aromatic polybasic acids such as anhydride, 5-sodium sulfoisophthalic acid, tetrachlorohydride phthalic acid, tetrabromohydride phthalic acid;

Methyl esterified products of aromatic polybasic acids such as dimethyl terephthalic acid and dimethyl 2,6-naphthalenedicarboxylic acid; and the like; one type or a combination of two or more types can be used.

The polyhydric alcohol may be a diol or a trifunctional or higher functional polyol, and the diol may be, for example, ethylene glycol, diethylene glycol, 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-pentane Diol, 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesane, 2,2,4-trimethyl-1,3-pentanediol, etc. Aliper diol;

Ether glycol such as polyoxyethylene glycol and polyoxypropylene glycol;

Modifications obtained by ring-opening polymerization of the aliphatic diol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether diol;

A lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as lactanoid and ε-caprolactone;

Bisphenols such as bisphenol A and bisphenol F;

Examples thereof include an alkylene oxide adduct of bisphenol obtained by adding ethylene oxide, proprene oxide, etc. to bisphenol such as bisphenol A and bisphenol F.

The trifunctional or higher functional polyol is an aliphatic polyol such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, or pentaerythritol;

Modifications obtained by ring-opening polymerization of the aliphatic polyol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Polyether polyol;

Examples thereof include a lactone-based polyester polyol obtained by a polycondensation reaction between the aliphatic polyol and various lactones such as ε-caprolactone.

In the present invention, in order to develop crystallinity in the crystalline polyester polyol (A1) and to make the cured coating film of the adhesive described later having excellent moldability, adipic acid and succinic acid are used as polybasic acid or a derivative thereof. At least one selected from acid, fumaric acid, sebacic acid, and terephthalic acid is an essential component, and at least one selected from 1,4-butanediol or 1,6-hexanediol as a polyvalent alcohol is an essential component and is cyclic. It is preferable to use at least one selected from the group consisting of a polyvalent carboxylic acid having a structure, a polyvalent alcohol having a branched alkylene structure, and a polyvalent alcohol having a cyclic structure.

Examples of the polyvalent carboxylic acid having a cyclic structure include isophthalic acid, orthophthalic acid, 1,4-cyclohexanedicarboxylic acid and the like, and examples of the polyvalent alcohol having a branched alkylene structure include 1,2-propanediol and 2-methyl-1. , 3-Propanediol, Neopentyl glycol, 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-isoamyl-1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3 -Butandiol, 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-hexanenediol, 1,2-octanediol, 2-methyl-1,8-octanediol, trimethylolethane, Examples thereof include trimethylolpropane and pentaerythritol. Polyhydric alcohols having a cyclic structure include 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 4- (hydroxymethyl) cyclohexanol, 4-( 2-Hydroxyethyl) cyclohexanol, 1,4-cyclohexanedimethanol, 4,4'-bicyclohexanol, 1,3-adamantandiol, 1,3,5-adamantantriol, 3- (hydroxymethyl) -1-adaman Tanol, Tricyclo [5.2.1.0 ^2.6 ] -decanedimethanol, 1,2-benzenedimethanol, 1,4-benzenedimethanol, 4,4-dihydroxybiphenol, 4,4'-bisphenyl Dimethanol, 2,2'-methylenediphenol, 2,4'-methylenediphenol, 4,4'-methylenediphenol, 4,4'-ethylidene 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 and the like.

Adipic acid, succinic acid, fumaric acid, sebacic acid, terephthalic acid, 1,4-butanediol, and 1,6-hexanediol can impart crystallinity to the polyester polyol. Of these, it is preferable to use adipic acid and terephthalic acid as the polybasic acid or a derivative thereof, and 1,4-butanediol and 1,6-hexanediol as the polyhydric alcohol.
A polyvalent carboxylic acid having a cyclic structure, a polyhydric alcohol having a branched alkylene structure, and a polyhydric alcohol having a cyclic structure reduce the crystallinity of the crystalline polyester polyol (A1) to ensure adhesive strength and crystallinity. The glass transition temperature and melting point of the polyester polyol (A1) are adjusted to suitable ranges to improve crystallinity, heat resistance, and moisture heat resistance, and further impart storage stability in a solvent. 1,4-Cyclohexanedimethanol is preferably used.

Adipic acid is blended in the range of 15 mol% or more and 50 mol% or less of the polyvalent basic acid or its derivative component, and terephthalic acid is blended in the range of 40 mol% or more and 80 mol% or less, and 5 mol% or more and 40 mol%. It is preferable to blend a polyvalent carboxylic acid having a cyclic structure in the following range. Further, at least one selected from 1,4-butanediol or 1,6-hexanediol is blended in the range of 40 mol% or more and 80 mol% or less of the polyhydric alcohol component, and the range of 20 mol% or more and 60 mol% or less. It is preferable to blend at least one selected from the group consisting of a polyhydric alcohol having a branched alkylene structure and a polyhydric alcohol having a cyclic structure.

In the present invention, the crystalline polyester polyol (A1) may be a polyester polyurethane polyol containing a polybasic acid or a derivative thereof, a polyhydric alcohol, and a polyisocyanate as essential raw materials. Examples of the polyisocyanate used in that case include a diisocyanate compound and a trifunctional or higher functional polyisocyanate compound. Each of these polyisocyanates may be used alone, or two or more of them may be used in combination.

Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate. Aliphatic diisocyanates such as isocyanate and lysine diisocyanate;

Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexanediisocyanate, isopropyridene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate, etc. Alicyclic diisocyanate;

1,5-naphthylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediocyanate , 1,4-phenylenediocyanate, tolylene diisocyanate and other aromatic diisocyanates.

Examples of the trifunctional or higher functional polyisocyanate compound include an adduct-type polyisocyanate compound having a urethane bond site in the molecule and a nurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule.

The adduct-type polyisocyanate compound having a urethane bond site in the molecule is obtained, for example, by reacting a diisocyanate compound with a polyhydric alcohol. Examples of the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more. In addition, examples of the polyol compound used in the reaction include various polyol compounds exemplified as the polyhydric alcohol, polyester polyol obtained by reacting the polyhydric alcohol with a polybasic acid, and the like, and these are used alone. You may use it, or you may use two or more kinds together.

A nurate-type polyisocyanate compound having an isocyanurate ring structure in the molecule is obtained, for example, by reacting a diisocyanate compound with a monoalcohol and / or a diol. Examples of the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more. The monoalcohols used in the reaction include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, and n-. Heptadecanol, n-octadecanol, n-nonadecanol, eikosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol , 2-octyldodecanol, 2-decyltetradecanol and the like, and examples of the diol include the aliphatic diol exemplified by the polyhydric alcohol. These monoalcohols and diols may be used alone or in combination of two or more.

The crystalline polyester polyol (A1) used in the present invention is a reaction product of a polybasic acid or a derivative thereof and a polyvalent alcohol, and is a polybasic acid or a derivative thereof having an aromatic ring in the polybasic acid or a derivative thereof. The ratio of is preferably 30 mol% or more. This makes it possible to obtain an adhesive having excellent storage stability. Further, since moldability and heat resistance are improved, the proportion of the polybasic acid having an aromatic ring or its derivative in the polybasic acid or its derivative is more preferably 50 mol% or more, more preferably 60 mol% or more. Is more preferable. The upper limit of the blending amount of the polybasic acid or a derivative thereof is not particularly limited, but as an example, it is preferably 85% or less, and more preferably 75% or less.

Alternatively, the crystalline polyester polyol (A1) used in the present invention may be a reaction product of a polybasic acid or a derivative thereof, a polyhydric alcohol, and a polyisocyanate, and an aromatic ring in the polybasic acid or a derivative thereof. The ratio of the polybasic acid having the above or a derivative thereof is preferably 30 mol% or more. This makes it possible to obtain an adhesive having excellent storage stability. Further, since moldability and heat resistance are improved, the proportion of the polybasic acid having an aromatic ring or its derivative in the polybasic acid or its derivative is more preferably 50 mol% or more, more preferably 60 mol% or more. Is more preferable. The upper limit of the blending amount of the polybasic acid or a derivative thereof is not particularly limited, but as an example, it is preferably 85% or less, and more preferably 75% or less.

The hydroxyl value of the crystalline polyester polyol (A1) used in the present invention is preferably in the range of 1 to 40 mgKOH / g, more preferably 3 mgKOH / g or more, and 30 mgKOH / g because it is superior in adhesive strength. It is as follows.

The number average molecular weight (Mn) of the crystalline polyester polyol (A1) used in the present invention is in the range of 2000 to 30,000, more preferably 3,000 to 15,000, still more preferably 4000 to 12000. When the number average molecular weight is in this range, the crystalline polyester polyol (A1) can be appropriately stretched in the cured coating film, and an adhesive having excellent moldability can be obtained.

In the present invention, the number average molecular weight (Mn) is a value measured by gel permeation chromatography (GPC) under the following conditions.

Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran Tetrahydrofuran flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

The solid acid value of the crystalline polyester polyol (A1) used in the present invention is not particularly limited, but is preferably 10.0 mgKOH / g or less. It is preferable that the amount is 5.0 mgKOH / g or less because of its excellent moisture and heat resistance. The lower limit of the solid acid value is not particularly limited, but is 0.5 mgKOH / g or more as an example. It may be 0 mgKOH / g.

The glass transition temperature of the crystalline polyester polyol (A1) used in the present invention is −20 ° C. or higher and 10 ° C. or lower, more preferably −15 ° C. or higher and 5 ° C. or lower.

The melting point of the crystalline polyester polyol (A1) used in the present invention is 80 ° C. or higher and 160 ° C. or lower, more preferably 90 ° C. or higher and 145 ° C. or lower, and further preferably 100 ° C. or higher and 130 ° C. or lower. In the present invention, the crystalline polyester polyol has a melting point and has a heat of fusion of 0.1 J / g or more.

The glass transition temperature, melting point, and heat of fusion in the present invention are measured as follows.
Differential scanning calorimeter (SII Nano Technology Co. DSC-7000, hereinafter referred to as DSC) using a temperature of the sample 5mg to _{T 1} ° C. in 20 mL / min 30 ° C. in a nitrogen stream from 10 ° C. / min and 10 minute hold after was allowed, and thereafter cooled at 10 ° C. / min up to _{T 2} ° C. to remove the thermal history. After holding at T ₂ ° C for 5 minutes, raise the temperature again to T ₃ ° C at 10 ° C / min to measure the DSC curve, and set the baseline on the low temperature side in the measurement results observed in the second temperature raising step. The intersection of the straight line extending to the high temperature side and the tangent line drawn at the point where the slope of the curve of the stepped portion of the glass transition is maximized is defined as the glass transition point, and the temperature at this time is defined as the glass transition temperature. Further, the maximum peak temperature of the endothermic curve observed in the second temperature raising step is set as the melting point, and the amount of heat of fusion is calculated from the area surrounded by this maximum peak and the baseline.

T ₂ <T ₃ ≤ T ₁ , T ₂ is sufficiently lower than the glass transition temperature of the crystalline polyester polyol (A1), and T ₁ and T ₃ are at least 30 ° C. higher than the melting point of the crystalline polyester polyol. Is. As an example, T ₁ is 200 ° C., T ₂ is −80 ° C., and T ₃ is 200 ° C., which are appropriately adjusted according to the sample to be measured.

The amount of heat of fusion of the crystalline polyester polyol (A1) used in the present invention is preferably 0.1 J / g or more and 50 J / g or less, preferably 0.15 J / g, because it is excellent in storage stability and coating suitability. It is more preferably 30 J / g or more, and further preferably 0.2 J / g or more and 20 J / g or less.

The reason why the adhesiveness, moldability, heat resistance, and moisture heat resistance are improved by using the crystalline polyester polyol (A1) is not clear, but it is presumed as follows. Since the polyester polyol (A1) has crystallinity, the molecular motion is partially suppressed below the melting point even after the glass transition temperature is exceeded. For this reason, a pseudo-mesh structure is formed by methylene chains or the like near room temperature at which the molding process is performed, and the coexistence of the pseudo-mesh portion and the rubber region portion makes it possible to achieve both high elasticity and high toughness, resulting in excellent moldability. Shown. In addition, the presence of the pseudo-mesh structure suppresses the flow of the adhesive layer during heating, so that heat resistance and moisture heat resistance can be improved.

(Polyester polyol (A2))
The polyol composition (A) used in the adhesive of the present invention may contain a polyester polyol (A2) in addition to the crystalline polyester polyol (A1). The polyester polyol (A2) is obtained by using a polybasic acid or a derivative thereof and a polyhydric alcohol as essential raw materials, and may be crystalline or amorphous. As the polybasic acid or its derivative and the polyhydric alcohol used for the synthesis of the polyester polyol (A2), the same ones as those of the polyester polyol (A1) can be used.

The polyester polyol (A2) preferably has a glass transition temperature of −70 ° C. or higher and lower than −20 ° C., and more preferably −70 ° C. or higher and −30 ° C. or lower. By using the crystalline polyester polyol (A1) and such a polyester polyol (A2) in combination, the coating suitability is improved, and an adhesive having more excellent adhesive strength and moldability can be obtained.

The hydroxyl value of the polyester polyol (A2) is preferably in the range of 1 to 40 mgKOH / g, more preferably 3 mgKOH / g or more, and 30 mgKOH / g or less because it is superior in adhesive strength.

The solid acid value of the polyester polyol (A2) is not particularly limited, but is preferably 10.0 mgKOH / g or less. It is preferable that the amount is 5.0 mgKOH / g or less because of its excellent moisture and heat resistance. The lower limit of the solid acid value is not particularly limited, but is 0.5 mgKOH / g or more as an example. It may be 0 mgKOH / g.

The number average molecular weight (Mn) of the polyester polyol (A2) is preferably in the range of 3,000 to 15,000, and more preferably 4000 to 12000. When the number average molecular weight is in this range, the solvent solubility is high and the adhesiveness can be improved by the entanglement of the molecular chains.

The blending amount of the polyester polyol (A2) is the polyester polyol (A2) with respect to the total mass of the crystalline polyester polyol (A1) and the polyester polyol (A2) from the viewpoint of maintaining heat resistance while improving the adhesive strength and moldability. ) Is preferably added in an amount of 10% by mass or less, and more preferably 8% by mass or less.

(Manufacturing method of polyester polyol)
In the synthesis of crystalline polyester polyol (A1) and polyester polyol (A2), the reaction of a polybasic acid or its derivative with a polyhydric alcohol, or the reaction of a polybasic acid or its derivative with a polyhydric alcohol and a polyisocyanate is It may be carried out by a known method.

For example, the reaction of a polybasic acid or a derivative thereof with the polyhydric alcohol can be carried out by a polycondensation reaction. Further, the reaction of the polybasic acid or its derivative with the polyhydric alcohol and the polyisocyanate requires a polyester polyol obtained by reacting the polybasic acid or its derivative with the polyhydric alcohol by the method and the polyisocyanate. The polyester polyol of the present invention can be obtained by reacting in the presence of a known and commonly used urethanization catalyst.

In the esterification reaction of a polybasic acid or a derivative thereof and a polyhydric alcohol, the polybasic acid or a derivative thereof, the polyhydric alcohol, and a polymerization catalyst are charged into a reaction vessel equipped with a stirrer and a rectification facility, and the mixture is stirred. The temperature is raised to about 130 ° C. at normal pressure. Then, the generated water is distilled off while raising the temperature at a reaction temperature in the range of 130 to 260 ° C. at a rate of 5 to 10 ° C. per hour. After the esterification reaction for 4 to 12 hours, a polyester polyol is produced by distilling off excess polyhydric alcohol and accelerating the reaction while gradually increasing the degree of depressurization from normal pressure to the range of 1 to 300 trr. Can be done.

The polymerization catalyst used in the esterification reaction is composed of at least one metal selected from the group consisting of

groups

2, 4, 12, 13, 14, and 15 of the periodic table, or a compound of the metal. A polymerization catalyst is preferred. Examples of the polymerization catalyst composed of such a metal or a metal compound thereof include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge, compounds of these metals, and more specifically titanium tetraisopropoxide and titanium. Tetrabutoxide, titanium oxyacetylacetonate, tin octanoate, 2-ethylhexanetin, acetylacetonate zinc, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium And so on.

Commercially available polymerization catalysts that can be used in the esterification reaction include Organtics TA series, TC series, ZA series, ZC series, AL series manufactured by Matsumoto Fine Chemicals, organic tin catalysts manufactured by Nitto Kasei, and inorganic metals. Preferred examples include catalysts and inorganic tin compounds.

The amount of these polymerization catalysts used is not particularly limited as long as the esterification reaction can be controlled and a polyester polyol of good quality can be obtained, but as an example, the sum of the polybasic acid or its derivative and the polyhydric alcohol. It is 10 to 1000 ppm, preferably 20 to 800 ppm with respect to the amount. In order to suppress the coloring of the polyester polyol, it is more preferably 30 to 500 ppm.

Further, the polyester polyurethane polyol used in the present invention is obtained by chain-extending the polyester polyol obtained by the above method with polyisocyanate. As a specific production method, a polyester polyol, a polyisocyanate, a chain extension catalyst, and a good solvent of the polyester polyol and the polyisocyanate used as needed are charged in a reaction vessel, and the reaction temperature is 60 to 90 ° C. Stir with. The reaction is carried out until the isocyanate group derived from the polyisocyanate used is substantially eliminated to obtain the polyester polyurethane polyol used in the present invention.

As the chain extension catalyst, a known and public catalyst used as a normal urethanization catalyst can be used. Specific examples thereof include organic tin compounds, organic carboxylic acid tin salts, lead carboxylates, bismuth carboxylates, titanium compounds, zirconium compounds and the like, which can be used alone or in combination. The amount of the chain extension catalyst used may be an amount that sufficiently promotes the reaction between the polyester polyol and the polyisocyanate, and specifically, 5.0 mass by mass with respect to the total amount of the polyester polyol and the polyisocyanate. % Or less is preferable. In order to suppress hydrolysis and coloring of the resin by the catalyst, 1.0% by mass or less is more preferable. Further, these chain extension catalysts may be used in consideration of the action of the polyol composition (A) and the isocyanate composition (B) described later as a curing catalyst.

As a method for confirming the remaining amount of the isocyanate group, confirmation of the presence or absence of an absorption peak observed near 2260 cm ^-1, which is an absorption spectrum derived from the isocyanate group, by infrared absorption spectrum measurement, and quantification of the isocyanate group by the titration method. Can be mentioned.

Examples of a good solvent used for producing a polyester polyurethane polyol include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, xylene and the like. It may be used alone or in combination of two or more.

(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, the above-mentioned polyester polyol (A1), various diisocyanate compounds described as raw materials for the polyester polyol (A2), oligomers of diisocyanate compounds, and adduct-modified diisocyanates obtained by reacting various diisocyanate compounds with diol compounds. Compounds, these biuret modified products, allophanate modified products, and various trifunctional or higher functional polyisocyanate compounds can be used. Each of these isocyanate compounds (B) may be used alone, or two or more of them may be used in combination.

Of these, toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and adducts, biurets, and isocyanurates of these diisocyanates are preferably mentioned.

Further, the isocyanate compound (B) may be a polyester polyisocyanate obtained by reacting a crystalline polyester polyol (A1) with an excess amount of the isocyanate compound. As the isocyanate compound used for the reaction with the crystalline polyester polyol (A1), the above-mentioned ones can be used without particular limitation. Preferable examples thereof include toluene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, and adducts, biurets, and isocyanurates of these diisocyanates.

(Adhesive and other ingredients)
The adhesive of the present invention can be used in combination with other components as long as the effects of the present invention are not impaired. For example, the polyol composition (A) preferably contains a polycarbonate polyol compound in addition to the crystalline polyester polyol (A1). At this time, the total amount of the crystalline polyester polyol (A1) and the compounding ratio of the polycarbonate polyol compound are high in adhesiveness to various base materials and excellent in moisture and heat resistance, so that the total mass of both is increased. The total mass of the crystalline polyester polyol (A1) is preferably in the range of 30 to 99.5% by mass, preferably in the range of 60 to 99% by mass.

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

Further, the polyol composition (A) preferably contains a polyoxyalkylene-modified polyol compound in addition to the crystalline polyester polyol (A1). At this time, the total amount of the crystalline polyester polyol (A1) and the blending ratio of the polyoxyalkylene-modified polyol compound are high in adhesiveness to various substrates and excellent in moisture and heat resistance. The total mass of the crystalline polyester polyol (A1) is preferably in the range of 30 to 99.5% by mass, and preferably in the range of 60 to 99% by mass with respect to the mass.

The number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound is preferably in the range of 300 to 2,000 because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance. 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. Further, the polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.

The polyol composition (A) used in the present invention may contain other resin components in addition to the crystalline polyester polyol (A1). When other resin components are used, it is preferably used in an amount of 50% by mass or less, preferably 30% by mass or less, based on the total mass of the main agent. Specific examples of other resin components include epoxy resins. The epoxy resin is, for example, a bisphenol type epoxy resin such as a bisphenol A type epoxy resin or a bisphenol F type epoxy resin; a biphenyl type epoxy resin such as a biphenyl type epoxy resin or a tetramethyl biphenyl type epoxy resin; a dicyclopentadiene-phenol addition reaction. Examples include type epoxy resins. Each of these may be used alone, or two or more types may be used in combination. Among these, it is preferable to use a bisphenol type epoxy resin because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.

The number average molecular weight (Mn) of the epoxy resin is preferably in the range of 300 to 2,000 because it is an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance. The epoxy equivalent is preferably in the range of 150 to 1000 g / equivalent.

When the epoxy resin is used, the total amount of the crystalline polyester polyol (A1) and the blending ratio of the epoxy resin are high in adhesiveness to various substrates and excellent in moisture and heat resistance. The total mass of the polyester polyol (A1) is preferably in the range of 30 to 99.5 mass%, and preferably in the range of 60 to 99 mass% with respect to the mass.

The polyol composition (A) used in the present invention may contain a tackifier. Examples of the tackifier include a rosin-based or rosin ester-based tackifier, a terpene-based or terpenephenol-based tackifier, a saturated hydrocarbon resin, a kumaron-based tackifier, a kumaron-inden-based tackifier, and a styrene resin-based tackifier. Examples thereof include a tackifier, a xylene resin-based tackifier, a phenol-resin-based tackifier, a petroleum resin-based tackifier, and a ketone resin-based tackifier. Ketone resin-based tackifiers, rosin-based or rosin ester-based tackifiers are preferable, and ketone resin-based tackifiers are more preferable. Each of these may be used alone, or two or more types may be used in combination. When the tackifier is used, the total mass of the polyester polyol (A1) is preferably 80 to 99.99 mass%, preferably 85 to 99.9 mass%, based on the total mass of the polyester polyol (A1) and the tackifier. More preferably.

Examples of rosin-based or rosin ester-based rosins include polymerized rosins, disproportionated rosins, hydrogenated rosins, maleated rosins, fumarized rosins, and their glycerin esters, pentaerythritol esters, methyl esters, ethyl esters, butyl esters, and ethylene glycols. Examples thereof include esters, diethylene glycol esters and triethylene glycol esters.

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

Petroleum resin systems include petroleum resins obtained by polymerizing petroleum distillates having 5 carbon atoms obtained from penten, pentadiene, isoprene, etc., inden, methylinden, vinyltoluene, styrene, α-methylstyrene, β-methylstyrene, etc. A petroleum resin obtained by polymerizing a petroleum distillate having 9 carbon atoms, a C5-C9 copolymerized petroleum resin obtained from the various monomers, a petroleum resin obtained by hydrogenating these, and a petroleum resin obtained from cyclopentadiene and dicyclopentadiene; And hydrides of those petroleum resins; modified petroleum resins obtained by modifying those petroleum resins with maleic anhydride, maleic acid, fumaric acid, (meth) acrylic acid, phenol and the like can be exemplified.

As the phenolic resin system, a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin and the like, and these phenols and formaldehyde are subjected to an addition reaction with an alkali catalyst, or a condensation reaction is carried out with an acid catalyst. Examples thereof include Novolac obtained in the above. Further, a rosin phenol resin obtained by adding phenol to rosin with an acid catalyst and thermally polymerizing it can also be exemplified.

Examples of the ketone resin include known and commonly used ones, but formaldehyde resin, cyclohexanone / formaldehyde resin, ketone aldehyde condensed resin and the like can be preferably used.

A tackifier having various softening points can be obtained, but the softening point is 70 in terms of compatibility, color tone, thermal stability, etc. when mixed with other resins constituting the polyol composition (A). A ketone resin-based tackifier at ~ 160 ° C., preferably 80 to 100 ° C., or a rosin-based resin having a softening point of 80 to 160 ° C., preferably 90 to 110 ° C. and a hydrogenated derivative thereof are preferable, and the softening point is 70 to 70 to A ketone resin-based tackifier at 160 ° C., preferably 80 to 100 ° C. is more preferable. Further, a ketone resin-based tackifier having an acid value of 2 to 20 mgKOH / g and a hydroxyl value of 10 mgKOH / g or less and a hydrogenated rosin-based tackifier are preferable, and the acid value is 2 to 20 mgKOH / g and the hydroxyl value is A ketone tackifier of 10 mgKOH / g or less is more preferable.

In the adhesive of the present invention, as yet another good embodiment, known phosphoric acids or derivatives thereof can be used in combination. As a result, the initial adhesiveness of the adhesive is further improved, and troubles such as tunneling can be eliminated.

Phosphoric acids or derivatives thereof used here include phosphoric acids such as hypophosphoric acid, phosphoric acid, orthophosphoric acid, and hypophosphoric acid, such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Such as condensed phosphoric acids such as monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, monoethyl phosphite, phosphite. Monopropyl, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, dimethyl diphenyl phosphite, diethyl phosphite, dipropyl phosphite, sub Monos such as dibutyl phosphate, di-2-ethylhexyl phosphite, diphenyl phosphite, diesterates, monos from condensed phosphoric acid and alcohols, diesterates, such as the above phosphoric acids, such as ethylene oxide and propylene oxide. Examples thereof include those to which an epoxy compound such as the above is added, for example, epoxy phosphoric acid esters obtained by adding the above-mentioned phosphoric acids to an aliphatic or aromatic diglycidyl ether.

The above-mentioned phosphoric acids or derivatives thereof may be used alone or in combination of two or more. As a method of containing, it is sufficient to simply mix.

In addition, an adhesion promoter can also be used in the adhesive of the present invention. Examples of the adhesion accelerator include a silane coupling agent, a titanate-based coupling agent, an aluminum-based coupling agent, an epoxy resin, and the like.

Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) -γ. Aminosilanes such as -aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane; β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-gly Epoxysilanes such as sidoxylpropyltriethoxysilane; vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane; hexamethyldisilazane, γ-mercapto Propyltrimethoxysilane and the like can be mentioned.

Examples of the titanate-based coupling agent include tetraisopropoxytitanium, tetra-n-butoxytitanium, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctylene glycol titanate, titanium lactate, and tetrastearoxy. Titanium and the like can be mentioned.

Further, as the aluminum-based coupling agent, for example, acetalkoxyaluminum diisopropylate and the like can be mentioned.

It is preferable to use a silane coupling agent as the adhesion accelerator. The content (solid content) of the adhesion accelerator is preferably 0.1 part by mass or more, and preferably 0.3 part by mass or more, based on 100 parts by mass of the solid content of the polyol composition (A). It is more preferably 0.5 parts by mass or more, further preferably 0.7 parts by mass or more. The content (solid content) of the adhesion accelerator is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and 5 parts by mass with respect to 100 parts by mass of the solid content of the polyol composition (A). It is more preferably less than a part.

In the adhesive of the present invention, the compounding ratio of the polyol composition (A) and the polyisocyanate composition (B) is the total number of moles [OH] of hydroxyl groups contained in the polyol composition (A) and the polyisocyanate composition. The ratio [NCO] / [OH] to the number of moles [NCO] of the isocyanate group contained in (B) is preferably in the range of 1.2 to 30.0. As a result, it becomes a two-component adhesive having excellent moldability, heat resistance, and moisture heat resistance.

The adhesive of the present invention may be in either a solvent type or a solventless type. The "solvent type" adhesive referred to in the present invention means that the adhesive is applied to a base material and then heated in an oven or the like to volatilize the organic solvent in the coating film and then bonded to another base material. A method, a form used in the so-called dry laminating method. Either one or both of the polyol composition (A) and the polyisocyanate composition (B) can dissolve the polyol composition (A) or the polyisocyanate composition (B) used in the present invention. Contains highly soluble organic solvent. 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 be further used as a diluent in coating. Examples of highly soluble organic solvents include esters such as ethyl acetate, butyl acetate and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran and dioxane, and aromatics such as toluene and xylene. Examples thereof include group hydrocarbons, halogenated hydrocarbons such as methylene chloride and ethylene chloride, dimethyl sulfoxide, dimethyl sulfoamide and the like.

In the present specification, the “solvent-free” adhesive is substantially the highly soluble organic solvent as described above in the polyol composition (A) and the polyisocyanate composition (B), particularly ethyl acetate or methyl ethyl ketone. A form of adhesive used in the so-called non-solvent laminating method, which is a method in which an adhesive is applied to a base material and then bonded to another base material without a step of heating in an oven or the like to volatilize the solvent. Point to. The constituent components of the polyol composition (A) or the polyisocyanate composition (B) and the organic solvent used as the reaction medium in the production of the raw material thereof could not be completely removed, and the polyol composition (A) or the polyisocyanate composition (A) or the polyisocyanate composition ( If a small amount of organic solvent remains in B), it is understood that the organic solvent is substantially not contained. Further, when the polyol composition (A) contains a low molecular weight alcohol, the low molecular weight alcohol reacts with the polyisocyanate composition (B) and becomes a part of the coating film, so that it is not necessary to volatilize after coating. Therefore, such a form is also treated as a solvent-free adhesive.

When the adhesive of the present invention is of the solvent type, the viscosity can be reduced by diluting the solvent, so that the polyol composition (A) or the polyisocyanate composition (B) to be used can be used even if it has a slightly high viscosity. .. On the other hand, in the case of the solvent-free type, it is emphasized that the viscosity is low due to the characteristic that the viscosity is lowered by heating, and as a means for lowering the viscosity, the polyisocyanate composition (B) reduces the aromatic concentration that contributes to the viscosity. Things are often used.

Even if the adhesive of the present invention contains various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. good.

The use of the adhesive of the present invention is not particularly limited, but it can be suitably used as a packaging material for batteries as an example because it is excellent in adhesive strength, processability, moisture heat resistance, and heat resistance.

<Laminated body>
The laminate of the present invention has an adhesive layer for bonding the first base material and the second base material, and the adhesive layer is a cured product of the adhesive of the present invention. The laminate of the present invention is obtained by laminating a first base material and a second base material by a dry laminating method or a non-solvent laminating method using the adhesive of the present invention. As the base material, paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, carbonate resin, polyamide resin, Examples thereof include polyimide resins, polyphenylene ether resins, synthetic resin films obtained from polyphenylene sulfide resins and polyester resins, copper foils, metal foils such as aluminum foils, and the like.

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

<Battery packaging material>
As shown in FIG. 1, the packaging material for a battery is composed of at least a laminate in which an outer layer side base material layer 1, an adhesive layer 2, a metal layer 3, and a sealant layer 4 are sequentially laminated. In the battery packaging material of the present invention, the outer layer side base material layer 1 is the outermost layer, and the sealant layer 4 is the innermost layer. That is, when the battery is assembled, the sealant layers 4 located on the peripheral edge of the battery element are heat-sealed to seal the battery element, thereby sealing the battery element. Further, in the packaging material for a battery of the present invention, as shown in FIG. 2, an adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4 as needed for the purpose of enhancing their adhesiveness. You may. The adhesive of the present invention can be suitably used for the adhesive layer 2, but it can also be used as the adhesive layer 5 because of its excellent solvent resistance.

(Outer layer side base material layer 1)
In the battery packaging material of the present invention, the outer layer side base material layer 1 is a layer forming the outermost layer. The material forming the outer layer side base material layer 1 is not particularly limited as long as it has insulating properties, and polyester resin, polyamide resin, epoxy resin, acrylic resin, fluororesin, polyurethane resin, silicon resin, phenol resin, etc. And resin films such as mixtures and copolymers thereof. Among these, polyester resin and polyamide resin are preferable, and biaxially stretched polyester resin and biaxially stretched polyamide resin are more preferable. Specific examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, copolymerized polyester, and polycarbonate. Specific examples of the polyamide resin include nylon 6, nylon 6, 6, a copolymer of nylon 6 and nylon 6, 6, nylon 6, 10, and polymethoxylylen adipamide (MXD6). Be done.

The outer base material layer 1 may be formed of one layer of resin film, but in order to improve pinhole resistance and insulating property, it is made of two or more layers of resin film, for example, polyethylene terephthalate film and polyamide film. It may be formed of a plurality of layers. When the outer layer side base material layer 1 is formed of a multilayer resin film, the resin films may be laminated via an adhesive component such as an adhesive or an adhesive resin, and the type and amount of the adhesive component used may be used. The same applies to the case of the adhesive layer 2 or the adhesive layer 5 described later. The method of laminating two or more layers of resin films is not particularly limited, and a known method can be adopted. Examples thereof include a dry lamination method and a sand lamination method, and a dry lamination method is preferable. When laminating by the 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 physical properties, but is, for example, about 10 to 50 μm, preferably about 15 to 35 μm. When a polyester film is used, the thickness is preferably 9 μm to 50 μm, and when a polyamide film is used, the thickness is preferably 10 μm to 50 μm. Sufficient strength can be secured as a packaging material, stress during overhang molding and draw molding can be reduced, and moldability can be improved.

(Metal layer 3)
In the battery packaging material, the metal layer 3 is a layer that functions as a barrier layer for improving the strength of the battery packaging material and preventing water vapor, oxygen, light, etc. from entering the inside of the battery. Specific examples of the metal constituting the metal layer 3 include aluminum, stainless steel, titanium, and the like, and aluminum is preferable. The metal layer 3 can be formed by metal foil, metal vapor deposition, or the like, and is preferably formed of metal foil, and more preferably of aluminum foil. Further, it is preferable that at least one surface, preferably both sides, of the metal layer 3 is subjected to chemical conversion treatment in order to stabilize adhesion, prevent dissolution and corrosion, and the like. Here, the chemical conversion treatment refers to a treatment for forming an acid-resistant film on the surface of a metal layer.

The thickness of the metal layer 3 is not particularly limited as long as the packaging material for the battery satisfies the above physical properties, but can be, for example, about 10 to 50 μm, preferably about 25 to 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 in which the sealant layers are heat-sealed to each other when the battery is assembled to seal the battery element.

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

Specific examples of the polyolefin include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, and other polyethylene; homopolypropylene, polypropylene block copolymer (for example, propylene and ethylene block copolymer), and polypropylene. Polypropylene such as random copolymers of propylene and ethylene (eg, random copolymers of propylene and ethylene); ethylene-butene-propylene tarpolymers; and the like. Among these polyolefins, polyethylene and polypropylene are preferable.

The cyclic polyolefin is a copolymer of an olefin and a cyclic monomer, and examples of the olefin that is a constituent monomer of the cyclic polyolefin include ethylene, propylene, 4-methyl-1-pentene, styrene, butadiene, isoprene, and the like. Can be mentioned. Examples of the cyclic monomer which is a constituent monomer of the cyclic polyolefin include cyclic alkenes such as norbornene; specific examples thereof include cyclic diene such as cyclopentadiene, dicyclopentadiene, cyclohexadiene, and norbornadiene. Among these polyolefins, cyclic alkene is preferable, and norbornene is more preferable.

The carboxylic acid-modified polyolefin is a polymer modified by block-polymerizing or graft-polymerizing the polyolefin with a carboxylic acid. Examples of the carboxylic acid used for denaturation include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like.

The carboxylic acid-modified cyclic polyolefin means that a part of the monomer constituting the cyclic polyolefin is copolymerized in place of α, β-unsaturated carboxylic acid or its anhydride, or α, β with respect to the cyclic polyolefin. -A polymer obtained by block polymerization or graft polymerization of unsaturated carboxylic acid or its anhydride. The same applies to the cyclic polyolefin modified with carboxylic acid. The carboxylic acid used for the modification is the same as that used for the modification of the acid-modified cycloolefin copolymer.

The sealant layer 4 may be formed by one kind of resin component alone, or may be formed by a blend polymer in which two or more kinds of resin components are combined. Further, the sealant layer 4 may be formed of only one layer, but 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 packaging material for the battery satisfies the above physical properties, but is, for example, about 10 to 100 μm, preferably about 20 to 90 μm.

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

The adhesive layer 5 is formed of an adhesive capable of adhering the metal layer 3 and the sealant layer 4. Examples of the adhesive layer used for the adhesive layer 5 include an adhesive in which a polyolefin resin and a polyfunctional isocyanate are combined, an adhesive in which a polyol and a polyfunctional isocyanate are combined, a modified polyolefin resin, a heterocyclic compound and a curing agent. The adhesive contained can be used. Alternatively, an adhesive such as acid-modified polypropylene is melt-extruded onto a metal layer with a T-die extruder to form an adhesive layer 5, a sealant layer 4 is superposed on the adhesive layer 5, and the metal layer 3 and the sealant layer 4 are combined. Can also be pasted together.
If both the adhesive layer 2 and the adhesive layer 5 require aging, they can be aged together. By setting the aging temperature to room temperature to 90 ° C., curing is completed in 2 days to 2 weeks, and moldability is exhibited.

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

(Coating layer 6)
In the packaging material for batteries of the present invention, for the purpose of improving designability, electrolytic solution resistance, scratch resistance, moldability, etc., if necessary, above the outer layer side base material layer 1 (outer layer side base material layer). The coating layer 6 may be provided on the side opposite to the metal layer 3 of 1. The coating layer 6 is a layer located at 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, or the like, and is preferably formed of a two-component curable resin. Examples of the two-component curable resin forming the coating layer 6 include a two-component curable urethane resin, a two-component curable polyester resin, and a two-component curable epoxy resin. Moreover, you may mix the matting agent in the coating layer 6.

Examples of the matting agent include fine particles having a particle size of about 0.5 nm to 5 μm. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. The shape of the matting agent is also not particularly limited, and examples thereof include a spherical shape, a fibrous shape, a plate shape, an amorphous shape, and a balloon shape. Specific examples of the matting agent include talc, silica, graphite, kaolin, montmoriloid, montmorillonite, synthetic mica, hydrotalcite, silica gel, zeolite, aluminum hydroxide, magnesium hydroxide, zinc oxide, magnesium oxide, and aluminum oxide. , Neodium oxide, Antimon oxide, Titanium oxide, Serium oxide, Calcium sulfate, Barium sulfate, Calcium carbonate, Calcium silicate, Lithium carbonate, Calcium benzoate, Calcium silicate, Magnesium stearate, Carbon black, Carbon nanotubes, High melting point Examples thereof include nylon, crosslinked acrylic, crosslinked styrene, crosslinked polyethylene, benzoguanamine, gold, aluminum, copper and nickel. These matting agents may be used alone or in combination of two or more. Among these matting agents, silica, barium sulfate, and titanium oxide are preferable from the viewpoint of dispersion stability and cost. Further, the matting agent may be subjected to various surface treatments such as an insulating treatment and a highly dispersible treatment on the surface.

The method for forming the coating layer 6 is not particularly limited, and examples thereof include a method of applying a two-component curable resin for forming the coating layer 6 on one surface of the outer layer side base material layer 1. When the matting agent is blended, the matting agent may be added to the two-component curable resin, mixed, and then applied.

(Manufacturing method of packaging materials for batteries)
The method for producing the packaging material for a battery of the present invention is not particularly limited as long as a laminated body in which each layer having a predetermined composition is laminated can be obtained, but the following methods are exemplified.

First, a laminate in which the outer layer side base material layer 1, the adhesive layer 2, and the metal layer 3 are laminated in this order (hereinafter, may be referred to as "laminate A") is formed. Specifically, the laminate A is formed by applying the adhesive of the present invention onto the outer layer side base material layer 1 or the metal layer 3 whose surface has been chemically converted as needed, by an extrusion method, a gravure coating method, or a roll. It can be carried out by a dry lamination method in which the metal layer 3 or the outer layer side base material layer 1 is laminated and the adhesive layer 2 is cured after being applied and dried by a coating method such as a coating method.

Next, the sealant layer 4 is laminated on the metal layer 3 of the laminated body A. When the sealant layer 4 is directly laminated on the metal layer 3, the resin component constituting the sealant layer 4 may be applied on the metal layer 3 of the laminated body A by a method such as a gravure coating method or a roll coating method. .. When the adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4, for example, the adhesive layer 5 and the sealant layer 4 are co-extruded onto the metal layer 3 of the laminated body A to be laminated (a method). Coextrusion lamination method), a method of separately forming a laminated body in which the adhesive layer 5 and the sealant layer 4 are laminated, and laminating this on the metal layer 3 of the laminated body A by the thermal lamination method, or the metal of the laminated body A. An adhesive for forming an adhesive layer 5 is laminated on the layer 3 by an extrusion method, a solution-coated method, drying at a high temperature, or a baking method, and a sealant layer 4 is previously formed into a sheet on the adhesive layer 5. Is laminated by the thermal lamination method, or between the metal layer 3 of the laminated body A and the sealant layer 4 which has been formed into a sheet in advance, the melted adhesive layer 5 is poured through the adhesive layer 5. Examples thereof include a method of laminating the laminate A and the sealant layer 4 (sand lamination method).

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

As described above, the coating layer 6 provided as needed / the outer layer side base material layer 1 / the adhesive layer 2 / the metal layer whose surface has been chemically converted as needed 3 / the adhesive layer 5 provided as needed. / A laminate composed of the sealant layer 4 is formed, but in order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as needed, a hot roll contact type, a hot air type, near or far It may be subjected to heat treatment such as infrared type. Examples of the conditions for such heat treatment include 1 to 5 minutes at 150 to 250 ° C.

In the packaging material for batteries of the present invention, each layer constituting the laminated body improves or stabilizes film forming property, laminating process, aptitude for secondary processing (pouching, embossing) of the final product, etc., as necessary. Therefore, surface activation treatment such as corona treatment, blast treatment, oxidation treatment, ozone treatment and the like may be performed.

<Battery container>
The battery container of the present invention can be obtained by molding the above-mentioned battery packaging material so that the outer layer side base material layer 1 forms a convex surface and the sealant layer 4 forms a concave surface.
As a method for molding the concave portion, there are the following methods.
-Heat-compressed air molding method: The packaging material for batteries is sandwiched between a lower mold with holes for supplying high-temperature and high-pressure air and an upper mold with pocket-shaped recesses, and air is supplied while being heated and softened to form recesses. how to.
-Preheater flat plate type compressed air molding method: After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a recess.
-Drum type vacuum forming method: A method in which a battery packaging material is partially heated and softened with a heating drum, and then the concave portion of a drum having a pocket-shaped concave portion is evacuated to form the concave portion.
-Pin molding method: A method in which the bottom material sheet is heat-softened and then crimped with a pocket-shaped uneven mold.
-Preheater plug assist compressed air molding method: After heating and softening the packaging material for batteries, air is supplied by sandwiching it between a lower mold with holes for supplying high-pressure air and an upper mold with pocket-shaped recesses. A method of forming a concave portion, which assists molding by raising and lowering a convex plug at the time of molding.

Among them, the preheater plug assist compressed air molding method, which is a heating vacuum forming method, is preferable in that the wall thickness of the bottom material after molding can be uniformly obtained.

(Use of battery packaging material)
The battery packaging material of the present invention is used as a battery container for sealing and accommodating battery elements such as a positive electrode, a negative electrode, and an electrolyte.

Specifically, a battery element having at least a positive electrode, a negative electrode, and an electrolyte is used in the battery packaging material of the present invention, with metal terminals connected to each of the positive electrode and the negative electrode protruding outward. A battery using a battery packaging material can be produced by covering the peripheral edge of the element so that a flange portion (a region where the sealant layers contact each other) can be formed, and heat-sealing the sealant layers of the flange portion to seal each other. Provided. When the battery element is housed using the battery packaging material of the present invention, the sealant portion of the battery packaging material of the present invention is used so as to be inside (the surface in contact with the battery element).

The battery packaging material of the present invention may be used for either a primary battery or a secondary battery, but is preferably used for a secondary battery. The type of secondary battery to which the packaging material for a battery of the present invention is applied is not particularly limited, and for example, a lithium ion battery, a lithium ion polymer battery, a lead storage battery, a nickel / hydrogen storage battery, a nickel / cadmium storage battery, a nickel / Examples thereof include iron storage batteries, nickel / zinc storage batteries, silver oxide / zinc storage batteries, metal air batteries, polyvalent cation batteries, capacitors, and capacitors. Among these secondary batteries, lithium ion batteries and lithium ion polymer batteries can be mentioned as suitable application targets of the packaging material for batteries of the present invention.

<Other uses of laminated bodies and molded bodies>
The use of the laminate of the present invention and the molded body of the laminate is not limited to the packaging material for batteries. The laminate of the present invention may be used as a multilayer packaging material for the purpose of protecting foods, pharmaceuticals, and daily necessities. When used as a multi-layer packaging material, its layer structure may change depending on the contents, usage environment, and usage pattern.

As one form of the packaging material, there is a material obtained by laminating the surfaces of the sealant films of the laminated body facing each other and then heat-sealing the peripheral end portions thereof. As a bag-making method, the laminate of the present invention is bent or overlapped so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral end thereof is, for example, a side seal type or a two-way seal type. There are three-way seal type, four-way seal type, envelope-attached seal type, gassho-attached seal type, fold-attached seal type, flat-bottom seal type, square-bottom seal type, gusset type, and other heat-seal methods. Be done. The packaging material of the present invention can take various forms depending on the contents, the environment of use, and the form of use. Free-standing packaging materials (standing pouches), etc. are also possible. As a heat sealing method, a known method such as a bar seal, a rotary roll seal, a belt seal, an impulse seal, a high frequency seal, and an ultrasonic seal can be used.

Other forms of packaging material include blister packs (also called press-through packages or PTPs). The blister pack seals the storage portion by joining the cover film to the laminate in which one or more storage portions are formed. Since the laminate of the present invention is excellent in moldability, it may be used as a laminate for forming a storage portion or as a cover film.

The present invention can also be used for applications other than packaging materials, and examples thereof include, but are not limited to, the base material of a decorative molded sheet. It can be suitably used for applications that require one or more functions of moldability, heat resistance, and moisture heat resistance.

Hereinafter, the present invention will be described in more detail with reference to specific synthetic examples and examples, but the present invention is not limited to these examples. In the following examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Adjustment of polyester polyol>
(Synthesis Example 1) Synthesis of polyester polyol (A1-1) 410 parts of terephthalic acid, 66 parts of isophthalic acid, 173 parts of adipic acid, 238 parts of cyclohexanedimethanol, 116 parts of 1,4-butanediol, 1,6-hexanediol Polyester polyol was synthesized according to a conventional method using 142 parts. The obtained polyester polyol (A1-1) has crystallinity, has a number average molecular weight (Mn) of 10,000, a glass transition temperature (Tg) of 2 ° C., a melting point of 115 ° C., and a heat of fusion (ΔH) of 9. The hydroxyl value was 1.9 J / g, the hydroxyl value was 11 mgKOH / g, and the acid value was 1.7 mgKOH / g.

(Synthesis Example 2) Synthesis of polyester polyol (A1-2) 411 parts of terephthalic acid, 66 parts of isophthalic acid, 177 parts of adipic acid, 248 parts of cyclohexanedimethanol, 116 parts of 1,4-butanediol, 1,6-hexanediol Polyester polyol was synthesized according to a conventional method using 129 parts. The obtained polyester polyol (A1-2) has crystallinity, has a number average molecular weight (Mn) of 22,000, a glass transition temperature (Tg) of 4 ° C., a melting point of 141 ° C., and a heat of fusion (ΔH) of 0. The hydroxyl value was .49 J / g, the hydroxyl value was 4 mgKOH / g, and the acid value was 2.3 mgKOH / g.

(Synthesis Example 3) Synthesis of polyester polyol (A1-3) 415 parts of terephthalic acid, 68 parts of isophthalic acid, 180 parts of adipic acid, 192 parts of cyclohexanedimethanol, 146 parts of 1,4-butanediol, 1,6-hexanediol Polyester polyol was synthesized according to a conventional method using 146 parts. The obtained polyester polyol (A1-3) has crystallinity, a number average molecular weight (Mn) of 20,000, a glass transition temperature (Tg) of -2 ° C., a melting point of 133 ° C., and a heat of fusion (ΔH). The hydroxyl value was 0.30 J / g, the hydroxyl value was 5 mgKOH / g, and the acid value was 6.7 mgKOH / g.

(Synthesis Example 4) Synthesis of polyester polyol (A1-4) 395 parts of terephthalic acid, 70 parts of isophthalic acid, 176 parts of adipic acid, 244 parts of cyclohexanedimethanol, 109 parts of 1,4-butanediol, 1,6-hexanediol A polyester polyol was synthesized according to a conventional method using 133 parts and 17 parts of trimethylolpropane. The obtained polyester polyol (A1-4) has crystallinity, has a number average molecular weight (Mn) of 4,400, a glass transition temperature (Tg) of -3 ° C, a melting point of 116 ° C, and a heat of fusion (ΔH). The hydroxyl value was 5.7 J / g, the hydroxyl value was 25 mgKOH / g, and the acid value was 1.6 mgKOH / g.

(Synthesis Example 5) Synthesis of polyester polyol (A1'-1) A polyester polyol was synthesized according to a conventional method using 274 parts of terephthalic acid, 157 parts of isophthalic acid, 310 parts of adipic acid, and 429 parts of 1,4-butanediol. The obtained polyester polyol (A1'-1) has crystallinity, has a number average molecular weight (Mn) of 30,000, a glass transition temperature (Tg) of −26 ° C., and a melting point of 85 ° C. and a heat of fusion (ΔH). The hydroxyl value was 13.3 J / g, the hydroxyl value was 8 mgKOH / g, and the acid value was 2.1 mgKOH / g.

(Synthesis Example 4) Synthesis of Polyester Polyol (A1'-2) Using 170 parts of terephthalic acid, 395 parts of isophthalic acid, 10 parts of trimellitic anhydride, 369 parts of 1,6-hexanediol, and 54 parts of neopentyl glycol, a conventional method. Polyester polyol was synthesized according to the above. The obtained polyester polyol (A1'-2) is amorphous, has a number average molecular weight (Mn) of 6,200, a glass transition temperature (Tg) of 7 ° C., a hydroxyl value of 22 mgKOH / g, and an acid value of 0. It was .7 mgKOH / g.

(Synthesis Example 6) Synthesis of Polyester Polyester (A2-1) A polyester polyol was synthesized according to a conventional method using 438 parts of adipic acid and 312 parts of 1,2-propylene glycol. The obtained polyester polyol (A2-1) is amorphous, has a number average molecular weight (Mn) of 3,100, a glass transition temperature (Tg) of −50 ° C., a hydroxyl value of 25 mgKOH / g, and an acid value of 2 mgKOH. It was / g.

The physical properties of the polyester polyol were measured as follows.
(Molecular weight measurement method)
Measuring device; HLC-8320GPC manufactured by Tosoh Corporation
Column; TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran Tetrahydrofuran flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

(Glass transition temperature measurement method)
5 mg of the sample was heated from room temperature to 200 ° C. at 10 ° C./min under a nitrogen stream of 30 mL / min using DSC, cooled to -80 ° C. at 10 ° C./min, and again 10 ° C./to 150 ° C. The temperature was raised in min and the DSC curve was measured. In the measurement results observed in the second temperature rise step, 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 curve of the stepped part of the glass transition is maximized. The intersection of the above was taken as the glass transition point, and the temperature at this time was taken as the glass transition temperature.

(Melting point measurement method)
The DSC curve was measured in the same manner as in the glass transition temperature measurement method, and the maximum peak temperature of the heat absorption curve observed in the second temperature raising step was taken as the melting point.

(Chemical amount of melting)
The DSC curve was measured in the same manner as in the glass transition temperature measurement method, and the maximum peak of the heat absorption curve observed in the second temperature raising step and the area surrounded by the baseline were calculated.

(Acid value)
5.0 g of the sample was precisely weighed, 30 mL of tetrahydrofuran (TFF) was added to dissolve the sample, and titration was performed using a 0.1 mol / L potassium hydroxide solution (methanolic). Phenolphthalein was used as an indicator. The measurement result was converted into the amount of potassium hydroxide required to neutralize 1 g of the sample, and the unit was mgKOH / g.

(Hydroxy group value)
5 ml of an acetylating agent was added to the sample, and the sample was sealed and heated at 60 ° C. for 15 minutes. After adding 20 ml of a toluene solution of 0.5 mol / L di-n-butylamine, the mixture was cooled with running water. It was titrated with a 0.5 mol / L alcoholic acid hydrochloric acid solution. A blank test was conducted in parallel, and the hydroxyl value contained in 1 g of the sample and the equivalent number of mg of potassium hydroxide were determined by comparison with the titration result using the sample.
As the acetylating agent, 15 ml of acetic anhydride was added to 1 g of 4-dimethylaminopyridine to make the total amount 100 ml with toluene, and bromophenol blue was used as an indicator.

<Adhesive adjustment>
(Example 1)
KBM-403 (silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., non-volatile content: 100%) was added to the polyester polyol (A1-1), and the mixture was stirred well until KBM-403 was completely dissolved. To this, add Death Module L-75 (manufactured by Sumika Covestro Urethane Co., Ltd., TDI adhesive, non-volatile content 75%), add ethyl acetate so that the non-volatile content becomes 25%, and stir well. The adhesive of Example 1 was prepared. Table 1 shows the blending amount (solid content) of each component in the adhesive of Example 1.

(Example 2) to (Example 5)
The adhesives of Examples 2 to 5 were produced in the same manner as in Example 1 except that the materials and formulations used for adjusting the adhesive were adjusted to the values shown in Table 1.
(Example 6)
The adhesive of Example 6 was produced in the same manner as in Example 1 except that the materials and formulations used for adjusting the adhesive were adjusted to the values shown in Table 2.
(Comparative Example 1) to (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 formulations used for adjusting the adhesive were adjusted to the values shown in Table 1.
(Comparative Example 3)
The adhesive of Comparative Example 3 was produced in the same manner as in Example 1 except that the materials and formulations used for adjusting the adhesive were adjusted to the values shown in Table 2.
Other compounds in Tables 1 and 2 are as follows.
BYK-051N: Made by BYK-Chemie GmbH, antifoaming agent

<Manufacturing of packaging materials for batteries 1 Configuration of Fig. 2>
(Example 1)
The adhesive of Example 1 as the adhesive layer 2 was applied to the matte surface of the aluminum foil having a thickness of 40 μm as the metal layer 3 with a dry laminator in an amount of 4 g / square meter, and after the solvent was volatilized, the outer layer was applied. A stretched polyamide film having a thickness of 25 μm was laminated as the side base material layer 1.
Next, the adhesive for the adhesive layer 5 was applied to the glossy surface of the aluminum foil of the metal layer 3 of the obtained laminated film with a dry laminator in an amount of 4 g / square meter to volatilize the solvent. An unstretched polypropylene film having a thickness of 40 μm was laminated as the sealant layer 4, and then cured (aged) at 60 ° C. for 5 days to cure the adhesive to obtain a laminate.

(Example 2) to (Example 5)
In the same manner as in Example 1, the adhesives of Examples 2 to 5 were used as the adhesive layer 2 to obtain packaging materials for batteries of Examples 2 to 5.

(Comparative Example 1) to (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 packaging materials for batteries of Comparative Examples 1 and 2.

<Manufacturing of packaging materials for batteries 2>
(Example 6)
The adhesive prepared in Example 6 was applied to an aluminum foil having a thickness of 40 μm with a bar coater so as to have a dry coating amount of 5 g / m ² , dried at 80 ° C. for 1 minute, and then combined with a CPP film having a thickness of 40 μm. It was bonded at 100 ° C. Then, curing (aging) was carried out at 40 ° C. for 5 days to obtain a laminate of Example 6.
(Comparative Example 3)
A laminate of Comparative Example 3 was obtained in the same manner as in Example 6 except that the adhesive of Comparative Example 3 was used.

The evaluation of the battery packaging material was performed as follows. The results are shown in Tables 1 and 2.
<Adhesive strength>
Using "Autograph AGS-J" manufactured by Shimadzu Corporation, Examples 1 to 5, Comparative Example 1, under the conditions of normal temperature, peeling speed: 50 mm / min, peeling width: 15 mm, peeling form: 180 ° peeling, In the case of 2, the adhesive strength at the interface between the outer layer side base material layer 1 and the metal layer 3 was evaluated, and in the case of Example 6 and Comparative Example 3, the adhesive strength at the interface between the aluminum foil and the CPP film was evaluated. The higher the value, the more suitable as an adhesive.

<Moldability>
The battery packaging material of the example or comparative example was cut into a size of 60 × 60 mm to obtain a blank (material to be molded, material). Using "1ton desktop servo press (SBN-1000)" manufactured by Yamaoka Seisakusho Co., Ltd., the aluminum foil matte surface is on the convex side with respect to the blank, and the stroke speed is 3 mm / sec and the molding height is free. Overhang molding was performed by changing the molding height from 4.5 mm to 7.0 mm with a straight mold, and the moldability was evaluated by the maximum molding height at which breakage of the aluminum foil and floating between layers did not occur.

The punch shape of the mold used is a square with a side of 30 mm, a corner R2 mm, a punch shoulder R1 mm, and the die hole shape of the mold used is a square with a piece of 34 mm, a die hole corner R2 mm, and a die hole shoulder R: 1 mm. , The clearance between the punch and the die hole is 0.3 mm on one side. The clearance causes an inclination according to the molding height.
〇: 6.0 mm or more (excellent in practical use)
Δ: 5.0 mm (practical range)
X: At 4.5 mm, breakage of aluminum foil and floating between each layer occur.

<Heat resistance>
Cut the battery packaging material of the example or comparative example into a size of 60 x 60 mm, and use "1ton desktop servo press (SBN-1000)" manufactured by Yamaoka Seisakusho Co., Ltd. so that the aluminum foil matte surface is on the outside. Then, overhang molding was performed with a straight mold having a molding height of 5.0 mm at a molding height of 5.0 mm. A heat seal bar at 190 ° C. for 3 seconds was applied to the flange portion of the obtained 30 mm square tray so as to be in contact with the side wall portion, and the appearance near the boundary portion between the flange portion and the side wall portion was confirmed, and the stretched polyamide film and the aluminum foil were used. It was evaluated whether there was any floating between the two.
○: No float (excellent in practical use)
×: Float occurs

<Moisture resistance>
Cut the battery packaging material of the example or comparative example into a size of 60 x 60 mm, and use "1ton desktop servo press (SBN-1000)" manufactured by Yamaoka Seisakusho Co., Ltd. so that the aluminum foil matte surface is on the outside. Then, overhang molding was performed with a straight mold having a molding height of 5.0 mm at a molding height of 5.0 mm. The obtained 30 mm square tray was placed in a constant temperature and humidity chamber at 85 ° C. and an 85% RH atmosphere, and allowed to stand for 48 hours. The tray was taken out from the constant temperature and humidity chamber, the appearance in the vicinity of the boundary between the flange portion and the side wall portion was confirmed, and it was evaluated whether or not floating was generated between the stretched polyamide film and the aluminum foil.
○: No float (excellent in practical use)
×: Float occurs

<Electrolyte resistance>
The laminate of Example or Comparative Example was immersed in 35 g of a mixed solution of ethylene carbonate: ethyl methyl carbonate: dimethyl carbonate = 1: 1: 1 (mass%) at 60 ° C. for 14 days. After the laminate after immersion was dried, the adhesive strength was measured and evaluated from the retention rate of the adhesive strength before and after immersion in three stages.
〇: 80% or more Δ: 60% or more and less than 80% ×: less than 60%

From this result, by using the adhesive of the present invention, it has excellent moldability, and after heat fusion between the sealant layers performed to seal the battery element, and for a long period of time under high temperature and high humidity. It is clear that even after the durability test, there is no decrease in the adhesive strength between the layers, and it is possible to obtain a packaging material for a battery in which appearance defects such as floating between layers are suppressed.

1: Outer layer side base material layer 2: Adhesive layer 3: Metal layer 4: Sealant layer 5: Adhesive layer

Claims

A polyol composition (A) containing a crystalline polyester polyol (A1) and
Containing a polyisocyanate composition (B) containing an isocyanate compound (B),
The glass transition temperature of the crystalline polyester polyol (A1) is −20 ° C. or higher and 10 ° C. or lower, the melting point is 80 ° C. or higher and 160 ° C. or lower, and the number average molecular weight is 2,000 or higher and 30,000 or lower. A characteristic two-component adhesive.
The two-component adhesive according to claim 1, wherein the crystalline polyester polyol (A1) has a heat of fusion of 0.1 J / g or more and 50 J / g or less.
The two-component adhesive according to any one of claims 1 or 2, wherein the polyol composition (A) contains a polyester polyol (A2) having a glass transition temperature of −70 ° C. or higher and lower than −20 ° C.
The two-component adhesive according to claim 3, wherein the blending amount of the polyester polyol (A2) is 10% by mass or less with respect to the total mass of the crystalline polyester polyol (A1) and the polyester polyol (A2).
The two-component adhesive according to any one of claims 1 to 4, which is used as a packaging material for batteries.
It has an adhesive layer for bonding the first base material, the second base material, the first base material, and the second base material.
A laminate in which the adhesive layer is a cured product of the adhesive according to any one of claims 1 to 5.
The packaging material for a battery 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 sequentially laminated, and the adhesive layer 2 is the one according to any one of claims 1 to 5. A packaging material for batteries, which is a cured product of a two-component adhesive.
A battery container obtained by molding the battery packaging material according to claim 7.
A battery using the battery container according to claim 8.