WO2012114776A1

WO2012114776A1 - Laminate for nonaqueous electrolyte secondary cell container, method for producing same, nonaqueous electrolyte secondary cell, and adhesive composition

Info

Publication number: WO2012114776A1
Application number: PCT/JP2012/001309
Authority: WO
Inventors: 堀口　雅之; 諭志前田; 猛吉川
Original assignee: 東洋インキＳｃホールディングス株式会社
Priority date: 2011-02-25
Filing date: 2012-02-24
Publication date: 2012-08-30
Also published as: JP6020438B2; JPWO2012114776A1

Abstract

Provided is a highly reliable laminate for a nonaqueous electrolyte secondary cell container. This laminate for a nonaqueous electrolyte secondary cell container comprises a metal foil, a thermofusible film, and an adhesive layer for joining the foil and the film. The adhesive layer comprises styrene thermoplastic elastomer (A), adhesion-imparting agent (B), and polyisocyanate (C). A total 100 wt% of elastomer (A) and adhesion-imparting agent (B) consists of 20 to 90 wt% of elastomer (A) and 10 to 80 wt% of adhesion-imparting agent (B); elastomer (A) has 0.003 to 0.04 mmol/g of amino group- or hydroxyl group-derived active hydrogen; the ratio of functional group-derived active hydrogen in adhesion-imparting agent (B) is 0 to 15 mol per 1 mol of elastomer (A)-derived active hydrogen; and the ratio of isocyanate groups in polyisocyanate (C) is within a range of 3 to 15 mol per a total of 1 mol of active hydrogen derived from elastomer(A) and adhesion-imparting agent (B).

Description

Non-aqueous electrolyte secondary battery container laminate, manufacturing method thereof, non-aqueous electrolyte secondary battery, and adhesive composition

The present invention relates to an adhesive composition that can be suitably applied to a laminate for forming a battery container of a non-aqueous electrolyte secondary battery. Moreover, it is related with the laminated body for nonaqueous electrolyte secondary battery containers formed using the adhesive composition, and its manufacturing method. Furthermore, it is related with the nonaqueous electrolyte secondary battery which comprises the laminated body for the nonaqueous electrolyte secondary battery container.

In recent years, with the rapid growth of electronic devices such as mobile phones and portable personal computers, the demand for lightweight and small non-aqueous electrolyte secondary batteries is increasing. In particular, the use of bag-like or tray-like battery containers made of a composite film such as a metal foil represented by aluminum foil and a resin film that can be made lighter and more compact is drawing attention. Collecting.

A secondary battery using a bag-like or tray-like battery container is often obtained as follows.
Step 1: A battery container laminate for forming a bag-shaped or tray-shaped battery container is formed. The battery container laminate is generally a laminate of a heat-sealable film in which at least a heat-sealable film is formed on the outer layer / metal foil / outermost layer, and each constituent member is an adhesive composition ( For example, they are bonded according to Patent Documents 1 to 5).
Step 2: In the battery container laminate, at least one outermost layer is a heat-fusible film having a heat-fusible film as an inner surface, and at least one end of the bag or tray is formed.
Step 3: In the obtained bag or tray, a plurality of electrode terminals connected to the secondary battery main body and the positive and negative electrodes of the secondary battery main body (the other end of the electrode terminals are arranged so as to protrude from the bag or tray. And electrolyte.
Step 4: Next, in the case of a bag shape, the heat-fusible films near the open end are opposed to each other, and the other end portion of the electrode terminal protrudes from the open end to the outside of the bag. The secondary battery body, the electrolyte, and the like are sealed by heat-sealing the adhesive film. On the other hand, in the case of a tray shape, the heat-fusible film constituting the flat laminate is opposed to the heat-fusible film on the edge of the tray, and the other end of the electrode terminal is placed from the tray edge to the outside of the tray. The secondary battery main body and the electrolyte are sealed by thermally fusing the heat-fusible film at the edge of the tray in the protruding state.

In laminates for battery containers forming a battery container enclosing a secondary battery and an electrolyte, the performance of the adhesive composition for joining the film materials is important from the viewpoint of durability and prevention of electrolyte leakage. Various proposals have heretofore been made. Patent Document 1 (Japanese Patent Laid-Open No. 2001-236932) discloses a battery package in which a modified olefin resin layer containing hydrotalcite, which is an acid receiving layer, is provided between a metal foil and an olefin resin layer. A material is disclosed. As the modified olefin resin, maleic anhydride polypropylene is disclosed.

Patent Document 2 (Japanese Patent Application Laid-Open No. 2003-123708) describes an unstretched polypropylene film formed using an adhesive composition containing a maleic acid-modified styrene thermoplastic elastomer (A) and a coupling agent (B). A secondary battery using an adhesive layer / aluminum foil / nylon film as a packaging material is disclosed. In addition, it is described that the adhesive composition may contain a tackifier.

Patent Document 3 (International Publication No. 2004/041954) discloses an adhesive composition containing a carboxyl group-containing thermoplastic elastomer, a polyolefin polyol, a tackifier, and a polyfunctional isocyanate. The carboxyl group-containing thermoplastic elastomer is obtained by introducing a carboxyl group into the thermoplastic elastomer. Preferred examples of the thermoplastic elastomer include a styrene-butadiene block copolymer.

Patent Document 4 (Japanese Patent Application Laid-Open No. 2005-063685) discloses an adhesive composition containing polyolefin polyol and polyfunctional isocyanate as essential components. The polyolefin polyol used as the main agent has a hydrocarbon skeleton similar to that of the low molecular weight polyolefin and has a plurality of hydroxyl groups. Examples thereof include polybutanediene diol and hydrogenated polybutadiene diol. It is described that the adhesive composition may contain a thermoplastic elastomer such as a styrene elastomer and an olefin elastomer, and a tackifier.

Further, Patent Document 5 (Japanese Patent Application Laid-Open No. 2004-10719) discloses an adhesive / adhesive composition containing a block copolymer, a crosslinking agent, and a tackifier resin. Specifically, the block copolymer (a) is mainly composed of a polymer block composed mainly of an aromatic vinyl compound unit and mainly composed of a conjugated diene unit, and at least a part of the carbon-carbon unsaturated double bond is hydrogenated. And the block copolymer contains a block copolymer having hydroxyl groups at both ends; and the cross-linking agent (b) has a viscosity having at least two isocyanate groups in the molecule. An adhesive composition is disclosed.

JP 2001-236932 A JP 2003-123708 A International Publication No. 2004/041954 Japanese Patent Laying-Open No. 2005-063685 JP 2004-010719 A

袋 Bag-shaped and tray-shaped battery containers can realize light weight and compactness, but the sealing performance without leakage of electrolyte is extremely important. In order to satisfy these various characteristics, the battery container generally comprises a laminate of an outer layer / metal foil (aluminum foil) / inner layer as described above, and the constituent members are joined by an adhesive layer. Yes. Therefore, in order to achieve high reliability, it is important not only to optimize each component member and the combination thereof, but also to increase the reliability of the adhesive composition for joining them. That is, the adhesive layer formed from the adhesive composition is not easily damaged by the electrolyte itself, or the electrolyte is decomposed by moisture, and the resulting hydrolyzate or the like, or the solvent dissolving the electrolyte, It is important that the adhesive performance is not easily lowered. In addition, the long usable time of the adhesive composition (hereinafter also referred to as “pot life”) means that the reliability of the adhesive composition, and further, a laminate having an adhesive layer formed using the adhesive composition, etc. It is demanded from the point of raising.

The present invention has been made in view of the above background, and its object is to provide a highly reliable laminate for a non-aqueous electrolyte secondary battery container, a method for producing the same, and a non-aqueous electrolyte two. It is to provide an adhesive composition suitable for forming a secondary battery and the aforementioned laminate for a nonaqueous electrolyte secondary battery container.

The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and, as shown below, contain a component having a specific structure in a specific ratio, and the activity derived from a specific amount of a specific functional group in the constituent component. It has been found that the above-mentioned problems can be solved by satisfying all the conditions of having hydrogen and further having an isocyanate group at a specific ratio, and have completed the present invention.

The laminate for a non-aqueous electrolyte secondary battery container according to the present invention comprises at least a metal foil, a heat-fusible film, and an adhesive layer that joins the metal foil and the heat-fusible film. The adhesive layer contains a styrenic thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C), and the styrenic thermoplastic elastomer (A) and the tackifier. The styrenic thermoplastic elastomer contains 20 to 90% by weight of the styrenic thermoplastic elastomer (A) and 10 to 80% by weight of the tackifier (B) in a total of 100% by weight with the agent (B). (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or hydroxyl group, and the pressure-sensitive adhesive against 1 mol of the active hydrogen derived from the styrenic thermoplastic elastomer (A). The active hydrogen derived from the functional group of the additive (B) is 0 to 15 mol, and the polyisocyanate (C) includes the active hydrogen derived from the styrenic thermoplastic elastomer (A) and the tackifier (B ) Derived from an adhesive composition comprising an isocyanate group in a range of 3 to 150 mol with respect to a total of 1 mol of the above-mentioned active hydrogen.
A preferred position of the amino group or the hydroxyl group in the styrenic thermoplastic elastomer (A) is at least one position of the end of the main chain. Moreover, the more preferable position of the said amino group or the said hydroxyl group in the said styrene-type thermoplastic elastomer (A) is making it only into the terminal of a principal chain.
The adhesive composition further includes an elastomer composite resin (D), and the elastomer composite resin (D) includes at least one of a polyester resin portion and a polyurethane resin portion, a styrenic thermoplastic elastomer structure, It is preferable to contain.
A preferred example of the polyisocyanate (C) is an isocyanurate structure.
The content of the elastomer composite resin (D) is preferably 2 to 60 parts by weight with respect to a total of 100 parts by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B).

According to the laminate for a non-aqueous electrolyte secondary battery container according to the present invention, the adhesive strength of the laminate can be maintained at a high level even when contacting with the electrolyte by using the above-described adhesive composition. Therefore, a highly reliable laminate for a non-aqueous electrolyte secondary battery container can be provided. Further, since the adhesive composition to be used has an excellent effect that the pot life is long, the stability of the adhesive composition is improved, and the non-aqueous electrolyte secondary having the adhesive layer formed using the same is used. High reliability of the battery container laminate can be realized.

A non-aqueous electrolyte secondary battery according to the present invention includes a secondary battery body, a battery container that houses the secondary battery body, and an electrolyte sealed in the battery container. The laminate for a non-aqueous electrolyte secondary battery container according to the above aspect is provided.

The adhesive composition according to the present invention contains a styrenic thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C), and the styrenic thermoplastic elastomer (A), The styrenic thermoplastic elastomer (A) is contained in an amount of 20 to 90% by weight and the tackifier (B) is contained in an amount of 10 to 80% by weight in a total of 100% by weight with the tackifier (B). The thermoplastic elastomer (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or a hydroxyl group, and with respect to 1 mol of active hydrogen derived from the styrenic thermoplastic elastomer (A), The active hydrogen derived from the functional group of the tackifier (B) is 0 to 15 mol, and the polyisocyanate (C) is the active water derived from the styrenic thermoplastic elastomer (A). If, with respect to the total 1 mol of the active hydrogen of the derived tackifier (B), and the isocyanate group is contained in the range of 3 to 150 mol.
The adhesive composition of this invention is used suitably for the use which forms the laminated body for nonaqueous electrolyte secondary battery containers.
A preferable position of the amino group or the hydroxyl group of the styrene-based thermoplastic elastomer (A) can include at least one end of the main chain. Moreover, the more preferable position of the said amino group or the said hydroxyl group in the said styrene-type thermoplastic elastomer (A) is making it only into the terminal of a principal chain.
A preferred example of the polyisocyanate (C) is an isocyanurate structure.
Furthermore, an elastomer composite resin (D) is included, and the elastomer composite resin (D) preferably includes at least one of a polyester resin portion and a polyurethane resin portion, and a styrene-based thermoplastic elastomer structure.
A preferable content of the elastomer composite resin (D) is in the range of 2 to 60 parts by weight with respect to a total of 100 parts by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B). .

In the method for producing a laminate for a nonaqueous electrolyte secondary battery container according to the present invention, the adhesive composition of the above aspect is applied to one surface of a metal foil or a heat-fusible film and dried to be uncured. Forming an adhesive layer and forming the laminated structure of the metal foil, the adhesive layer, and the heat-fusible film on the surface of the uncured adhesive layer, or The metal foil is stacked, the uncured adhesive layer is cured, and the metal foil and the heat-fusible film are bonded together.

According to the present invention, a highly reliable laminate for a nonaqueous electrolyte secondary battery container, a manufacturing method thereof, a nonaqueous electrolyte secondary battery, and the aforementioned laminate for a nonaqueous electrolyte secondary battery container are formed. It has the outstanding effect that the adhesive composition suitable for carrying out can be provided.

Hereinafter, embodiments of the present invention will be described in detail. In addition, as long as it agree | coincides with the meaning of this invention, other embodiment can also belong to the category of this invention. In the present specification, the description “any number A to any number B” means a range larger than the numbers A and A but smaller than the numbers B and B. In addition, the expression “(meth) acrylate” described in the present specification and claims includes both the compound read as “acrylate” and the compound read as “methacrylate”.

The non-aqueous electrolyte secondary battery of the present invention includes a secondary battery body, a battery container that accommodates the secondary battery body, an electrolyte that is sealed in the battery container, and a plurality of joints that are respectively joined to the positive electrode and the negative electrode of the secondary battery body. And so on. A battery container has the laminated body for nonaqueous electrolyte secondary battery containers formed by laminating | stacking metal foil and a heat-fusible film through the adhesive composition of this invention mentioned later. In a state where the other end portions of the plurality of terminals protrude from the battery container by heat fusion of a part of the heat-fusible film provided on the inner layer side of the laminate, the secondary battery body, the plurality of terminals, And the electrolyte is sealed inside the battery container. In addition, although the electrolyte of this specification is generally a liquid thing, it includes a gel form and a solid form. The liquid state includes an electrolyte solution in addition to the electrolyte itself being a liquid. In the present invention, a layer positioned on the side closer to the electrolyte with the metal foil as a boundary is referred to as an “inner layer”, and a layer positioned on the side farther from the electrolyte with the metal foil as a boundary is referred to as an “outer layer”.

The laminate for a non-aqueous electrolyte secondary battery container of the present invention has at least a metal foil, a heat-fusible film, and an adhesive layer for joining them. The heat-fusible film may be composed of a single-layer heat-fusible film, or may be composed of a multilayer laminate comprising the heat-fusible film. In the case of a multilayer laminate, the innermost layer surface (exposed surface in contact with the electrolyte) may be a heat-fusible film. A heat-fusible film that is a multilayer laminate can be obtained, for example, by co-extrusion of different types of heat-fusible resins when forming a film. Or it can also obtain by laminating | stacking a heat-fusible film and another film using an adhesive agent. Since the adhesive composition of the present invention has excellent chemical resistance as will be described later, it is particularly effective for bonding with an inner layer located on the inner side of the metal foil. Specifically, it is suitable for adhesion between the metal foil and the heat-fusible film. Moreover, when a heat-fusible film is a multilayer laminated body, it is suitable also for adhesion | attachment of each layer. Moreover, it can utilize suitably for adhesion | attachment of the laminated body by which chemical resistance is calculated | required. Of course, the adhesive composition of the present invention is also suitably used for adhesion between the outer layer and the metal foil. Moreover, it can utilize also for adhesion | attachment of various members other than having mentioned above.

Examples of the metal of the metal foil include aluminum, copper, and nickel. These metal foils may be subjected to various surface treatments. Examples of the surface treatment include, for example, physical treatment such as sand blast treatment and polishing treatment, degreasing treatment by vapor deposition, chemical treatment such as etching treatment and primer treatment applying a coupling agent. In the present invention, the thickness of the metal foil is not particularly limited, and includes a thin film to a sheet. Moreover, plate shape may be sufficient.

Examples of the heat-fusible film include polyolefin films such as polyethylene and polypropylene, and an unstretched film is particularly preferably used. The thickness of the heat-fusible film is not limited within a range not departing from the gist of the present invention, and includes a thin film to a sheet / plate.

The laminate for a nonaqueous electrolyte secondary battery container may have an outer layer member such as an outer layer film disposed on a metal foil. That is, the metal foil may be sandwiched between the heat-fusible film and the outer layer member. Examples of the outer layer member include stretched films such as polyester resin and polyamide resin (nylon).

There are two types of battery containers: a pouch type for a bag-like container and a tray-type container type formed by molding a flat laminate using a mold. One form of a bag-like container is illustrated in FIG. 8 of JP-A-2007-294381. Further, one form of the tray-like container is shown in FIG. 9 of the publication, and the other form is shown in FIG. The laminate using the adhesive composition of the present invention can be used to form both types of containers, bags and trays. In either case, a part of the heat-fusible film is heat-sealed in a state where the heat-fusible film faces inward and the tips of the plurality of terminals protrude to the outside. Seal the electrolyte.

The adhesive composition of the present invention comprises a styrenic thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C), and the following (i) to (iv) The above conditions are satisfied. That is, (i) 20 to 90% by weight of the styrene-based thermoplastic elastomer (A) is added to the total amount of 100% by weight of the styrene-based thermoplastic elastomer (A) and the tackifier (B). 10 to 80% by weight of the agent (B) is contained. (Ii) The styrenic thermoplastic elastomer (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or a hydroxyl group. (Iii) The active hydrogen derived from the functional group of the tackifier (B) is 0 to 15 mol with respect to 1 mol of active hydrogen derived from the styrene-based thermoplastic elastomer (A). (Iv) The polyisocyanate (C) contains 3 to 150 mol of isocyanate groups with respect to 1 mol in total of the active hydrogen of the styrenic thermoplastic elastomer (A) and the active hydrogen of the tackifier (B). It is included in the range.

The styrenic thermoplastic elastomer (A) (hereinafter also simply referred to as “elastomer (A)”) used in the present invention will be described. The “thermoplastic elastomer” in the present invention refers to a resin that has a rubber elasticity at room temperature, that is, a thermoplastic resin that has a rubber elasticity without performing vulcanization treatment. The chemical structure generally has an ABA type block or an (AB) n type multi-block structure.

The styrenic thermoplastic elastomer (A) preferably has a polystyrene structure in the molecule because of its excellent electrolyte resistance and heat resistance. Specific examples include styrene-butadiene block copolymers, styrene- Ethylene propylene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylenepropylene-styrene copolymer, etc. Can be mentioned. As used herein, “electrolytic resistance” refers to resistance not only to the electrolyte but also to a substance that can be generated by using a nonaqueous electrolyte secondary battery.

As a polymerization method of the styrenic thermoplastic elastomer (A), generally, an aromatic vinyl compound such as styrene and a conjugated diene compound are sequentially formed by anionic polymerization reaction in an inert solvent using a polymerization catalyst such as an organic lithium compound. There is a method in which polymerization is terminated by adding a compound containing active hydrogen such as alcohols and carboxylic acids (hereinafter referred to as a terminal modifier) to the living terminal. Thereby, a conjugated diene-containing copolymer is obtained. The amount of the conjugated diene can be adjusted by subjecting the obtained copolymer to a hydrogenation reaction in the presence of a hydrogenation catalyst such as a Ziegler catalyst.

Styrenic thermoplastic elastomer (A) forms a crosslinked structure by reacting with polyisocyanate (C) described later. As the styrene-based thermoplastic elastomer (A), a single type may be used or a plurality of types may be used in combination. In order to realize high adhesive strength and excellent electrolyte resistance of the adhesive composition, the styrenic thermoplastic elastomer (A) contains 0.003 to 0.04 mmol / g of active hydrogen derived from amino groups or hydroxyl groups. Have. In other words, the active hydrogen is in the range of 0.003 to 0.04 mmol / g, and the functional group having active hydrogen is substantially derived from an amino group or a hydroxyl group. However, the structure having active hydrogen composed of other functional groups is not excluded without departing from the spirit of the present invention. In addition, as the styrene thermoplastic elastomer (A), one having either an amino group or a hydroxyl group in one molecule is preferably used, and both functional groups of amino group and hydroxyl group are contained in one molecule. It may be included. Moreover, the styrene-type thermoplastic elastomer (A) which has an amino group, and the styrene-type thermoplastic elastomer (A) which has a hydroxyl group may be mixed.

Examples of a method for introducing an amino group or a hydroxyl group into the styrene-based thermoplastic elastomer (A) include a method in which a graft reaction is performed on the side chain of the elastomer (A), and a method in which the amino group or hydroxyl group is introduced into the main chain terminal of the elastomer (A). By using these methods in combination, amino groups and hydroxyl groups can be introduced into the main chain terminals and side chains.

As a method for introducing an amino group or a hydroxyl group into the side chain of the styrene thermoplastic elastomer (A), a method of grafting a styrene elastomer and a polymerizable monomer having an amino group or a hydroxyl group using an organic peroxide. Is mentioned.

Examples of the polymerizable monomer having an amino group or a hydroxyl group include, but are not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth). Examples include acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified hydroxy (meth) acrylate, and the like. These may be used alone or in any combination.

Examples of the organic peroxide include, but are not limited to, di-t-butyl peroxide, dicumyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dilauryl peroxide, cumene. Hydroperoxide, t-butyl hydroperoxide, 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, cyclohexanone Oxide, t-butylperoxybenzoate, t-butylperoxyisobutyrate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy-2-ethylhexanoate, t- Butyl peroxy isopropyl carbonate, cumyl par Kishio Que door benzoate, and the like. These may be used alone or in any combination.

As a method for introducing a functional group into the main chain terminal of the styrene-based thermoplastic elastomer (A), a method in which a terminal modifier is reacted at the living terminal when polymerizing the styrene-based elastomer, an amino group or a hydroxyl group is protected. Examples thereof include a method of performing a deprotection reaction after polymerizing a styrene elastomer using a polymerization catalyst. By using these methods in combination, an amino group or a hydroxyl group can be introduced into both ends of the main chain of the elastomer (A) or one end of the main chain.

As a method of introducing an amino group or a hydroxyl group using a terminal modifier at the main chain terminal of the styrene-based thermoplastic elastomer (A), for example, at the living terminal when synthesizing the styrene-based thermoplastic elastomer (A), Examples thereof include a method in which an end modifier having an amino group or a hydroxyl group and / or a terminal modifier that forms an amino group or a hydroxyl group by reacting with a living end is subjected to an addition reaction. Further, when the styrene-based thermoplastic elastomer (A) is a hydride of a styrene-based elastomer, an aminoalkali metal compound such as an organolithium compound is reacted with the styrenic thermoplastic elastomer (A), and the copolymer to which the organic alkali metal is added is added to the amino acid. Examples thereof include a method in which an end modifier containing a group or a hydroxyl group is subjected to an addition reaction.

Examples of the terminal modifier for introducing an amino group having active hydrogen at the end of the main chain of the styrenic thermoplastic elastomer (A) include 1,3-dimethyl-2-imidazolidinone and 1,3-diethyl-2. -Imidazolidinone, N-methylpyrrolidone, N, N'-dimethylpropylene urea and the like.

Examples of the terminal modifier for introducing a hydroxyl group into the main chain terminal of the styrenic thermoplastic elastomer (A) include ε-caprolactone, δ-valerolactone, butyrolactone, γ-caprolactone, γ-valerolactone, and 4-methoxy. Examples include benzophenone, 4-ethoxybenzophenone, 4,4′-bis (methoxy) benzophenone, 4,4′-bis (ethoxy) benzophenone, and the like.

The number of modifiers introduced into the ends of the main chain of the styrenic thermoplastic elastomer (A) is preferably in the range of 0.5 to 1 on average, and more preferably in the range of 0.7 to 1 on average. When the number of modifiers introduced at the end of the main chain of the elastomer (A) is less than 0.5 on average, the cross-linked structure formed by reaction with the polyisocyanate (C) described later becomes sparse, and sufficient adhesion Electrolyte resistance may not be obtained.

Depending on the type of modifier used when introducing the functional group at the end of the main chain of the styrenic thermoplastic elastomer (A), hydroxyl groups and amino groups generally become organometallic salts at the stage of reaction of the modifier. In that case, a hydroxyl group, an amino group, or the like can be obtained by treatment with a compound having active hydrogen such as water or alcohol.

The amount of the terminal modifier used is preferably in the range of 0.5 to 10 equivalents, more preferably in the range of 1 to 4 equivalents with respect to 1 equivalent of the living terminal of the polymer. When the amount of the terminal modifier is less than 0.5 equivalent, sufficient functional groups cannot be introduced into the main chain terminal of the styrenic thermoplastic elastomer (A). There exists a possibility that the terminal modifier | denaturant to make worse adhesive force and pot life.

As a method of introducing the functional group using a polymerization catalyst in which the functional group is protected at the end of the main chain of the styrenic thermoplastic elastomer (A), 3- (t-butyldimethylsiloxy) -2,2- Functional groups such as dimethyl-1-propyllithium, 3- (trimethylsiloxy) -2,2-dimethyl-1-propyllithium, 3- (t-butoxy) -2,2-dimethyl-1-propyllithium are protected A method of reacting a deprotecting agent after polymerizing a styrene-based elastomer using the prepared polymerization initiator is mentioned.

Examples of the deprotecting agent include proton acidic compounds such as hydrochloric acid, sulfonic acid and carboxylic acid, Lewis acidic compounds such as boron trifluoride and tin chloride, tetrabutylammonium fluoride, ammonium fluoride and potassium fluoride. And an alkaline fluorine-ison containing compound.

The styrene thermoplastic elastomer (A) preferably contains 5 to 60% by weight of styrene units in the elastomer (A), more preferably 10 to 40% by weight. When the styrene unit of the styrene-based thermoplastic elastomer (A) is less than 5% by weight, sufficient viscoelasticity may not be obtained. When the styrene unit is more than 60% by weight, the solubility in a solvent is increased. May decrease and impair solution stability.

The number average molecular weight of the styrenic thermoplastic elastomer (A) is preferably 30,000 to 300,000, and more preferably 40,000 to 150,000. When the number average molecular weight of the styrene-based thermoplastic elastomer (A) is lower than 30,000, sufficient viscoelasticity may not be obtained. When the number average molecular weight is higher than 300,000, the viscosity is too high and the coating property is large. May get worse. The molecular weight is expressed in terms of polystyrene by gel permeation chromatography (GPC).

The styrenic thermoplastic elastomer (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from amino groups or hydroxyl groups. The amount is preferably 0.005 to 0.035 mmol / g, and more preferably 0.008 to 0.03 mmol / g. Hereinafter, the amount of active hydrogen derived from the hydroxyl group or amino group of the styrene-based thermoplastic elastomer (A) is referred to as the amount of active hydrogen of the styrene-based thermoplastic elastomer (A).
The amount of active hydrogen in the styrene-based thermoplastic elastomer (A) can be obtained by the following formula (1).
[Equation 1]
Active hydrogen content of styrenic thermoplastic elastomer (A)
= (Number of active hydrogens derived from functional group of elastomer (A) × 1,000) / number average molecular weight of elastomer (A) (Formula 1)
The number of active hydrogens derived from the functional group is obtained by HPLC and NMR measurement of the number of modifiers introduced per molecule of the elastomer (A), and the number average molecular weight of the elastomer (A) is obtained by GPC measurement.

Examples of commercially available styrenic thermoplastic elastomers (A) used in the present invention include Tuftec MP10 (amino group main chain terminal modified SEBS) manufactured by Asahi Kasei Chemical Co., Ltd., and DYNARON 8630P (amino group main chain manufactured by JSR). End-modified SEBS), Kuraray Septon HG-252 (hydroxyl main chain terminal-modified SEEPS), and the like. These may be used alone or in any combination of two or more.

When the adhesive composition is prepared, that is, when the elastomer (A) is combined with a tackifier (B) or polyisocyanate (C) described later, the crosslinking reaction gradually proceeds between the molecules of the elastomer (A). As the crosslinking reaction proceeds, thickening occurs. As a result, the wettability to the substrate is lowered, and the adhesive strength is gradually lowered. However, when an elastomer (A) having a functional group responsible for crosslinking at the end, notably at one end of the main chain, is used instead of the side chain of the main chain, the adhesive can be used even if the cross-linking reaction between the elastomer molecules proceeds. An increase in the viscosity of the composition can be effectively suppressed. In other words, when the styrenic thermoplastic elastomer (A) has an amino group or a hydroxyl group only at the end of the main chain, the amino group or Compared with the case where the hydroxyl group is present in the side chain, the progress of the crosslinking reaction can be more effectively suppressed between the molecules of the elastomer (A), and the thickening can be further suppressed. Therefore, the styrenic thermoplastic elastomer (A) preferably has an amino group or a hydroxyl group only at the end of the main chain of the elastomer (A). When the increase in viscosity of the adhesive composition is small, high adhesive strength can be exhibited regardless of the elapsed time after the preparation of the adhesive composition. From this viewpoint, the elastomer (A) preferably has a functional group responsible for crosslinking only at the end of the main chain, particularly at one end of the main chain.

The adhesive composition of the present invention contains 0.003 to 0.04 mmol / g of a styrene thermoplastic elastomer (A) having an active hydrogen derived from an amino group or a hydroxyl group within predetermined conditions. In addition, a styrenic thermoplastic elastomer that does not have a functional group derived from an amino group or a hydroxyl group may be included as long as the physical properties are not impaired. The blending amount of such a styrenic thermoplastic elastomer having no functional group is within a range not departing from the gist of the present invention. For example, it is 50 parts by weight or less, more preferably 30 parts by weight or less, based on 100 parts by weight of the styrenic thermoplastic elastomer (A). When more than 50 parts by weight of a styrene thermoplastic elastomer having no functional group is blended with 100 parts by weight of the styrene thermoplastic elastomer (A), the styrene thermoplastic elastomer (A) occupies the entire adhesive. , The proportion of the tackifier (B), and the polyisocyanate (C) described later is relatively reduced, and as a result, the cross-linked structure formed by the reaction with the polyisocyanate (C) described later becomes sparse and sufficient. Adhesion and electrolyte resistance may not be obtained.

Next, the tackifier (B) used in the present invention will be described. In the present invention, the tackifier (B) is used for imparting high adhesive strength between the metal foil and the heat-fusible film. As the tackifier (B) used in the present invention, known ones can be used. Polyterpene resins, rosin resins, aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins and water Examples include petroleum resin. These may be used alone or in any combination of two or more.

Specific examples of the polyterpene-based resin include α-pinene polymers, β-pinene polymers, and copolymers thereof with phenol or bisphenol A. Examples of commercially available products include YS made by Yasuhara Chemical Co., Ltd. Resin PX, YS resin A, YS polyster T, etc. are mentioned.

Examples of the rosin resin include natural rosin, polymerized rosin, and ester derivatives thereof. Commercially available products include, for example, Pencel A, Superester A, Pine Crystal KR-85, KR- manufactured by Arakawa Chemical Industries, Ltd. 612, KR-614, KE-100, KE-311, KE-359, KE-604 and the like.

The aliphatic petroleum resin is generally a resin synthesized from a C5 fraction of petroleum. Examples of commercially available products include Escorez manufactured by Tonex, Quinton manufactured by Zeon Corporation, and Wing Duck manufactured by Goodyear.

The alicyclic petroleum resin is a resin that is generally synthesized from a C9 fraction of petroleum. Examples of commercially available products include Marukaretsu manufactured by Maruzen Petrochemical Co., Ltd.

The copolymerized petroleum resin is generally a resin obtained by copolymerizing petroleum C5 fraction / C9 fraction. Examples of commercially available products include Toho High Resin from Toho Chemical Industry Co., Ltd.

As the hydrogenated petroleum resin, for example, the above-described tackifier resin is hydrogenated. Commercially available products include, for example, Alcon manufactured by Arakawa Chemical Industries, Clearon manufactured by Yashara Chemical Co., and Escolez manufactured by Tonex.

The softening point of the tackifier (B) used in the present invention is preferably 60 to 160 ° C, and more preferably 80 to 150 ° C. When the softening point of the tackifier (B) is lower than 60 ° C., there is a possibility that sufficient effect of improving the adhesive strength cannot be obtained. Moreover, when the softening point of a tackifier (B) is higher than 160 degreeC, there exists a possibility that the cohesive force of an adhesive agent may be impaired and the adhesive strength may fall.

The tackifier (B) used in the present invention may have a functional group having active hydrogen such as a carboxyl group or a hydroxyl group. Depending on the type of heat-fusible film used for the lamination, a higher adhesive strength may be obtained immediately after the lamination by using a tackifier having a carboxyl group.

The acid value of the tackifier (B) used in the present invention is preferably 0 to 150 mgKOH / g, more preferably 0 to 100 mgKOH / g. As described above, it may be preferable to use a tackifier resin (B) having an acid value. On the other hand, if the acid value is too large, it will be difficult to dissolve in toluene or the like used for the adhesive, or the compatibility with other components constituting the adhesive, such as the styrene-based thermoplastic elastomer (A), may be deteriorated. To do. Accordingly, the acid value of the tackifier (B) is preferably 0 to 150 mgKOH / g.

The hydroxyl value of the tackifier (B) used in the present invention is preferably 0 to 50 mgKOH / g. This is because even if the time after the preparation of the adhesive composition elapses, a high level of adhesive force can be stably expressed.

The adhesive composition of the present invention comprises 20 to 90% by weight of the elastomer (A) in the total of 100% by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B). It is important to contain 10 to 80% by weight of B), preferably 30 to 80% by weight of the elastomer (A) and 20 to 70% by weight of the tackifier (B).

When the content of the styrene-based thermoplastic elastomer (A) is less than 20% by weight, the adhesive composition may not have sufficient cohesive strength to obtain sufficient adhesive strength. Moreover, when there is more content of styrene-type thermoplastic elastomer (A) than 90 weight%, there exists a possibility that solution viscosity may become high too much and coating property may deteriorate.

On the other hand, when the content of the tackifier (B) is less than 10% by weight, there is a possibility that the effect of improving the adhesive strength by adding the tackifier (B) may not be obtained. Moreover, when there is more content of tackifier (B) than 80 weight%, there exists a possibility that the cohesive force of an adhesive bond layer may become insufficient and sufficient adhesive strength may not be obtained.

Furthermore, in the adhesive composition of the present invention, the active hydrogen derived from the functional group of the tackifier (B) is 0 to 15 mol relative to 1 mol of the active hydrogen derived from the styrenic thermoplastic elastomer (A). Is important, preferably 0 to 10 mol, and more preferably 0 to 1.5 mol.
If the active hydrogen derived from the functional group of the tackifier (B) exceeds 15 moles, compatibility with other components deteriorates and sufficient adhesive strength cannot be obtained, or polyisocyanate (C) and styrene thermoplasticity. Since the reaction rate with the elastomer (A) may be reduced, sufficient electrolyte resistance may not be obtained.

The adhesive composition of the present invention contains polyisocyanate (C) as a curable component that reacts with the styrenic thermoplastic elastomer (A) and the tackifier (B).

The polyisocyanate (C) is not limited to the following, but known diisocyanates and compounds derived therefrom can be preferably used.
For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, bis (4-isocyanatocyclohexyl) methane, or water Diisocyanates such as diphenylmethane diisocyanate and compounds derived therefrom, that is, diisocyanurate, trimethylolpropane adduct, biuret type, prepolymer having an isocyanate residue (low polymer obtained from diisocyanate and polyol), Examples thereof include uretdione bodies having an isocyanate residue, allophanate bodies, and complexes thereof. In may be used, may also be used in an arbitrary combination of two or more thereof.

As the polyisocyanate (C), those having no urethane bond in the structure are preferable because of excellent electrolyte resistance. When a styrenic thermoplastic elastomer (A) having a hydroxyl group is used, the urethane bond formed by reaction with the polyisocyanate (C) has better electrolyte resistance than the urethane bond in the polyisocyanate (C) structure. ing. Possible reasons for this include steric hindrance and hydrophobicity due to the elastomer (A).

The number of isocyanate groups of the polyisocyanate (C) used in the present invention is preferably 2 to 7 on average per molecule, more preferably 2 to 3.5. When the number of isocyanate groups in one molecule of polyisocyanate (C) is less than 2, a sufficient amount of crosslinking cannot be obtained, and the electrolyte resistance may be deteriorated. Also, if the number of isocyanate groups in one molecule of polyisocyanate (C) is more than 7, the possibility that a plurality of elastomers (A) react with one molecule of polyisocyanate (C) increases. There is a possibility that the coating property is deteriorated due to remarkable thickening.

The functional group amount of the isocyanate group of the polyisocyanate (C) is preferably in the range of 1.5 to 6 mmol / g, more preferably 2.0 to 5.5 mmol / g. When the functional group amount of the isocyanate group of the polyisocyanate (D) is less than 1.5 mmol / g, a sufficient cross-linked structure cannot be formed, and the electrolyte resistance may be deteriorated. Moreover, when there are more functional group amounts of the isocyanate group of polyisocyanate (C) than 6 mmol / g, there exists a possibility that compatibility with the component of an adhesive composition and a solvent may deteriorate.

The adhesive composition of the present invention comprises polyisocyanate (A) based on a total of 1 mole of active hydrogen derived from the functional group of the styrenic thermoplastic elastomer (A) and active hydrogen derived from the functional group of the tackifier (B). C) is contained in the range of 3 to 150 mol of isocyanate groups, preferably in the range of 5 to 70 mol, more preferably in the range of 10 to 50 mol.
If the isocyanate group is less than 3 mol, the amount of isocyanate group is small relative to the total of active hydrogen derived from the functional group of the styrene-based thermoplastic elastomer (A) and active hydrogen derived from the functional group of the tackifier (B). For this reason, after preparing the adhesive composition, the styrene-based thermoplastic elastomer (A) may be intermolecularly cross-linked through the polyisocyanate (C) to increase the molecular weight. When the molecular weight is increased, the viscosity of the adhesive composition is remarkably increased, and the coating property is deteriorated. Moreover, as a result of the decrease in wettability during coating due to the increase in viscosity, the adhesive strength is decreased.
On the other hand, if the amount of the isocyanate group is moderately large relative to the active hydrogen derived from the styrene-based thermoplastic elastomer (A) and the tackifier (B), the styrene-based thermoplastic elastomer ( Since the increase in the molecular weight due to the intermolecular crosslinking in A) is suppressed, the viscosity is hardly increased. That is, the elastomer (A) or tackifier (B) having an isocyanate group in which the functional groups in the styrene-based thermoplastic elastomer (A) or the tackifier (B) are sealed with an adequately large number of isocyanate groups. Is generated. And when the isocyanate group in the adhesive composition reacts with the isocyanate group during lamination and during the aging process, or the functional group of the elastomer (A) or the tackifier (B) remains, It reacts with the remaining functional groups to form a sufficient crosslinked structure. As a result, when the blending amount of isocyanate groups is reasonably large, a laminate having excellent adhesive strength and electrolyte resistance can be obtained.
However, when the amount of the isocyanate group is excessively large, specifically more than 150 moles, the proportion of the excess isocyanate group remaining unreacted even after aging increases. As a result, the adhesive layer There is a possibility that the adhesive strength is lowered due to the deterioration of elasticity or the electrolyte resistance is deteriorated.

In the adhesive composition of the present invention, a known additive may be blended in addition to the styrene-based thermoplastic elastomer (A) and the tackifier (B). Various additives can be blended together with the polyisocyanate (C), or can be blended prior to blending the polyisocyanate (C).

The adhesive composition of the present invention comprises a styrenic thermoplastic elastomer structure and at least one of a polyester resin part and a polyurethane resin part in order to improve adhesion to a metal substrate and to express a greater adhesive force. It is preferable to further use the elastomer composite resin (D). The elastomer composite polyester resin, elastomer composite polyurethane resin, and elastomer composite polyester polyurethane resin are collectively referred to as “elastomer composite resin (D)”.
The polyester resin portion and the polyurethane resin component in the elastomer composite resin (D) contribute to improving the adhesion to the metal substrate. Since the elastomer composite resin (D) has a styrene-based thermoplastic elastomer structure, it contributes to improved compatibility with the styrene-based elastomer (A) and the tackifier (B).
The elastomer composite resin (D) only needs to have a styrene-based thermoplastic elastomer structure portion, a polyester resin portion, and a polyurethane resin portion, and the balance of each portion in the elastomer composite resin (D) is not particularly limited. .

There are various methods for producing the elastomer composite resin (D). For example, (1) a method in which a functional group of a polyester resin or the like and a functional group of a styrene thermoplastic elastomer are directly reacted, and (2) a polyester resin or the like and a styrene thermoplastic elastomer are bonded via a crosslinking agent. The method of letting it be mentioned. The functional group contributing to the reaction and the kind of the reaction are not particularly limited, and it is sufficient that the polyester resin portion and the styrene-based thermoplastic elastomer structure are provided as a result of the reaction.

Although not limited to the following methods, examples of the method (1) include the following methods. For example, (1-1) a method of obtaining an elastomer composite resin (D) in which a polyester resin having a carboxyl group and a styrene-based thermoplastic elastomer having a hydroxyl group are esterified and bonded via an ester bond; (1-2) A method of obtaining an elastomer composite resin (D) obtained by reacting a polyurethane resin having an isocyanate group with a styrene thermoplastic elastomer having a hydroxyl group and bonding them via a urethane bond; ) A method of obtaining an elastomer composite resin (D) in which a polyester resin having a hydroxyl group and a styrene-based thermoplastic elastomer having a carboxyl group are esterified and bonded via an ester bond.

Although not limited to the following methods, examples of the method (2) include the following methods. For example, (2-1) a polyester resin having a hydroxyl group, a styrenic thermoplastic elastomer having a hydroxyl group, and a crosslinking agent having a plurality of functional groups capable of reacting with a hydroxyl group are reacted, and both portions are interposed via the crosslinking agent. A method for obtaining a bonded elastomer composite resin (D); (2-2) a polyester resin having a hydroxyl group, a styrenic thermoplastic elastomer having an amino group, and a functional group capable of reacting with both the hydroxyl group and the amino group A method of obtaining an elastomer composite resin (D) in which both parts are bonded via a crosslinking agent; (2-3) a polyester resin having a carboxyl group and the like, and a carboxyl group A styrenic thermoplastic elastomer is reacted with a cross-linking agent having a plurality of functional groups capable of reacting with a carboxyl group, and both are reacted via the cross-linking agent. Minute bound, a method for obtaining an elastomer composite resin (D), and the like.

In the case of the above methods (2-1), (2-2), and (2-3), the polyester resin, the styrene thermoplastic elastomer, and the crosslinking agent can be reacted at a stretch. A polyester resin or the like and a crosslinking agent are reacted under an excess of the crosslinking agent to obtain a polyester resin or the like having a functional group derived from the crosslinking agent, and then the obtained polyester resin or the like having a functional group derived from the crosslinking agent is styrene. It can also be obtained by reacting with a thermoplastic elastomer. Alternatively, the styrenic thermoplastic elastomer and the crosslinking agent are reacted under an excess of the crosslinking agent to obtain a styrene thermoplastic elastomer having a functional group derived from the crosslinking agent, and then having the functional group derived from the obtained crosslinking agent. It can also be obtained by reacting a styrenic thermoplastic elastomer with a polyester resin or the like.

Examples of the styrenic thermoplastic elastomer having a hydroxyl group and the styrenic thermoplastic elastomer having an amino group used in the above (1-1), (1-2), (2-1), and (2-2) are as described above. The same thing as the styrene-type thermoplastic elastomer (A) can be illustrated.

The styrene-based thermoplastic elastomer having a carboxyl group used in the above (1-3) and (2-3) is an appropriate amount in the polymerization of the monomer for producing the above-mentioned styrene-based thermoplastic elastomer. A method of copolymerizing an ethylenically unsaturated carboxylic acid such as maleic acid or maleic anhydride or an anhydride of the unsaturated carboxylic acid, or synthesizing a styrenic thermoplastic elastomer, and then an appropriate amount of maleic acid or maleic anhydride It can be obtained by a grafting reaction method using an ethylenically unsaturated carboxylic acid or an anhydride of the unsaturated carboxylic acid and a peroxide.
Commercially available styrene thermoplastic elastomers having a carboxyl group include Toughtech M1911, M1913 manufactured by Asahi Kasei Chemicals Co., Ltd., and Kraton FG1901 manufactured by Kraton Polymer Japan Co., Ltd. (above, carboxyl group-containing hydrogenated styrene-butadiene-styrene copolymer) Etc.

The polyester resin having a carboxyl group used in the above (1-1) and (2-3) can be obtained, for example, as follows.
In general, a polyester resin is obtained by reacting a dibasic acid component with a diol component. If the dibasic acid component is used in excess of the diol component, a polyester resin having a carboxyl group can be obtained. Alternatively, a polyester resin having a hydroxyl group can be obtained, and the carboxyl group can be introduced by reacting the hydroxyl group with an acid anhydride such as maleic anhydride.
In general, the urethane resin is obtained by reacting a diol component and a diisocyanate component. By using a diol component having a carboxyl group as the diol component, a urethane resin having a carboxyl group can be obtained. Alternatively, a urethane resin having a hydroxyl group can be obtained, and the carboxyl group can be introduced by reacting the hydroxyl group with an acid anhydride such as maleic anhydride.

Examples of the diol component used for obtaining a polyester resin or a urethane resin include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 3-methyl-1 In addition to low-molecular polyols such as 1,5-pentanediol, trimethylolpropane, and glycerin, polymer polyols such as polycarbonate polyol and polyether polyol are also included. These may be used alone or in any combination of two or more. Trifunctional or higher functional polyol components can also be used. In the case of obtaining a urethane resin, a polyester polyol can also be used. Examples of the diol component having a carboxyl group include dimethylolpropionic acid and dimethylolbutanoic acid.

The dibasic acid component used when obtaining a polyester resin includes isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride And dibasic acids such as hexahydrophthalic anhydride, maleic anhydride, itaconic anhydride, and ester compounds of these dibasic acids. The dibasic acid and its ester compound are collectively referred to as “dibasic acid component”.

As the diisocyanate component used when obtaining the urethane resin, well-known diisocyanates and compounds derived therefrom, such as those exemplified as polyisocyanate (C), can be preferably used. An isocyanate component having more than two functional groups can be used as long as it does not gel. A branched polyurethane resin can be obtained by using a component having a functional number higher than bifunctionality. A diamine component as a chain extender can also be used.

The polyester resin having a hydroxyl group used in the above (1-3), (2-1), and (2-2) can be obtained, for example, as follows. If the diol component is used in excess as compared with the dibasic acid component, a polyester resin having a hydroxyl group can be obtained. If the diol component is used in excess as compared with the diisocyanate component, a urethane resin having a hydroxyl group can be obtained. Each component used when obtaining a polyester resin or a urethane resin is as described above.

The polyurethane resin having an isocyanate group used in the above (1-2) can be obtained, for example, as follows. If the diisocyanate component is used in excess as compared with the diol component, a urethane resin having an isocyanate group can be obtained.

The cross-linking agent that functions for both components having a hydroxyl group used in (2-1) has a polyfunctional isocyanate component such as a diisocyanate compound, a dibasic acid component, and a plurality of acid anhydrides in the molecule. Compounds and the like.

As the polyfunctional isocyanate component, well-known diisocyanates and compounds derived from these as exemplified as polyisocyanate (C) can be preferably used. By using the polyfunctional isocyanate component as a crosslinking agent, an elastomer composite resin (D) in which a polyester resin having a hydroxyl group and a styrene thermoplastic elastomer having a hydroxyl group are bonded via a urethane bond can be obtained.

As the dibasic acid component, a well-known one exemplified as a constituent material of the polyester resin can be used. By using the dibasic acid component as a crosslinking agent, an elastomer composite resin (D) in which a polyester resin having a hydroxyl group and a styrene thermoplastic elastomer having a hydroxyl group are bonded via an ester bond can be obtained.

As the compound having a plurality of acid anhydrides in the molecule, a compound such as pyromellitic anhydride can be used. Elastomer composite resin (D) in which a polyester resin having a hydroxyl group and a styrene-based thermoplastic elastomer having a hydroxyl group are bonded via an ester bond by using a compound having a plurality of acid anhydrides in the molecule as a crosslinking agent Can be obtained.

Examples of the crosslinking agent that functions for the component having a hydroxyl group and the component having an amino group used in the above (2-2) include polyfunctional isocyanate components such as a diisocyanate compound as in the case of (2-1). It is done.

Examples of the crosslinking agent that functions for both components having a carboxyl group used in the above (2-3) include a polyfunctional epoxy component, a polyfunctional aziridine component, a polyfunctional oxazoline component, a polyfunctional isocyanate component, and a polyfunctional carbodiimide component. Is mentioned. Moreover, when a carboxyl group is in the state of an acid anhydride, a polyfunctional polyol component, a polyfunctional polyamine component, etc. can also be used as a crosslinking agent.

When using the elastomer composite resin (D) in the present invention, it is preferable to use 2 to 60 parts by weight with respect to a total of 100 parts by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B). More preferably, it is 2 to 50 parts by weight.
When an elastomer composite resin (D) exists in the said range, while improving the adhesiveness to a metal base material, electrolyte resistance can be maintained. If the amount of the elastomer composite resin (D) is too large, the ratio of the polyester resin portion and the polyurethane resin portion in the adhesive is relatively increased, which may deteriorate the electrolyte resistance.

Examples of commercially available products used as the elastomer composite resin (D) in the present invention include Kuraray's Septon S5265, S5865 (chemically bonded substance of polyurethane and hydrogenated styrene elastomer).

As a known additive used in the present invention, a known reaction accelerator can be used when it is desired to accelerate the curing reaction. In this case, it is preferable to blend prior to blending the polyisocyanate (C).
Examples of the reaction accelerator used in the present invention include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; 1,8-diaza-bicyclo (5,4,0) undecene And tertiary amines such as -7,1,5-diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7. These may be used alone or in any combination of two or more.

The compounding amount of the reaction accelerator used in the present invention is in the range of 0.001 to 0.2 parts by weight with respect to 100 parts by weight in total of the styrenic thermoplastic elastomer (A) and the tackifier (B). The amount is preferably 0.005 to 0.1 parts by weight. If the addition amount of the reaction accelerator is less than 0.001 part by weight, there is a possibility that a sufficient acceleration effect of the curing reaction may not be obtained. The pot life may be spoiled.

A laminate using the adhesive composition of the present invention can be obtained, for example, as follows. One side of a metal foil (or heat-fusible film) is coated with the adhesive composition of the present invention, and the solvent is stripped (dried) to form an uncured adhesive layer. After applying a heat-sealable film (or metal foil) on the surface of the uncured adhesive layer under pressure at ℃, leave it still at 40-80 ℃ for about 3-7 days. It is cured (also referred to as aging), and the metal foil and the heat-fusible film are bonded together. For coating of the adhesive composition, a general coating machine such as a comma coater can be used. The thickness (amount) of the cured adhesive layer at the time of dry curing is preferably about 1 to 30 g / m ² .

When an exterior sheet is provided as an outer layer member, it is laminated on a metal foil in advance using an adhesive composition (which may be the same as or different from the adhesive composition of the present invention). Alternatively, after obtaining a laminate of a metal foil and a heat-fusible film using the adhesive composition of the present invention, an exterior sheet can be laminated on the metal foil.

In the nonaqueous electrolyte secondary battery, the electrolyte starts to penetrate from the heat-fusible film toward the metal foil. For example, the electrolyte of a lithium battery includes a lithium salt such as lithium hexafluorophosphate and a solvent such as propylene carbonate, ethylene carbonate, diethyl carbonate, and dimethyl carbonate. When the electrolyte is put into the secondary battery container, the solvent passes through the heat-fusible film, reaches the adhesive layer, and causes a decrease in the adhesive strength between the heat-fusible film and the metal foil. Further, when moisture enters the electrolyte from the outside of the secondary battery container, a lithium salt such as lithium hexafluorophosphate reacts with water to generate hydrofluoric acid. The generated hydrofluoric acid reaches the heat-fusible film and the adhesive layer, degrades the adhesive layer, and remarkably lowers the adhesive force between the heat-fusible film and the metal foil. Therefore, the adhesive layer for bonding the heat-fusible film and the metal foil is required to have resistance to the electrolyte.

The adhesive composition described in Patent Document 2 has insufficient electrolyte resistance, and the viscosity after mixing is quick because the reaction between the elastomer (A) and the coupling agent (B) is fast. There was a problem that the usable time (pot life) of the adhesive composition was short. Further, the adhesive described in Patent Document 3 has a problem that the viscosity of the adhesive and the adhesive force after sticking are not stable. This is because some of the acid in the elastomer is in the state of an anhydride derived from maleic acid, and after blending each component, the acid anhydride in the elastomer reacts with the polyolefin polyol as time passes. This is because the anhydride derived from maleic acid opens by reacting with water mixed in the adhesive or reacting with the humidity (moisture) of the environment where the adhesive is placed. In addition, since the reaction between the inherently high-viscosity elastomer and the polyfunctional isocyanate that is the curing agent is fast, the viscosity of the adhesive increases in a short period of time during the coating of the adhesive, and there is a problem in terms of coating stability. there were. Moreover, in patent document 4, there existed a subject in adhesive strength.

On the other hand, according to the laminate for a non-aqueous electrolyte secondary battery container of the present invention, a component having a specific structure is contained in a specific ratio as the adhesive composition, and the amount of active hydrogen having the specific structure described above is specified as described above. Furthermore, since the isocyanate group has the above-mentioned specific ratio, the pot life can be lengthened, and even when immersed in an electrolyte, the adhesive strength can be maintained at a high level. That is, the laminated body for nonaqueous electrolyte secondary battery containers which is excellent in chemical resistance can be provided. As a result, problems such as electrolyte leakage can be prevented, and a highly reliable laminate for a nonaqueous electrolyte secondary battery container can be provided.

In addition, a battery container formed using a laminate for a nonaqueous electrolyte secondary battery using the adhesive composition of the present invention can contribute to safety and life extension of the nonaqueous electrolyte secondary battery. Therefore, a highly reliable nonaqueous electrolyte secondary battery can be provided. Therefore, it leads to the spread of non-aqueous electrolyte secondary batteries, and contributes to environmental conservation from the viewpoint of highly efficient use of energy as a new energy material.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, a following example does not restrict | limit the right range of this invention at all. In addition, each evaluation in an Example followed the following method. In the examples, parts are parts by weight,% is% by weight, and the acid value is mgKOH / g.

<Measurement of number average molecular weight>
The number average molecular weight of the styrene-based thermoplastic elastomer (A) was measured using GPC (Gel Permeation Chromatography) “HPC-8020” manufactured by Tosoh Corporation, tetrahydrofuran as the solvent, and standard polystyrene conversion.

<Measurement of active hydrogen content of elastomer (A)>
The average number of functional groups of one molecule of the synthesized styrene-based thermoplastic elastomer (A) was determined by HPLC and NMR measurement, and the amount of active hydrogen of the elastomer (A) was determined by the above mathematical formula (1). Specifically, the average number of functional groups of the elastomer (A) was divided by the number average molecular weight determined from GPC measurement to determine the amount of active hydrogen per gram (mmol / g).

<Elastomer A-1> (SEEPS having a hydroxyl group at the end of the main chain)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 182 g of sufficiently dehydrated styrene and 59.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 935 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to carry out a polymerization reaction for 1 hour, and then 182 g of styrene was added to carry out the polymerization reaction for 1 hour. Thereafter, 10 g of ethylene oxide was added, and finally methanol was added to stop the reaction, thereby synthesizing a styrene- (butadiene / isoprene) -styrene type block copolymer having a hydroxyl group at one end. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained is distilled off under reduced pressure, and the resulting block copolymer solid is designated as elastomer A-1.
The elastomer A-1 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-1 determined from GPC is 61,000, and from HPLC, the number of hydroxyl groups on the main chain terminal per molecule of the elastomer A-1. The number was 0.95. From the above measured values, the amount of active hydrogen in Elastomer A-1 can be calculated as 0.016 mmol / g.

<Elastomer A-2> (SEBS having a hydroxyl group at the end of the main chain)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 182 g of sufficiently dehydrated styrene and 59.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 935 g of butadiene was added to conduct a polymerization reaction for 1 hour, and then 182 g of styrene was added to conduct a polymerization reaction for 1 hour. Thereafter, 10 g of ethylene oxide was added, and finally methanol was added to stop the reaction, thereby synthesizing a styrene-butadiene-styrene type block copolymer having a hydroxyl group at one end. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained is distilled off under reduced pressure, and the resulting block copolymer solid is designated as elastomer A-2.
The elastomer A-2 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-2 obtained from GPC is 61,000, and the number of main chain terminal hydroxyl groups per molecule of the elastomer A-2 is determined by HPLC. The number was 0.94. From the above measured values, the amount of active hydrogen in Elastomer A-2 can be calculated as 0.015 mmol / g.

<Elastomer A-3> (SEEPS having a hydroxyl group at the end of the main chain)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 182 g of fully dehydrated styrene and a cyclohexane solution (18 wt%) of 3- (t-butyldimethylsiloxy) -2,2-dimethyl-1-propyllithium (59 wt%) 3 g was added and the polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 935 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to carry out a polymerization reaction for 1 hour, and then 182 g of styrene was added to carry out the polymerization reaction for 1 hour. Thereafter, 10 g of ethylene oxide is added, and finally methanol is added to stop the reaction. A styrene- (butadiene / isoprene) -styrene block copolymer having a hydroxyl group at one end and a protected hydroxyl group at the other end is added. A polymer was synthesized. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. Further, the obtained hydrogenated product was subjected to deprotection reaction at 60 ° C. for 7 hours using hydrochloric acid in tetrahydrofuran to obtain SEEPS having hydroxyl groups at both ends. The solvent contained in the block copolymer thus obtained is distilled off under reduced pressure, and the resulting block copolymer solid is designated as elastomer A-3.
The elastomer A-3 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-3 determined from GPC is 62,000, and from HPLC, the number of main chain terminal hydroxyl groups per molecule of the elastomer A-3. The number was 1.89. From the above measured values, the amount of active hydrogen in elastomer A-3 can be calculated as 0.03 mmol / g.

<Elastomer A-4> (SEEPS having an amino group at the end of the main chain)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 182 g of sufficiently dehydrated styrene and 59.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 935 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to carry out a polymerization reaction for 1 hour, and then 182 g of styrene was added to carry out the polymerization reaction for 1 hour. Thereafter, 12 g of N-methylpyrrolidone was added, and finally methanol was added to stop the reaction, thereby synthesizing a styrene- (butadiene / isoprene) -styrene type block copolymer having an amino group at one end. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained is distilled off under reduced pressure, and the resulting block copolymer solid is designated as elastomer A-4.
The elastomer A-4 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-4 determined from GPC is 61,000, and from HPLC, the main chain terminal amino groups per molecule of the elastomer A-3. The number of was 0.95. From the above measured values, the amount of active hydrogen in Elastomer A-4 can be calculated as 0.016 mmol / g.

<Elastomer A-5> (SEEPS without functional groups)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 182 g of sufficiently dehydrated styrene and 59.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 935 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to carry out a polymerization reaction for 1 hour, and then 182 g of styrene was added to carry out the polymerization reaction for 1 hour. Thereafter, methanol was added to stop the reaction, and a styrene- (butadiene / isoprene) -styrene type block copolymer having no functional group was synthesized. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained is distilled off under reduced pressure, and the resulting block copolymer solid is designated as elastomer A-4.
The elastomer A-5 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-5 determined from GPC is 62,000, and the amount of active hydrogen of the elastomer A-5 can be calculated as 0 mmol / g.

<Elastomer A-6> (SEEPS having a hydroxyl group in the side chain)
In a pressure vessel equipped with a stirrer, 500 g of elastomer A-5 and 200 g of toluene were added and heated and dissolved at 100 ° C. with stirring in a nitrogen atmosphere, and then 1.5 g of di-t-butyl peroxide and 2-methacrylic acid 2- 3 g of hydroxyethyl was added dropwise and reacted for 3 hours. The solvent contained in the block copolymer thus obtained was distilled off under reduced pressure, and the resulting block copolymer solid was designated as elastomer A-6.
The elastomer A-6 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-6 obtained from GPC is 62,000, and from HPLC, the number of hydroxyl groups introduced into the side chain per molecule of the elastomer A-6. The number was 1.62. From the above measured values, the amount of active hydrogen of A-6 in the elastomer can be calculated as 0.026 mmol / g.

<Elastomer A-7> (SEEPS having a hydroxyl group in the side chain)
In a pressure vessel equipped with a stirrer, 500 g of elastomer A-5 and 200 g of toluene were added and heated and dissolved at 100 ° C. with stirring in a nitrogen atmosphere, and then 1.5 g of di-t-butyl peroxide and 2-methacrylic acid 2- Hydroxyethyl (5 g) was added dropwise and reacted for 3 hours. The solvent contained in the block copolymer thus obtained was distilled off under reduced pressure, and the resulting block copolymer was designated as elastomer A-7.
The elastomer A-7 has a styrene content of 28% by weight, the number average molecular weight of the elastomer A-7 determined from GPC is 62,500, and from HPLC, the number of hydroxyl groups introduced into the side chain per molecule of the elastomer A-7. The number was 3.19. From the above measured values, the amount of active hydrogen of A-7 in the elastomer can be calculated as 0.051 mmol / g.

<Elastomer A-8> (SEEPS having a hydroxyl group at the end of the main chain)
In a pressure-resistant vessel equipped with a stirrer, 5.06 kg of cyclohexane, 117 g of sufficiently dehydrated styrene and 120.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 1065 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to conduct a polymerization reaction for 1 hour, and then 117 g of styrene was added to carry out the polymerization reaction for 1 hour. Thereafter, 10 g of ethylene oxide was added, and finally methanol was added to stop the reaction, thereby synthesizing a styrene- (butadiene / isoprene) -styrene type block copolymer having a hydroxyl group at one end. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained was distilled off under reduced pressure, and the resulting block copolymer solid was designated as elastomer A-8.
The elastomer A-8 has a styrene content of 18% by weight, the number average molecular weight of the elastomer A-1 determined from GPC is 35,000, and from HPLC, the number of main chain terminal hydroxyl groups per molecule of the elastomer A-8. The number was 0.98. From the above measured values, the amount of active hydrogen in Elastomer A-8 can be calculated as 0.028 mmol / g.

<Elastomer A-9> (SEEPS having a hydroxyl group at the end of the main chain)
In a pressure vessel equipped with a stirrer, 5.06 kg of cyclohexane, 260 g of sufficiently dehydrated styrene and 120.3 g of a cyclohexane solution of sec-butyllithium (11 wt%) were added, and a polymerization reaction was carried out at 40 ° C. for 1 hour. Next, 779 g of a mixture of isoprene and butadiene (molar ratio 1: 1) was added to perform a polymerization reaction for 1 hour, and then 260 g of styrene was added to perform a polymerization reaction for 1 hour. Thereafter, 10 g of ethylene oxide was added, and finally methanol was added to stop the reaction, thereby synthesizing a styrene- (butadiene / isoprene) -styrene type block copolymer having a hydroxyl group at one end. The block copolymer thus obtained was subjected to a hydrogenation reaction at 90 ° C. for 7 hours under a hydrogen atmosphere using a Ziegler catalyst to obtain a hydrogenated product. The solvent contained in the block copolymer thus obtained was distilled off under reduced pressure, and the resulting block copolymer solid was designated as elastomer A-9.
The elastomer A-9 has a styrene content of 40% by weight, the number average molecular weight of the elastomer A-9 determined from GPC is 110,000, and from HPLC, the number of hydroxyl groups on the main chain terminal per molecule of the elastomer A-9. The number was 0.97. From the above measured values, the amount of active hydrogen in Elastomer A-9 can be calculated as 0.009 mmol / g.

<Resin D-1> (Elastomer composite resin having SEEPS structure, number average molecular weight 62,800)
In a pressure vessel equipped with a stirrer, 500 g of elastomer A-1 having a hydroxyl group at the end of the main chain and 200 g of toluene were added and heated and dissolved at 80 ° C. with stirring in a nitrogen atmosphere, and then 1.78 g of isophorone diisocyanate was added dropwise. By making it react for 3 hours, SEEPS of the isocyanate group terminal was obtained.
8.8 g of a polyester resin having a number average molecular weight of 2000 and a terminal hydroxyl group composed of isophthalic acid and 2-methyl-1,3-propanediol was added to the isocyanate group-terminated SEEPS, and the mixture was further reacted for 3 hours. Thereafter, the solvent is distilled off under reduced pressure, and the resulting elastomer composite resin (solid matter) having a SEEPS structure is referred to as Resin D-1.

<Resin D-2> (Elastomer composite resin having a SEEPS structure, number average molecular weight 68,000)
Add 10.0 g of diphenylmethane diisocyanate and 50 g of toluene to a pressure-resistant vessel equipped with a stirrer, and add 109.0 g of polyester polyol having a molecular weight of 3000 consisting of adipic acid and 1,4-butanediol while stirring in a nitrogen atmosphere. Was reacted at 80 ° C. for 3 hours to obtain an isocyanate group-terminated polyurethane resin.
500 g of elastomer A-1 having a hydroxyl group at the main chain end was added to the isocyanate group-terminated polyurethane resin, and the mixture was further reacted for 3 hours. Thereafter, the solvent is distilled off under reduced pressure, and the resulting elastomer composite resin (solid material) having a SEEPS structure is referred to as Resin D-2.

<Resin D-3> (Elastomer composite resin having a SEEPS structure, number average molecular weight 74,000)
200 g of toluene in a pressure-resistant vessel equipped with a stirrer, composed of polycarbonate polyol having a molecular weight of 2000 having a composition ratio of 1,6-hexanediol: 3-methyl-1,5-pentanediol = 1: 1 and isophorone diisocyanate 50 g of a polyurethane resin having a molecular weight of 12,000 and an isocyanate group at the end and 572.9 g of an elastomer A-4 having an amino group at the end of the main chain are added and dissolved by heating at 80 ° C. with stirring in a nitrogen atmosphere. Reacted for hours. Thereafter, the solvent is distilled off under reduced pressure, and the resulting elastomer composite resin (solid matter) having a SEEPS structure is referred to as Resin D-3.

<Resin D-4> (Elastomer composite resin having a SEEPS structure, number average molecular weight 42,000)
In a pressure-resistant vessel equipped with a stirrer, 10.0 g of diphenylmethane diisocyanate and 50 g of toluene were added, and 84.2 g of polytetramethylene glycol having a molecular weight of 3000 was added while stirring in a nitrogen atmosphere, followed by reaction at 80 ° C. for 3 hours. A base end polyurethane resin was obtained.
900 g of elastomer A-8 having a hydroxyl group at the end of the main chain was added to the isocyanate group-terminated polyurethane resin, and the mixture was further reacted for 3 hours. Thereafter, the solvent is distilled off under reduced pressure, and the resulting elastomer composite resin (solid material) having a SEEPS structure is referred to as Resin D-4.

<Resin D-5> (Elastomer composite resin having SEEPS structure, number average molecular weight 126,000)
In a pressure vessel equipped with a stirrer, 50 g of toluene, 10.0 g of diphenylmethane diisocyanate, 76.5 g of polyester polyol having a molecular weight of 2000 composed of adipic acid and 1,4-butanediol, elastomer A- having a hydroxyl group at the end of the main chain 400 g of 9 was added while stirring under a nitrogen atmosphere, and the mixture was reacted at 80 ° C. for 3 hours.
Thereafter, the solvent is distilled off under reduced pressure, and the obtained elastomer composite resin (solid matter) having a SEEPS structure is referred to as Resin D-5.

<Main agent 1>
Elastomer A-1 (SEEPS having a hydroxyl group at one end of the main chain, styrene content 28% by weight, functional group content 0.016 mmol / g): 85 parts as a styrenic thermoplastic elastomer (A), tackifier (B) As a rosin ester pine crystal KE-100 (softening point 100 ° C., acid value 6 mg KOH / g): 15 parts, put into a container and diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 The mixture was stirred at 3 ° C. for 3 hours to obtain a solution of the main agent 1 (solid content 30%).

<Main agent 2>
Elastomer A-1: 23 parts as a styrenic thermoplastic elastomer (A), and Arakawa Chemical Industries, Ltd. fully hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value) as a tackifier (B): 77 parts was put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 2 (solid content 30%).

<Main agent 3>
Elastomer A-2 (SEBS having a hydroxyl group at one end of the main chain, styrene content 28 wt%, functional group content 0.015 mmol / g): 40 parts as a styrenic thermoplastic elastomer (A), tackifier (B) As a hydrogenated dicyclopentadiene resin Escorez 5320 (softening point 125 ° C., no acid value): 60 parts in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 at 3 ° C. The mixture was heated and stirred for a time to obtain a solution of the main agent 3 (solid content 30%).

<Main agent 4>
60 parts of elastomer A-2 as styrene-based thermoplastic elastomer (A) and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as tackifier (B): 40 parts was put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 4 (solid content 30%).

<Main agent 5>
Elastomer A-3 (SEEPS having hydroxyl groups at both ends of the main chain, styrene content 28% by weight, functional group amount 0.03 mmol / g): 60 parts as a styrenic thermoplastic elastomer (A), tackifier (B) Arakawa Chemical Industries, Ltd. fully hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value): 25 parts and Arakawa Chemical Industries rosin ester Pine Crystal KR-50M (softening point 150 ° C., acid value 95 mg KOH) / G): 15 parts were put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 5 (solid content 30%).

<Main agent 6>
As a styrenic thermoplastic elastomer (A), elastomer A-4 (SEEPS having an amino group at one end of a main chain, styrene content 28 wt%, functional group content 0.016 mmol / g): 55 parts, a tackifier (B ) Hydrogenated terpene resin Clearon P-85 (softening point 85 ° C., no acid value): 45 parts in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and 3 at 50 ° C. The mixture was heated and stirred for a time to obtain a solution of the main agent 6 (solid content 30%).

<Main agent 7>
55 parts of elastomer A-4 as styrenic thermoplastic elastomer (A) and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as tackifier (B): 30 parts and rosin ester Pine Crystal KE-100 (softening point 100 ° C., acid value 6 mg / KOH) manufactured by Arakawa Chemical Industries, Ltd .: 15 parts are put in a container and diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 to obtain 50 parts. The mixture was heated and stirred at 0 ° C. for 3 hours to obtain a solution of the main agent 7 (solid content 30%).

<Main agent 8>
Elastomer A-6 as styrenic thermoplastic elastomer (A) (SEEPS having a hydroxyl group in the side chain, styrene content 28 wt%, functional group content 0.026 mmol / g): 70 parts, Tonex as tackifier (B) Company hydrogenated dicyclopentadiene resin Escorez 5320 (softening point 125 ° C., no acid value): 30 parts is placed in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 and heated at 50 ° C. for 3 hours. The mixture was stirred to obtain a solution of the main agent 8 (solid content 30%).

<Main agent 9>
55 parts of an elastomer A-1 as a styrenic thermoplastic elastomer (A), and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as a tackifier (B): 45 parts was put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 9 (solid content 30%).

<Main agent 10>
55 parts of elastomer A-3 as styrenic thermoplastic elastomer (A) and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as tackifier (B): 45 parts was put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 10 (solid content 30%).

<Main agent 11>
50 parts of elastomer A-1 as styrene-based thermoplastic elastomer (A), and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as tackifier (B): 40 parts and 10 parts of resin D-1 (elastomer composite resin having a SEEPS structure, number average molecular weight 62,800): 10 parts as an elastomer composite resin (D) having a styrene-based thermoplastic elastomer structure, The mixture was diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 11 (solid content 30%). The resin D-1 is about 11.1 parts by weight relative to 100 parts by weight of the total of the elastomer A-1 and the tackifier (B).

<Main agent 12> to <Main agent 14>
Main agents 12, 13, and 14 were obtained in the same manner as in the main agent 11, except that the amount of the resin D-1 was about 22.5 parts, about 48.4 parts, and about 60 parts, respectively. The resin D-1 is about 25 parts by weight, 53.8 parts by weight, and about 66.7 parts by weight with respect to 100 parts by weight of the total of the elastomer A-1 and the tackifier (B).

<Main agent 15> to <Main agent 18>
Main agents 15, 16, 17, and 18 were obtained in the same manner as in the case of Main agent 11, except that resin D-1 was Resin D-2, Resin D-3, Resin D-4, and Resin D-5, respectively. .

<Main agent 19> to <Main agent 20>
Main agent 19 and main agent 20 were obtained in the same manner as in main agent 11, except that resin A-1 was changed to resin A-8 and resin A-9, respectively.

<Main agent 101 for comparative example>
Elastomer A-4: 5 parts as a styrenic thermoplastic elastomer (A), and fully hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as a tackifier (B): 95 parts were put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 101 (solid content 30%).

<Main Example 102 for Comparative Example>
100 parts of elastomer A-4 as a styrenic thermoplastic elastomer (A) is put in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 102 (solid 30%).

<Main agent 103 for comparative example>
55 parts of elastomer A-4 as styrenic thermoplastic elastomer (A) and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as tackifier (B): 45 parts was put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 103 (solid content 30%).

<Main Example 104 for Comparative Example>
A-5 (SEEPS without functional group, styrene content 28% by weight, functional group amount 0 mmol / g): 55 parts as styrenic thermoplastic elastomer (A), and Arakawa Chemical Industries, Ltd. as tackifier (B) Rosin ester Pine Crystal KE-100 (softening point 100 ° C., acid value 6 mg KOH / g): 45 parts is put into a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours. As a result, a solution of the main agent 104 (solid content 30%) was obtained.

<Main agent 105 for comparative example>
A-7 (SEEPS having a hydroxyl group in the side chain, styrene content 28% by weight, functional group amount 0.051 mmol / g) as styrene thermoplastic elastomer (A): 55 parts, and Arakawa Chemical as tackifier (B) Completely hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value): 45 parts in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and stirred at 50 ° C. for 3 hours The mixture was heated and stirred to obtain a solution of main agent 105 (solid content 30%).

<Main Example 106 for Comparative Example>
A-4: 55 parts as a styrenic thermoplastic elastomer (A), and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries, Ltd. as a tackifier (B): 30 Rosin ester Pine Crystal KE-85 (softening point 85 ° C., acid value 170 mg / KOH): 15 parts in a container and diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 The mixture was heated and stirred at 0 ° C. for 3 hours to obtain a solution of the main agent 106 (solid content 30%).

<Main Example 107 for Comparative Example>
A-4: 55 parts as a styrenic thermoplastic elastomer (A), and fully hydrogenated C9 resin Arcon P-140 (softening point 140 ° C., no acid value) manufactured by Arakawa Chemical Industries as a tackifier (B): 45 Was diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2, and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 107 (solid content 30%).

<Main agent 108 for comparative example>
Tuftec M1913 (SEBS having a carboxyl group in the side chain, manufactured by Asahi Kasei Kogyo Co., Ltd., styrene content 30% by weight, carboxyl group amount 0.19 mmol / g as a styrene-based thermoplastic elastomer (A). 4 parts): 55 parts and, as a tackifier (B), Arakawa Chemical Industries, Ltd. fully hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value): 45 parts in a container The mixture was diluted with a mixed solvent of / methyl ethyl ketone = 8/2 and heated and stirred at 50 ° C. for 3 hours to obtain a solution of the main agent 108 (solid content 30%).

<Main agent 109 for comparative example>
Epaul (polyolefin polyol, manufactured by Idemitsu Kosan Co., Ltd., styrene content 0% by weight, active hydrogen content 0.91 mmol / g): 55 parts as styrene thermoplastic elastomer (A), and Arakawa Chemical Industries, Ltd. as tackifier (B) Completely hydrogenated C9 resin Alcon P-140 (softening point 140 ° C., no acid value): 45 parts is placed in a container, diluted with a mixed solvent of toluene / methyl ethyl ketone = 8/2 and stirred at 50 ° C. for 3 hours. As a result, a solution of the main agent 109 (solid content 30%) was obtained.

<Curing agent 1>
Curing agent 1 is obtained by diluting a trimer of isophorone diisocyanate (functional amount of isocyanate group: 4.08 mmol / g, average number of isocyanate groups per molecule: 3) with toluene to give a solid content of 50%.

<Curing agent 2>
A curing agent 2 is obtained by diluting a trimer of hexamethylene diisocyanate (functional amount of isocyanate group 5.19 mmol / g, average number of isocyanate groups 3 per molecule 3) with toluene to give a solid content of 50%. .

<Curing agent 3>
Curing a tolylene diisocyanate adduct with trimethylolpropane (functional amount of isocyanate group 4.13 mmol / g, average number of isocyanate groups 3 per molecule) diluted with toluene to give a solution with a solid content of 50% Agent 3 is used.

<Examples 1 to 21>, <Comparative Examples 1 to 9>
The amount of the isocyanate group of the polyisocyanate (C) is expressed with respect to 1 mol in total of the active hydrogen derived from the functional group of the styrenic thermoplastic elastomer (A) and the active hydrogen derived from the functional group of the tackifier (B). Various main agent solutions and curing agent solutions are blended so as to have the values shown in 1A, Table 1B, Table 2A, and Table 2B, and diluted with toluene to adjust the solid content to 20%.
Immediately after preparing each adhesive solution, it was applied to one side of an aluminum foil having a thickness of 50 μm and dried at 100 ° C. for 1 minute (adhesive amount when dried: 2 to 3 g / m ² ). Next, an unstretched polypropylene film (hereinafter referred to as CPP) having a thickness of 30 μm was superposed on the adhesive layer and passed between two rolls set at 60 ° C. to obtain a laminate. Thereafter, the obtained laminate was cured (aging) at 40 ° C. for 5 days to sufficiently cure the adhesive layer. The aluminum foil / CPP laminate film thus obtained is hereinafter referred to as “Al / CPP laminate film”.
Moreover, after preparing each adhesive agent solution and leaving still at 25 degreeC environment for 24 hours, the Al / CPP laminated film was produced similarly.
About each Al / CPP laminated film, the peeling strength by the method mentioned later was calculated | required. Further, each Al / CPP laminated film was immersed in an electrolyte solution at 85 ° C. for 14 days, and the peel strength was determined in the same manner. The results are shown in Table 2A and Table 2B.

Abbreviations shown in Table 1A and Table 1B are as follows.
<Styrenic thermoplastic elastomer (A)>
Tuftec M1913: SEBS (styrene-ethylene-butylene-styrene) manufactured by Asahi Kasei Kogyo Co., Ltd., styrene content: 30% by weight, number average molecular weight 60,000, carboxyl group content: 0.19 (mmol / g) per molecule Contains 11.4 carboxyl groups. Epol: Hydrogenated polyolefin polyol manufactured by Idemitsu Kosan Co., Ltd., styrene content: 0% by weight, number average molecular weight: 2,500, active hydrogen: 0.91 (mmol / g)

<Tackifier (B)>
Pine crystal KE-100: rosin ester manufactured by Arakawa Chemical Industries, softening point: 100 ° C., acid value: 6 (mgKOH / g)
Pine crystal KR-50M: Rosin ester manufactured by Arakawa Chemical Industries, softening point: 150 ° C., acid value: 95 (mgKOH / g)
Pine crystal KE-85: Rosin ester manufactured by Arakawa Chemical Industries, softening point: 85 ° C., acid value: 170 (mgKOH / g)
Alcon P-140: Completely hydrogenated C9 resin manufactured by Arakawa Chemical Industries, softening point: 140 ° C., acid value: 0 (mgKOH / g)
Clearon P-85: Hydrogenated terpene resin manufactured by Yasuhara Chemical Co., Ltd., softening point: 85 ° C., acid value: 0 (mgKOH / g)
Escoretz 5320: Hydrogenated dicyclopentadiene resin manufactured by Tonex, softening point: 125 ° C., acid value: 0 (mgKOH / g)

<Polyisocyanate (C)>
IPDI trimer: trimer of isophorone diisocyanate HDI trimer: trimer of hexamethylene diisocyanate TDI-TMP: adduct of tolylene diisocyanate with trimethylolpropane

<Elastomer composite resin (D)>
Resin D-1: Modified polyester resin having a SEEPS (styrene-ethylene-ethylene-propylene-styrene) structure, number average molecular weight: 62,800
Resin D-2: Modified polyurethane resin having a SEEPS (styrene-ethylene-ethylene-propylene-styrene) structure, number average molecular weight: 68,000
Resin D-3: Modified polyurethane resin having a SEEPS (styrene-ethylene-ethylene-propylene-styrene) structure, number average molecular weight: 74,000
Resin D-4: Modified polyurethane resin having a SEEPS (styrene-ethylene-ethylene-propylene-styrene) structure, number average molecular weight: 42,000
Resin D-5: Modified polyurethane resin having a SEEPS (styrene-ethylene-ethylene-propylene-styrene) structure, number average molecular weight: 126,000

<Performance tests and evaluation criteria>
[25 ° C peeling test]
Each Al / CPP laminated film was allowed to stand for 6 hours in an environment of 25 ° C. and 65% humidity, then cut to a size of 200 mm × 15 mm, and a tensile tester was applied in accordance with the test method of ASTM-D1876-61. The T-type peel test was performed at a load rate of 300 mm / min in an environment of 25 ° C. and 65% humidity. The peel strength (N / 15 mm width) between the aluminum foil / CPP is shown as an average value of five test pieces.
◎ Excellent in practical use: 7N / 15mm or more ○ Practical range: 5-7N / 15mm
△ Practical lower limit: 2-5N / 15mm
× Not practical: Less than 2N / 15mm

[Electrolytic resistance test]
Each Al / CPP laminated film was allowed to stand in an environment of 25 ° C. and 65% humidity for 1 day, and then cut into a size of 200 mm × 15 mm, and the test piece was subjected to electrolyte [lithium hexafluorophosphate in ethylene carbonate. / Diethyl carbonate / dimethyl carbonate = 1/1/1 (volume ratio) and a 1 mol / L lithium hexafluorophosphate solution] was immersed at 85 ° C. for 14 days. Thereafter, the test piece was taken out, washed with running water for about 10 minutes, wiped off with a paper wiper, then allowed to stand in an environment of 25 ° C. and humidity 65% for 1 day and dried.
The test piece after drying was subjected to a T-type peel test at a load rate of 300 mm / min using a tensile tester in an environment of 25 ° C. and a humidity of 65% according to the test method of ASTM-D1876-61. The peel strength (N / 15 mm width) between the aluminum foil / CPP is shown as an average value of five test pieces. The evaluation criteria are as follows.
◎ Excellent in practical use: 90% or higher peel strength retention before and after electrolyte resistance test ○ Practical range: 60% to 90% peel strength retention before and after electrolyte resistance test
△ Practical lower limit: 20% to 60% retention of peel strength before and after electrolyte resistance test
× Not practical: The peel strength retention before and after the electrolyte resistance test is less than 20%, or delaminate

As shown in Table 2B, Comparative Example 1 is an example in which the blending amount of the styrenic thermoplastic elastomer (A) is less than 20% by weight of the blending amount at which the effect of the present invention appears. As a result of the evaluation, there was obtained a result that the elasticity of the adhesive was not expressed and the adhesive strength was significantly reduced.

Comparative Example 2 is an example not containing a tackifier (B). As a result of the evaluation, the cohesive force of the adhesive was insufficient and the adhesive strength was significantly reduced.

Comparative Example 3 is an example in which the amount of polyisocyanate (C) is less than the specific range of the present invention. As a result of the evaluation, the cross-linking reaction between the elastomer (A) and the polyisocyanate (C) proceeds while the adhesive is blended and allowed to stand for 24 hours, the viscosity increases, and the wettability to the aluminum foil or CPP film. Was lower than that immediately after preparation, and the adhesive strength was significantly reduced.

Comparative Example 4 is an example in which the styrene-based thermoplastic elastomer (A) does not contain a functional group. As a result of the evaluation, the compatibility with the other components of the adhesive composition is deteriorated, the viscoelasticity of the adhesive layer is deteriorated, and a crosslinked structure with the polyisocyanate (C) is not formed, and the adhesive strength is remarkably increased. The result of getting worse was obtained.

Comparative Example 5 is an example in which an elastomer having an active hydrogen amount derived from the functional group of the styrene-based thermoplastic elastomer (A) is larger than 0.04. As a result of the evaluation, it showed high adhesive strength and electrolyte resistance immediately after blending, but the cross-linking reaction between the elastomer (A) and the polyisocyanate (C) progressed while standing for 24 hours, resulting in significant thickening. As a result, the adhesive could not be applied and evaluated.

In Comparative Example 6, the amount of active hydrogen of the styrenic thermoplastic elastomer (A) is higher than 15.0 mol with respect to 1 mol of active hydrogen derived from the functional group of the tackifier (B) contained in the adhesive. This is an example of blending. As a result of the evaluation, a cross-linked structure due to the reaction between the polyisocyanate (C) and the styrenic thermoplastic elastomer (A) is insufficient, and the adhesive strength and the electrolyte resistance are remarkably deteriorated.

In Comparative Example 7, the polyisocyanate (C) was compared with the sum of the amount of active hydrogen derived from the functional group of the styrenic thermoplastic elastomer (A) and the amount of active hydrogen derived from the functional group of the tackifier (B). It is an example mix | blended in excess from the specified range of invention. As a result of the evaluation, it was obtained that the excess polyisocyanate (C) deteriorates the viscoelasticity of the adhesive, and the adhesive strength and the electrolyte resistance are remarkably deteriorated.

Comparative Example 8 is an example in which the styrenic thermoplastic elastomer (A) has a carboxyl group in the molecular chain and contains 11 carboxyls per molecule of the elastomer. As a result of the evaluation, it showed high adhesive strength and electrolyte resistance immediately after blending, but the cross-linking reaction between the elastomer (A) and the polyisocyanate (C) progressed while standing for 24 hours, resulting in significant thickening. As in Comparative Example 5, the result was that the adhesive could not be applied and evaluated.

Comparative Example 9 is an example in which a polyolefin polyol is used instead of a styrene elastomer as the styrene thermoplastic elastomer (A). As a result of the evaluation, it was found that sufficient adhesive strength could not be obtained and the electrolyte resistance was remarkably deteriorated.

On the other hand, as shown in Table 2A, Examples 1 to 21 satisfying all the conditions (i) to (iv) described above have initial adhesive strength, adhesive strength after aging, and adhesive strength after a moist heat resistance test. The result was that all were well-balanced.

Among them, Examples 7, 9, and 12 to 21 showed high performance in all tests. In the adhesives of Examples 7, 9, and 12 to 21, the content of the styrenic thermoplastic elastomer (A) is in a preferable range of 30 to 80% by weight, and the content of the tackifier (B) is also 20 to 20%. It is considered that it was in the preferred range of 70%, had a good balance of viscoelasticity of the adhesive, and exhibited better adhesive strength and electrolyte resistance.

The adhesives of Examples 7, 9, and 12 to 21 are examples in which polyisocyanate (C) is blended at a suitable blending ratio in terms of the amount of isocyanate groups. As a result of the evaluation, it was found that superior adhesive strength and electrolyte resistance were obtained as compared with Examples 3, 4, and 11. This is considered because sufficient crosslinking density and viscoelasticity are obtained.

The adhesives of Examples 7, 9, and 12 to 21 were derived from the functional group of the styrenic thermoplastic elastomer (A) with respect to 1 mol of active hydrogen derived from the functional group of the tackifier (B). This is an example in which the amount of active hydrogen is in a preferred range. As a result of the evaluation, a sufficient cross-linked structure was obtained by the reaction of the styrenic thermoplastic elastomer (A) and the polyisocyanate (C) as compared with Example 5 outside the preferred range, and the adhesive strength and electrolyte resistance were good. I got a result.
The adhesives of Examples 7, 9, and 12 to 21 are examples in which the polyisocyanate (C) has an isocyanurate structure in the structure. As a result of the evaluation, it was found that the high resistance to the electrolytic solution was excellent as compared with Example 6 in which the polyisocyanate (C) did not contain an isocyanurate structure in the structure.

In addition, Example 8 using a styrenic thermoplastic elastomer (A) having a functional group introduced into the side chain, or a styrene thermoplastic elastomer (A) having a functional group introduced at both ends of the main chain is used. In Example 10, after the adhesive solution was prepared, the cross-linking reaction between the styrenic thermoplastic elastomer (A) and the polyisocyanate (C) progressed while standing for 24 hours. It was considered that the peel strength was slightly decreased because the wettability of the film was lower than that immediately after the preparation. In addition, it is thought that the adhesive strength is improved after the electrolyte resistance test afterwards because the wettability to the base material is improved by the heat during the electrolyte resistance test.

On the other hand, in the adhesives of Examples 7, 9, and 12 to 21, since a functional group is introduced at the main chain terminal of the styrene elastomer (A), the crosslinking reaction with the polyisocyanate (C) does not proceed excessively. Therefore, even if it uses the adhesive immediately after preparation or the adhesive 24 hours after preparation, it shows the peel strength stable at a high level.

Since the elastomer composite resin (D) was blended in the adhesives of Examples 12 to 21 as compared with Examples 7 and 9, adhesion with the aluminum foil was improved and high adhesive strength was exhibited. In particular, the adhesives of Examples 12 to 14 and 16 to 21 are blended in a suitable range of 2 to 60 parts by weight of the elastomer composite resin (D) as compared with Example 15, so that higher adhesive strength and resistance can be obtained. It showed electrolyte properties.

<Example 22> [vinyl chloride vinyl acetate copolymer layer / CPP laminated film]
Apply a carboxyl group-containing vinyl chloride vinyl acetate copolymer resin (SOLBIN M manufactured by Nissin Chemical Industry Co., Ltd.) methyl ethyl ketone solution adjusted to a solid content of 30% on the surface of 50 μm thick aluminum foil, heat and dry, Vinyl vinyl acetate copolymer layer (thickness: about 5 μm) / Al foil] was obtained. This is designated as a base material E-1.
Except that the adhesive solution of Example 19 was coated on the vinyl chloride / vinyl acetate copolymer layer of the substrate E-1, CPP was overlaid on the adhesive layer in the same manner as in Example 19, and so on. Then, [vinyl chloride vinyl acetate copolymer layer / CPP laminated film] was obtained, and the adhesion performance was evaluated by the method described later.

<Example 23> [Acid-modified polypropylene layer / CPP laminated film]
After heat-extrusion of an acid-modified polypropylene grafted with an unsaturated carboxylic acid (Admer QE800 manufactured by Mitsui Chemicals, Inc.) with a T-die extruder to a thickness of 15 μm on the surface of an aluminum foil having a thickness of 50 μm, the polypropylene The surface of the layer was subjected to corona discharge treatment to obtain [acid-modified polypropylene layer / Al foil]. This is designated as a base material E-2. Except that the adhesive solution of Example 19 was coated on the acid-modified polypropylene layer of the substrate E-2, CPP was overlaid on the adhesive layer in the same manner as in Example 19, and thereafter [Acid Modified polypropylene layer / CPP laminated film] was obtained and evaluated in the same manner.

<Example 24> [Nylon / CPP laminated film]
A 25-μm thick Unitika Co., Ltd. biaxially stretched nylon film Emblem ON (single-sided corona treatment) was used as the base material E-3, and the adhesive solution of Example 19 was applied to the untreated surface of the base material E-3. In the same manner as in Example 19, CPP was superimposed on the adhesive layer, and thereafter, [Nylon / CPP laminated film] was obtained and evaluated in the same manner.

<Example 25> [Polyethylene terephthalate / CPP laminated film]
This was carried out except that a polyethylene terephthalate film S10 (single-sided corona treatment) manufactured by Toray Industries, Inc. with a thickness of 25 μm was used as the base E-4, and the adhesive solution of Example 19 was applied to the untreated side of the base E-4. In the same manner as in Example 19, CPP was superimposed on the adhesive layer, and thereafter, [Polyethylene terephthalate / CPP laminated film] was obtained and evaluated in the same manner.

<Example 26>, <Comparative example 10> [Polyethylene terephthalate / CPP laminated film]
In Example 26, the adhesive solution used in Example 12 was used in place of the adhesive solution used in Example 19, and Comparative Example 10 was used except that the adhesive solution used in Comparative Example 4 was used. [Polyethylene terephthalate / CPP laminated film] was obtained in the same manner as in Example 24 and evaluated in the same manner.

<Performance tests and evaluation criteria>
[Initial peel strength]
Each CPP laminated film obtained in Examples 22 to 26 and Comparative Example 10 was allowed to stand for 6 hours in an environment of 25 ° C. and 65% humidity, and then cut into a size of 200 mm × 15 mm. Then, according to the test method of ASTM-D1876-61, a T-type peel test was performed at a load speed of 300 mm / min using a tensile tester in an environment of 25 ° C. and a humidity of 65%. The peel strength (N / 15 mm width) of the adhesive layer is shown as an average value of five test pieces.
◎ Excellent in practical use: 7N / 15mm or more ○ Practical range: 5-7N / 15mm
△ Practical lower limit: 2-5N / 15mm
× Not practical: Less than 2N / 15mm

[Peel strength after alcohol immersion]
Each CPP laminated film obtained in Examples 22 to 26 and Comparative Example 10 was allowed to stand for 1 day in an environment of 25 ° C. and a humidity of 65%, and then cut into a size of 200 mm × 15 mm. For 14 days at 65 ° C. Thereafter, the test piece was taken out, washed with running water for about 10 minutes, wiped off with a paper wiper, then allowed to stand in an environment of 25 ° C. and a humidity of 65% for 1 day and dried.
The peel strength of the adhesive layer of the test piece after drying was measured in the same manner as in the initial peel strength measurement. The evaluation criteria are as follows.
◎ Excellent in practical use: 90% or higher peel strength retention before and after alcohol resistance test ○ Practical range: 60% to 90% peel strength retention before and after alcohol resistance test
△ Practical lower limit: 20% to 60% peel strength retention before and after alcohol resistance test
× Not practical: Retention strength retention less than 20% before or after alcohol resistance test, or delaminate

In Comparative Example 10, as shown in Table 3, since the styrenic thermoplastic elastomer (A) does not contain a functional group, the compatibility with the other components of the adhesive composition deteriorates, and the viscoelasticity of the adhesive layer In addition, since the crosslinked structure with the polyisocyanate (C) was not formed, the adhesive strength was significantly deteriorated. Even in the alcohol resistance test, the adhesive strength swelled due to insufficient rack strength, resulting in a significant decrease in adhesive strength.

On the other hand, as shown in Table 3, Examples 22 to 26, which are examples satisfying all the conditions (i) to (iv) described above, have initial adhesive strength, alcohol, etc., even in configurations other than the Al / CPP laminated film. All the adhesive strengths after immersion were satisfied in a well-balanced manner. In particular, the adhesive of Example 26 showed higher adhesion strength with improved adhesion to the substrate interface as compared with the adhesives of Examples 22-25. This is considered to be an effect by blending the elastomer composite resin (D).

This application claims priority based on Japanese Patent Application No. 2011-039145 filed on February 25, 2011, the entire disclosure of which is incorporated herein.

According to the adhesive composition of the present invention, an adhesive composition excellent in pot life can be provided. Moreover, the adhesive composition which can maintain adhesive strength at a high level even if immersed in an electrolyte can be provided. Therefore, it can be particularly suitably used for adhesion to a film inside the metal foil of the laminate for a nonaqueous electrolyte secondary battery container. Of course, it can be suitably applied to various adhesive applications including joining of the outer layer of the non-aqueous electrolyte secondary battery and the metal foil. In particular, since the laminate bonded with the adhesive composition of the present invention is excellent in chemical resistance of the adhesive layer, it can be used, for example, for forming a laminate of a packaging material for pharmaceuticals and foodstuffs. Moreover, it can utilize suitably for joining with not only metal foil but general metal materials as adhesion object. The heat-fusible film can also be used in a wide range of resin films including polyolefin resins. Furthermore, the adhesive composition of the present invention is also suitable for joining resin films such as heat-fusible films including polyolefin resins.

Claims

Metal foil,
A heat-fusible film;
Comprising at least an adhesive layer for joining the metal foil and the heat-fusible film;
The adhesive layer contains a styrenic thermoplastic elastomer (A), a tackifier (B), and a polyisocyanate (C),
In a total of 100% by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B), 20 to 90% by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B) 10 to 80% by weight,
The styrenic thermoplastic elastomer (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or a hydroxyl group,
The active hydrogen derived from the functional group of the tackifier (B) is 0 to 15 mol relative to 1 mol of the active hydrogen derived from the styrenic thermoplastic elastomer (A),
The polyisocyanate (C) has 3 to 3 isocyanate groups for a total of 1 mol of the active hydrogen derived from the styrenic thermoplastic elastomer (A) and the active hydrogen derived from the tackifier (B). A laminate for a non-aqueous electrolyte secondary battery container, which is formed from an adhesive composition that is contained within a range of 150 moles.
The laminate for a nonaqueous electrolyte secondary battery container according to claim 1, wherein the amino group or the hydroxyl group is located at least one of the ends of the main chain of the styrene-based thermoplastic elastomer (A).
The laminate for a nonaqueous electrolyte secondary battery container according to claim 1 or 2, wherein the amino group or the hydroxyl group is located only at one end of the main chain of the styrenic thermoplastic elastomer (A). .
The adhesive composition further includes an elastomer composite resin (D),
The elastomer composite resin (D) according to any one of claims 1 to 3, wherein the elastomer composite resin (D) includes at least one of a polyester resin portion and a polyurethane resin portion, and a styrenic thermoplastic elastomer structure. The laminated body for nonaqueous electrolyte secondary battery containers as described.
The laminate for a nonaqueous electrolyte secondary battery container according to any one of claims 1 to 4, wherein the polyisocyanate (C) has an isocyanurate structure.
The elastomer composite resin (D) is contained in an amount of 2 to 60 parts by weight with respect to a total of 100 parts by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B). 4. A laminate for a non-aqueous electrolyte secondary battery container according to 4.
A secondary battery body;
A battery container containing the secondary battery body;
An electrolyte sealed in the battery container,
The non-aqueous electrolyte secondary battery, wherein the battery container comprises the laminate for a non-aqueous electrolyte secondary battery container according to any one of claims 1 to 6.
A styrenic thermoplastic elastomer (A);
A tackifier (B);
Polyisocyanate (C), and
In a total of 100% by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B), 20 to 90% by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B) 10 to 80% by weight,
The styrenic thermoplastic elastomer (A) has 0.003 to 0.04 mmol / g of active hydrogen derived from an amino group or a hydroxyl group,
The active hydrogen derived from the functional group of the tackifier (B) is 0 to 15 mol relative to 1 mol of active hydrogen derived from the styrenic thermoplastic elastomer (A),
The polyisocyanate (C) has 3 to 3 isocyanate groups for a total of 1 mol of the active hydrogen derived from the styrenic thermoplastic elastomer (A) and the active hydrogen derived from the tackifier (B). An adhesive composition contained in a range of 150 moles.
The adhesive composition according to claim 8, which is used for forming a laminate for a nonaqueous electrolyte secondary battery container.
The adhesive composition according to claim 8 or 9, wherein the amino group or the hydroxyl group is located at at least one end of the main chain of the styrenic thermoplastic elastomer (A).
The adhesive composition according to any one of claims 8 to 10, wherein the amino group or the hydroxyl group is located only at one end of the main chain of the styrenic thermoplastic elastomer (A).
The adhesive composition according to any one of claims 8 to 11, wherein the polyisocyanate (C) has an isocyanurate structure.
Furthermore, an elastomer composite resin (D) is included,
The elastomer composite resin (D) includes at least one of a polyester resin portion and a polyurethane resin portion, and a styrenic thermoplastic elastomer structure, according to any one of claims 8 to 12. Adhesive composition.
The elastomer composite resin (D) is contained in an amount of 2 to 60 parts by weight with respect to a total of 100 parts by weight of the styrenic thermoplastic elastomer (A) and the tackifier (B). Item 14. The adhesive composition according to Item 13.
On one side of the metal foil or heat-fusible film,
The adhesive composition according to any one of claims 8 to 14 is applied and dried to form an uncured adhesive layer,
Overlaying the heat-fusible film or the metal foil on the surface of the uncured adhesive layer so that a laminated structure of the metal foil, the adhesive layer, and the heat-fusible film is formed,
The manufacturing method of the laminated body for nonaqueous electrolyte secondary battery containers which hardens the said uncured adhesive bond layer, and bonds the said metal foil and the said heat-fusible film.