JP2016132716A - Composition, coating agent, adhesive, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating agent having excellent electrolyte resistance; an adhesive made of the same; a laminate having an adhesive layer formed from the same; and a composition contained in the coating agent.SOLUTION: A composition contains a thermoplastic resin (A) made of at least one selected from the group consisting of a modified olefin polymer, an olefin-α,β-unsaturated carboxylic acid copolymer, an ion crosslinked body of the olefin-α,β-unsaturated carboxylic acid copolymer, a stylene-base thermoplastic elastomer, and a modified body of the stylene-base thermoplastic elastomer; and an additive (B) having a structure derived from phosphoric acid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition, a coating agent, an adhesive and a laminate, and more particularly to a composition, a coating comprising the composition, an adhesive comprising the composition, and a laminate comprising an adhesive layer formed therefrom.

  2. Description of the Related Art Conventionally, a laminate including an aluminum foil layer (base material), a thermoplastic resin film layer (inner layer) bonded to the inner surface thereof, and an adhesive layer interposed therebetween is used as a lithium ion secondary battery. It is known to be used as a packaging material (packaging material for battery case).

  As an adhesive layer provided in the above-described laminate, for example, a polymer of an α-olefin having 2 to 20 carbon atoms containing a structural unit derived from an α-olefin having 4 to 20 carbon atoms reacts with an isocyanate group. There has been proposed an adhesive layer formed from an adhesive containing a modified olefin polymer and a polyisocyanate obtained by modification with a monomer having a functional group (for example, patent document) 1).

International Publication No. 2014 / 123183A1 Brochure

  However, in the case where the laminate including the adhesive layer of Patent Document 1 is used for a battery case packaging material or the like, further improvement in resistance to electrolytic solution is desired.

  An object of the present invention is to provide a coating agent having good electrolytic solution resistance, a laminate comprising an adhesive comprising the same and an adhesive layer formed therefrom, and a composition contained in the coating agent. .

  The composition of the present invention includes a modified olefin polymer, an olefin-α, β unsaturated carboxylic acid copolymer, an ionic crosslinked product of the olefin-α, β unsaturated carboxylic acid copolymer, a styrenic thermoplastic elastomer, and And a thermoplastic resin (A) composed of at least one selected from the group consisting of modified styrenic thermoplastic elastomers and an additive (B) having a phosphoric acid-derived structure.

In the composition of the present invention, the thermoplastic resin (A) has a heat of fusion of 0 J / g or more and 50 J / g or less measured according to JIS K7122, and a weight average molecular weight measured by GPC method is 1. It is preferably composed of a modified olefin polymer which is not less than × 10 ^{4 and not} more than 1,000 × 10 ⁴ and is modified with a monomer having a polar group.

  In the composition of the present invention, it is preferable that the phosphoric acid having a structure derived from phosphoric acid is a phosphite ester or a phosphate ester.

  In the composition of the present invention, it is preferable that the phosphoric acid is a phosphite.

  In the composition of the present invention, the additive (B) is preferably a titanate coupling agent.

  Moreover, in the composition of this invention, it is suitable that polyisocyanate (C) is further included.

  Moreover, in the composition of this invention, it is suitable that the mixture ratio of the said polyisocyanate (C) is 1-30 mass parts with respect to 100 mass parts of the said thermoplastic resins (A).

  The composition of the present invention preferably further includes a hydrocarbon-based synthetic oil (D) having a kinematic viscosity at 40 ° C. of 30 to 500,000 cSt.

  Moreover, in the composition of this invention, it is suitable that the mixture ratio of the said hydrocarbon type synthetic oil (D) is 6-50 mass parts with respect to 100 mass parts of said thermoplastic resins (A).

  Moreover, the coating agent of this invention is characterized by including an above-described composition.

  The adhesive of the present invention is characterized by comprising the above-mentioned coating agent.

  In addition, the laminate of the present invention includes a base material and an adhesive layer that is laminated on one side surface or one side surface and the other side surface of the base material and is formed from the above-described adhesive. .

  Moreover, in the laminated body of this invention, it is suitable that the said base material is aluminum foil.

  In the laminate of the present invention, it is preferable that the base material is an untreated aluminum foil that has not been subjected to any surface treatment of anodizing treatment, immersion type chemical conversion treatment, and coating type chemical conversion treatment.

  Moreover, in the laminated body of this invention, it is suitable to further provide the to-be-adhered body adhere | attached through the said adhesive bond layer on the one side surface of the said base material, or one side surface and the other side surface.

  The laminate of the present invention comprising the adhesive of the present invention comprising the coating agent of the present invention containing the composition of the present invention and the adhesive layer formed therefrom can have good electrolytic solution resistance.

FIG. 1 shows a cross-sectional view of a battery case packaging material according to an embodiment of the laminate of the present invention. FIG. 2 shows a cross-sectional view of a battery including a battery case packaging material according to an embodiment of the laminate of the present invention.

  The composition of the present invention contains a thermoplastic resin (A) and an additive (B).

  Hereinafter, each of a thermoplastic resin (A) and an additive (B) is explained in full detail.

1. Thermoplastic resin (A)
The thermoplastic resin (A) includes a modified olefin polymer, an olefin-α, β unsaturated carboxylic acid copolymer, an ionic crosslinked product of an olefin-α, β unsaturated carboxylic acid copolymer, a styrenic thermoplastic elastomer, and And at least one selected from the group consisting of modified styrenic thermoplastic elastomers.

  The thermoplastic resin (A) is preferably composed of a modified olefin polymer.

  When the thermoplastic resin (A) is a modified olefin polymer, a coating agent (described later) that is more excellent in resistance to electrolytic solution can be obtained.

  The modified olefin polymer is obtained by modifying the polymer (a) of an α-olefin having 2 to 20 carbon atoms with a monomer having a polar group.

  Specifically, the polymer (a) of a C2-C20 alpha-olefin contains the structural unit derived from a C4-C20 alpha-olefin.

  That is, the polymer (a) of an α-olefin having 2 to 20 carbon atoms is a homopolymer composed of an α-olefin having 4 to 20 carbon atoms, or an α-olefin having 4 to 20 carbon atoms and 2 carbon atoms. It is a copolymer with ~ 3 α-olefin.

  Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Examples include linear or branched α-olefins such as 1-hexadecene, 1-octadecene and 1-eicocene.

  The α-olefin having 4 to 20 carbon atoms is preferably a linear olefin having 4 to 10 carbon atoms, more preferably a linear olefin having 4 to 6 carbon atoms, still more preferably 1-butene. Can be mentioned. If 1-butene is used as the α-olefin having 4 to 20 carbon atoms, both good solvent solubility and excellent resin strength can be achieved. These can be used alone or in combination of two or more.

  Examples of the α-olefin having 2 to 3 carbon atoms include ethylene and propylene, and preferably propylene.

  Examples of the α-olefin having 2 to 20 carbon atoms include the above-described α-olefin having 2 to 3 carbon atoms and the above-described α-olefin having 4 to 20 carbon atoms. These can be used alone or in combination of two or more.

  Preferred examples of the α-olefin having 2 to 20 carbon atoms include ethylene, propylene, and 1-butene, and more preferred is a combination of propylene and 1-butene.

  Specifically, as the α-olefin having 2 to 20 carbon atoms, for example, one or more selected from α-olefins having 4 to 20 carbon atoms and one or more selected from α-olefins having 2 to 3 carbon atoms. For example, one or more homopolymers or copolymers selected from α-olefins having 4 to 20 carbon atoms. Preferably, a copolymer is used, more preferably, a copolymer of one or more α-olefins selected from α-olefins having 4 to 20 carbon atoms and ethylene and / or propylene is further included. Preferably, a copolymer of 1-butene and propylene is used. If it is a copolymer of 1-butene and propylene, it is possible to achieve both good solvent solubility and excellent resin strength.

  Examples of the copolymer include a random copolymer and a block copolymer. Preferably, a random copolymer is used.

  The content ratio of the structural unit derived from the α-olefin having 4 to 20 carbon atoms is, for example, 5 mol% or more with respect to 100 mol% of the structural unit derived from the α-olefin having 2 to 20 carbon atoms, 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and for example, 100 mol% or less, preferably 60 mol% or less, more preferably 50 mol% or less. More preferably, it is 40 mol% or less. If the said content rate is below the said upper limit, the outstanding resin intensity | strength can be ensured. On the other hand, if the said content rate is more than the said minimum, the outstanding solvent solubility can be ensured.

  In addition, the C2-C20 α-olefin polymer (a) includes a structural unit derived from a C2-C20 (including C4-20) α-olefin as an essential structural unit, If necessary, a structural unit derived from an unsaturated monomer other than an α-olefin (referred to as another unsaturated monomer) can also be included as an arbitrary structural unit. Examples of other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethridene-2-norbornene, and 5-vinyl-2. Non-conjugated polyenes such as -norbornene, 5-methylene-2-norbornene, and 2,5-norbonadiene.

  On the other hand, in the polymer (a) of an α-olefin having 2 to 20 carbon atoms, the structural unit excluding the structural unit derived from the α-olefin having 4 to 20 carbon atoms is preferably all having 2 to 3 carbon atoms. A structural unit derived from an α-olefin, more preferably a structural unit derived from all propylene.

  In other words, in the polymer (a) of an α-olefin having 2 to 20 carbon atoms, all the structural units excluding the structural unit derived from the α-olefin having 2 to 3 carbon atoms (preferably propylene) are all carbon atoms. It is a structural unit derived from 4 to 20 α-olefin. Preferably, the polymer is a copolymer of at least one selected from α-olefins having 4 to 20 carbon atoms and α-olefins (specifically propylene) having 2 to 3 carbon atoms, and It does not contain components derived from other unsaturated monomers described above.

  In this case, the content rate of the structural unit derived from a C2-C3 alpha-olefin (preferably propylene) is 100 mol% of the structural unit derived from a C2-C20 alpha-olefin. For example, 40 mol% or more, preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 65 mol% or more, and for example, 95 mol% or less, preferably 90 mol%. % Or less, More preferably, it is 80 mol% or less, More preferably, it is 70 mol% or less. If the said content rate is below the said upper limit, melting | fusing point (Tm) and heat of fusion ((DELTA) H) of a copolymer can be reduced. On the other hand, if the said content rate is more than the said minimum, the outstanding resin intensity | strength can be ensured.

  The α-olefin polymer (a) having 2 to 20 carbon atoms described above is a compound having 2 to 2 carbon atoms in the presence of a known solid Ti catalyst or metallocene catalyst usually used for the production of α-olefin polymers. It is obtained by polymerizing 20 α-olefins. Metallocene catalysts include, for example, metallocene compounds such as rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, organoaluminum oxy compounds such as methylaluminoxane, and triisobutylaluminum. It consists of an organoaluminum compound. More specifically, the polymer (a) is obtained, for example, by a method described in International Publication No. 2004/87775 pamphlet.

  The weight average molecular weight (Mw) of the obtained polymer (a) measured by gel permeation chromatography (GPC) and converted to standard polystyrene is, for example, 10,000 or more and 1,000,000 or less. In addition, the molecular weight distribution (dispersion degree) is 1 or more and 3 or less. The molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

  In addition, the melting point (Tm) of the polymer is, for example, less than 120 ° C., preferably less than 100 ° C.

  A polar group is a group with an uneven distribution of charge inside.

  The polar group is preferably a functional group capable of reacting with an isocyanate group, and the functional group capable of reacting with an isocyanate group is a group having active hydrogen.

  Examples of such functional groups include hydroxyl groups, amino groups, epoxy groups, carboxyl groups, and acid anhydride groups represented by the following formula (1). These polar groups (preferably the above functional groups) can be used alone or in combination, and preferably include a carboxyl group, an acid anhydride group, and more preferably an acid anhydride group.

  In the present invention, when referred to as an acid anhydride group, a part or all of the acid anhydride group may be hydrolyzed to form a dibasic acid (specifically, a dicarboxylic acid).

Particularly preferably, all of the polar groups (preferably the above functional groups) are carboxyl groups and / or acid anhydride groups, most preferably acid anhydride groups. When the polar group (preferably, the above functional group) is a carboxyl group and / or an acid anhydride group, preferably an acid anhydride (specifically, all of the polar group (preferably, the above functional group) is a carboxyl group. Groups and / or acid anhydride groups, preferably acid anhydride groups), when forming and curing an adhesive layer from the composition, preferably carboxyl groups and / or acid anhydride groups, The base of the modified olefin polymer (for example, the acid anhydride group reacts efficiently with the isocyanate group of the polyisocyanate (C) (described later) or via the additive (B) (described later). The affinity for an adhesive layer to a base material (for example, an aluminum foil) can be further improved. Moreover, electrolyte solution resistance can be improved.
: Formula (1)

  Examples of the monomer (b) having the above-described polar group (preferably the above functional group) include, for example, a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, and an epoxy group-containing ethylenically unsaturated compound. , Unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, vinyl ester compound, and derivatives thereof (excluding unsaturated carboxylic acid anhydride).

  Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( Hydroxyl group-containing (meth) acrylic acid esters such as (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2- (6-hydrohexanoyloxy) ethyl acrylate, 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acryloyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, Examples include allyloxyethanol, 2-butene 1,4-diol, and glycerin monoalcohol.

  Examples of the amino group-containing ethylenically unsaturated compound include vinyl monomers having at least one amino group or substituted amino group represented by the following formula.

-NHR _1-
In the formula, R ₁ is, for example, a hydrogen atom, such as an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, such as a cycloalkyl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms. It is. In addition, said alkyl group and cycloalkyl group may have a substituent further.

  Specifically, the amino group-containing ethylenically unsaturated compound includes, for example, aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, methacryl Alkyl ester derivatives of acrylic acid or methacrylic acid such as phenylaminomethyl acid and cyclohexylaminoethyl methacrylate, for example, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, such as acrylamide, methacrylamide, Acrylamide derivatives such as N-methylacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminopropylacrylamide, such as p-aminohexyl succinimide, 2-aminoethyl succinate Imides such as imide.

  As the epoxy group-containing ethylenically unsaturated compound, for example, a monomer having at least one unsaturated bond group and epoxy group polymerizable in one molecule is used.

Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. , Endo-cis-bicyclo [2,2,1] hept-5-ene-2, 3-dicarboxylic acid (Nadic acid ^TM ), endo-cis-bicyclo [2,2,1] hept-5-ene-2 -Monoglycidyl ester of unsaturated dicarboxylic acid such as methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ) (C1-C12 of alkyl group in the case of monoglycidyl ester), alkylglycidyl of p-styrene carboxylic acid Ester, allyl glycidyl ether, 2-methylallyl glycidyl Ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3 -Methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo [2,2,1] hept And unsaturated carboxylic acids such as 2-ene-5,6-dicarboxylic acid.

  Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic anhydride Etc.

  Derivatives include, for example, maleyl chloride, maleenylimide, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept- Derivatives of unsaturated carboxylic acids such as dimethyl 2-ene-5,6-dicarboxylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate and aminopropyl methacrylate Is mentioned.

  Examples of vinyl ester compounds include vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl persate, vinyl laurate, vinyl stearate, vinyl benzoate, and salicylic acid. Examples thereof include vinyl and vinyl cyclohexanecarboxylate.

  The monomer (b) can be used alone or in combination of two or more.

  The monomer (b) is preferably an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, more preferably an unsaturated carboxylic acid anhydride, and still more preferably maleic anhydride. Also preferably, all of the monomer (b) is an unsaturated carboxylic acid anhydride, more preferably all of the monomer (b) is maleic anhydride.

  When monomer (b) is an unsaturated carboxylic acid anhydride (specifically, maleic anhydride) (preferably, all of monomer (b) is an unsaturated carboxylic acid anhydride (specifically, ), The unsaturated carboxylic acid anhydride (more specifically, maleic anhydride) is converted into the polyisocyanate (C) when the adhesive layer is formed from the composition and cured. While reacting with (described later) or via additive (B) (described later), the affinity of the modified olefin polymer for the substrate (for example, aluminum foil) is increased, and the adhesive layer substrate ( For example, the adhesion to an aluminum foil or the like can be further improved.

  In the present invention, for example, the monomer (b) having the above polar group and the monomer (b ′) having no polar group (for example, ethylenic acid such as (meth) acrylic acid alkyl ester). The polymer (a) can be modified by using together with an unsaturated compound or the like. Preferably, the polymer (a) is modified only by the monomer (b) having a polar group described above without using the monomer (b ′) having no polar group. If modified in this way, the polymer (a) is modified by the monomer (b) having a polar group without the presence of the monomer (b ′) having no polar group. Thereby, the modified olefin polymer and the polyisocyanate (C) (described later) can be reacted efficiently, or the interaction between the modified olefin polymer and the additive (B) (described later) becomes stronger, Therefore, the resistance to electrolytic solution can be improved.

In order to prepare the modified olefin polymer, the monomer (b) may be polymerized in the presence of the polymer (a), whereby the polymer (a) is converted into the monomer (b). Or it is modified by the polymer. Specifically, in order to prepare the modified olefin polymer, the following methods (1) to (4) may be mentioned.
(1) The polymer (a) is dissolved in the organic solvent, the monomer (b) and the radical polymerization initiator are added, and the mixture is heated and stirred, whereby the polymer (a) is replaced with the monomer (b). A method of denaturation and reaction.
(2) The polymer (a) is heated and melted, and the monomer (b) and the radical polymerization initiator are added to the resulting melt, followed by stirring, whereby the polymer (a) is converted into the monomer (b). ) And denatured to react.
(3) The polymer (a), the monomer (b) and the radical polymerization initiator are mixed in advance, and the resulting mixture is supplied to an extruder and heated and kneaded while the polymer (a) is mixed with the monomer ( A method of modifying and reacting in b).
(4) The polymer (a) is impregnated with a solution obtained by dissolving the monomer (b) and the radical polymerization initiator in an organic solvent, and then heated to the maximum temperature at which the polymer (a) does not dissolve. A method in which the polymer (a) is modified with the monomer (b) and reacted.

  The blending ratio of the monomer (b) is not particularly limited as long as it is blended so that the final modified amount of the monomer (b) can be obtained. The polymer (a) and the monomer (b) Is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 30 parts by mass or less, preferably 20 parts by mass or less, more preferably 15 parts by mass or less.

  The reaction temperature is, for example, 50 ° C. or more, preferably 80 ° C. or more, and for example, 250 ° C. or less. The reaction time is, for example, about 1 minute to 10 hours.

  As the reaction system, a batch system or a continuous system can be mentioned. In order to carry out the denaturation reaction uniformly, a batch system is preferably used.

  Examples of radical polymerization initiators include organic peroxides and organic peresters.

  Examples of organic peroxides include dicumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate). ) Hexin-3,1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 2,5- Examples thereof include dimethyl-2,5-di (tert-butyl peroxide) hexane, tert-butyl peroxybenzoate and the like. Examples of the organic perester include tert-butyl peracetate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl persec-octoate, tert-butyl perpivalate, cumyl perpivalate, Examples thereof include tert-butyl perdiethyl acetate. Furthermore, examples of the radical polymerization initiator include other azo compounds such as azobis-isobutylnitrile and dimethylazoisobutylnitrile.

  Of the radical polymerization initiators, preferably organic peroxides, more preferably dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne- Examples include dialkyl peroxides such as 3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene.

  The blending ratio of the radical polymerization initiator is, for example, 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the modified olefin polymer.

  The modified olefin polymer is prepared in the above methods (1) to (4) in the presence of a solvent or without a solvent.

  Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, octane, and decane, and alicyclic hydrocarbons such as cyclohexane, cyclohexene, and methylcyclohexane. Alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, and phenol, for example, ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, acetophenone, and cyclohexanone, such as methyl cellosolve Cellsolves such as ethyl cellosolve, for example, esters such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, Ethylene, dichloroethylene, and halogenated hydrocarbons such as chlorobenzene and the like. In these, Preferably, an aromatic hydrocarbon, an aliphatic hydrocarbon, a ketone, and ester are mentioned. A solvent can be used individually by 1 type or in combination of 2 or more types.

  When the modification of the α-olefin polymer (a) is carried out in the presence of a solvent, the resulting modified olefin polymer is prepared as a solution, specifically as a varnish.

The weight average molecular weight (Mw) of the modified olefin polymer measured by GPC method and converted to standard polystyrene is, for example, 1 × 10 ⁴ or more, preferably 2 × 10 ⁴ or more, more preferably 3 × 10. ⁴ or more, for example, 1,000 × 10 ⁴ or less, preferably 100 × 10 ⁴ or less, and more preferably 50 × 10 ⁴ or less.

When the weight average molecular weight of the modified olefin polymer is not less than the above lower limit, the strength of the coating film can be sufficiently increased, and the adhesion strength is improved. On the other hand, when the weight average molecular weight of the modified olefin polymer is not more than the above upper limit, the solubility in a solvent is good, and solidification and precipitation hardly occur. In particular, if the weight average molecular weight of the modified olefin polymer is 50 × 10 ⁴ or less, the adhesion performance tends to be particularly excellent.

  The melting point (Tm) of the modified olefin polymer is, for example, less than 120 ° C., preferably less than 100 ° C., more preferably 90 ° C. or less, and for example, 40 ° C. or more, preferably 50 ° C. or more.

  The melting point (Tm) of the modified olefin polymer is determined by differential scanning calorimetry (DSC measurement) according to JIS K7122, specifically, the temperature is raised from 30 ° C. to 180 ° C. at 10 ° C./min for 3 minutes. Held at a temperature, then lowered to 0 ° C. at 10 ° C./min, held at that temperature for 3 minutes, and then again raised to 150 ° C. at 10 ° C./min, It is obtained from the thermogram according to JIS K7122.

  If the melting point (Tm) of the modified olefin polymer is less than or equal to the above upper limit, a decrease in adhesive strength can be suppressed even after the composition is applied and cured at a low temperature to form an adhesive layer (described later). . Moreover, if the melting point (Tm) of the modified olefin polymer is not less than the above lower limit, excellent resin strength can be ensured.

  The heat of fusion (ΔH) of the modified olefin polymer is 0 J / g or more, preferably 3 J / g or more, more preferably 5 J / g or more, and 50 J / g or less, preferably 40 J / g or less. More preferably, it is 30 J / g or less.

  If the heat of fusion (ΔH) of the modified olefin polymer is not more than the above upper limit, the adhesive strength can be obtained even after the coating agent (described later) made of the composition is applied and then cured at a low temperature to form an adhesive layer (described later). Can be suppressed. On the other hand, if the heat of fusion (ΔH) of the modified olefin polymer is not less than the above lower limit, a coating agent (described later) made of the composition was applied to the base, and then the coating film was excellent when forming a coating film. Strength can be imparted.

  The heat of fusion (ΔH) is determined by differential scanning calorimetry (DSC measurement) according to JIS K7122, and is specifically calculated from the peak area of the thermogram obtained in the temperature rising process at 10 ° C./min. At the time of the measurement, in the present invention, for the purpose of canceling the heat history before the measurement, the temperature is raised to 180 ° C. at 10 ° C./min before the measurement, held at that temperature for 3 minutes, and then at 0 ° C./min. After the temperature is lowered to 0 ° C. and held at that temperature for 3 minutes, the heat of fusion (ΔH) is measured.

The kinematic viscosity of the modified olefin polymer at 40 ° C. preferably exceeds 500,000 cSt (5,000 cm ² / s). Here, the kinematic viscosity exceeding 500,000 cSt is a concept including the case where the fluidity is low and the kinematic viscosity cannot be measured.

  Further, the modified amount (introduced amount) of the monomer (b) in the modified olefin polymer, that is, the content ratio of the structural unit derived from the monomer (b) in the modified olefin polymer is 100 masses of the modified olefin polymer. Parts by weight, for example, 0.1 parts by weight or more, preferably 0.5 parts by weight or more, and for example, 15 parts by weight or less, preferably 10 parts by weight or less, more preferably 5 parts by weight. Hereinafter, it is more preferably 4 parts by mass or less, and particularly preferably 2 parts by mass or less.

  By making the content ratio of the monomer (b) in the above range, the modified olefin polymer and the polyisocyanate (C) (described later) can be efficiently reacted, or the modified olefin polymer and the addition are added. The interaction with the agent (B) (described later) is strengthened, and therefore, the resistance to the electrolytic solution can be improved. On the other hand, when the content ratio of the monomer (b) exceeds the above upper limit, the amount of polar groups increases, and the resistance to electrolytic solution may decrease. On the other hand, if the content ratio of the monomer (b) is less than the above lower limit, the adhesion with the substrate cannot be ensured, the adhesive strength is lowered, and the electrolytic solution resistance may be lowered.

The above-described modification amount is set by a known means such as ¹ H-NMR measurement. Specific conditions for ¹ H-NMR measurement include the following conditions.

That is, using an ECX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., the solvent is deuterated orthodichlorobenzene, the sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 ° C., the observation nucleus is ¹ H (400 MHz), and the sequence is The single pulse, the pulse width is 5.12 μsec (45 ° pulse), the repetition time is 7.0 seconds, and the number of integration is 500 times or more. The standard chemical shift is 0 ppm for hydrogen of tetramethylsilane. For example, the same result can be obtained by setting the peak derived from the residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm and setting the standard value for chemical shift. Can be obtained. A peak such as ¹ H derived from the monomer (b) can be assigned by a conventional method.

  In the case where an unsaturated carboxylic acid or an anhydride thereof is used as the monomer (b) as an amount that serves as a measure of the amount of the polar group (preferably the functional group) introduced into the modified olefin polymer. For example, an acid value can be used.

  The acid value of the modified olefin polymer is, for example, 0.1 mgKOH / g or more, preferably 0.5 mgKOH / g or more, and, for example, 100 mgKOH / g or less, preferably 30 mgKOH / g or less, more preferably 10 mg KOH / g or less.

  Here, the following are mentioned as a measuring method of an acid value.

  That is, the basic operation conforms to JIS K-2501-2003. Specifically, about 10 g of the modified olefin polymer is accurately measured and charged into a 200 mL tall beaker. As a titration solvent, 150 mL of a mixed solvent obtained by mixing xylene and dimethylformamide at 1: 1 (volume ratio) is added. A few drops of 1 w / v% phenolphthalein ethanol solution (Wako Pure Chemical Industries, Ltd.) is added as an indicator, and the liquid temperature is heated to 80 ° C. to dissolve the sample. After the liquid temperature becomes constant at 80 ° C., titration is performed using a 0.1 mol / L potassium hydroxide 2-propanol solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value is determined from the titration amount.

The calculation formula is: Acid value (mgKOH / g) = (EP1-BL1) × FA1 × C1 / SIZE
It is.

  Here, in the above calculation formula, EP1 is a titration amount (mL), BL1 is a blank value (mL), FA1 is a factor of a titrant (1.00), and C1 is a concentration conversion value (5.611 mg / mL: 0.00). 1mo1 / L KOH 1 mL of potassium hydroxide equivalent), SIZE represents the amount of sample collected (g).

  This measurement is repeated three times and the average value is taken as the acid value.

  The modified olefin polymer can be used alone or in combination of two or more.

  In addition, the modified olefin polymer includes the modified olefin polymer prepared by the method of (i) above, and a polymer of an α-olefin having 2 to 20 carbon atoms before modification (that is, an unmodified polymer). It can also be prepared as a composition, that is, a modified olefin polymer composition.

  The unmodified polymer (a) is a modified olefin polymer based on 100 parts by mass of the modified olefin polymer composition, that is, a total of 100 parts by mass of the modified olefin polymer and the unmodified polymer (a). Is mixed with the modified olefin polymer so that the blending ratio thereof is 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 15 parts by mass or less, preferably 10 parts by mass or less.

  The physical properties of the modified olefin polymer composition are generally the same as the physical properties of the modified olefin polymer described above.

  The olefin-α, β unsaturated carboxylic acid copolymer is, for example, a multi-component copolymer obtained by copolymerizing at least an olefin and an α, β unsaturated carboxylic acid, for example, an olefin and an α, β unsaturated carboxylic acid. Examples thereof include a binary copolymer obtained by copolymerization with an acid, and a terpolymer obtained by copolymerization of an olefin, an α, β unsaturated carboxylic acid and other copolymerization components.

  Olefin is an unsaturated chain hydrocarbon having one or more unsaturated bonds in the molecule, such as ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutylene (isobutene), 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3- Examples thereof include unsaturated chain hydrocarbons (olefins) having 2 to 20 carbon atoms such as hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene and 1-decene, preferably And ethylene. These olefins can be used alone or in combination of two or more.

  The α, β unsaturated carboxylic acid is a carboxylic acid in which a carboxyl group and an unsaturated bond are conjugated, and examples thereof include 4 to 8 carbon atoms such as acrylic acid, methacrylic acid, fumaric acid, maleic acid, and crotonic acid. An α, β unsaturated carboxylic acid can be mentioned, and acrylic acid and methacrylic acid are preferable. These α, β unsaturated carboxylic acids can be used alone or in combination of two or more.

  Other copolymer components include, for example, α, β unsaturated carboxylic acid esters (for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate) Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and isobutyl methacrylate, for example, maleic acid alkyl esters such as dimethyl maleate and diethyl maleate), vinyl esters (for example, vinyl acetate, vinyl propionate, etc.) , Vinyl sulfate, vinyl nitrate, vinyl halide (eg, vinyl chloride, vinyl fluoride, etc.), vinyl group-containing primary or secondary amine compounds (eg, vinylamine, N-methylvinylamine, etc.), carbon monoxide, sulfur dioxide etc Preferably, an α, β unsaturated carboxylic acid ester is used.

  More preferable examples of the copolymer component include alkyl acrylates and alkyl methacrylates, and more preferably alkyl acrylates.

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

  The production method of the olefin-α, β unsaturated carboxylic acid copolymer is not particularly limited, and can be obtained by a known polymerization method.

  Examples of the olefin-α, β unsaturated carboxylic acid copolymer include a block copolymer, a random copolymer, and a graft copolymer, and preferably a random copolymer.

  These olefin-α, β unsaturated carboxylic acid copolymers can be used alone or in combination of two or more.

  The ionic crosslinked product of the olefin-α, β unsaturated carboxylic acid copolymer is, for example, neutralizing at least a part of the carboxyl groups in the olefin-α, β unsaturated carboxylic acid copolymer with a metal ion. And a crosslinked polymer.

  Examples of the metal ions include divalent metal ions such as magnesium ions, calcium ions, zinc ions, barium ions, and cadmium ions, and polyvalent metal ions such as trivalent metal ions such as aluminum ions. These metal ions can be used alone or in combination of two or more.

  The production method of the ionic crosslinked product of the olefin-α, β unsaturated carboxylic acid copolymer is not particularly limited, and can be obtained by a known production method.

  These ionic crosslinked products of olefin-α, β unsaturated carboxylic acid copolymer can be used alone or in combination of two or more.

  Examples of the styrene thermoplastic elastomer include a block copolymer of a styrene compound and a conjugated diene compound.

  Examples of the styrene compound include alkyl styrene such as styrene, α-methyl styrene, p-methyl styrene, and pt-butyl styrene, p-methoxy styrene, vinyl naphthalene, and preferably styrene. . These styrenic compounds can be used alone or in combination of two or more.

  Examples of the conjugated diene include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and the like. Examples thereof include butadiene and isoprene. These conjugated dienes can be used alone or in combination of two or more.

  The production method of the styrene-based thermoplastic elastomer is not particularly limited, and can be obtained by a known polymerization method.

  These styrenic thermoplastic elastomers can be used alone or in combination of two or more.

  The modified body of the styrene thermoplastic elastomer can be obtained, for example, by modifying the above styrene thermoplastic elastomer with a monomer having the above polar group (preferably the above functional group).

  The modified product of the styrene-based thermoplastic elastomer can be obtained, for example, in the same manner as the method for preparing the modified olefin polymer described above.

  These modified styrenic thermoplastic elastomers can be used alone or in combination of two or more.

2. Additive (B)
The additive (B) has a structure derived from phosphoric acid, which is a structural unit derived from phosphoric acid.

  When the composition contains the additive (B) having a phosphoric acid-derived structure, the affinity with the base material (preferably an aluminum foil) (described later) is dramatically improved, so that the resistance to the electrolytic solution is improved. be able to.

  Examples of phosphoric acids include phosphoric acid, phosphorous acid, phosphonic acid, phosphonous acid, phosphinic acid, phosphinic acid and esters thereof, condensed phosphoric acid, phosphine oxide, and phosphine oxide derivatives.

  As phosphoric acid, Preferably, phosphoric acid ester and phosphorous acid ester are mentioned, More preferably, phosphorous acid ester is mentioned.

  If the phosphoric acid is a phosphoric acid ester or a phosphorous acid ester, especially a phosphorous acid ester, an anti-electrolytic solution of an adhesive (described later) containing a composition containing an additive (B) having a structure derived from the phosphoric acid Can be improved.

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

  Examples of the additive (B) having a phosphoric acid-derived structure include a coupling agent having a phosphoric acid-derived structure, preferably a titanate coupling agent having a phosphoric acid-derived structure. (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphate) titanate (titanate coupling agent, phosphite derived structure, trade name: Plenact KR-55, manufactured by Ajinomoto Fine Techno Co., Ltd.) , Tetraoctyl bis (ditridecyl phosphate) titanate (titanate coupling agent, phosphite derived structure, trade name: Preneact KR-46B, manufactured by Ajinomoto Fine Techno Co.), tetraisopropyl bis (dioctyl phosphate) titanate (Titanate coupling agent, Containing acid ester-derived structure, trade name: Preneact KR-41B, Ajinomoto Fine Techno Co., Ltd., Isopropyltris (dioctylpyrophosphate) titanate (titanate coupling agent, phosphate ester-derived structure containing, trade name: Preneact KR -38S, manufactured by Ajinomoto Fine-Techno Co., Ltd.), bis (dioctylpyrophosphate) oxyacetate titanate (titanate-based coupling agent, phosphate ester-derived structure, trade name: Preneact KR-138S, manufactured by Ajinomoto Fine Techno Co., Ltd.), bis (Dioctyl pyrophosphate) Ethylene titanate (titanate coupling agent, phosphate ester-derived structure, trade name: Preneact KR-238S, manufactured by Ajinomoto Fine-Techno Co., Ltd.), isopropyl dioctyl pyrov Scan phosphate titanate (titanate coupling agent, derived from phosphoric acid ester structure-containing, trade name: PLENACT KR-338x, manufactured by Ajinomoto Fine-Techno Co., Ltd.).

  If the additive (B) having a phosphoric acid-derived structure is a coupling agent having a phosphoric acid-derived structure, an adhesive (described later) containing a composition containing the phosphoric acid-derived structure (B) Electrolytic solution resistance can be improved.

  As the additive (B) having a phosphate-derived structure, preferably, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphate) titanate, tetraoctyl bis (ditridecyl phosphate) titanate, Tetraisopropyl bis (dioctyl phosphate) titanate.

  These additives (B) having a phosphoric acid-derived structure can be used alone or in combination of two or more.

3. Polyisocyanate (C)
The composition may further contain polyisocyanate (C).

  When a composition contains polyisocyanate (C), the adhesive strength of a base material and a to-be-adhered body and the electrolyte solution resistance of an adhesive agent can be improved.

  As polyisocyanate (C), a polyisocyanate monomer, a polyisocyanate modified body, etc. are mentioned, for example.

  Examples of the polyisocyanate monomer include aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 , 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl capate Group diisocyanate and the like.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate, these Trans, Trans - body, Trans, Cis body, Cis, Cis body, or mixtures _thereof)) (H 12 _MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane Isocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane Or a mixture thereof) (H ₆ XDI) and the like.

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

Preferred examples of the polyisocyanate monomer include aliphatic polyisocyanates and alicyclic polyisocyanates, and more preferred are 1,5-pentamethylene diisocyanate (PDI) and bis (isocyanatomethyl) cyclohexane (1,3 -Or 1,4-bis (isocyanatomethyl) cyclohexane or a mixture thereof) (H ₆ XDI) 1,6-hexamethylene diisocyanate (HDI), more preferably 1,6-hexamethylene diisocyanate (HDI) Is mentioned.

  The polyisocyanate-modified product has an average functional group number exceeding 2, for example, the above-described polyisocyanate monomer multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazine). Dione-modified products), pentamers, heptamers, etc.), allophanate-modified products (for example, the above-mentioned polyisocyanate monomers and monools (for example, monools having 1 to 20 carbon atoms such as octadecanol) An allophanate modified product produced from the reaction of the above, a polyol modified product (for example, a polyisocyanate monomer and a low molecular weight polyol (a compound having two or more hydroxyl groups and a number average molecular weight of 40 or more and less than 400), Modified polyol (alcohol adduct) produced by reaction with trihydric alcohol such as trimethylolpropane) Etc.), biuret-modified products (for example, biuret-modified products produced by reaction of the above-mentioned polyisocyanate monomer with water or amines), urea-modified products (for example, the above-mentioned polyisocyanate monomer and diamine) Modified with urea, etc.), oxadiazine trione modified (for example, oxadiazine trione produced by reaction of the above polyisocyanate monomer and carbon dioxide), carbodiimide modified (such as poly Carbodiimide modified products produced by decarboxylation condensation reaction of isocyanate monomers), uretdione modified products, uretonimine modified products, and the like.

  Furthermore, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) and the like are also exemplified as the polyisocyanate-modified product.

  These polyisocyanate-modified products can be used alone or in combination of two or more.

  The polyisocyanate-modified product preferably includes a multimer of the above-described polyisocyanate monomer and a polyol-modified product, and more preferably includes a trimer of the above-described polyisocyanate monomer.

These polyisocyanate-modified products may be prepared by known methods, and are commercially available (for example, Takenate D-170N (trimer-modified product of 1,6-hexamethylene diisocyanate (trimer), manufactured by Mitsui Chemicals), Takenate D-120N (H ₆ XDI polyol modified, manufactured by Mitsui Chemicals, Inc.) may be used.

  These polyisocyanates (C) can be used alone or in combination of two or more.

4). Hydrocarbon synthetic oil (D)
The composition may further contain a hydrocarbon-based synthetic oil (D).

  When the composition contains the hydrocarbon-based synthetic oil (D), the adhesive strength between the substrate and the adherend can be improved.

  Examples of the hydrocarbon-based synthetic oil (D) include olefin polymers having 2 to 20 carbon atoms. Among these, Preferably, the oligomer obtained by homopolymerizing a C2-C20 olefin, or the oligomer obtained by copolymerizing the arbitrary mixtures of 2 or more types of these olefins are mentioned. Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-octene, 1-decene, and 1-dodecene.

  Here, as the hydrocarbon-based synthetic oil (D), an ethylene-based copolymer containing a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms can be suitably used. In this case, the amount of the structural unit derived from ethylene is, for example, 30 mol% or more, preferably 100 mol% in total with the structural unit derived from ethylene and the structural unit derived from an α-olefin having 3 to 20 carbon atoms. Is 40 mol% or more, for example, 70 mol% or less, preferably 60 mol% or less.

  A hydrocarbon synthetic oil (D) can be used individually by 1 type or in combination of 2 or more types.

  More preferably, the hydrocarbon-based synthetic oil (D) includes an ethylene copolymer containing a structural unit derived from ethylene and a structural unit derived from propylene, and more preferably a structural unit derived from ethylene. Examples thereof include an ethylene copolymer composed of a structural unit derived from propylene.

  The hydrocarbon-based synthetic oil (D) is obtained by polymerizing the olefin having 2 to 20 carbon atoms in the presence of a known polymerization catalyst by the same method as the preparation of the polymer (a) described above. . Examples of the polymerization catalyst include vanadium oxy compounds such as vanadium oxyethoxide dichloride, organoaluminum compounds such as ethylaluminum sesquichloride, and the like. The polymerization catalyst can be used alone or in combination of two or more.

The hydrocarbon-based synthetic oil (D) has a kinematic viscosity at 40 ° C. of, for example, 30 cSt (0.3 cm ² / s) or more, preferably 300 cSt (3 cm ² / s) or more, more preferably 5,000 cSt ( 50 cm ² / s) or more, more preferably 20,000 cSt (200 cm ² / s), for example, 500,000 cSt (5,000 cm ² / s) or less, preferably 400,000 cSt (4,000 cm). ² / s) or less, more preferably 300,000 cSt (3,000 cm ² / s) or less, and still more preferably 100,000 cSt (1,000 cm ² / s).

  If the kinematic viscosity at 40 ° C. of the hydrocarbon-based synthetic oil (D) is within the above range, the adhesive strength between the substrate (described later) and the adherend (described later) can be improved.

5. Preparation method of composition In order to prepare the composition, the above-described thermoplastic resin (A), additive (B), and if necessary, polyisocyanate (C) and / or hydrocarbon-based synthetic oil (D) Is blended.

  The blending ratio of the additive (B) is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). Part or more, for example, 3 parts by mass or less, preferably 2 parts by mass or less, and more preferably 1.0 part by mass or less.

  When the blending ratio of the additive (B) is within the above range, the affinity with the substrate (preferably an aluminum foil) (described later) can be efficiently improved.

  The blending ratio of the polyisocyanate (C) blended as necessary is, for example, 1 part by mass or more, preferably 2 parts by mass or more, more preferably 3 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). For example, it is 30 parts by mass or less, preferably 20 parts by mass or less, and more preferably 10 parts by mass or less.

  If the blending ratio of the polyisocyanate (C) is within the above range, the thermoplastic resin (A) and the polyisocyanate (C) can be reacted efficiently to improve the electrolytic solution resistance.

  The equivalent ratio of the polar group (preferably the above functional group) of the thermoplastic resin (A) to the isocyanate group of the polyisocyanate (C) to be blended (isocyanate group (NCO group) / polar group (preferably Is, for example, 0.01 or more, preferably 0.1 or more, more preferably 0.5 or more, still more preferably 1.0 or more, and for example 50 or less. , Preferably, it is 40 or less, More preferably, it is 30 or less, More preferably, it is 10 or less.

  If the equivalent ratio of the polar group of the thermoplastic resin (A) and the isocyanate group of the polyisocyanate (C) is within the above range, the thermoplastic resin (A) and the polyisocyanate (C) are reacted efficiently, Electrolytic solution resistance can be improved.

  In addition, the blending ratio of the hydrocarbon-based synthetic oil (D) blended as necessary is, for example, 6 parts by mass or more, preferably 15 parts by mass or more, more preferably with respect to 100 parts by mass of the thermoplastic resin (A). Is 20 parts by mass or more, and for example, 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

  When the blending ratio of the hydrocarbon-based synthetic oil (D) is within the above range, the adhesive strength between the base material (described later) and the adherend (described later) can be improved.

  Further, it is necessary for the composition or each component constituting it, specifically, thermoplastic resin (A), additive (B), polyisocyanate (C), and hydrocarbon-based synthetic oil (D). Depending on the case, any or all of them include epoxy resins, curing catalysts, leveling agents, antifoaming agents, stabilizers such as antioxidants and UV absorbers (including light stabilizers and heat stabilizers), plasticizers, Surfactant, pigment, thixotropic agent, thickener, tackifier, surface conditioner, antisettling agent, weathering agent, pigment dispersant, antistatic agent, filler, organic or inorganic fine particles, antifungal agent, silane You may mix | blend other additives, such as a coupling agent.

  In the above preparation, the above-mentioned solvent can be blended to prepare a varnish.

  Examples of the solvent include the same solvents as described above. Preferably, toluene, methylcyclohexane / methylisobutylketone mixed solvent, methylcyclohexane / methylethylketone mixed solvent, methylcyclohexane / ethyl acetate mixed solvent, cyclohexane / methylethylketone mixed solvent, cyclohexane / An ethyl acetate mixed solvent and a cellsolves / cyclohexanone mixed solvent are mentioned, More preferably, toluene is mentioned. Water can also be used as a dispersion medium.

  Preferably, the composition is used as a varnish by blending a solvent from the viewpoint of processability. More preferably, the composition is used by dissolving in a solvent.

  The solvent has a non-volatile content of 100 parts by mass of varnish, for example, 5 parts by mass or more, preferably 10 parts by mass or more, and for example, 50 parts by mass or less, preferably 40 parts by mass or less. And blended into the composition.

  In addition, when the thermoplastic resin (A) is prepared as a varnish, the solvent which comprises a varnish can also be used as a solvent for the said preparation as it is.

5. Coating Agent The composition thus prepared can be used as a coating agent.

  This coating agent is suitable for use as a primer, paint, hot melt adhesive, or optically transparent double-sided tape. Moreover, the laminated body which has at least 1 layer obtained from this coating agent is used suitably as a decorating film.

  Moreover, when using as a coating agent, an additive can also be added in a suitable ratio as needed. Examples of the additive include pigments such as titanium oxide (rutile type), zinc oxide, and carbon black, for example, thixotropic agents, for example, thickeners, for example, tackifiers such as rosin resin and terpene resin, , Antifoaming agents, surface conditioning agents, antisettling agents, antioxidants, weathering agents, heat stabilizers, light stabilizers, pigment dispersants, antistatic agents and the like.

  There is no restriction | limiting in particular as a method of forming a coating film from a coating agent, It can implement by a well-known method. For example, die coating method, flow coating method, spray coating method, bar coating method, gravure coating method, gravure reverse coating method, kiss reverse coating method, micro gravure coating method, roll coating method, blade coating method, rod coating method, roll doctor Coating method based on coating method such as coating method, air knife coating method, comma roll coating method, reverse roll coating method, transfer roll coating method, kiss roll coating method, curtain coating method, screen printing method and dipping coating method After coating, it is dried by an appropriate method such as natural drying or forced heating drying. Thereby, a coating film is obtained.

  The thickness of the coating film after drying is, for example, 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 50 μm or less.

  When using the laminated body which has at least 1 layer of the coating film formed from a coating agent as a decorating film, it can be used in combination with the film which has a well-known design property. For example, a film previously decorated by printing, painting, vapor deposition or the like, or a film decorated by a combination thereof is used as a design layer, and a coating film formed from a coating agent is laminated.

  Here, examples of the film having a design layer include thermoplastic films such as acrylic film, PET film, polycarbonate film, COC (cyclic olefin copolymer) film, polyolefin film, vinyl chloride film, and ABS.

  When using the laminated body which has at least 1 layer of the coating film formed from a coating agent as a decoration film, there is no restriction | limiting in particular as a manufacturing method of a decoration film, The adherend of the decoration film which has a design layer A method of dry laminating the coating film on the surface facing the surface, a method of providing a design layer directly on the coating film by printing, etc., forming a clear layer, another paint layer, coating film on the above film by sequential printing, etc. How to go.

  When a laminate having at least one coating film formed from a coating agent is used as a decorative film, for example, an existing vacuum forming method such as a vacuum forming method or a compressed air vacuum forming method, an insert forming method, and an in-mold. By using a molding method, or a TOM method using a “vacuum molding apparatus” described in Japanese Patent No. 3733564, a molded product having a complicated three-dimensional structure can be decorated. Examples of the adherend of the decorative film include polyolefin materials such as PP, polyamide resins such as nylon, polar resins such as ABS, PC, PET, PPS, and acrylic resins, such as ED steel plates, Mg alloys, and SUS. Inorganic materials such as (stainless steel), aluminum, aluminum alloy, and glass can be used. In addition, an adherend in which the resin and the inorganic material are combined is also included. In the decorative film, for example, a coating film obtained from a coating agent adheres to the adherend.

  As the molded body obtained by the above-described decoration method, for example, members for automobile interior and exterior, for example, various front panels such as AV equipment, surface decorative materials such as buttons and emblems, information home appliances such as mobile phones and cameras, etc. Various parts such as housings, housings, display windows, buttons, etc., for example, exterior materials for furniture, eg, interior materials for buildings, such as bathrooms, walls, ceilings, floors, eg, outer walls, such as siding, fences, roofs, gates , Architectural exterior materials such as windbreak boards, for example, surface decorative materials for furniture such as window frames, doors, handrails, sills, duck, etc., for example, optical members such as various displays, lenses, mirrors, goggles, window glass, etc. , Members for interior and exterior of various vehicles other than automobiles such as trains, airplanes, ships, etc., and various packaging containers such as bottles, cosmetic containers, accessory cases, and packaging materials Prize, and the like various other applications such as miscellaneous goods and accessories.

6). Use of Coating Agent as Adhesive The coating agent is also used as an adhesive of the present invention for forming an adhesive layer, preferably as an adhesive for laminating. That is, the adhesive of the present invention includes the above-described composition and includes the above-described coating agent.

  When using a coating agent as an adhesive, for example, an epoxy resin, a curing catalyst, a leveling agent, an antifoaming agent, a stabilizer such as an antioxidant or an ultraviolet absorber, a plasticizer, a surfactant, a pigment, You may mix | blend additives, such as a filler, organic or inorganic fine particles, an antifungal agent, and a silane coupling agent.

  Hereinafter, specific examples when used as an adhesive will be described. Specifically, the adhesive layer is laminated on the surface (one side surface) of the substrate, or on the front and back surfaces (one side surface and the other side surface), and a laminate is formed from the substrate and the adhesive layer. (For example, an adhesive sheet) is formed.

  As a base material, for example, a film made of polyolefin material such as PP, for example, a film made of polar resin such as ABS, PC, PET, PPS, polyamide, acrylic resin, for example, ED steel plate, Mg alloy, SUS (stainless steel) Metal foil made of aluminum, aluminum alloy, etc., more preferably metal foil, and still more preferably aluminum foil. These base materials can be used alone or in combination of two or more.

  By using an aluminum foil as a base material, a laminate with high chemical resistance can be obtained.

  The thickness of the substrate is 1 μm or more, preferably 5 μm or more, and for example, 500 μm or less, preferably 100 μm or less.

  When an aluminum foil is used as a base material, the surface of the aluminum foil may or may not be subjected to a surface treatment such as an anodizing treatment, a dip type chemical conversion treatment, or a coating type chemical conversion treatment. No processing is performed.

  That is, when an aluminum foil is used as the substrate, an untreated aluminum foil that has not been subjected to any surface treatment of anodizing treatment, immersion type chemical conversion treatment, or coating type chemical conversion treatment is preferably used.

  By using an untreated aluminum foil as the substrate, the cost for surface treatment of the aluminum foil can be reduced.

  In order to laminate the adhesive layer on the surface of the substrate or on the front and back surfaces, for example, the coating agent is applied by the application method described above. Then, when a coating agent contains a solvent, the solvent is distilled off by heating the applied coating agent. Thereby, an adhesive layer is formed.

  The thickness of the adhesive layer is, for example, 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 50 μm or less.

  Thus, a laminate including the base material and the adhesive layer is manufactured.

  Furthermore, an adherend can be provided on the surface (one side surface) or the front and back surfaces (one side surface and the other side surface) of the above-mentioned adhesive layer, and a laminate composed of them can be formed.

  Examples of the adherend include polyolefin materials such as PP, polar resins such as ABS, PC, PET, PPS, polyamide, and acrylic resin, such as ED steel sheet, Mg alloy, SUS (stainless steel), aluminum, and aluminum alloy. And inorganic materials such as glass. In addition, an adherend in which the resin and the inorganic material are combined is also included. Preferably, the film and molded object which consist of polyolefin materials are mentioned. Note that a treatment such as a corona treatment can be applied to the adhesion surface of the adherend (the surface in contact with the adhesive layer). These adherends can be used alone or in combination of two or more.

  In order to provide an adherend on the surface of the adhesive layer, the adherend is brought into contact with the surface of the adhesive layer. Thus, an adhesive layer is interposed between the base material and the adherend. That is, a laminate including a substrate, an adherend, and an adhesive layer is manufactured.

  Then, an adhesive bond layer is hardened by heating a laminated body. Thereby, a base material and a to-be-adhered body mutually adhere | attach by an adhesive bond layer.

  As heating conditions, appropriate conditions are selected, for example, 80 ° C. or less, preferably 70 ° C. or less, and for example, at a low temperature of 40 ° C. or more, for example, 1 day or more, preferably 3 days or more. For example, a method of curing for a long time of 7 days or less (low temperature curing method), or 100 ° C. or higher, preferably 120 ° C. or higher, for example, at a high temperature of 200 ° C. or lower, for example, 0.1 seconds. As mentioned above, Preferably, the method (high temperature thermocompression bonding method) of thermocompression bonding for 0.5 second or more, for example, for a short time of 60 seconds or less is selected. The pressure in the high-temperature thermocompression bonding method is, for example, 0.1 MPa or more, preferably 0.2 MPa or more, and 2 MPa or less.

  Preferably, a low temperature curing method is selected.

When the polyisocyanate (C) is blended in the composition by the heating described above, the adhesive layer is cured. That is, the polar group (preferably the functional group) of the thermoplastic resin (A) reacts with the isocyanate group of the polyisocyanate (C). Thereby, the base material and the adherend are firmly bonded via the adhesive layer. The thickness of the adhesive layer is, for example, 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 50 μm or less.
7). Use of laminated body Such a laminated body is preferably used as a packaging material for a lithium secondary battery case, such as a packaging material for a battery case having excellent electrolytic solution resistance.
7-1. Battery Case Wrapping Material and Battery Battery Case Wrapping Material will be described with reference to FIG. In FIG. 1, description will be made with the upper side on the paper as the outer side and the lower side on the paper as the inner side.

  As shown in FIG. 1, the battery case packaging material 1 includes a base material 2, an inner layer 3 bonded to the inner side of the base material 2, an outer layer 4 bonded to the outer side of the base material 2, and a base An inner adhesive layer 5 interposed between the material 2 and the inner layer 3 and an outer adhesive layer 6 interposed between the substrate 2 and the outer layer 4 are provided.

  The substrate 2 corresponds to the above-described substrate and is not particularly limited, but preferably a metal foil, more preferably an aluminum foil or a SUS foil.

  The inner layer 3 corresponds to the adherend described above and is not particularly limited. However, in order to impart chemical resistance and heat sealability to the battery case packaging material, preferably an unstretched polypropylene film or the like. And thermoplastic polyolefin film.

  The inner adhesive layer 5 corresponds to the above-described adhesive layer.

  The outer layer 4 is not particularly limited, but is preferably a polyester film or polyamide in order to impart heat resistance in the heat sealing process during battery production, moldability during processing, pinhole resistance, and insulation during distribution. Examples thereof include a multilayer film in which stretched or unstretched films such as films and polypropylene films are laminated in a single layer or in two or more layers.

  The thickness of the battery case packaging material 1 is, for example, 60 to 160 μm.

  And the adhesive of this invention should just be used by the inner side adhesive layer 5, and if the adhesive of the outer side adhesive layer 6 can ensure the adhesiveness of the outer layer 4 and the base material 2, it will be this invention. In addition to these adhesives, any other adhesive such as a dry laminating adhesive and a solventless adhesive can be used.

  Next, a battery including a battery case packaging material in which the above-described adhesive is used for the inner adhesive layer will be described with reference to FIG.

  As shown in FIG. 2, the battery 10 includes a battery case packaging material 1 and an electrolyte solution 11 packaged in the battery case packaging material 1. The battery 10 also includes a positive electrode 17, a negative electrode 18, and a separator 19 that are accommodated in the battery case packaging material 1.

  The battery case packaging material 1 is configured in a bag (laminate cell) shape so that an electrolyte solution 11 to be described below is in contact with the inner surface of the inner layer 3 of the battery case packaging material 1. Specifically, the battery case packaging material 1 wraps the electrolyte solution 11 so that the inner layer 3 contacts the electrolyte solution 11.

  The electrolytic solution 11 is not particularly limited, and examples thereof include a nonaqueous electrolytic solution in which a supporting salt is dissolved in an organic solvent.

Examples of the supporting salt include LiPF ₆ (lithium hexafluorophosphate), LiClO ₄ , LiAsF ₆ , LiBF ₄ , Li (CF ₃ SO ₂ ) ₂ N, Li (CF ₃ SO ₃ ), LiN (C ₂ F ₅ Known lithium salts such as SO ₂ ) can be mentioned. These supporting salts can be used alone or in combination of two or more.

  As an organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (γ-BL), diethyl carbonate (DEC), dimethyl carbonate (DMC) and the like are used for conventional secondary batteries and capacitors. An organic solvent is mentioned. These organic solvents can be used alone or in combination of two or more.

  The concentration of the supporting salt is, for example, 0.1 to 2.0 mol / L.

  The positive electrode 17 and the negative electrode 18 are disposed so as to be in contact with the electrolyte solution 11 and spaced from each other. The separator 19 is disposed so as to be sandwiched between the positive electrode 17 and the negative electrode 18.

  The above-described battery 10 is used as, for example, a lithium ion secondary battery. In that case, the battery case packaging material 1 is used as a lithium ion secondary battery case packaging material.

8). Effect of Embodiment A laminate including an adhesive containing the above-described composition and an adhesive layer formed therefrom is excellent in an anti-electrolytic solution and can sufficiently suppress a decrease in adhesive strength.

  Therefore, the composition can be suitably used for various applications including coating applications such as adhesive applications as a composition having excellent reliability.

  For example, as shown in FIG. 1 and FIG. 2, the battery case packaging material 1 and the battery 10 are excellent in resistance to electrolytic solution and suppression of a decrease in adhesive strength between the base material 2 and the inner layer 3.

  Specifically, as shown in FIG. 1, the inner adhesive layer 5 in the battery case packaging material 1 has excellent electrolytic solution resistance. That is, even when the battery case packaging material 1 is used over a long period of time, it is possible to effectively suppress the decrease in the adhesive strength of the inner adhesive layer 5, among others. The battery case packaging material 1 is excellent in long-term reliability, in particular, durability under a severe use environment where hydrogen fluoride (hydrofluoric acid) is generated. Therefore, the adhesive of the present invention can be suitably used as a packaging material for lithium ion secondary battery cases having excellent durability and reliability.

  The above-described composition is not limited to a battery case packaging material, and has resistance to highly polar solvents such as an electrolytic solution, alkali resistance, and alcohol resistance, and has excellent electrolytic solution resistance between a film and an adhesive layer. It can be used as a laminating adhesive, and a laminate including an adhesive layer formed from the laminating adhesive can be used as a packaging material for a highly alkaline solution or a packaging material for an alcohol-containing solution.

  In FIG. 1, the inner adhesive layer 5 is directly provided (laminated) on the surface (one side surface) of the base material 2. For example, although not shown in FIG. 1, one side of the base material 2 is provided. By providing a printing layer or the like (inside or outside), the inner adhesive layer 5 can be provided on one side (inside or outside) of the substrate 2 via the printing layer.

Specific numerical values such as blending ratio (content ratio), physical property values, and parameters used in the following description are described in the above-mentioned “Mode for Carrying Out the Invention”, and the corresponding blending ratio (content ratio) ), Physical property values, parameters, etc. The upper limit value (numerical value defined as “less than” or “less than”) or lower limit value (number defined as “greater than” or “exceeded”) may be substituted. it can.
1. Physical properties of compounds Physical properties of each compound were evaluated according to the following.
[Content ratio of structural units derived from propylene, ethylene and 1-butene]
The content rate of the structural unit originating in each of propylene, ethylene, and 1-butene was calculated | required using < ¹³ > C-NMR.
[Melting point (Tm), heat of fusion (ΔH)]
The melting point (Tm) and heat of fusion (ΔH) were determined using a differential scanning calorimeter (TA Instruments; DSC-Q1000).

Specifically, in a differential scanning calorimeter, the temperature is raised from 30 ° C. to 180 ° C. at 10 ° C./min, held at that temperature for 3 minutes, and then lowered to 0 ° C. at 10 ° C./min. In the process of holding for 3 minutes and again raising the temperature up to 150 ° C. at 10 ° C./min, the melting point (Tm) and heat of fusion (ΔH) were determined from the thermogram at the second temperature rise according to JIS K7122. .
[Kinematic viscosity at 40 ° C]
The kinematic viscosity at 40 ° C. was measured based on ASTM D 445.
[Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)]
The weight average molecular weight (Mw) and molecular weight distribution (dispersion degree) (Mw / Mn) were measured using a gel permeation chromatograph (manufactured by Shimadzu Corporation; LC-10 series) under the following conditions.

・ Detector: Shimadzu Corporation; C-R4A
Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation)
・ Moving bed: Tetrahydrofuran ・ Temperature: 40 ℃
・ Flow rate: 0.8mL / min
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were calculated using a calibration curve prepared with monodisperse standard polystyrene.
[Modification amount of maleic anhydride]
The content ratio (modification amount) of maleic anhydride was determined from measurement by ¹ H-NMR.

<Synthesis of polymer>
[Synthesis Example 1: Synthesis of propylene / 1-butene copolymer]
A 2 L autoclave thoroughly purged with nitrogen was charged with 900 mL of hexane and 90 g of 1-butene, 1 mmol of triisobutylaluminum was added, the temperature was raised to 70 ° C., and propylene was supplied to give a total pressure of 7 kg / cm ² G (gauge Pressure), 0.31 mmol of methylaluminoxane, 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atom was added, and propylene was continuously added. The polymerization was carried out for 30 minutes while supplying and maintaining the total pressure at 7 kg / cm ² G (gauge pressure). After the polymerization, the polymer was degassed and the polymer was recovered in a large amount of methanol and dried under reduced pressure at 110 ° C. for 12 hours. The resulting propylene / 1-butene copolymer had a melting point (Tm) of 78.3 ° C., a heat of fusion (ΔH) of 29.2 J / g, a weight average molecular weight (Mw) of 330,000, a molecular weight distribution (dispersion degree). ) (Mw / Mn) was 2, the content of structural units derived from propylene was 67.2 mol%, and the content of structural units derived from 1-butene was 32.8 mol%.
[Synthesis Example 2: Synthesis of maleic anhydride-modified propylene / 1-butene copolymer]
3 kg of the propylene / 1-butene copolymer was added to 10 L of toluene, and the temperature was raised to 145 ° C. in a nitrogen atmosphere to dissolve the propylene / 1-butene copolymer in toluene. Further, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours under stirring, and then stirred at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the maleic anhydride-modified propylene / 1-butene copolymer, filtered, washed with acetone, and then vacuum dried.

The resulting maleic anhydride-modified propylene / 1-butene copolymer (thermoplastic resin (A-1)) had a melting point (Tm) of 75.8 ° C., a heat of fusion (ΔH) of 28.6 J / g, and a weight average. The molecular weight (Mw) was 110,000, the molecular weight distribution (Mw / Mn) was 2, and the modification amount of maleic anhydride was 1 part by mass with respect to 100 parts by mass of maleic anhydride-modified propylene / 1-butene copolymer. .
<Preparation of modified olefin polymer varnish>
[Preparation Example 1: Modified Olefin Polymer Varnish]
100 g of maleic anhydride-modified propylene / 1-butene copolymer produced in Synthesis Example 2 was dissolved in 400 g of toluene to prepare a modified olefin polymer varnish.
<Preparation of polyisocyanate>
[Preparation Example 1: Preparation of modified trimer]
A trimer modified product of 1,6-hexamethylene diisocyanate (trade name: Takenate D-170N, trimer, average functional group number of 3 or more, isocyanate group content 21.0%, manufactured by Mitsui Chemicals, Inc.) Prepared as polyisocyanate (polyisocyanate (C-1)).
<Manufacture of hydrocarbon-based synthetic oil>
[Production Example 1: Production of ethylene / propylene copolymer (hydrocarbon synthetic oil)]
Ethyl aluminum sesquichloride (Al (C ₂ H ₅ ) _1.5 · Cl _1.5 ) adjusted to 96 mmol / L as a catalyst by adding 1 L of dehydrated and purified hexane to a continuous polymerization reactor equipped with stirring blades sufficiently purged with nitrogen A hexane solution of vanadium oxyethoxide dichloride (VO (OC ₂ H ₅ ) Cl ₂ ) adjusted to 16 mmol / L as a catalyst after continuously supplying a hexane solution of 500 mL / h for 1 hour, and Hexane was continuously fed in an amount of 500 mL / h, respectively. At this time, the polymerization solution was continuously extracted from the upper part of the polymerization reactor so that the polymerization solution in the polymerization reactor was always 1 L. Next, ethylene gas and propylene were copolymerized by supplying ethylene gas in amounts of 47 L / h, propylene gas in amounts of 47 L / h, and hydrogen gas in amounts of 20 L / h, respectively, using a bubbling tube. At this time, the reaction temperature of the copolymerization reaction was set to 35 ° C. by circulating a refrigerant through a jacket attached to the outside of the polymerization reactor. The obtained polymerization solution was deashed with hydrochloric acid, poured into a large amount of methanol to precipitate an ethylene / propylene copolymer, and then dried under reduced pressure at 130 ° C. for 24 hours.

The obtained ethylene / propylene copolymer (hydrocarbon synthetic oil (D-1)) had an ethylene content of 55.9 mol%, a kinematic viscosity at 40 ° C. of 37,500 cSt (375 cm ² / s), a molecular weight distribution ( Mw / Mn) was 1.9.
<Production of Composite Film (Aluminum (Al) Foil / Adhesive Layer / Polypropylene (PP) Film Laminate)>
Example 1
The non-volatile content of the modified olefin polymer varnish of Preparation Example 1 and the trimer-modified product of Preparation Example 1 were mixed so as to have the ratio shown in Table 1 on a mass basis to prepare a laminating adhesive. Next, the laminating adhesive is diluted with toluene, and on the glossy surface of an aluminum foil (surface untreated) having a thickness of 40 μm so as to have a basis weight of 3.3 g / m ² (solid content) using a bar coater. It apply | coated at normal temperature and it was made to dry at 80 degreeC for 1 minute, and the solvent was volatilized. Then, the laminating layer is obtained by quickly laminating the coated surface of the laminating adhesive on the aluminum foil and the corona-treated surface of a 60 μm thick unstretched polypropylene film (single-sided corona-treated product) and curing at 60 ° C. for 3 days. The adhesive was cured, and the aluminum foil and the unstretched polypropylene film were adhered to each other to obtain a composite film as a laminate of the aluminum foil, the adhesive layer, and the unstretched polypropylene film.

Examples 2 to 10 and Comparative Examples 1 to 8
A composite film was obtained in the same manner as in Example 1 except that each component was mixed according to the formulation shown in Table 1 to prepare a laminating adhesive.
<Evaluation>
(1) Measurement of initial adhesive strength (normal strength) The composite film of each example and each comparative example was cut into a size of 150 mm in length and 15 mm in width to produce a test piece. Using the apparatus, a 180 ° peel test was performed at a crosshead speed of 50 mm / min to measure the adhesive strength of the composite film. The results are shown in Table 1.
(2) Electrolytic solution resistance test and measurement of adhesive strength (after electrolytic solution immersion) The composite films of each Example and each Comparative Example were prepared by using ethylene carbonate, diethyl carbonate, and 1 mol / L lithium hexafluorophosphate, It was immersed in a mixed solvent (electrolytic solution) containing dimethyl carbonate at a 1/1/1 mass ratio at 85 ° C. for 168 hours. After immersion, the composite film was taken out and immediately immersed in water (in this case, hydrogen fluoride (HF) was generated and dissolved in water to become hydrofluoric acid). Then, after taking out from water and wiping off the moisture, using an autograph (AGS-500B manufactured by Shimadzu Corporation), the polypropylene film adherend is peeled off from the aluminum foil at 180 ° under a condition of 50 mm / min. 180 ° peeling A test was conducted to measure the adhesive strength. The results are shown in Table 1.

The abbreviations of prescriptions in Table 1 are as follows.
A-1: Maleic anhydride-modified propylene / 1-butene copolymer synthesized in Synthesis Example 2 B-1: Isopropyltriisostearoyl titanate (titanate coupling agent, trade name: Plenact KR-TTS, Ajinomoto Fine Techno Co., Ltd.) Made)
B-2: Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphate) titanate (titanate coupling agent, phosphite-derived structure contained, trade name: Plenact KR-55, Ajinomoto (Fine Techno)
B-3: Tetraoctyl bis (ditridecyl phosphate) titanate (containing titanate coupling agent, phosphite ester-derived structure, trade name: Preneact KR-46B, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-4: Tetraisopropylbis (dioctylphosphate) titanate (titanate coupling agent, phosphite-derived structure contained, trade name: Preneact KR-41B, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-5: Isopropyltris (dioctyl pyrophosphate) titanate (containing titanate coupling agent, phosphate ester-derived structure, trade name: Preneact KR-38S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-6: Bis (dioctylpyrophosphate) oxyacetate titanate (containing titanate coupling agent, phosphate ester-derived structure, trade name: Preneact KR-138S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-7: Bis (dioctylpyrophosphate) ethylene titanate (containing titanate coupling agent, phosphate ester-derived structure, trade name: Preneact KR-238S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-8: Isopropyldioctyl pyrophosphate titanate (containing titanate coupling agent, phosphate ester-derived structure, trade name: Preneact KR-338X, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-9: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (silane coupling agent, trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-10: p-styryltrimethoxysilane (silane coupling agent, trade name: KBM-1403, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-11: 3-Methacryloxypropyltrimethoxysilane (silane coupling agent, trade name: KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-12: 3-aminopropyltriethoxysilane (silane coupling agent, trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-13: 3-isocyanatopropyltriethoxysilane (silane coupling agent, trade name: KBM-9007, manufactured by Shin-Etsu Chemical Co., Ltd.)
B-14: Trimethylolpropane tristhioglycolate (TMTG) (thioglycolic acid ester, manufactured by Sakai Chemical Co., Ltd.)
C-1: A trimer-modified product of 1,6-hexamethylene diisocyanate prepared in Preparation Example 1 (trade name: Takenate D-170N, manufactured by Mitsui Chemicals)
D-1: Ethylene / propylene copolymer produced in Production Example 1 <Discussion>
The laminated body of Examples 1-10 in which the additive (B) contained in the composition has a phosphoric acid-derived structure, and the additive (B) that does not contain the additive (B) in the composition or is contained in the composition Compared with the laminates of Comparative Examples 1 to 8 that do not have a phosphoric acid-derived structure, the laminates of Comparative Examples 1 to 8 have a considerably reduced adhesive strength after immersion in the electrolyte solution. It can be seen that in the laminates 1 to 10, a decrease in the adhesive strength after immersion in the electrolyte solution is suppressed.

  From this, it can be seen that when the composition contains an additive (B) having a phosphoric acid-derived structure, a decrease in adhesive strength due to the electrolytic solution can be suppressed.

  Moreover, when the laminated body of Examples 1-3 which uses phosphite as phosphoric acid is compared with the laminated body of Examples 4-6 using phosphate ester, Examples 1-3 are compared. It turns out that the fall of the adhesive strength after electrolyte solution immersion is suppressed rather than the laminated body of Examples 4-6.

  From this, it can be seen that when a phosphite is used as the phosphoric acid, a decrease in adhesive strength due to the electrolytic solution can be suppressed.

  Also, when the laminate of Example 2 containing polyisocyanate (C) and the laminate of Example 8 containing no polyisocyanate (C) are compared in the composition, the laminate of Example 8 is Compared to the laminate of Example 2, both the initial adhesive strength and the adhesive strength after immersion in the electrolytic solution are low. By including polyisocyanate (C) in the composition, the initial adhesive strength is improved and the electrolytic solution is used. It can be seen that the decrease in adhesive strength can be suppressed.

  Moreover, when the laminated body of Example 2 which contains a hydrocarbon type synthetic oil (D) in the composition and the laminated body of Example 9 which does not contain a hydrocarbon type synthetic oil (D) are compared, implementation is carried out. The laminated body of Example 9 has lower initial adhesive strength than the laminated body of Example 2, and the initial adhesive strength can be improved by including the hydrocarbon-based synthetic oil (D) in the composition. I can see that

DESCRIPTION OF SYMBOLS 1 Battery case packaging material 2 Base material 3 Inner layer 4 Outer layer 5 Inner adhesive layer 6 Outer adhesive layer

Claims (15)

Modified Olefin Polymer, Olefin-α, β Unsaturated Carboxylic Acid Copolymer, Ionic Crosslinked Product of Olefin-α, β Unsaturated Carboxylic Acid Copolymer, Styrenic Thermoplastic Elastomer, and Styrenic Thermoplastic Elastomer A thermoplastic resin (A) consisting of at least one selected from the group consisting of
A composition comprising an additive (B) having a phosphoric acid-derived structure. The thermoplastic resin (A) is
The heat of fusion measured according to JIS K7122 is 0 J / g or more and 50 J / g or less,
The weight average molecular weight measured by GPC method is 1 × 10 ⁴ or more and 1000 × 10 ⁴ or less,
The composition according to claim 1, comprising a modified olefin polymer modified with a monomer having a polar group.   The composition according to claim 1, wherein the phosphoric acid having a structure derived from phosphoric acid is a phosphite ester or a phosphate ester.   The composition according to claim 3, wherein the phosphoric acid is a phosphite.   The composition according to claim 3 or 4, wherein the additive (B) is a titanate coupling agent.   Furthermore, polyisocyanate (C) is contained, The composition as described in any one of Claims 2-5 characterized by the above-mentioned.   The composition according to claim 6, wherein the blending ratio of the polyisocyanate (C) is 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).   The composition according to any one of claims 1 to 7, further comprising a hydrocarbon-based synthetic oil (D) having a kinematic viscosity at 40 ° C of 30 to 500,000 cSt.   The composition according to claim 8, wherein a blending ratio of the hydrocarbon-based synthetic oil (D) is 6 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A).   The coating agent characterized by including the composition as described in any one of Claims 1-9.   An adhesive comprising the coating agent according to claim 10. A substrate;
A laminate comprising: an adhesive layer formed on the one side surface of the base material, or one side surface and the other side surface, and formed from the adhesive according to claim 11.   The laminate according to claim 12, wherein the substrate is an aluminum foil.   The laminate according to claim 13, wherein the base material is an untreated aluminum foil that has not been subjected to any surface treatment of anodizing treatment, immersion type chemical conversion treatment, and coating type chemical conversion treatment.   Furthermore, the adherend adhere | attached through the said adhesive bond layer is provided in the one side surface of the said base material, or one side surface and the other side surface, In any one of Claims 12-14 characterized by the above-mentioned. The laminated body of description.

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