JP6427014B2 - Composition, coating agent, adhesive and laminate - Google Patents

Description

  The present invention relates to a composition, a coating agent, an adhesive and a laminate, in particular, a composition, a coating containing the same, an adhesive comprising the same, and a laminate comprising an adhesive layer formed therefrom.

  Conventionally, a lithium ion secondary battery is a laminate including an aluminum foil layer (base material), a thermoplastic resin film layer (inner layer) adhered to the inner surface thereof, and an adhesive layer interposed therebetween. It is known to use as a packaging material (a packaging material for a battery case).

  As the adhesive layer provided in the above-described laminate, for example, a polymer of a C2 to C20 α-olefin containing a structural unit derived from a C4 to C20 α-olefin is reacted with an isocyanate group An adhesive layer formed from an adhesive containing a modified olefin polymer and a polyisocyanate, which is obtained by being modified with a monomer having a functional group capable of 1).

International Publication 2014/123183 A1 Brochure

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

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

  The composition of the present invention comprises 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, A thermoplastic resin (A) comprising at least one selected from the group consisting of modified products of styrenic thermoplastic elastomers, and an additive (B) having a phosphoric acid-derived structure.

Further, in the composition of the present invention, the thermoplastic resin (A) has a heat of fusion of 0 J / g to 50 J / g as measured according to JIS K 7122 and a weight average molecular weight of 1 as measured by GPC method. × 10 ⁴ or more and 1,000 × 10 ⁴ or less, it is preferable made of modified olefin polymer modified by monomers having a polar group.

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

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

  Further, in the composition of the present invention, it is preferable that the additive (B) is a titanate coupling agent.

  Moreover, in the composition of the present invention, it is preferable to further include a polyisocyanate (C).

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

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

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

  Moreover, the coating agent of the present invention is characterized by containing the above-mentioned composition.

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

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

  Further, in the laminate of the present invention, it is preferable that the substrate is an aluminum foil.

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

  Further, in the laminate of the present invention, it is preferable to further include an adherend adhered to the one side surface or the one side surface and the other side surface of the substrate via the adhesive layer.

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

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

  The composition of the present invention comprises 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) is 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 styrene-based thermoplastic elastomer, and And at least one selected from the group consisting of modified products of styrenic thermoplastic elastomers.

  The thermoplastic resin (A) preferably comprises a modified olefin polymer.

  If the thermoplastic resin (A) is a modified olefin polymer, it is possible to obtain a coating agent (described later) which is more excellent in electrolytic solution resistance.

  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 consisting 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 alpha-olefin.

  As the C 4-20 α-olefin, for example, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, Linear or branched α-olefins such as 1-hexadecene, 1-octadecene, 1-eicosene and the like can be mentioned.

  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, and still more preferably 1-butene. It can be mentioned. If 1-butene is used as the C4 to C20 alpha-olefin, it is possible to achieve both good solvent solubility and excellent resin strength. These can be used alone or in combination of two or more.

  As C2-C3 alpha-olefin, ethylene and propylene are mentioned, for example, Preferably, propylene is mentioned.

  As C2-C20 alpha-olefin, the above-mentioned C2-C3 alpha-olefin and above-mentioned C4-C20 alpha-olefin are mentioned, for example. These can be used alone or in combination of two or more.

  As C2-C20 alpha-olefin, Preferably, ethylene, propylene, 1-butene is mentioned, More preferably, combined use of propylene and 1-butene is mentioned.

  Specifically, the α-olefin having 2 to 20 carbon atoms is, for example, one or more selected from α-olefins having 4 to 20 carbon atoms, and at least one selected from α-olefins having 2 to 3 carbon atoms. And copolymers thereof, for example, one or more homopolymers or copolymers selected from α-olefins of 4 to 20 carbon atoms. Preferably, a copolymer is mentioned, 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 mentioned, and further, Preferably, a copolymer of 1-butene and propylene is mentioned. If it is a copolymer of 1-butene and propylene, both good solvent solubility and excellent resin strength can be achieved.

  As a copolymer, a random copolymer and a block copolymer are mentioned, for example. Preferably, a random copolymer is mentioned.

  The content ratio of the structural unit derived from an α-olefin having 4 to 20 carbon atoms is, for example, 5 mol% or more, preferably 100 mol% of the structural unit derived from an α-olefin having 2 to 20 carbon atoms. 10 mol% or more, more preferably 20 mol% or more, 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, outstanding resin strength can be ensured. On the other hand, when the above content ratio is at least the above lower limit, excellent solvent solubility can be secured.

  In addition, the polymer (a) of a C2-C20 alpha-olefin contains the structural unit derived from the alpha-olefin of C2-C20 (a C4-C20 containing) as an essential structural unit, If necessary, constituent units derived from unsaturated monomers other than α-olefins (referred to as other unsaturated monomers) can also be included as arbitrary constituent units. Other unsaturated monomers include, for example, conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene-2 norbornene, 5-vinyl-2 Non-conjugated polyenes such as norbornene, 5-methylene-2-norbornene, 2,5-norbornadiene and the like.

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

  In this case, the content ratio of the structural unit derived from a C 2 -C 3 α-olefin (preferably propylene) is 100% by mole relative to the structural unit derived from a C 2 -C 20 α-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 80 mol% or less, still more preferably 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, when the content ratio is equal to or more than the above lower limit, excellent resin strength can be secured.

  The polymer (a) of the above-mentioned α-olefin having 2 to 20 carbon atoms has 2 to 2 carbon atoms in the presence of a known solid Ti catalyst, metallocene catalyst or the like generally used for the production of α-olefin polymers. It is obtained by polymerizing 20 α-olefins. The metallocene catalyst includes, for example, a metallocene compound such as rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, an organoaluminum oxy compound such as methylaluminoxane, and a triisobutylaluminum or the like. It consists of an organoaluminum compound. More specifically, the polymer (a) can be obtained, for example, by the method described in WO 2004/87775.

  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 (degree of dispersion) is 1 or more and 3 or less. In addition, molecular weight distribution is ratio (Mw / Mn) with respect to the number average molecular weight (Mn) of a weight average molecular weight (Mw).

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

  The polar group is a group having 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 the isocyanate group is a group having an active hydrogen.

  As such a functional group, for example, a hydroxyl group, an amino group, an epoxy group, a carboxyl group, an acid anhydride group represented by the following formula (1) and the like can be mentioned. These polar groups (preferably, the above functional groups) can be used alone or in combination and are preferably carboxyl groups, acid anhydride groups, and more preferably acid anhydride groups.

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

Most preferably, all of the polar groups (preferably, the above functional groups) are carboxyl 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 the polar groups (preferably the above functional group) are carboxyl Group and / or acid anhydride group, preferably when it is an acid anhydride group), when forming an adhesive layer from the composition and curing, a carboxyl group and / or acid anhydride group, preferably The acid anhydride group reacts efficiently with the isocyanate group of the polyisocyanate (C) (described later), or via the additive (B) (described later), the base material of the modified olefin polymer (for example, The affinity to an aluminum foil or the like can be enhanced to further improve the adhesion of the adhesive layer to a substrate such as an aluminum foil or the like. In addition, the electrolytic solution resistance can be improved.
: Formula (1)

  Examples of the monomer (b) having the polar group (preferably, the above functional group) include a hydroxyl group-containing ethylenic unsaturated compound, an amino group-containing ethylenic unsaturated compound, and an epoxy group-containing ethylenic unsaturated compound And unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, vinyl ester compounds, and derivatives thereof (excluding unsaturated carboxylic acid anhydrides) and the like.

  As a hydroxyl group-containing ethylenic unsaturated compound, for example, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy-propyl (meth) acrylate , 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylolethane mono (meth) acrylate, butanediol mono ( Hydroxyl-containing (meth) acrylic acid esters such as meta) acrylates, polyethylene glycol mono (meth) acrylates, 2- (6-hydrohexanoyloxy) ethyl acrylates, and the like 10-undecen-1-ol, 1-octen-3-ol, 2-methanol norbornene, hydroxystyrene, N-methylol acrylamide, 2- (meth) acroyloxy ethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, Allyloxy ethanol, 2-butene 1,4-diol, glycerin monoalcohol and the like can be mentioned.

  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, for example, an alkyl group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, for example, a cycloalkyl group having 6 to 12 carbon atoms, preferably 6 to 9 carbon atoms It is. The above-mentioned alkyl group and cycloalkyl group may further have a substituent.

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

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

As such epoxy group-containing ethylenic unsaturated compounds, for example, glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, 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 - (1 to 12 carbon atoms in the alkyl group in the case of monoglycidyl ester) monoglycidyl esters of unsaturated dicarboxylic acids such as methyl-2,3-dicarboxylic acid (methylnadic acid ^TM), alkyl glycidyl of p- styrene carboxylic acid Ester, allyl glycidyl ether, 2-methyl allyl 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 unsaturated carboxylic acids 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] hepto. Unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid can be mentioned.

  As unsaturated carboxylic acid anhydride, for example, maleic anhydride, itaconic acid anhydride, citraconic acid anhydride, tetrahydrophthalic acid anhydride, bicyclo [2,2,1] hept-2-ene-5,6-dicarboxylic acid anhydride Etc.

  As derivatives, for example, malenyl chloride, malenyl imide, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, 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 Can be mentioned.

  As a vinyl ester compound, for example, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl parserate, vinyl laurate, vinyl stearate, vinyl benzoate, salicylic acid Vinyl, cyclohexane carboxylate vinyl, etc. are mentioned.

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

  As monomer (b), Preferably, unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, More preferably, unsaturated carboxylic acid anhydride, More preferably, maleic anhydride is mentioned. Also preferably, all of the monomers (b) are unsaturated carboxylic acid anhydrides, more preferably all of the monomers (b) are maleic anhydride.

  When monomer (b) is unsaturated carboxylic acid anhydride (specifically, maleic anhydride) (preferably, all of monomer (b) is unsaturated carboxylic acid anhydride (specifically, (Maleic anhydride)), when the adhesive layer is formed from the composition and cured, the unsaturated carboxylic acid anhydride (more specifically, maleic anhydride) is a polyisocyanate (C) While reacting with (described later), or via an additive (B) (described later), the affinity of the modified olefin polymer to a substrate (such as aluminum foil) is enhanced, and the substrate of the adhesive layer ( 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 polar group described above and the monomer (b ′) not having the polar group described above (eg, ethylenic properties such as alkyl (meth) acrylate) The polymer (a) can also be modified using an unsaturated compound or the like in combination. Preferably, the polymer (a) is modified only with the above-mentioned monomer (b) having a polar group without using the monomer (b ') having no polar group in combination. If modified in this manner, the polymer (a) is modified with the polar group-containing monomer (b) without the presence of the polar group-free monomer (b ′). By this, the modified olefin polymer and the polyisocyanate (C) (described later) can be efficiently reacted, or the interaction between the modified olefin polymer and the additive (B) (described later) becomes strong, Therefore, the electrolyte resistance 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 to the monomer (b). Or modified by the polymer. Specifically, in order to prepare a modified olefin polymer, the following methods (1) to (4) may be mentioned.
(1) The polymer (a) is dissolved in an organic solvent, the monomer (b) and the radical polymerization initiator are added, and the mixture is heated and stirred to form the polymer (a) into the monomer (b). Method to denature and react.
(2) The polymer (a) is heated and melted, the monomer (b) and the radical polymerization initiator are added to the obtained melt, and the polymer (a) is converted to the monomer (b) by stirring. Method to denature and 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 for heating and kneading while the polymer (a) is converted to a monomer ( Method to denature by b) and make it react.
(4) After impregnating the polymer (a) with a solution obtained by dissolving the monomer (b) and the radical polymerization initiator in an organic solvent, the polymer (a) is heated to the highest temperature at which the polymer (a) does not dissolve. A method in which the polymer (a) is denatured with the monomer (b) and reacted.

  The compounding ratio of the monomer (b) is not particularly limited as long as the required modified amount of the monomer (b) is finally obtained, and the polymer (a) and the monomer (b) are not particularly limited. 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, relative to a total amount of 100 parts by mass of , 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, and the reaction time is, for example, about 1 minute to 10 hours.

  As a reaction system, a batch system, a continuous system is mentioned, In order to implement modification | denaturation reaction uniformly, Preferably, a batch system is mentioned.

  As a radical polymerization initiator, organic peroxide, organic perester, etc. are mentioned, for example.

  As organic peroxide, for example, 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- Dimethyl-2, 5-di (tert-butylperoxide) hexane, tert-butylperoxybenzoate and the like can be mentioned. Also, as the organic perester, for example, tert-butyl peracetate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl persec-octoate, tert-butyl perpivalate, cumyl perpivalate, A tert- butyl purge ethyl acetate etc. are mentioned. Furthermore, as a radical polymerization initiator, other azo compounds such as azobis-isobutyl nitrile and dimethylazoisobutyl nitrile are also mentioned.

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

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

  In addition, preparation of the modified olefin polymer is carried out in the presence of a solvent or in the absence of a solvent in the methods (1) to (4) above.

  As the solvent, for example, aromatic hydrocarbons such as benzene, toluene and xylene, for example, aliphatic hydrocarbons such as hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclohexane, cyclohexene and methylcyclohexane, for example Alcohols such as methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, eg acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, acetophenone, ketones such as cyclohexanone, eg methyl cellosolve And cellosolves 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. Among these, preferred are aromatic hydrocarbons, aliphatic hydrocarbons, ketones and esters. The solvents can be used singly or in combination of two or more.

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

The weight average molecular weight (Mw) of the modified olefin polymer measured by the 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 ^{It is 4} or more, for example, 1,000 × 10 ⁴ or less, preferably 100 × 10 ⁴ or less, more preferably 50 × 10 ⁴ or less.

When the weight average molecular weight of the modified olefin polymer is at least the above lower limit, the strength of the coating film can be sufficiently high, and the adhesion strength is good. On the other hand, when the weight average molecular weight of the modified olefin polymer is less than or equal to the above upper limit, the solubility in a solvent is good, and solidification and precipitation hardly occur. In particular, when 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 K 7122. Specifically, the temperature is raised from 30 ° C. to 180 ° C. at 10 ° C./min for 3 minutes The temperature is maintained, then the temperature is lowered at 10 ° C./min to 0 ° C., held at that temperature for 3 minutes, and then raised again at 10 ° C./min to 150 ° C. From the thermogram, it can be obtained according to JIS K7122.

  If the melting point (Tm) of the modified olefin polymer is below the above-mentioned upper limit, the adhesive strength can be suppressed even if it is cured at low temperature after application of the composition to form an adhesive layer (described later) . In addition, when the melting point (Tm) of the modified olefin polymer is equal to or higher than the above lower limit, excellent resin strength can be secured.

  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 may be obtained by applying a coating agent (described later) comprising the composition and curing at low temperature to form an adhesive layer (described later) Can be suppressed. On the other hand, when the heat of fusion (ΔH) of the modified olefin polymer is the above lower limit or more, a coating agent (described later) consisting of a composition is applied to a base and then a coating is formed. Strength can be given.

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

The kinematic viscosity at 40 ° C. of the modified olefin polymer 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 flowability is low and the kinematic viscosity can not 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 mass of the modified olefin polymer For example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 15 parts by mass or less, preferably 10 parts by mass or less, more preferably 5 parts by mass The following is more preferably 4 parts by mass or less, particularly preferably 2 parts by mass or less.

  By setting 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 intensified, so that the electrolytic solution resistance can be improved. On the other hand, when the content rate of a monomer (b) exceeds the said upper limit, the quantity of a polar group may increase and electrolyte resistance may fall. Moreover, adhesiveness with a base material can not be ensured as the content rate of a monomer (b) is less than the said lower limit, adhesive strength may fall, and electrolyte resistance may fall.

The amount of modification described above is set by a known means such as ¹ H-NMR measurement, for example. As specific ¹ H-NMR measurement conditions, the following conditions can be exemplified.

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

  When unsaturated carboxylic acid and its anhydride are used as the monomer (b) as an amount to be a measure of the amount of polar group (preferably, the above functional group) introduced into the modified olefin polymer For example, it is also possible to use an acid value.

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

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

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

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

  Here, in the above equation, EP1 is a titration amount (mL), BL1 is a blank value (mL), FA1 is a factor of a titration solution (1.00), C1 is a concentration conversion value (5.611 mg / mL: 0. 1 mo1 / L KOH equivalent to 1 mL of potassium hydroxide), SIZE represents a sampled amount (g), respectively.

  This measurement is repeated three times to make the average value the acid value.

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

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

  The unmodified polymer (a) is 100 parts by mass of the modified olefin polymer composition, that is, 100 parts by mass of the modified olefin polymer and the unmodified polymer (a) in total. The modified olefin polymer is mixed in such a manner that the blending ratio of 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 multicomponent copolymer obtained by copolymerizing at least an olefin and an α, β-unsaturated carboxylic acid, and, for example, an olefin and an α, β-unsaturated carboxylic acid Examples thereof include binary copolymers obtained by copolymerizing an acid and ternary copolymers obtained by copolymerizing an olefin, an α, β-unsaturated carboxylic acid and another copolymer component.

  The olefin is an unsaturated chain hydrocarbon having one or more unsaturated bonds in the molecule, and examples thereof include 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- C2-C20 unsaturated chain hydrocarbon (olefin) such as hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. may be mentioned, 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 has, for example, 4 to 8 carbon atoms such as acrylic acid, methacrylic acid, fumaric acid, maleic acid and crotonic acid. Examples thereof include α, β-unsaturated carboxylic acids, preferably acrylic acid and methacrylic acid. These α, β unsaturated carboxylic acids can be used alone or in combination of two or more.

  Other copolymerization components include, for example, acrylic acid alkyl esters such as α, β-unsaturated carboxylic acid esters (eg, methyl acrylate, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, isooctyl acrylate, etc.) And methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate and isobutyl methacrylate, eg, maleic acid alkyl esters such as dimethyl maleate and diethyl maleate, vinyl esters (eg, vinyl acetate and vinyl propionate) , Vinyl sulfate, vinyl nitrate, vinyl halides (eg, vinyl chloride, vinyl fluoride etc.), vinyl group-containing primary or secondary amine compounds (eg, vinyl amine, N-methylvinylamine etc.), carbon monoxide, sulfur dioxide etc Preferably, α, β-unsaturated carboxylic acid esters are mentioned.

  As other copolymerization components, more preferably, acrylic acid alkyl ester and methacrylic acid alkyl ester are mentioned, and still more preferably, acrylic acid alkyl ester is mentioned.

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

  The method for producing 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 cross-linked body of the olefin-α, β-unsaturated carboxylic acid copolymer is, for example, that at least a part of carboxyl groups in the above-mentioned olefin-α, β-unsaturated carboxylic acid copolymer is neutralized with a metal ion And polymers crosslinked by

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

  The method for producing the ionic cross-linked 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 crosslinkers of the olefin-α, β unsaturated carboxylic acid copolymer can be used alone or in combination of two or more.

  Examples of the styrene-based thermoplastic elastomer include block copolymers of a styrene-based compound and a conjugated diene compound.

  Examples of styrenic compounds include styrene, α-methylstyrene, alkylstyrenes such as p-methylstyrene, p-t-butylstyrene and the like, p-methoxystyrene, vinyl naphthalene and the like, preferably styrene . These styrenic compounds can be used alone or in combination of two or more.

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

  The method for producing 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 styrene-based thermoplastic elastomer can be obtained, for example, by modifying the above-described styrene-based thermoplastic elastomer with the above-described monomer having a polar group (preferably, the above-described functional group).

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

  These styrene-based thermoplastic elastomer modified products can be used alone or in combination of two or more.

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

  Since the composition contains the additive (B) having a phosphoric acid-derived structure, the affinity with a substrate (preferably, an aluminum foil) (described later) is dramatically improved, and thus the electrolytic solution resistance is improved. be able to.

  Phosphoric acids include, for example, 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 acids, Preferably, phosphoric acid ester and phosphite ester are mentioned, More preferably, phosphite ester is mentioned.

  Electrolyte-resistant solution of adhesive (described later) including a composition containing an additive (B) having a phosphoric acid-derived structure, if the phosphoric acid is a phosphoric acid ester or a phosphorous acid ester, particularly a phosphoric acid ester It is possible to improve the quality.

  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, and specifically, (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl phosphate) titanate (titanate coupling agent, containing phosphite ester derived structure, trade name: Prenact KR-55, manufactured by Ajinomoto Fine Techno Co., Ltd.) , Tetraoctyl bis (ditridecyl phosphate) titanate (titanate based coupling agent, containing phosphite ester derived structure, trade name: Prenact KR-46B, manufactured by Ajinomoto Fine Techno Co., Ltd.), tetraisopropyl bis (dioctyl phosphate) titanate (Titanate coupling agent, Acid ester-derived structure-containing, trade name: Prenact KR-41 B, manufactured by Ajinomoto Fine Techno Co., Ltd., isopropyl tris (dioctyl pyrophosphate) titanate (titanate coupling agent, phosphate ester-derived structure contained, trade name: Prenact KR -38S, manufactured by Ajinomoto Fine Techno Co., Ltd., bis (dioctyl pyrophosphate) oxyacetate titanate (titanate based coupling agent, containing phosphate ester-derived structure, trade name: Prenact KR-138S, manufactured by Ajinomoto Fine Techno Co., Ltd.), bis (Dioctyl pyrophosphate) Ethylene titanate (titanate based coupling agent, containing phosphate ester derived structure, trade name: Prenact KR-238S, manufactured by Ajinomoto Fine Techno Co., Ltd.), isopropyl dioctyl Pyrof 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 additive (B) having a phosphoric acid-derived structure Electrolyte resistance can be improved.

  Preferably, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphate) titanate, tetraoctylbis (ditridecylphosphate) titanate, as the additive (B) having a phosphoric acid-derived structure, And tetraisopropyl bis (dioctyl phosphate) titanate.

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

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

  When the composition contains the polyisocyanate (C), the adhesive strength between the substrate and the adherend and the electrolytic solution resistance of the adhesive can be improved.

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

  As a polyisocyanate monomer, aromatic polyisocyanate, aromatic aliphatic polyisocyanate, aliphatic polyisocyanate etc. are mentioned, for example.

  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), Aromatic diisocyanates such as 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenylether diisocyanate, etc. may be mentioned.

  As the aromatic aliphatic polyisocyanate, for example, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethyl xylylene diisocyanate (1,3- or 1,4-tetramer) And aromatic aliphatic diisocyanates such as methyl xylylene diisocyanate or a mixture thereof (TMXDI), ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of aliphatic polyisocyanates include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1 Fatty acids such as 5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate Family diisocyanates and the like.

Aliphatic polyisocyanates also include alicyclic polyisocyanates. Examples of alicyclic polyisocyanates include 1,3-cyclopentadiisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3 5,5-trimethylcyclohexyl isocyanate (isophoro diisocyanate) (IPDI), methylene bis (cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'- methylene bis (cyclohexyl isocyanate, their 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 cycloaliphatic diisocyanates such as mixtures thereof) (H ₆ XDI).

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

As a polyisocyanate monomer, Preferably, aliphatic polyisocyanate and alicyclic polyisocyanate are mentioned, More preferably, 1, 5- pentamethylene diisocyanate (PDI), bis (isocyanato methyl) 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) Can be mentioned.

  The polyisocyanate-modified product has an average functional group number exceeding 2, and, for example, a multimer of the above-mentioned polyisocyanate monomer (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 monomer and monool (for example, monool having 1 to 20 carbon atoms such as octadecanol)) Allophanate modified products produced by the reaction of (a), polyol modified products (eg, polyisocyanate monomer and low molecular weight polyol (having two or more hydroxyl groups), a compound having a number average molecular weight of 40 or more and less than 400, Polyol modified product (alcohol adduct) formed by reaction with trihydric alcohol such as trimethylolpropane Etc.), biuret-modified products (for example, biuret-modified products produced by the reaction of the above-mentioned polyisocyanate monomer with water and amines), urea-modified products (for example, the above-mentioned polyisocyanate monomer and diamine A urea modified product produced by the reaction of (a), an oxadiazine trione modified product (eg, an oxadiazine trione produced by a reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), a carbodiimide modified product (the above poly Examples thereof include carbodiimide-modified products produced by decarboxylation condensation reaction of isocyanate monomers, uretdione-modified products, uretone imine-modified products and the like.

  Furthermore, as a polyisocyanate modified substance, polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) and the like can also be mentioned.

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

  As a polyisocyanate modified body, Preferably, the multimer of the above-mentioned polyisocyanate monomer, a polyol modified body are mentioned, More preferably, the trimer of the above-mentioned polyisocyanate monomer is mentioned.

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

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

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

  When the composition contains a 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 polymers of olefins having 2 to 20 carbon atoms. Among them, preferred are oligomers obtained by homopolymerizing an olefin having 2 to 20 carbon atoms, and oligomers obtained by copolymerizing any mixture of two or more of these olefins. As said C2-C20 olefin, ethylene, propylene, 1-butene, 1-octene, 1-decene, 1-dodecene etc. are mentioned, for example.

  Here, as the hydrocarbon-based synthetic oil (D), an ethylene-based copolymer including 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 constituent units derived from ethylene is, for example, preferably 30 mol% or more, preferably 100 mol% in total of the constituent units derived from ethylene and the constituent units derived from α-olefins having 3 to 20 carbon atoms. Is 40 mol% or more, for example, 70 mol% or less, preferably 60 mol% or less.

  The hydrocarbon-based synthetic oil (D) can be used singly or in combination of two or more.

  The hydrocarbon-based synthetic oil (D) more preferably includes an ethylene-based copolymer containing a structural unit derived from ethylene and a structural unit derived from propylene, and more preferably a structural unit derived from ethylene and The ethylene-type copolymer which consists of a structural unit derived from propylene is mentioned.

  The synthetic hydrocarbon oil (D) can be obtained by polymerizing the above-mentioned olefin having 2 to 20 carbon atoms in the presence of a known polymerization catalyst by the same method as the preparation of the above-mentioned polymer (a). . Examples of the polymerization catalyst include vanadium oxy compounds such as vanadium oxyethoxide dichloride, and organic aluminum compounds such as ethyl aluminum sesquichloride. The polymerization catalysts 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), and 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, 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. Method of preparing the composition In order to prepare the composition, the above-described thermoplastic resin (A), the additive (B) and, if necessary, the polyisocyanate (C) and / or the hydrocarbon synthetic oil (D) Formulate.

  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). Or more, for example, 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1.0 parts by mass or less.

  If the blend ratio of the additive (B) is within the above range, the affinity to the base material (preferably aluminum foil) (described later) can be efficiently improved.

  The proportion of the polyisocyanate (C) compounded if 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) The above is, for example, 30 parts by mass or less, preferably 20 parts by mass or less, 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 efficiently reacted to enhance the electrolytic solution resistance.

  In addition, 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 as required (isocyanate group (NCO group) / polar group (preferably Is the above functional group) 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) to the isocyanate group of the polyisocyanate (C) is within the above range, the thermoplastic resin (A) and the polyisocyanate (C) are efficiently reacted, Electrolyte resistance can be improved.

  In addition, the blending ratio of the hydrocarbon synthetic oil (D) blended according to need 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.

  If 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.

  In addition, the composition or each component constituting it, specifically, the thermoplastic resin (A), the additive (B), the polyisocyanate (C), and the hydrocarbon synthetic oil (D), are required. In accordance with any or all of them, stabilizers (such as light stabilizers and heat stabilizers) such as epoxy resins, curing catalysts, leveling agents, antifoaming agents, antioxidants and ultraviolet light absorbers, plasticizers, Surfactant, pigment, thixotropic agent, thickener, tackifier, surface conditioner, anti-settling agent, weathering agent, pigment dispersant, antistatic agent, filler, organic or inorganic fine particles, mildew agent, silane Other additives such as coupling agents may be blended.

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

  Examples of the solvent include the same solvents as described above, preferably toluene, methylcyclohexane / methyl isobutyl ketone mixed solvent, methylcyclohexane / methyl ethyl ketone mixed solvent, methylcyclohexane / ethyl acetate mixed solvent, cyclohexane / methyl ethyl ketone mixed solvent, cyclohexane / Ethyl acetate mixed solvent, cellosolves / cyclohexanone mixed solvent may be mentioned, and more preferably toluene may be mentioned. In addition, water can also be used as a dispersion medium.

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

  The solvent is such that the content ratio of non-volatile components to 100 parts by mass of varnish is, 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 Is formulated 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, a paint, a hot melt adhesive, an optically clear double-sided tape. In addition, a laminate having at least one layer obtained from the coating agent is suitably used as a decorative film.

  Moreover, when using as a coating agent, an additive can also be added in an appropriate ratio as needed. Additives include, for example, pigments such as titanium oxide (rutile type), zinc oxide, carbon black, for example, thixotropic agents, for example, thickeners, for example, tackifiers such as rosin resin and terpene resin, and the like Defoamers, surface conditioners, anti-settling 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 to form 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, microgravure coating method, roll coating method, blade coating method, rod coating method, roll doctor method Coating agent on the substrate by 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 dip coating method After the application, it is dried by an appropriate method such as natural drying or heating forced drying. A coating is obtained by this.

  The thickness of the coated 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 a laminate having at least one layer of a coating film formed of a coating agent is used as a decorative film, it can be used in combination with a film having a known design. For example, a film previously decorated by printing, painting, vapor deposition or the like, or a film decorated by a combination of these is used as a design layer, and this is laminated with a coating film formed from a coating agent.

  Here, as a film which has a design layer, thermoplastic films, such as an acrylic film, a PET film, a polycarbonate film, a COC (cyclic olefin copolymer) film, a polyolefin film, a vinyl chloride film, and ABS, are mentioned.

  When a laminate having at least one layer of a coating film formed of a coating agent is used as a decorative film, the method for producing the decorative film is not particularly limited, and an adherend of the decorative film having a design layer On the surface facing the film, a method of dry laminating the coating film by transfer, a method of providing a design layer directly on the coating film by printing, etc., forming a clear layer, another coating layer, and a coating film sequentially on the film And the like.

  When a laminate having at least one layer of a coating film formed from a coating agent is used as a decorative film, for example, existing vacuum forming methods such as vacuum forming method and pressure vacuum forming method, insert forming method and in-mold method By utilizing the molding method, the TOM method by the “vacuum forming apparatus” described in Japanese Patent No. 3733564, or the like, it is possible to decorate a molded body having a complicated three-dimensional structure. The adherend of the decorative film is, for example, a polyolefin material such as PP, a polyamide resin such as nylon, for example, a polar resin such as ABS, PC, PET, PPS, acrylic resin, for example, ED steel plate, Mg alloy, SUS Inorganic materials such as (stainless steel), aluminum, aluminum alloy, glass and the like can be mentioned. Moreover, the to-be-adhered body in which the said resin and the said inorganic material were compounded is also mentioned. In the decorative film, for example, a coating film obtained from a coating agent adheres to an adherend.

  As a molded object obtained by the above-mentioned decoration method, for example, members for interior and exterior of car, for example, various front panels such as AV equipment, for example, surface cosmetic materials such as buttons and emblems, for example, information home appliances such as mobile phones and cameras Housings, housings, display windows, buttons, etc., for example, exterior materials for furniture, for example, interior materials for buildings such as bathroom, wall, ceiling, floor, etc., for example, outer wall such as siding, roof, roof, gate , Exterior materials for building such as a panel, for example, surface coverings of furniture such as a window frame, door, handrail, sill, sill, for example, optical members such as various displays, lenses, mirrors, goggles, window glass, for example , Interior and exterior members of various vehicles other than cars such as trains, aircrafts, ships etc., and various kinds of packaging containers such as bottles, cosmetics containers, accessory cases, packaging materials Prize, and the like various other applications such as miscellaneous goods and accessories.

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

  When a coating agent is used as an adhesive, if necessary, for example, an epoxy resin, a curing catalyst, a leveling agent, a defoamer, a stabilizer such as an antioxidant or a UV absorber, a plasticizer, a surfactant, a pigment, Additives such as fillers, organic or inorganic fine particles, mildewproofing agents, and silane coupling agents may be blended.

  Hereinafter, the specific example at the time of using as an adhesive agent is demonstrated. That is, specifically, the adhesive layer is laminated on the surface (one side) of the substrate, or on the front and back (one side and the other side), and a laminate is obtained from this substrate and the adhesive layer. (For example, an adhesive sheet) is formed.

  As the substrate, for example, a film made of a polyolefin material such as PP, for example, a film made of a polar resin such as ABS, PC, PET, PPS, polyamide, acrylic resin, etc., for example, ED steel plate, Mg alloy, SUS (stainless steel) And metal foils made of aluminum, aluminum alloy or the like, more preferably metal foils, further preferably aluminum foils. These substrates can be used alone or in combination of two or more.

  By using an aluminum foil as the substrate, a laminate having 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 aluminum foil is used as the substrate, the surface of the aluminum foil may or may not be subjected to surface treatment such as anodizing treatment, immersion type chemical conversion treatment, coating type chemical conversion treatment, etc. Preferably, the surface is the surface of the aluminum foil Do not process.

  That is, when using an aluminum foil as a base material, Preferably, the untreated aluminum foil to which any surface treatment of anodizing treatment, immersion type chemical conversion treatment, and coating type chemical conversion treatment is not given is used.

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

  In order to laminate the adhesive layer on the front surface or the front and back surfaces of the substrate, a coating agent is applied, for example, by the application method described above. Thereafter, when the coating agent contains a solvent, the applied coating agent is evaporated by heating. This forms an 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.

  This produces a laminate comprising a substrate and an adhesive layer.

  Furthermore, an adherend can be provided on the surface (one side) or the front and back (one side and the other side) of the adhesive layer described above to form a laminate made of them.

  As the adherend, for example, polyolefin materials such as PP, for example, polar resins such as ABS, PC, PET, PPS, polyamide, acrylic resin, etc., for example, ED steel plate, Mg alloy, SUS (stainless steel), aluminum, aluminum alloy And inorganic materials such as glass. Moreover, the to-be-adhered body in which the said resin and the said inorganic material were compounded is also mentioned. Preferably, films and molded articles made of polyolefin materials can be mentioned. A treatment such as corona treatment can also be applied to the adhesive 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. An adhesive layer is thereby interposed between the substrate and the adherend. That is, a laminate including the base, the adherend, and the adhesive layer is manufactured.

  Thereafter, the adhesive layer is cured by heating the laminate. Thus, the base material and the adherend adhere to each other by the adhesive layer.

  As the heating conditions, appropriate conditions are selected, for example, at a temperature of 80 ° C. or less, preferably 70 ° C. or less, and for example, 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 at a high temperature of 100 ° C. or higher, preferably 120 ° C. or higher, for example, 200 ° C. or lower, for example, 0.1 seconds As described above, preferably, a method (high temperature thermocompression bonding method) of thermocompression bonding is selected for a short time of, for example, 0.5 seconds or more and, for example, 60 seconds or less. 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 cure is selected.

When the polyisocyanate (C) is blended in the composition, the adhesive layer is cured by the heating described above. That is, the polar group (preferably, the above functional group) of the thermoplastic resin (A) and the isocyanate group of the polyisocyanate (C) react with each other. Thus, the substrate and the adherend are firmly adhered 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 used, for example, as a packaging material for a battery case which is excellent in electrolytic solution resistance, more preferably as a packaging material for a lithium secondary battery case.
7-1. Battery Case Packaging Material and Battery Battery Case Packaging Material will be described with reference to FIG. In FIG. 1, the upper side of the drawing is described as the outer side, and the lower side of the drawing is as the inner side.

  As shown in FIG. 1, the battery case packaging material 1 includes a base 2, an inner layer 3 bonded to the inner side of the base 2, an outer layer 4 bonded to the outer side of the base 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 includes metal foil, more preferably aluminum foil and 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, an unstretched polypropylene film or the like is preferably used. Thermoplastic polyolefin films and the like.

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

  The outer layer 4 is not particularly limited, but preferably a polyester film, polyamide, in order to impart heat resistance in a heat sealing step during battery production, moldability during processing, pinhole resistance, and insulation during circulation. Examples of the film include multilayer films in which an oriented or unoriented film such as a film or a polypropylene film is laminated in a single layer or two or more layers.

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

  And, the adhesive of the present invention may be used at least in the inner adhesive layer 5, and the adhesive of the outer adhesive layer 6 may be of the present invention as long as the adhesiveness between the outer layer 4 and the substrate 2 can be secured. In addition to the above-mentioned adhesives, it is possible to use any other adhesive such as an adhesive for dry lamination, a non-solvent type adhesive and the like.

  Next, a battery including the 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 electrolytic solution 11 packaged in the battery case packaging material 1. In addition, the battery 10 includes a positive electrode 17, a negative electrode 18, and a separator 19 which are accommodated in the battery case packaging material 1.

  The battery case packaging material 1 is formed in a bag (laminated cell) shape so that the electrolytic solution 11 described below contacts the inner surface of the inner layer 3 in the battery case packaging material 1. Specifically, the battery case packaging material 1 packages the electrolytic solution 11 such that the inner layer 3 is in contact with the electrolytic solution 11.

  The electrolyte solution 11 is not particularly limited, and examples thereof include non-aqueous electrolyte solutions in which a support salt is dissolved in an organic solvent.

As the supporting salt, for example, 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 the organic solvent, for example, ethylene carbonate (EC), propylene carbonate (PC), γ-butyrolactone (γ-BL), diethyl carbonate (DEC), dimethyl carbonate (DMC), etc. are used in conventional secondary batteries and capacitors Organic solvents are 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 opposite to each other at a distance from each other so as to be in contact with the electrolytic solution 11. The separator 19 is disposed so as to be sandwiched by the positive electrode 17 and the negative electrode 18.

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

8. Effects of the Embodiment The adhesive including the composition described above and the laminate including the adhesive layer formed therefrom are excellent in the electrolytic solution, and can sufficiently suppress the 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, in the battery case packaging material 1 and the battery 10, the resistance to an electrolytic solution and the reduction in the adhesion strength between the base 2 and the inner layer 3 are excellent.

  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 for 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 a lithium ion secondary battery case, which is excellent in durability and reliability.

  The composition described above is not limited to the packaging material for the battery case, but has resistance to high polar solvents such as electrolyte, alkali resistance, and alcohol resistance, and has excellent electrolyte resistance in the film and the adhesive layer. It can be used also as an adhesive for lamination, and a laminate provided with an adhesive layer formed from the adhesive for lamination can be used as a packaging material for highly alkaline solution or a packaging material for alcohol-containing solution.

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

Specific numerical values such as blending ratios (content ratios), physical property values, parameters, etc. used in the following description are the blending ratios (content ratios) corresponding to those described in the above-mentioned "embodiments for carrying out the invention" ), Physical property values, parameters, etc. may be substituted for the upper limit (numerical values defined as “below”, “less than”) or lower limit (numerical values defined as “above”, “exceed”), etc. it can.
1. Physical Properties of Compounds Physical properties of each compound were evaluated according to the following.
[Content ratio of constituent units derived from propylene, ethylene and 1-butene]
The content ratio of the structural unit derived from each of propylene, ethylene and 1-butene was determined using ¹³ C-NMR.
[Melting point (Tm), heat of fusion (ΔH)]
The melting point (Tm) and the heat of fusion (ΔH) were determined using a differential scanning calorimeter (manufactured by 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 for 3 minutes at that temperature, then lowered to 10 ° C./min to 0 ° C. In the process of holding for 3 minutes and raising the temperature again to 10 ° C./min to 150 ° C., the melting point (Tm) and the heat of fusion (ΔH) were determined according to JIS K 7122 from the thermogram at the second temperature rise. .
[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 the molecular weight distribution (degree of dispersion) (Mw / Mn) were measured under the following conditions using a gel permeation chromatograph (manufactured by Shimadzu Corporation; LC-10 series).

・ Detector: Shimadzu Corporation make; C-R4A
-Column: TSKG 6000H-TSKG 4000 H-TSKG 3000 H-TSKG 2000 H (made by Tosoh Corporation)
Mobile phase: Tetrahydrofuran Temperature: 40 ° C
・ Flow rate: 0.8mL / min
The weight average molecular weight (Mw) and the molecular weight distribution (Mw / Mn) were calculated using a calibration curve prepared with monodispersed standard polystyrene.
[Modified amount of maleic anhydride]
The content rate (modified amount) of maleic anhydride was determined from the measurement by ¹ H-NMR.

<Synthesis of polymer>
Synthesis Example 1: Synthesis of Propylene / 1-Butene Copolymer
900 mL of hexane, 90 g of 1-butene, 1 mmol of triisobutylaluminum was added to a fully nitrogen-replaced 2 L autoclave, the temperature was raised to 70 ° C., and then propylene was fed to total pressure 7 kg / cm ² G (gauge Pressure), add 0.30 mmol of methylaluminoxane, 0.001 mmol of rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride in terms of Zr atoms, and add propylene continuously. Polymerization was carried out for 30 minutes while maintaining the total pressure at 7 kg / cm ² G (gauge pressure). After polymerization, the polymer was degassed in a large amount of methanol and degassed under reduced pressure at 110 ° C. for 12 hours. Melting point (Tm) of the obtained propylene / 1-butene copolymer is 78.3 ° C., heat of fusion (ΔH) is 29.2 J / g, weight average molecular weight (Mw) is 330,000, molecular weight distribution (dispersion degree 2.) (Mw / Mn) 2, the content ratio of the structural unit derived from propylene was 67.2 mol%, and the content ratio of the structural unit 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, the temperature was raised to 145 ° C. under a nitrogen atmosphere, and the propylene / 1-butene copolymer was dissolved in toluene. Furthermore, under stirring, 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were supplied to the system over 4 hours, followed by stirring at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate a maleic anhydride-modified propylene / 1-butene copolymer, which was filtered, washed with acetone, and then vacuum dried.

Melting point (Tm) of the obtained maleic anhydride modified propylene / 1-butene copolymer (thermoplastic resin (A-1)) is 75.8 ° C., heat of fusion (ΔH) is 28.6 J / g, weight average The molecular weight (Mw) was 110,000, the molecular weight distribution (Mw / Mn) was 2, and the modified amount of maleic anhydride was 1 part by mass with respect to 100 parts by mass of the maleic anhydride-modified propylene / 1-butene copolymer .
<Preparation of Modified Olefin Polymer Varnish>
Preparation Example 1: Modified Olefin Polymer Varnish
100 g of the maleic anhydride-modified propylene / 1-butene copolymer prepared 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 Trimmer Denatured Body
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 of 21.0%, manufactured by Mitsui Chemicals, Inc.) It prepared as a polyisocyanate (polyisocyanate (C-1)).
<Manufacture of hydrocarbon-based synthetic oil>
Preparation Example 1: Preparation of ethylene / propylene copolymer (hydrocarbon-based synthetic oil)
Ethylaluminum 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 with a stirring blade sufficiently substituted with nitrogen. After continuously supplying a hexane solution of 500 mL / h for 1 hour, a hexane solution of vanadium oxyethoxide dichloride (VO (OC ₂ H ₅ ) Cl ₂ ) further adjusted to 16 mmol / L as a catalyst, and And hexane were continuously supplied in an amount of 500 mL / h, respectively. Under the present circumstances, the polymerization liquid was continuously extracted from the polymerization reactor upper part so that the polymerization liquid in a polymerization reactor might always be 1L. Next, ethylene and propylene were copolymerized by supplying ethylene gas at 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using bubbling pipes, respectively. At this time, the reaction temperature of the copolymerization reaction was 35 ° C. by circulating the refrigerant through a jacket attached to the outside of the polymerization reactor. The obtained polymerization solution was deashed with hydrochloric acid, then 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 ethylene content of the obtained ethylene / propylene copolymer (hydrocarbon-based synthetic oil (D-1)) is 55.9 mol%, the kinematic viscosity at 40 ° C. is 37,500 cSt (375 cm ² / s), and the 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 component 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 described in Table 1 on a mass basis, to prepare a laminating adhesive. Next, the laminating adhesive is diluted with toluene, and a bar coater is used to coat a 40 μm thick aluminum foil (surface untreated) to a basis weight of 3.3 g / m ² (solid content). It apply | coated under normal temperature, dried at 80 degreeC for 1 minute, and the solvent was volatilized. Thereafter, the coated surface of the aluminum foil with the adhesive for lamination and the corona-treated surface of the unstretched polypropylene film (one-sided corona-treated product) having a thickness of 60 μm are bonded together, and cured at 60 ° C. for 3 days. The adhesive for curing was cured to bond between the aluminum foil and the unstretched polypropylene film 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
Each component was mixed according to the formulation shown in Table 1 to prepare a composite adhesive, except that a laminating adhesive was prepared.
<Evaluation>
(1) Measurement of initial adhesive strength (normal strength) The composite film of each example and each comparative example is cut out into a size of 150 mm in length and 15 mm in width to prepare a test piece, and the universal tensile measurement of this test piece Using an 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) Measurement of electrolytic solution resistance test and measurement of adhesive strength (after electrolytic solution immersion) Ethylene carbonate, diethyl carbonate and composite film of each example and each comparative example containing 1 mol / L of lithium hexafluorophosphate It was immersed at 85 ° C. for 168 hours in a mixed solvent (electrolytic solution) containing dimethyl carbonate at a mass ratio of 1/1/1. 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 be hydrofluoric acid). Then, after taking out from water and wiping off moisture, using an autograph (AGS-500B manufactured by Shimadzu Corporation), the polypropylene film adherend is peeled off from the aluminum foil at 180 ° under the condition of 50 mm / min 180 ° peeling Tests were conducted to determine adhesion strength. The results are shown in Table 1.

The description of the abbreviations of the prescription in Table 1 is as follows.
A-1: Maleic anhydride-modified propylene / 1-butene copolymer B-1 synthesized in Synthesis Example 2: isopropyl triisostearoyl titanate (titanate coupling agent, trade name: Prenact KR-TTS, Ajinomoto Fine Techno Co., Ltd.) Made)
B-2: Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecylphosphate) titanate (titanate coupling agent, containing a phosphite ester-derived structure, trade name: Prenact KR-55, Ajinomoto Co., Ltd.) Made by Fine Techno Co.)
B-3: Tetraoctyl bis (ditridecyl phosphate) titanate (titanate coupling agent, containing a phosphite ester-derived structure, trade name: Prenact KR-46B, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-4: Tetraisopropyl bis (dioctyl phosphate) titanate (titanate coupling agent, containing a phosphite ester-derived structure, trade name: Prenact KR-41B, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-5: Isopropyl tris (dioctyl pyrophosphate) titanate (titanate coupling agent, containing a phosphate ester-derived structure, trade name: Prenact KR-38S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-6: Bis (dioctyl pyrophosphate) oxyacetate titanate (titanate coupling agent, containing a phosphate ester-derived structure, trade name: Prenact KR-138S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-7: Bis (dioctyl pyrophosphate) ethylene titanate (titanate coupling agent, containing a phosphate ester-derived structure, trade name: Prenact KR-238S, manufactured by Ajinomoto Fine Techno Co., Ltd.)
B-8: Isopropyl dioctyl pyrophosphate titanate (titanate coupling agent, containing a phosphate ester-derived structure, trade name: Prenact 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-methacryloxypropyl trimethoxysilane (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 tristhioglycollate (TMTG) (thioglycolic acid ester, manufactured by Sakai Chemical Co., Ltd.)
C-1: trimer modified product of 1,6-hexamethylene diisocyanate prepared in Preparation Example 1 (trade name: Takenate D-170N, manufactured by Mitsui Chemicals, Inc.)
D-1: Ethylene / propylene copolymer prepared in Preparation Example 1 <Discussion>
Additive (B) contained in the composition is the laminate of Examples 1 to 10 having a structure derived from phosphoric acids, and additive (B) contained in the composition or containing additive (B) in the composition In comparison with the laminates of Comparative Examples 1 to 8 in which the structure does not have a phosphoric acid-derived structure, in the laminates of Comparative Examples 1 to 8, the adhesive strength after immersion in the electrolytic solution is considerably reduced, It is understood that in the laminates of 1 to 10, the decrease in adhesive strength after immersion in the electrolytic solution is suppressed.

  From this, it is understood that when the composition contains the additive (B) having a phosphoric acid-derived structure, it is possible to suppress the decrease in the adhesive strength by the electrolytic solution.

  Moreover, when the laminated body of Examples 1-3 which uses phosphite as phosphoric acids and the laminated body of Examples 4-6 which uses phosphoric acid ester are compared, It can be seen that in the laminate, the decrease in adhesive strength after immersion in the electrolytic solution is suppressed more than in the laminates of Examples 4 to 6.

  From this, it is understood that the use of a phosphite as the phosphoric acid can suppress the decrease in adhesion strength due to the electrolytic solution.

  Moreover, when the laminate of Example 2 containing the polyisocyanate (C) and the laminate of Example 8 not containing the polyisocyanate (C) in the composition are compared, the laminate of Example 8 Compared with the laminate of Example 2, the initial adhesive strength and the adhesive strength after immersion in the electrolytic solution are lower, and by including the polyisocyanate (C) in the composition, the initial adhesive strength is improved and the electrolytic solution is used. It turns out that the fall of adhesive strength can be suppressed.

  Moreover, when the laminated body of Example 2 which contains hydrocarbon synthetic oil (D) in a composition, and the laminated body of Example 9 which does not contain hydrocarbon synthetic oil (D) are compared, The laminate of Example 9 has lower initial adhesive strength as compared with the laminate of Example 2, and it is possible to improve the initial adhesive strength by including the hydrocarbon synthetic oil (D) in the composition. I know what I can do.

1 Battery Case Packaging Material 2 Base Material 3 Inner Layer 4 Outer Layer 5 Inner Adhesive Layer 6 Outer Adhesive Layer

Claims (12)

A thermoplastic resin (A) comprising a modified olefin polymer,
Additives having a phosphoric acid-derived structure and (B) seen including,
The phosphoric acid having a phosphoric acid-derived structure is a phosphoric acid ester or a phosphorous acid ester,
Wherein said additive (B), wherein the Rukoto der titanate coupling agent, composition. 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 the GPC method is 1 × 10 ⁴ or more and 1000 × 10 ⁴ or less,
The composition according to claim 1, wherein the composition comprises a modified olefin polymer modified with a monomer having a polar group. The composition according to claim 1 , further comprising a polyisocyanate (C). The composition according to claim 3 , wherein a 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 4 , further comprising a hydrocarbon-based synthetic oil (D) having a kinematic viscosity of 30 to 500,000 cSt at 40 ° C. The composition according to claim 5 , wherein a blending ratio of the hydrocarbon synthetic oil (D) is 6 to 50 parts by mass with respect to 100 parts by mass of the thermoplastic resin (A). A coating agent comprising the composition according to any one of claims 1 to 6 . An adhesive comprising the coating agent according to claim 7 . A substrate,
The adhesive agent layer laminated | stacked on the one side of the said base material, or one side, and the other side, and is formed from the adhesive agent of Claim 8 , The laminated body characterized by the above-mentioned. The laminate according to claim 9 , wherein the substrate is an aluminum foil. The laminate according to claim 10 , wherein the base material is an untreated aluminum foil which has not been subjected to any surface treatment of anodizing treatment, immersion type chemical conversion treatment and coating type chemical conversion treatment. The substrate according to any one of claims 9 to 11 , further comprising an adherend adhered to the one side surface or the one side surface and the other side surface of the substrate via the adhesive layer. Description laminate.

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