JPWO2019225254A1 - Coatings, films, laminates and packaging materials for battery cases - Google Patents

Abstract

An object of the present invention is to provide a coating agent having excellent heat resistance and electrolytic solution resistance, and capable of forming a moldable adhesive layer without causing whitening, breakage, peeling, or the like. The coating agent of the present invention contains an olefin polymer (A), an olefin polymer (B) and an organic solvent, and the olefin polymer (A) contains 97 mol% or more and 100 mol% or less of the propylene-derived structural unit (a1). An olefin polymer containing 0 mol% or more and 3 mol% or less of a structural unit (a2) derived from α-olefin (excluding propylene) having 2 to 20 carbon atoms, based on the total amount of the total olefin polymer. The content ratio of the structural unit derived from propylene is 89.0 mol% or more and 97.4 mol% or less, the melting point of the olefin polymer (A) is 150 to 170 ° C., and the melting point of the olefin polymer (B) is. The temperature is 70 to 145 ° C., and the olefin polymer (A) is contained in a dispersed state in an organic solvent.

Description

The present invention relates to coating agents, films, laminates and packaging materials for battery cases.

Conventionally, a lithium ion secondary battery is a laminate in which an aluminum foil layer as a base material, an adhesive layer, and a film layer (inner layer) made of a thermoplastic resin such as polypropylene as an adherend are laminated in this order. It is known to be used as a packaging material (packaging material for a battery case).

As the adhesive layer provided in the above-mentioned laminate, for example, a carboxyl group obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid or an acid anhydride thereof on a homopolymer of propylene or a copolymer of propylene and ethylene. An adhesive layer containing the modified polyolefin resin having the above and a polyfunctional isocyanate compound has been proposed (see, for example, Patent Document 1).

The adhesive layer of Patent Document 1 has electrolytic solution resistance that suppresses a decrease in adhesive strength between the aluminum foil layer and the thermoplastic resin film layer over time due to contact with the electrolytic solution of the lithium ion secondary battery. have.

However, the adhesive layer is required to further improve the electrolytic solution resistance and the adhesive strength, and the adhesive layer described in Patent Document 1 has a problem that such requirements cannot be sufficiently satisfied. ..

In view of such problems, the applicant has proposed an adhesive having excellent durability and capable of sufficiently suppressing a decrease in adhesive strength, a laminate having an adhesive layer formed from the adhesive, and the like. (See Patent Document 2).

Japanese Unexamined Patent Publication No. 2010-09203 International Publication No. 2014/12183

However, further improvement in heat resistance and electrolytic solution resistance to the adhesive layer is required, and with conventional adhesives, there may be a problem that the stretched portion is whitened when partially stretched at room temperature during molding. there were.

The present invention is a coating agent having excellent heat resistance and electrolytic solution resistance, and capable of forming a moldable adhesive layer without causing whitening, breakage, peeling, etc., and a film obtained from the coating agent. An object of the present invention is to provide a laminate containing an adhesive layer obtained from the coating agent, a packaging material for a battery case containing the laminate, and the like.

As a result of diligent studies, the present inventors have found that the above problems can be solved by a coating agent having the following constitution, and have completed the present invention. A configuration example of the present invention is as follows.

[1] A coating agent containing an olefin polymer (A), an olefin polymer (B), and an organic solvent.
The olefin polymer (A) contains 97 mol% or more and 100 mol% or less of the structural unit (a1) derived from propylene, and the structural unit (a2) 0 derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is an olefin polymer containing mol% or more and 3 mol% or less (however, the total of the constituent units (a1) and the constituent units (a2) is 100 mol%).
The olefin polymer (B) contains 70 mol% or more and less than 97 mol% of the structural unit (b1) derived from propylene, and the structural unit (b2) 3 derived from α-olefin (excluding propylene) having 2 to 20 carbon atoms. It is an olefin polymer containing more than mol% and 30 mol% or less (however, the total of the structural unit (b1) and the structural unit (b2) is 100 mol%).
The content ratio of the structural unit derived from propylene to the total amount of the total olefin polymer is 89.0 mol% or more and 97.4 mol% or less.
The olefin polymer (A) has a melting point of 150 to 170 ° C., and the olefin polymer (B) has a melting point of 70 to 145 ° C.
The olefin polymer (A) is contained in a state of being dispersed in an organic solvent.
Coating agent.

[2] The coating agent according to Item [1], wherein a part or all of the olefin polymer (A) or (B) is a modified olefin polymer graft-modified with a polar group-containing monomer.
[3] The coating agent according to Item [2], wherein the modified olefin polymer contains a structural unit derived from the polar group-containing monomer in an amount of 0.1 to 15% by mass.
[4] The coating agent according to Item [2] or [3], wherein the polar group-containing monomer contains at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.
[5] The coating agent according to any one of Items [1] to [4], which further contains a curing agent (C).
[6] The coating agent according to Item [5], wherein the curing agent (C) contains at least one selected from the group consisting of an aliphatic polyisocyanate and a multimer of an aliphatic polyisocyanate.
[7] The coating agent according to Item [5], wherein the curing agent (C) contains at least one compound selected from the group consisting of an epoxy compound and an oxazoline compound.
[8] The coating agent according to any one of Items [5] to [7], which further contains a catalyst (D) having a pKa of 11 or more.
[9] The coating agent according to any one of Items [1] to [8], wherein the structural unit (a2) or the structural unit (b2) is a structural unit derived from ethylene or 1-butene.
[10] The coating agent according to any one of Items [1] to [9], which further contains a liquid or semi-solid hydrocarbon (E) having a kinematic viscosity at 200 ° C. of 10 to 100,000 mm ^{2 / s.}
[11] The coating agent according to Item [10], wherein the hydrocarbon (E) is a polymer of an olefin having 2 to 20 carbon atoms (excluding the olefin polymers (A) and (B)).
[12] The coating agent according to any one of Items [1] to [10], wherein the total amount of the total olefin polymer is the total amount of the olefin polymer (A) and the olefin polymer (B).
[13] The coating agent according to any one of items [1] to [12], which is an adhesive.
[14] A film obtained from the coating agent according to any one of Items [1] to [13].
[15] The film according to Item [14], wherein the elongation at break measured according to JIS C2151 is 4.7% or more.
[16] A laminate having a base material and a layer made of the coating agent according to any one of Items [1] to [13].
[17] The coating agent according to any one of Items [1] to [13] includes a laminate in which a metal foil, an adhesive layer, and an adherend are laminated in this order. A packaging material for a battery case, which is a layer of material.
[18] A step of forming an adhesive layer by applying the coating agent according to any one of Items [1] to [13] to the metal foil and then baking the metal foil, and the above-mentioned step of forming the adhesive layer. A method for manufacturing a packaging material for a battery case, which comprises a step of laminating an adherend on a surface opposite to the metal foil by an extrusion laminating method.

According to the present invention, a coating agent having excellent heat resistance and electrolytic solution resistance and capable of forming a moldable adhesive layer without causing whitening, breakage, peeling, etc., is obtained from the coating agent. A film, a laminate containing an adhesive layer obtained from the coating agent, and a packaging material for a battery case containing the laminate can be provided.

It is the schematic sectional drawing of one Embodiment of the battery using the packaging material for a battery case of this invention.

Hereinafter, the present invention will be described in detail.
[Coating agent]
The coating agent of the present invention contains an olefin polymer (A), an olefin polymer (B) and an organic solvent.
The olefin polymer (A) contains 97 mol% or more and 100 mol% or less of the structural unit (a1) derived from propylene, and the structural unit (a2) 0 derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is an olefin polymer containing mol% or more and 3 mol% or less (however, the total of the constituent units (a1) and the constituent units (a2) is 100 mol%).
The olefin polymer (B) contains 70 mol% or more and less than 97 mol% of the structural unit (b1) derived from propylene, and the structural unit (b2) 3 derived from α-olefin (excluding propylene) having 2 to 20 carbon atoms. It is an olefin polymer containing more than mol% and 30 mol% or less (however, the total of the structural unit (b1) and the structural unit (b2) is 100 mol%).
The content ratio of the structural unit derived from propylene to the total amount of the total olefin polymer is 89.0 mol% or more and 97.4 mol% or less.
The olefin polymer (A) has a melting point of 150 to 170 ° C., and the olefin polymer (B) has a melting point of 70 to 145 ° C.
The olefin polymer (A) is contained in a state of being dispersed in an organic solvent.
It is characterized by that. Further, the coating agent of the present invention further contains a curing agent (C) and / or a liquid or semi-solid hydrocarbon (E) having a ^{kinematic viscosity of 10 to 100,000 mm 2 / s at 200 ° C., if necessary.} When the curing agent (C) is contained, the catalyst (D) having a pKa of 11 or more may be further contained. Hereinafter, each component will be described in detail.

<Olefin polymers (A) and (B)>
The olefin polymer (A) contains the structural unit (a1) in an amount of more than 97 mol% and 100 mol% or less, preferably 97.5 mol% or more and 100 mol% or less, and more preferably 98 mol% or more and 100 mol% or less. The constituent unit (a2) is contained in an amount of 0 mol% or more and less than 3 mol%, preferably 0 mol% or more and 2.5 mol% or less, and more preferably 0 mol% or more and 2 mol% or less. (However, the total of the structural unit (a1) and the structural unit (a2) is 100 mol%).

As described above, the olefin polymer (A) may be a homopolymer of propylene or a copolymer of propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene). When the olefin polymer (A) is a copolymer, it may be a random copolymer or a block copolymer, but it is preferably a random copolymer.

Further, the olefin polymer (B) contains the structural unit (b1) of 70 mol% or more and less than 97 mol%, preferably 71 mol% or more and less than 97 mol%, and more preferably 72 mol% or more and 97 mol% or less. The constituent unit (b2) is contained in an amount of more than 3 mol% and 30 mol% or less, preferably more than 3 mol% and 29 mol% or less, and more preferably more than 3 mol% and 28 mol% or less (provided that it is contained in an amount of more than 3 mol% and 30 mol% or less. , The total of the structural unit (b1) and the structural unit (b2) is 100 mol%).

As described above, the olefin polymer (B) is a copolymer of propylene and α-olefin having 2 to 20 carbon atoms (excluding propylene), and may be a random copolymer or a block copolymer. However, it is preferably a random copolymer.

Examples of the α-olefin having 2 to 20 carbon atoms (excluding propylene) forming the structural units (a2) and (b2) include ethylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl. Examples thereof include -1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like, and among these, ethylene and 1-butene are preferable. These may be used alone or in combination of two or more. Further, the structural units (a2) and (b2) may be structural units derived from the same α-olefin or may be structural units derived from different α-olefins.

The olefin polymers (A) and (B) are unsaturated monomers other than propylene and α-olefins having 2 to 20 carbon atoms (excluding propylene) (hereinafter, “”, as long as the effects of the present invention are not impaired. It can also contain structural units derived from "other unsaturated monomers"). Examples of other unsaturated monomers include conjugated polyenes such as butadiene and isoprene, 1,4-hexadiene, 1,7-octadien, dicyclopentadiene, 5-ethridene-2 norbornene, and 5-vinyl-2. Non-conjugated polyenes such as −norbornene, 5-methylene-2-norbornene and 2,5-norbornene can be mentioned.

In the coating agent of the present invention, the content ratio of the structural unit derived from propylene to the total amount of the total olefin polymer is 89.0 mol% or more and 97.4 mol% or less, preferably 90.0 mol% or more and 97.4. It is less than mol%. When the content ratio of the propylene-derived structural unit is within the above range, an adhesive layer having excellent heat resistance, electrolytic solution resistance and moldability can be formed. In one aspect of the present invention, the total amount of the total olefin polymer is the total amount of the propylene polymer (A) and the propylene polymer (B).

The melting point (Tm) of the olefin polymer (A) is 150 to 170 ° C., preferably 150 to 165 ° C., more preferably 155 to 160 ° C. On the other hand, the melting point (Tm) of the olefin polymer (B) is 70 to 145 ° C, preferably 75 to 145 ° C, and more preferably 75 to 100 ° C. As described above, by using the olefin polymer (A) which is a high melting point component and the olefin polymer (B) which is a low melting point component in combination, heat resistance, electrolytic solution resistance and moldability are excellent. An adhesive layer can be formed.

In the present invention, Tm is determined by differential scanning calorimetry (DSC measurement) according to JIS K7122, and specifically, the temperature is raised from 30 ° C. to 180 ° C. at 10 ° C./min and then held at that temperature for 3 minutes. Then, in the process of lowering the temperature to 0 ° C. at 10 ° C./min, holding at that temperature for 3 minutes, and then raising the temperature again to 150 ° C. at 10 ° C./min, from the thermogram at the time of the second temperature rise, Obtained according to JIS K7122.

In the coating agent of the present invention, the olefin polymer (B) is dissolved or dispersed in an organic solvent, and the olefin polymer (A) is contained in a state of being dispersed in an organic solvent.

The weight average molecular weight (Mw) of the olefin polymers (A) and (B) measured by gel permeation chromatography (GPC) and converted into standard polystyrene is, for example, 10,000 or more and 1,000,000 or less. The molecular weight distribution (dispersity) is, for example, 1 or more and 3 or less. The molecular weight distribution is a ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn).

The olefin polymers (A) and (B) are α-olefins having 2 to 20 carbon atoms in the presence of known solid Ti catalysts, metallocene catalysts, etc., which are usually used in the production of α-olefin polymers. Obtained by polymerization. Examples of the metallocene catalyst include metallocene compounds such as rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride, organoaluminum oxy compounds such as methylaluminoxane, and triisobutylaluminum. Examples include catalysts containing organoaluminum compounds. More specific methods for producing the olefin polymers (A) and (B) include the methods described in International Publication No. 2004/87775 pamphlet.

In the present invention, a part or all of the olefin polymer (A) or (B) may be a modified olefin polymer graft-modified with a polar group-containing monomer. By containing the modified olefin polymer, the adhesive force of the adhesive layer to the base material (for example, aluminum foil) can be further improved, and the electrolytic solution resistance can be improved.

Examples of the polar group-containing monomer include a hydroxyl group-containing ethylenically unsaturated compound, an amino group-containing ethylenically unsaturated compound, an epoxy group-containing ethylenically unsaturated compound, an unsaturated carboxylic acid and its anhydride and a derivative thereof, and a vinyl ester. Compounds, vinyl chloride and the like can be mentioned, but unsaturated carboxylic acids and their anhydrides are preferable.

Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. , 3-Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, pentaerythritol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate, tetramethylol ethanemono (meth) acrylate, butanediol mono ( Hydroxyl-containing (meth) acrylic acid esters such as meta) acrylates, polyethylene glycol mono (meth) acrylates and 2- (6-hydrohexanoyloxy) ethyl acrylates, as well as 10-undecene-1-ol and 1-octene- 3-ol, 2-methanol norbornene, hydroxystyrene, N-methylolacrylamide, 2- (meth) acroyloxyethyl acid phosphate, glycerin monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene 1,4-diol , Glycerin monoalcolate and the like.

Examples of the amino group-containing ethylenically unsaturated compound include vinyl-based monomers having at least one amino group or a substituted amino group as represented by the following formula.
−NR ₁ R ₂
In the formula, R ₁ is a hydrogen atom, a methyl group or an ethyl group, and R ₂ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and 8 to 12 carbon atoms, preferably 6. ~ 9 cycloalkyl groups. The above alkyl group and cycloalkyl group may further have a substituent.

Examples of such amino group-containing ethylenically unsaturated compounds include aminomethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminoethyl methacrylate, aminopropyl (meth) acrylate, and phenyl methacrylate. Acrylic acids such as aminomethyl and cyclohexylaminoethyl methacrylate or alkyl ester derivatives of methacrylate, vinylamine derivatives such as N-vinyldiethylamine and N-acetylvinylamine, acrylamide, methacrylicamide, N-methylacrylamide, N , N-Dimethylacrylamide, N, N-Dimethylaminopropylacrylamide and other imides such as acrylamide derivatives can be mentioned.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one unsaturated bond group and an epoxy group that can be polymerized in one molecule is used.
Examples of such an epoxy group-containing ethylenically unsaturated compound include glycidyl esters of unsaturated carboxylic acids such as glycidyl acrylate and glycidyl methacrylate, or maleic acid, fumaric acid, crotonic acid, tetrahydrophthalic acid, itaconic acid, and citraconic acid. , Endo-cis-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid ( ^TM nagic acid), endo-cis-bicyclo [2,2,1] hept-5-en-2 Monoglycidyl ester of unsaturated dicarboxylic acid such as −methyl-2,3-dicarboxylic acid (methylnadic acid ^TM ) (1-12 carbon atoms of alkyl group in the case of monoglycidyl ester), alkylglycidyl of p-styrene carboxylic acid Ester, allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy- Examples thereof include 1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monooxide 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, norbornenedicarboxylic acid, and bicyclo [2,2,1] hepto. Examples thereof include unsaturated carboxylic acids such as -2-ene-5,6-dicarboxylic acid or derivatives thereof (for example, acid anhydrides, acid halides, amides, imides, esters, etc.).

Derivatives of unsaturated carboxylic acid include, for example, malenyl chloride, maleylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo [2,2,1] hept-2-ene-5,6. -Dicarboxylic acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconic acid, diethyl citraconic acid, dimethyl tetrahydrophthalate, bicyclo [2,2,1] hept-2-ene-5 , 6-Dicarboxylate dimethyl, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, aminoethyl methacrylate, aminopropyl methacrylate and the like.

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

These polar group-containing monomers can be used alone or in combination of two or more.
The modified olefin polymer contains a structural unit derived from the polar group-containing monomer, preferably 0.1 to 15% by mass, more preferably 0.2 to 10% by mass, still more preferably 0.5 to 50% by mass. Included in an amount of 5% by weight.

The content (modification amount) of these polar group-containing monomers can be adjusted by the charging ratio when the olefin polymer and the polar group-containing monomer are reacted in the presence of a radical initiator or the like. The amount of modification can be determined by a known means such as ^{1 H NMR measurement.} The following conditions can be exemplified as specific NMR measurement conditions.

^{1 For 1} H NMR measurement, use ECX400 type nuclear magnetic resonance device manufactured by JEOL Ltd., use deuterated orthodichlorobenzene as the solvent, sample concentration 20 mg / 0.6 mL, measurement temperature 120 ° C, observation nucleus ¹ The conditions are H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μsec (45 ° pulse), the repetition time is 7.0 seconds, and the number of integrations is 500 or more. In the standard chemical shift, the hydrogen content of tetramethylsilane is set to 0 ppm. For example, the same result can be obtained by setting the peak derived from residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm and using it as the reference value for the chemical shift. be able to. Peak, such as ¹ H-derived functional group-containing compound can assign a conventional manner.

When a monomer having an acidic functional group such as the unsaturated carboxylic acid and its anhydride is used as the polar group-containing monomer, the amount of the functional group introduced into the modified olefin polymer can be used as a guide. It is also possible to use, for example, an acid value as the amount of the compound. Here, as a method for measuring the acid value, the following can be mentioned.

(Measurement of acid value)
The basic operation conforms to JIS K2501-2003.
Accurately weigh about 10 g of the modified olefin polymer and place it in a 200 mL tall beaker. As a titration solvent, 150 mL of a mixed solvent prepared by mixing xylene and dimethylformamide in a ratio of 1: 1 (volume ratio) is added thereto. A few drops of a 1 w / v% phenolphthalein ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) are added as an indicator, and the liquid temperature is heated to 80 ° C. to dissolve the sample. After the liquid temperature becomes constant at 80 ° C., titration is performed using a 2-propanol solution of potassium hydroxide of 0.1 mol / L (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value is determined from the titration amount.

The calculation formula is acid value (mgKOH / g) = (EP1-BL1) x FA1 x C1 / SIZE
Is.

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

This measurement is repeated 3 times and the average value is taken as the acid value.
The acid value of the modified olefin polymer is preferably 0.1 to 100 mgKOH / g, more preferably 0.5 to 60 mgKOH / g, and even more preferably 0.5 to 30 mgKOH / g. Here, in the case of a modified olefin polymer composition obtained by mixing a graft-modified olefin polymer and an unmodified olefin polymer, the modified olefin polymer composition as a whole has the above-mentioned acid value. Is preferable.

When maleic anhydride is used as the polar group-containing monomer, the amount of graft is determined based on the absorption of the carbonyl group of maleic anhydride detected in the vicinity of ^{1790 cm -1 using an infrared spectrophotometer.} You can also do it.

Various methods can be mentioned as a method for graft-copolymerizing a polar group-containing monomer with the olefin polymer (A) and / or the olefin polymer (B). For example, a method in which an unmodified olefin polymer is dissolved in an organic solvent, a polar group-containing monomer and a radical polymerization initiator are added, and the mixture is heated and stirred to cause a graft copolymerization reaction, and the unmodified olefin polymer is heated. A method of adding a polar group-containing monomer and a radical polymerization initiator to the obtained melt after melting and stirring to carry out graft copolymerization, an unmodified olefin polymer, a polar group-containing monomer and radical polymerization initiation. A method in which the agents are mixed in advance, the obtained mixture is supplied to an extruder, and a graft copolymerization reaction is carried out while heating and kneading. A polar group-containing monomer and a radical polymerization initiator are used as an organic solvent in an unmodified olefin polymer. Examples thereof include a method in which the unmodified olefin polymer is impregnated with the dissolved solution and then heated to the maximum temperature at which the unmodified olefin polymer is not dissolved to cause a graft copolymerization reaction.

The reaction temperature is preferably 50 ° C. or higher, particularly 80 to 200 ° C., and the reaction time is about 1 minute to 10 hours.
The reaction method may be either a batch method or a continuous method, but the batch method is preferable in order to carry out the graft copolymerization uniformly.

The radical polymerization initiator used is not limited as long as it promotes the reaction between the unmodified olefin polymer and the polar group-containing monomer, but organic peroxides and organic peroxides are particularly preferable.

Specifically, 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, tert-butylperacetate, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (tert) -Butyl Peroxide) Hexane, tert-Butyl Benzoate, tert-Butyl Perphenyl Acetate, tert-Butyl Perisobutyrate, tert-Butyl Per-sec-Octoate, tert-Butyl Perpivarate, Cumyl Perpivarate and tert-Butyl There is perdiethyl acetate, and there are other azo compounds such as azobis-isobutylnitrile and dimethylazoisobutylnitrile.

Of these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (tert). Dialkyl peroxides such as −butylperoxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred.

The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass with respect to 100 parts by mass of the unmodified olefin polymer.
As described above, the graft reaction can be carried out in an organic solvent or in a solvent-free manner, and when the reaction is carried out in an organic solvent, the coating agent or the like is prepared as it is or by adding an organic solvent of the same type or another type. Is also possible. When the graft reaction is carried out without using an organic solvent, the organic solvent is added again to prepare the coating agent of the present invention. When the graft-modified olefin polymer and the unmodified olefin polymer are mixed and used, they may be mixed in advance and then used for preparing the coating agent, and may be used in the solvent when preparing the coating agent. May be mixed with.

As described above, the organic solvent for preparing the coating agent of the present invention in addition during or after the reaction is not particularly limited, but for example, aromatic hydrocarbons such as benzene, toluene and xylene, hexane, heptane, and the like. Aliper hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane and decahydronaphthalin, methanol, ethanol, isopropyl alcohol, butanol, pentanol, hexanol, propanediol, phenol, etc. Alcohol, acetone, methylisobutylketone, methylethylketone, pentanone, hexanone, isophorone, acetophenone and other ketone solvents, methylcelsolve, ethylcelsolve and other cellsolves, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, formic acid. Examples thereof include esters such as butyl, halogenated hydrocarbons such as trichloroethylene, dichloroethylene, and chlorobenzene. Among these, aromatic hydrocarbons, aliphatic hydrocarbons and ketones are preferable. These may be used alone or in combination of two or more.
In the present invention, such a graft-modified olefin polymer may be used alone or in combination of two or more.

<Curing agent (C)>
The coating agent of the present invention may contain a curing agent (C), if necessary, in addition to the above-mentioned olefin polymers (A) and (B). When the coating agent of the present invention contains the curing agent (C), there is an advantage that the strength of the coating film is improved and the adhesion, heat resistance, and chemical resistance are excellent.

The curing agent (C) is not particularly limited, and examples thereof include a polyisocyanate monomer and a polyisocyanate modified product. Of these, the polyisocyanate monomer is a monomer compound having a plurality of isocyanate groups in one molecule, and examples of such a polyisocyanate monomer include aromatic polyisocyanates and aromatic aliphatic polyisocyanates. , Aliphatic polyisocyanate and the like.

Here, examples of the aromatic polyisocyanate include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI) and phenylenedi isocyanate (m-, p-phenylenedi isocyanate or a mixture thereof). , 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'-or 2,2'-diphenylmethane diisosinate or a mixture thereof) ( MDI), 4,4'-toluidine diisocyanate (TODI), aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate and the like can be mentioned.

Examples of the aromatic aliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylene diisocyanate or a mixture thereof) (XDI) and tetramethylxylene diisocyanate (1,3- or 1,4-tetra). Methylxylene diisocyanate or a mixture thereof) (TMXDI), aromatic aliphatic diisocyanates such as ω, ω'-diisocyanate-1,4-diethylbenzene and the like can be mentioned.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), and 1 , 5-Pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcapate and other fats Examples include group diisocyanate.

Further, the aliphatic polyisocyanate includes an alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate include 1,3-cyclopentanediisocyanate, 1,3-cyclopentenediisocyanate, cyclohexanediisocyanate (1,4-cyclohexanediisocyanate, 1,3-cyclohexanediisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isoholodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'-or 2,2'-methylenebis (cyclohexylisocyanate), Trans, these Trans-form, Trans, Cis-form or Cis, Cis-form, or a mixture thereof) (H ₁₂ MDI), methylcyclohexanediisocyanate (methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate) , Norbornan diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3- or 1,4-bis (isocyanatomethyl) cyclohexane, or a mixture thereof) (H ₆ XDI) Such as alicyclic diisocyanate can be mentioned.
These polyisocyanate monomers can be used alone or in combination of two or more.

On the other hand, examples of the polyisocyanate modified product include a modified product obtained by reacting the above-mentioned polyisocyanate monomers with each other and a modified product obtained by reacting the above-mentioned polyisocyanate monomer with another compound. Usually, those having an average number of functional groups exceeding 2 can be used. Here, the "other compound" refers to a compound other than the above-mentioned polyisocyanate monomer that can react with the above-mentioned polyisocyanate monomer, and as an example, a monohydric alcohol (hereinafter, "monool"). ), Polyhydric alcohols (hereinafter referred to as "polyols"), compounds having active hydrogen such as amines and water, and carbon dioxide.

Here, examples of the monool that can be used in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, and tetradecyl allure (myristyl). Alcohol), pentadecyl alcohol, hexadecyl alcohol (cetyl alcohol), heptadecyl alcohol, octadecyl alcohol (stearyl alcohol, octadecanol), nonadecil alcohol, and their isomers (2-methyl-1-propanol (iso-) Butanol), as well as other alkanols (C20-50 alcohols) and alkenyl alcohols such as oleyl alcohols, alkazienols such as octadienol, and aliphatics such as polyethylene butylene monool. Mono-alcohol can be mentioned. Further, examples of the monool include alicyclic monools such as cyclohexanol and methylcyclohexanol, and aromatic aliphatic monools such as benzyl alcohol.

Further, examples of the polyol that can be used in the present invention include compounds having two or more hydroxyl groups generally used in the field of urethane resins, which may have a monomeric form or are heavy. It may have a form of coalescence.

Among these, as an example of a polyol having a monomeric form,
Alkylene glycols such as ethylene glycol and propylene glycol, cyclohexanediol, cyclohexanedimethanol, and dihydric alcohols such as benzenedimethanol;
Trihydric alcohols such as glycerin, trimethylolmethane, trimethylolethane, and trimethylolpropane;
Examples thereof include alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol. In addition, in this specification, a polyol having such a monomeric form may also be referred to as a "low molecular weight polyol".

On the other hand, examples of the polyol having a polymer form include polymer polyols generally used in the field of urethane resins, such as polyester polyols and polyether polyols.

Specific examples of such a polyisocyanate modified product include a multimer of the above-mentioned polyisocyanate monomer, an allophanate modified product, a polyol modified product, a biuret modified product, a urea modified product, an oxadiazine trione modified product, and a carbodiimide modified product. Examples include uretdione denatured products and ureton imine denatured products.

Here, examples of the multimer include a dimer, a trimer, a pentamer, and a heptameric of a polyisocyanate monomer. Among these, examples of trimers of polyisocyanate monomers include isocyanurate-modified products and iminooxadiazinedione-modified products.

In addition, examples of the modified allophanate include an allophanate modified product produced by reacting the above-mentioned polyisocyanate monomer with monool (for example, monool exemplified above such as octadecanol).

Examples of the polyol modified product include a polyol modified product (alcohol adduct) produced by the reaction of a polyisocyanate monomer and a low molecular weight polyol (for example, a trihydric alcohol).

Examples of the modified biuret include the modified biuret produced by reacting the above-mentioned polyisocyanate monomer with water or amines.
Examples of the urea-modified product include a urea-modified product produced by the reaction of the polyisocyanate monomer and diamine described above.

Examples of the oxaziazine trione modified product include oxadiazine trione produced by the reaction of the above-mentioned polyisocyanate monomer with carbon dioxide gas.
Examples of the carbodiimide modified product include a carbodiimide modified product produced by the decarboxylation condensation reaction of the polyisocyanate monomer described above.

Further, as the polyisocyanate modified product, in addition to those described above, polymethylene polyphenyl polyisocyanate (crude MDI, polypeptide MDI) and the like can also be mentioned.
In the present invention, among the above-mentioned polyisocyanate monomers and polyisocyanate modified products, aliphatic polyisocyanates and their multimers are particularly preferably used. That is, in a preferred embodiment of the present invention, the curing agent (C) is an aliphatic polyisocyanate or a multimer of an aliphatic polyisocyanate.

These may be used alone or in combination of two or more.
When the coating agent of the present invention contains a polyisocyanate monomer or a polyisocyanate modified product as the curing agent (C), the amount of the curing agent (C) added is the olefin polymers (A) and (B). When the total of the hydrocarbon (E) described later and the hydrocarbon (E) described later is 100 parts by mass, it is preferably 2 to 30 parts by mass.

As the curing agent (C), at least one compound selected from an epoxy compound and an oxazoline compound can also be used. In this case, the coating agent of the present invention preferably contains at least one modified olefin polymer as the olefin polymer (A) and / or (B). As a result, a coating agent having a small volume change during curing and curable at a low temperature can be obtained, and in particular, an adhesive layer having excellent adhesive strength can be obtained.

The epoxy compound is a crosslinkable compound having two or more epoxy groups in one molecule. Examples of such epoxy compounds include bisphenol type epoxy resins such as bisphenol A type epoxy resin (different from hydrogenated bisphenol A type epoxy resin) and bisphenol F type epoxy resin; hydrogenated bisphenol type epoxy resin; novolak type epoxy. Resin; Biphenyl type epoxy resin; Stillben type epoxy resin; Hydroquinone type epoxy resin; Naphthalene skeleton type epoxy resin; Tetraphenylol ethane type epoxy resin; Trishydroxyphenylmethane type epoxy resin; Dicyclopentadienephenol type epoxy resin; 3', An alicyclic such as 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol. Epoxy resin; polyglycidyl ester of polybasic acid such as diglycidyl ester of hexahydrophthalic anhydride; sorbitol polyglycidyl ether, sorbitan polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, polypropylene glycol diglycidyl ether , Diglycerol polyglycidyl ether, glycerol polyglycidyl ether, hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and cyclohexanedimethanol diglycidyl ether, etc. Examples thereof include glycidylamine-type epoxy resins such as glycidyldiaminodiphenylmethane, tetraglycidylbisaminomethylcyclohexane, diglycidylaniline, and tetraglycidylmethoxylylylene diamine; and heterocyclic-containing epoxy resins such as triazine or hydantin.

Among the epoxy compounds, an adhesive layer having more excellent adhesive strength, particularly an adhesive layer capable of adhering an aluminum foil layer and a film layer made of a thermoplastic resin such as polypropylene with higher strength can be obtained. , Bisphenol A type liquid epoxy resin, alicyclic epoxy compound, trimethylolpropanpolyglycidyl ether are preferable.

The bisphenol A type liquid epoxy resin is not particularly limited as long as it is a resin that is liquid at room temperature (25 ° C.), and a commercially available product may be used.
Examples of the commercially available products include EPICLON840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC Corporation), jER828EL, 827 (manufactured by Mitsubishi Chemicals Corporation), and Epomic R-. 140P (manufactured by Mitsui Chemicals, Inc.) can be mentioned.

The alicyclic epoxy compound is a compound having at least one epoxycycloalkyl group or an epoxycycloalkenyl group in the molecule, or at least a group in which at least one epoxy group is bonded to the alicyclic by a single bond in the molecule. It refers to a compound having one.

Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate, 3', 4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate. 3,4-Epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-m-dioxane, bis (3,4) -Epoxycyclohexylmethyl) adipate, vinylcyclohexendioxide, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxy Rate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxyside, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), 1,2,8 , 9-Diepoxy limonene, 1,2-epoxy-4- (2-oxylanyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, the compound described in JP-A-2008-214555 Can be mentioned.

As the alicyclic epoxy compound, a commercially available product may be used, and examples of the commercially available product include celloxide 2021P, EHPE3150, EHPE3150CE, and Epolide GT401 (all manufactured by Daicel Corporation).

As the alicyclic epoxy compound, 1,2-epoxy-4- (1,2-epoxy-4- (2,2-bis (hydroxymethyl) -1-butanol) of 2,2-bis (hydroxymethyl) -1-butanol can be obtained from the viewpoint that an adhesive layer having more excellent adhesive strength can be obtained. 2-Oxylanyl) cyclohexane adduct is preferred.

Examples of the trimethylolpropane polyglycidyl ether include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.

As the trimethylolpropane polyglycidyl ether, a commercially available product may be used, and examples of the commercially available product include EX-321L (manufactured by Nagase ChemteX Corporation) and the like.

The oxazoline compound is a crosslinkable compound having two or more oxazoline groups in one molecule. Examples of such an oxazoline compound include a polymer of an oxazoline group-containing monomer and an oxazoline group-containing polymer such as a copolymer of an oxazoline group-containing monomer and another monomer.

Examples of the oxazoline group-containing monomer include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, and 2-isopropenyl-2-oxazoline. , 2-Isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline Can be mentioned. These may be used alone or in combination of two or more.

Examples of the other monomer include alkyl (meth) acrylate (alkyl group having about 1 to 14 carbon atoms); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, styrene sulfonic acid and salts thereof. Unsaturated carboxylic acids such as (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth) acrylamide, N-alkyl (meth) acrylamide, N , N-dialkyl (meth) acrylamide, (alkyl group: methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, 2-ethylhexyl group, cyclohexyl group, etc.), etc. Unsaturated amides; vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; containing vinyl chloride, vinylidene chloride, vinyl fluoride and the like. Halogen α, β-unsaturated monomers; α, β-unsaturated aromatic monomers such as styrene and α-methylstyrene can be mentioned. These may be used alone or in combination of two or more.

As the oxazoline compound, an oxazoline compound containing 2-isopropenyl-2-oxazoline is preferable from the viewpoint that an adhesive layer having more excellent adhesive strength can be obtained. Examples of commercially available products include the "Epocross" series manufactured by Nippon Shokubai Co., Ltd.

The epoxy equivalent of the epoxy compound and the oxazoline equivalent of the oxazoline compound are preferably 100 g / eq or more, more preferably 100 g / eq or more, from the viewpoints of obtaining an adhesive layer having more excellent adhesive strength, chemical resistance, and electrolytic solution resistance. Is 125 g / eq or more, preferably 1,600 g / eq or less, and more preferably 500 g / eq or less.

The equivalent can be measured based on JIS K7236.
When the coating agent of the present invention contains at least one compound selected from an epoxy compound and an oxazoline compound as the curing agent (C), the curing agent (C) contains an epoxy group and oxazoline in the curing agent (C). Base Equivalent / The equivalent of the functional group reactive with the epoxy group or oxazoline group in the olefin polymers (A) and (B) is preferably 0.01 or more, more preferably 0.1 or more, and more preferably. Is preferably 50 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 10 or less. When the blending amount of the curing agent (C) is within the above range, an adhesive layer having more excellent adhesive strength, chemical resistance, and electrolytic solution resistance can be obtained.

<Catalyst (D)>
The coating agent of the present invention may contain a catalyst (D) having a pKa of 11 or more. In this case, the coating agent of the present invention preferably contains the curing agent (C), and more preferably the curing agent (C) is at least one compound selected from an epoxy compound and an oxazoline compound.

By using the catalyst (D), the cross-linking reaction can be efficiently promoted even at a low temperature, an adhesive layer having excellent chemical resistance and electrolytic solution resistance can be formed, and the adhesive strength is excellent, particularly, an aluminum foil layer and polypropylene or the like. It is possible to obtain an adhesive layer capable of adhering to the thermoplastic resin film layer of the above with high strength.

The catalyst (D) may be used alone or in combination of two or more.
The catalyst (D) is not particularly limited as long as it is a compound having a pKa of 11 or more, but is preferably a compound capable of promoting the cross-linking reaction of the curing agent (C), and examples of such a compound include, for example. A phosphazene catalyst having a strongly basic tertiary amine such as 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,6-diazabicyclo [3.4.0] nonen-5, and a phosphazene base. However, DBU and phosphazene catalysts are preferable.

The pKa is an acid dissociation constant in an aqueous solution at 25 ° C. Further, for example, phosphoric acid has three pKa, that is, pKa ₁ , pKa _2, and pKa _3, but pKa in the present invention refers to pKa ₁ , that is, the first acid dissociation constant.

The blending amount of the catalyst (D) is preferably 1 ppm or more, more preferably 100 ppm or more, and preferably 1% by mass, based on 100% by mass of the non-volatile content (components other than the solvent) of the coating agent of the present invention. Hereinafter, it is more preferably 0.3% by mass or less. When the blending amount of the catalyst (D) is within the above range, a coating agent having an excellent curing rate can be obtained, and an adhesive layer having excellent chemical resistance, electrolytic solution resistance and adhesive strength can be obtained.

<Liquid or semi-solid hydrocarbon (E)>
The coating agent of the present invention may further contain a liquid or semi-solid hydrocarbon (E) having a kinematic viscosity at 200 ° C. of 10 to 100,000 mm ^{2 / s.} Thereby, an adhesive layer having higher adhesive strength can be obtained.

The hydrocarbon (E) is not particularly limited as long as it satisfies the kinematic viscosity, but a polymer of an olefin having 2 to 20 carbon atoms (however, excluding the olefin polymers (A) and (B)) is preferably mentioned. Be done. Among them, an oligomer or polymer obtained by homopolymerizing an olefin having 2 to 20 carbon atoms, or an oligomer or polymer obtained by copolymerizing an arbitrary mixture of two or more kinds of these olefins is preferably used.

Examples of the olefin having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene.
Specific examples of the hydrocarbon (E) include ethylene-propylene copolymer, isobutene-1-butene copolymer, polyisobutene and the like.

The content of the hydrocarbon (E) in the coating agent of the present invention is preferably 1 to 15 parts by mass with respect to 100 parts by mass in total of the olefin polymers (A) and (B) and the hydrocarbon (E). Parts, more preferably 2 to 10 parts by mass. When the content of the hydrocarbon (E) is within the above range, the adhesion tends to be excellent and the stability over time tends to be excellent, which is advantageous.

<Preparation method of coating agent>
The coating agent of the present invention can be prepared by mixing the above-mentioned components.
In addition to the above components (A) to (E), the coating agent of the present invention may contain another olefin resin (F) as long as the effects of the present invention are not impaired. The "other olefin-based resin (F)" is not particularly limited as long as it does not correspond to any of the above-mentioned olefin polymers (A) and (B) and the above-mentioned hydrocarbon (E), but polyethylene, polypropylene, and poly. Homopolymers of 1-butene and poly4-methyl-1-pentene, random or block copolymers of α-olefins such as ethylene, propylene and 4-methyl-1-pentene, ethylene / propylene copolymers, ethylene -Octen copolymer, propylene / octene copolymer, ethylene / propylene / 1-butene copolymer, ethylene / propylene / terpolymer, cyclic polyolefin, ethylene / vinyl acetate, ethylene / unsaturated carboxylic acid copolymer, Examples thereof include ethylene / vinyl alcohol and ionomer resin.

Further, if necessary, as long as the effects of the present invention are not impaired, transition metal compounds such as titanium oxide (rutyl type) and zinc oxide, pigments such as carbon black, rocking agents, thickeners, antistatic agents, etc. Paint additives such as defoamers, surface conditioners, antisettling agents, antioxidants, weather resistant agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents may be added.

<Use of coating agent>
The coating agent of the present invention is suitable for use as a primer, a paint, an adhesive (for example, a hot melt adhesive, an adhesive for dry laminating), an anchor coating agent at the time of extrusion film formation, an adhesive film, an adhesive film, and an adhesive sheet. Is.

[Laminate]
The laminate of the present invention (hereinafter, also referred to as "the present laminate") is not particularly limited as long as it has a base material and a layer composed of the coating agent of the present invention (hereinafter, also referred to as "the present coating agent"). , It may have a layer other than these. In the following description in the present specification, the layer made of the present coating agent may be referred to as a "coating film" by focusing on its shape, and may be referred to as an "adhesive layer" by focusing on its function. In some cases.

In the present laminate, the coating film (adhesive layer) may be present on one side of the base material, on both sides, or on the entire surface of these surfaces. It may be present in the department.

The thickness of the coating film (adhesive layer) may be appropriately selected depending on the desired application and the like, and is not particularly limited, but is, for example, 0.2 μm or more, preferably 1 μm or more, and for example 100 μm or less, preferably 100 μm or less. Is 20 μm or less.

In order to obtain a coating film (adhesive layer) that can be molded without whitening, breaking or peeling, the breaking elongation of the film formed from this coating agent measured according to JIS C2151 is 4.7. It is preferably% or more, and more preferably 5.0% or more.

The base material is not particularly limited as long as it is a base material on which the coating film (adhesive layer) is desired to be formed. For example, polyolefins such as polyethylene and polypropylene, ABS resin, polycarbonate (PC), and PET are not particularly limited. Resin base material made of polyester resin such as polyester resin such as polyphenylene sulfide (PPS), polyamide resin such as nylon, or resin such as acrylic resin; barrier film such as transparent vapor-deposited PET; ED steel plate, Mg alloy, SUS (stainless steel), Examples include a metal foil made of a metal such as aluminum and an aluminum alloy; an inorganic base material made of an inorganic material such as the metal and glass; a base material in which the resin and the inorganic material are composited; a decorative film and the like. Among these, metal foil, polyolefin base material and decorative film are preferable, and aluminum foil and polyolefin base material are more preferable.

The surface of the base material in contact with the coating film (adhesive layer) may be subjected to a conventionally known surface treatment such as corona treatment in order to improve the adhesive strength.
Examples of the decorative film include a film having a known design property. Specifically, the decorative film has a design property, which is a film in which the resin base material or the metal leaf is decorated in advance by printing, painting, vapor deposition, or the like. Examples thereof include a laminate of a film and the resin base material or metal foil.

Here, examples of the film having designability include a film obtained by imparting designability to a thermoplastic film such as an acrylic film, a PET film, a PC film, a COC (cyclic olefin copolymer) film, a vinyl chloride film, and an ABS film. The coating film (adhesive layer) may be imparted with design by a conventionally known method.

Examples of the method for imparting design (decoration method) are described in existing vacuum forming methods such as vacuum forming method and pneumatic vacuum forming method, insert molding method, in-mold molding method, and Japanese Patent No. 3733564. The TOM method using the "vacuum forming device" of the above can be mentioned. According to these methods, it is possible to impart designability to a laminated body having a complicated three-dimensional structure.

The thickness of the base material is preferably 1 μm or more, more preferably 5 μm or more, and preferably 500 μm or less, more preferably 100 μm or less.
This laminate is usually used by adhering a desired adherend to an adhesive layer. That is, the present laminate may be an adhesive in which the base material, the adhesive layer, and the adherend are laminated in this order. Examples of the adherend include those similar to the base material.

The method for producing the laminated body is not particularly limited, and a conventionally known method suitable for a desired application can be adopted.
This laminate is, for example, automobile interior / exterior members; various front panels such as AV equipment; surface decorative materials such as buttons and emblems; housings for information appliances such as mobile phones and cameras; various parts such as housings, display windows and buttons. Exterior materials for furniture; Interior materials for buildings such as bathroom surfaces, walls, ceilings, floors; Exterior materials for exterior walls such as siding, walls, roofs, gates, windshields, etc .; Window frames, doors, handrails, thresholds, etc. Interior materials such as roofs and furniture surface decorative materials; Optical materials such as various displays, lenses, mirrors, goggles, and windowpanes; Interior and exterior materials for various non-automotive vehicles such as trains, aircraft, and ships; Bottles, cosmetic containers , Various containers such as accessory cases; packaging materials; can be used for various other articles.

<Battery case packaging material>
The packaging material for a battery case according to an embodiment of the laminate of the present invention includes a laminate in which a metal foil, an adhesive layer, and an adherend are laminated in this order, and the adhesive layer is the coating agent of the present invention. It is a layer consisting of.

Since the packaging material for a battery case has the adhesive layer, it has excellent adhesive strength between the adherend and the metal foil, and also has excellent electrolytic solution resistance. Therefore, even if the battery case packaging material is used for a long period of time, it is possible to effectively prevent a decrease in the adhesive strength between the adherend and the metal foil, and a battery case packaging material having excellent long-term reliability can be obtained. be able to.

The packaging material for a battery case is not particularly limited as long as the metal foil, the adhesive layer, and the adherend are laminated in this order, and a conventionally known layer may be used for the layers or the surface of the laminate. Good. Here, a configuration example of a battery using the packaging material for a battery case of the present invention will be described with reference to FIG.

As shown in FIG. 1, the battery 10 includes a battery case packaging material 1 and an electrolytic solution 11 packaged in the battery case packaging material 1. Further, the battery 10 includes a positive electrode 17, a negative electrode 18, and a separator 19 housed in the battery case packaging material 1. In the battery, the battery case packaging material 1 is configured in a bag shape so that the electrolytic solution 11 comes into contact with the inner surface of the inner layer 3 of the battery case packaging material 1, and the battery case packaging material 1 is the battery case packaging material 1. From the inside, the inner layer 3, the inner adhesive layer 5, the base material 2, the outer adhesive layer 6 and the outer layer 4 are laminated in this order, and the inner adhesive layer 5 is the adhesive layer of the present laminated body. Corresponds to.

The inner layer 3 corresponds to the adherend of the present laminate, and specific examples of the adherend are as described above, but the packaging material for the battery case is provided with chemical resistance (electrolyte liquid property), heat sealability, and the like. It is preferable to use an unstretched polypropylene film, a thermoplastic polyolefin film such as a propylene / ethylene copolymer film, an extruded polyolefin layer, or the like.

The base material 2 corresponds to the metal foil of the present laminate, and examples of the metal foil include aluminum foil and SUS foil. Further, the surface of the metal foil may be subjected to chemical conversion treatment from the viewpoint of corrosion resistance and the like.

The outer adhesive layer 6 may be a layer in which the outer layer 4 and the base material 2 (metal foil) are adhered to each other, or may be a layer made of a cured product of the present coating agent, and may be an adhesive for dry lamination. The layer may be obtained by using a conventionally known adhesive such as an agent or a solvent-free adhesive.

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

The electrolytic solution 11 is not particularly limited, and examples thereof include an electrolytic solution containing a lithium salt such as ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium hexafluorophosphate.
The thickness of the packaging material for the battery case is, for example, 40 μm or more and 160 μm or less.

<Manufacturing method of packaging material for battery case>
The method for producing a packaging material for a battery case of the present invention comprises a step of forming an adhesive layer by applying the coating agent to a metal foil, drying it, and then baking it, and the metal foil of the adhesive layer. The opposite surface includes a step of laminating the adherend by an extrusion laminating method. It also includes a step of laminating the adherend on the surface of the adhesive layer opposite to the metal foil by an extrusion laminating method without going through a baking step after applying the coating agent.

The method of applying the present coating agent to the metal foil is not particularly limited, and conventionally known methods such as a die coating method, a flow coating method, a spray coating method, a bar coating method, a gravure coating method, a gravure reverse coating method, and a kiss Reverse coat method, micro gravure coat method, roll coat method, blade coat method, rod coat method, roll doctor coat method, air knife coat method, comma roll coat method, reverse roll coat method, transfer roll coat method, kiss roll coat method, A coating method such as a curtain coating method or a printing method can be adopted.

The method for baking the coating agent applied to the metal foil is, for example, in the range of 180 to 250 ° C., preferably 190 to 250 ° C., and more preferably 200 to 240 ° C. By heating at a temperature within the above range to bake the coating agent, the adhesion of the adhesive layer to the metal foil can be improved.

The method of laminating the adherend by the extrusion laminating method is not particularly limited, but for example, the adherend is extruded onto the adhesive layer formed on the metal foil using a known extruder, and cooled with a rubber roll. A method of laminating by sandwiching with a roll can be mentioned.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples.
1. 1. Physical Characteristics of Polymer The physical characteristics of the olefin polymer synthesized in Production Examples 1-1 to 1-4 and the hydrocarbon (E-1) synthesized in Production Example 2-1 were measured as follows.

<Content ratio of structural units derived from propylene, ethylene and 1-butene>
The content ratio of the structural units derived from each of propylene, ethylene and 1-butene in the polymer obtained in the following production example was ^{determined by using 13} C-NMR. The results are shown in Table 1.

<Measurement of melting point>
Using a differential scanning calorimeter (manufactured by TA Instruments; DSC-Q1000), the temperature is raised from 30 ° C to 180 ° C at 10 ° C / min, held at 180 ° C for 3 minutes, and lowered to 0 ° C at 10 ° C / min. In the process of raising the temperature to 150 ° C. at 10 ° C./min again, the melting point was determined according to JIS K7122 from the thermogram at the time of the second temperature rise. The results are shown in Table 1.

<Measurement of graft amount (modification amount) of polar group-containing monomer>
¹ Obtained from measurement by 1 H-NMR. The specific method is as described above. The results are shown in Table 1.

<Measurement of weight average molecular weight (Mw)>
The weight average molecular weight (Mw) was measured under the following conditions using gel permeation chromatography (manufactured by Shimadzu Corporation; LC-10 series).
-Detector: manufactured by Shimadzu Corporation; C-R4A
-Column: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation)
-Mobile phase: tetrahydrofuran-Temperature: 40 ° C
・ Flow rate: 0.8 ml / min
Mw was calculated using a calibration curve prepared from monodisperse standard polystyrene.

2. Production of Polymer <Production Example 1-1> Synthesis of Olefin Polymer (A-1) 100 parts by mass of propylene polymer with 100 mol% propylene unit and toluene in an autoclave with an internal volume of 1.5 L equipped with a stirrer. 435 parts by mass was added, and the temperature was raised to 140 ° C. with stirring to completely dissolve the propylene polymer. While maintaining this solution at 140 ° C., 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were simultaneously added dropwise over 4 hours with stirring. After completion of the dropping, the mixture was further stirred at 140 ° C. for 1 hour to carry out a post-reaction to obtain an olefin polymer (A-1). Next, the olefin polymer (A-1) -containing solution was cooled to room temperature, and acetone was added to the solution to precipitate the olefin polymer (A-1). The precipitated olefin polymer (A-1) was repeatedly washed with acetone and then dried to recover the olefin polymer (A-1). The amount of maleic anhydride grafted in the olefin polymer (A-1) was 1.1% by mass, and the melting point of the olefin polymer (A-1) was 159 ° C.

<Production Example 1-2> Synthesis of olefin polymer (A-2) 100 parts by mass of a propylene polymer having a propylene unit of 100 mol%, propylene / ethylene having a propylene unit of 99.25 mol% and an ethylene unit of 0.75 mol% An olefin polymer (A-2) was obtained in the same manner as in Production Example 1-1 except that the copolymer was changed to 100 parts by mass. The amount of maleic anhydride grafted in the olefin polymer (A-2) was 1.1% by mass, and the melting point of the olefin polymer (A-2) was 157 ° C.

<Production Example 1-3> Synthesis of olefin polymer (B-1) 100 parts by mass of a propylene polymer having a propylene unit of 100 mol%, propylene / ethylene having a propylene unit of 96.5 mol% and an ethylene unit of 3.5 mol% An olefin polymer (B-1) was obtained in the same manner as in Production Example 1-1 except that the copolymer was changed to 100 parts by mass and 16 parts by mass of maleic anhydride was changed to 30 parts by mass. .. The amount of maleic anhydride grafted in the olefin polymer (B-1) was 2.1% by mass, and the melting point of the olefin polymer (B-1) was 141 ° C.

<Production Example 1-4> Synthesis of olefin polymer (B-2) 900 ml of hexane and 80 g of 1-butene were placed in a 2 liter autoclave sufficiently substituted with nitrogen, 1 mmol of triisobutylaluminum was added, and the temperature was raised to 70 ° C. After warming, propylene is supplied to bring the total pressure to 7 kg / cm ² G, methylaluminoxane to 0.30 mmol, rac-dimethylsilylene-bis {1- (2-methyl-4-phenylindenyl)} zirconium dichloride. Was converted to Zr atoms and 0.001 mmol was added, and propylene was continuously supplied to carry out polymerization for 30 minutes while maintaining ^{the total pressure at 7 kg / cm 2 G.} After the polymerization, the polymer was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained propylene / 1-butene copolymer had a melting point of 79.5 ° C. and a propylene content of 74 mol%.

3 kg of the above propylene / 1-butene copolymer was added to 10 L of toluene, the temperature was raised to 145 ° C. under a nitrogen atmosphere, and the copolymer was dissolved in toluene. While keeping this solution at 145 ° C., 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were simultaneously added dropwise over 4 hours under stirring, and then stirring was further performed at 145 ° C. for 2 hours. After cooling, a large amount of acetone was added to precipitate the modified copolymer, which was filtered, washed with acetone, and then dried to recover the olefin polymer (B-2).
The amount of maleic anhydride grafted in the obtained olefin polymer (B-2) was 0.8% by mass, and the melting point of the olefin polymer (B-2) was 76 ° C. "

<Production Example 2-1> Synthesis of Hydrocarbon (E-1) Ethyl aluminum sesquichloride (Al) adjusted to 96 mmol / L by adding 1 liter of dehydrated and purified hexane to a continuous polymerization reactor with a stirring blade that has been sufficiently nitrogen-substituted. Hexane solution of (C ₂ H ₅ ) _1.5 · Cl _1.5 ) was continuously supplied at an amount of 500 ml / h for 1 hour, and then VO (OC ₂ H ₅ ) Cl ₂ hexane further adjusted to 16 mmol / L as a catalyst. Hexane was continuously supplied in an amount of 500 ml / h at an amount of 500 ml / h of the solution. On the other hand, the polymer solution was continuously withdrawn from the upper part of the polymerizer so that the amount of the polymer solution in the polymerizer was always 1 liter. Next, ethylene gas was supplied at 47 L / h, propylene gas at 47 L / h, and hydrogen gas at 20 L / h using a bubbling tube. The copolymerization reaction was carried out at 35 ° C. by circulating the refrigerant through a jacket attached to the outside of the polymerizer. The obtained polymerization solution was decalcified with hydrochloric acid, charged into a large amount of methanol to precipitate, and then dried under reduced pressure at 130 ° C. for 24 hours.

The obtained ethylene / propylene copolymer (hydrocarbon (E-1)) has an ethylene content of 53 mol%, a weight average molecular weight of 14,000, a kinematic viscosity at 40 ° C. of 37,500 cSt, and a kinematic viscosity at 200 ° C. of 132 cSt. there were.

3. 3. Preparation of coating material The coating material used in the examples was prepared as follows. Table 2 shows the composition (parts by mass) of each coating material.
<Production Example 3-1> Preparation of Coating Material X 25 g of the olefin polymer (A-1) and 75 g of toluene were placed in an autoclave equipped with a stirrer and heated to 130 ° C. to completely dissolve the olefin polymer. Then, the temperature was lowered to 95 ° C. at a cooling rate of 25 ° C./hour with stirring, and then cooled to 60 ° C. at a cooling rate of 2 ° C./hour. Then, the temperature was lowered to 30 ° C. at a cooling rate of 20 ° C./hour to obtain a uniform milky white dispersion coating material X having a solid content of 25% by mass.

<Production Example 3-2> Preparation of coating material Y 5.5 g of olefin polymer (A-2), 12.5 g of olefin polymer (B-1) and 82 g of toluene were placed in an autoclave with a stirrer and heated to 130 ° C. The olefin polymer was completely dissolved by heating. Then, the temperature was lowered to 85 ° C. at a cooling rate of 25 ° C./hour with stirring, and then cooled to 50 ° C. at a cooling rate of 2 ° C./hour. Then, the temperature was lowered to 30 ° C. at a cooling rate of 20 ° C./hour to obtain a uniform milky white dispersion coating material Y having a solid content of 18% by mass.

<Production Example 3-3> Preparation of coating material Z 16 g of olefin polymer (B-2) and 4 g of hydrocarbon (E-1) are dissolved in 80 g of toluene at 100 ° C. to obtain a transparent solution having a solid content of 20%. Material Z was obtained.

4. Production of Composite Film (Laminated Body) [Example 1]
An adhesive layer ^{having a coating amount of 2 g / m 2 is} applied by applying the coating material Y to the treated surface of a 40 μm-thick aluminum foil whose one side has been chemically converted by a gravure roll method and then passing through a hot air drying furnace at 200 ° C. Was formed. Next, a composite film was obtained by laminating and integrating the propylene / ethylene copolymer resin with a thickness of 40 μm on the adhesive layer by an extrusion laminating method.

[Example 2]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 85 parts by mass of the coating material X and 15 parts by mass of the coating material Z.

[Example 3]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 80 parts by mass of the coating material X and 20 parts by mass of the coating material Z.

[Example 4]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 70 parts by mass of the coating material X and 30 parts by mass of the coating material Z.

[Example 5]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 60 parts by mass of the coating material X and 40 parts by mass of the coating material Z.

[Comparative Example 1]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to the coating material X.

[Comparative Example 2]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 90 parts by mass of the coating material X and 10 parts by mass of the coating material Z.

[Comparative Example 3]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to a composition of 50 parts by mass of the coating material X and 50 parts by mass of the coating material Z.

[Comparative Example 4]
A composite film was obtained in the same manner as in Example 1 except that the coating material Y was changed to the coating material Z.

5. Evaluation [Evaluation of adhesive layer (coating film)]
<Measurement of breaking elongation>
The coating material and the coating material compounding liquid used in Examples 1 to 5 and Comparative Examples 1 to 4 were each transferred to a Teflon (registered trademark) petri dish and dried at 200 ° C. After cooling to room temperature, the dry coating film was taken out from the Teflon (registered trademark) petri dish, and the breaking elongation of the coating film was measured at a crosshead speed of 10 mm / min according to JIS C2151 using a universal tensile measuring device. The results are shown in Table 3.

[Evaluation of composite film]
The composite films obtained in Examples 1 to 5 and Comparative Examples 1 to 4 were evaluated by the following methods. The results are shown in Table 4.

<Normal adhesive strength>
The composite film was cut into a size of 60 mm in length and 15 mm in width to prepare a test piece. This test piece was subjected to a 180 ° peeling test at a crosshead speed of 50 mm / min using a universal tensile measuring device to measure the initial adhesive strength of the composite film. The evaluation was performed according to the following criteria according to the measured initial adhesive strength.
(Evaluation criteria)
⊚: 12N / 15mm or more 〇: 9N / 15mm or more, less than 12N / 15mm Δ: 7N / 15mm or more, less than 9N / 15mm ×: less than 7N / 15mm

<Strength after electrolyte resistance test>
To a mixed solvent in which ethylene carbonate and diethylene carbonate were mixed in a volume ratio of 3: 7, phosphorus hexafluoride lithium salt was added to a concentration of 1 mol / L, and 1000 ppm of distilled water was further added to a simulated electrolytic solution. Then, a test piece of the composite film cut to a width of 15 mm was immersed and stored in an oven at 85 ° C. for 1 week. After taking out the test piece, a 180 ° peeling test was carried out at a crosshead speed of 50 mm / min using a universal tensile measuring device to measure the adhesive strength of the composite film. The evaluation was performed according to the measured adhesive strength according to the following criteria.
(Evaluation criteria)
⊚: 11N / 15mm or more 〇: 9N / 15mm or more, less than 11N / 15mm Δ: 7N / 15mm or more, less than 9N / 15mm ×: less than 7N / 15mm

<Heat-resistant adhesive strength>
The composite film was cut into a size of 60 mm in length and 15 mm in width to prepare a test piece. This test piece was subjected to a 180 ° peeling test at a crosshead speed of 50 mm / min in an atmosphere of 100 ° C. using a universal tensile measuring device to measure the heat-resistant adhesive strength of the composite film. The evaluation was performed according to the measured heat-resistant adhesive strength according to the following criteria.
(Evaluation criteria)
⊚: 11N / 15mm or more 〇: 9N / 15mm or more, less than 11N / 15mm Δ: 7N / 15mm or more, less than 9N / 15mm ×: less than 7N / 15mm

<Moldability>
For each composite film, the appearance of the coated surface after being raised by 5 mm using an Eriksen testing machine under an atmosphere of 23 ° C. was visually observed from the adherend side, and evaluated according to the following criteria.
(Evaluation criteria)
〇: No whitening of the coating film is observed Δ: Slight decrease in transparency is observed in a part of the coating film ×: Whitening part is observed in the coating film

1 Battery case packaging material 2 Base material (metal leaf)
3 Inner layer (adhesive body)
4 Outer layer 5 Inner adhesive layer 6 Outer adhesive layer 10 Battery 11 Electrolyte 17 Positive electrode 18 Negative electrode 19 Separator

Claims (18)

A coating agent containing an olefin polymer (A), an olefin polymer (B), and an organic solvent.
The olefin polymer (A) contains 97 mol% or more and 100 mol% or less of the structural unit (a1) derived from propylene, and the structural unit (a2) 0 derived from an α-olefin having 2 to 20 carbon atoms (excluding propylene). It is an olefin polymer containing mol% or more and 3 mol% or less (however, the total of the constituent units (a1) and the constituent units (a2) is 100 mol%).
The olefin polymer (B) contains 70 mol% or more and less than 97 mol% of the structural unit (b1) derived from propylene, and the structural unit (b2) 3 derived from α-olefin (excluding propylene) having 2 to 20 carbon atoms. It is an olefin polymer containing more than mol% and 30 mol% or less (however, the total of the structural unit (b1) and the structural unit (b2) is 100 mol%).
The content ratio of the structural unit derived from propylene to the total amount of the total olefin polymer is 89.0 mol% or more and 97.4 mol% or less.
The olefin polymer (A) has a melting point of 150 to 170 ° C., and the olefin polymer (B) has a melting point of 70 to 145 ° C.
The olefin polymer (A) is contained in a state of being dispersed in an organic solvent.
Coating agent. The coating agent according to claim 1, wherein a part or all of the olefin polymer (A) or (B) is a modified olefin polymer graft-modified with a polar group-containing monomer. The coating agent according to claim 2, wherein the modified olefin polymer contains a structural unit derived from the polar group-containing monomer in an amount of 0.1 to 15% by mass. The coating agent according to claim 2 or 3, wherein the polar group-containing monomer contains at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. The coating agent according to any one of claims 1 to 4, further containing a curing agent (C). The coating agent according to claim 5, wherein the curing agent (C) contains at least one selected from the group consisting of an aliphatic polyisocyanate and a multimer of an aliphatic polyisocyanate. The coating agent according to claim 5, wherein the curing agent (C) contains at least one compound selected from the group consisting of an epoxy compound and an oxazoline compound. The coating agent according to any one of claims 5 to 7, further comprising a catalyst (D) having a pKa of 11 or more. The coating agent according to any one of claims 1 to 8, wherein the structural unit (a2) or the structural unit (b2) is a structural unit derived from ethylene or 1-butene. The coating agent according to any one of claims 1 to 9, further comprising a liquid or semi-solid hydrocarbon (E) having a kinematic viscosity at 200 ° C. of 10 to 100,000 mm ^{2 / s.} The coating agent according to claim 10, wherein the hydrocarbon (E) is a polymer of an olefin having 2 to 20 carbon atoms (however, excluding the olefin polymers (A) and (B)). The coating agent according to any one of claims 1 to 10, wherein the total amount of the total olefin polymer is the total amount of the olefin polymer (A) and the olefin polymer (B). The coating agent according to any one of claims 1 to 12, which is an adhesive. A film obtained from the coating agent according to any one of claims 1 to 13. The film according to claim 14, wherein the elongation at break measured according to JIS C2151 is 4.7% or more. A laminate having a base material and a layer made of the coating agent according to any one of claims 1 to 13. A battery case in which a metal foil, an adhesive layer, and an adherend are laminated in this order, and the adhesive layer is a layer made of the coating agent according to any one of claims 1 to 13. Packaging material. A step of forming an adhesive layer by applying the coating agent according to any one of claims 1 to 13 to the metal foil and then baking the metal foil.
A method for manufacturing a packaging material for a battery case, which comprises a step of laminating an adherend on a surface of the adhesive layer opposite to the metal foil by an extrusion laminating method.

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