TWI788563B - Packaging materials for coating agents, films, laminates, and battery cases - Google Patents

Abstract

The object of the present invention is to provide a coating agent that has excellent heat resistance and electrolyte solution resistance and can form a formable adhesive layer that does not cause whitening, cracking, or peeling. The coating agent of the present invention contains: an olefin polymer (A), an olefin polymer (B) and an organic solvent; wherein the olefin polymer (A) contains: a structural unit (a1)97 mole derived from propylene At least 100 mol% and 100 mol%, and olefin polymers with structural units (a2) derived from α-olefins with 2 to 20 carbon atoms (excluding propylene) at 0 mol% to 3 mol% ; Relative to the total amount of olefin polymers, the proportion of constituent units derived from propylene is more than 89.0 mol% and less than 97.4 mol%; The melting point of the body (B) is 70~145°C; the olefin polymer (A) is contained in the state of being dispersed in an organic solvent.

Description

Packaging materials for coating agents, films, laminates, and battery cases

The present invention relates to a coating agent, a film, a laminate, and a packaging material for a battery case.

It is known that there will be laminated in sequence: the aluminum foil layer belonging to the base material, the adhesive layer, and the laminated body of a thermoplastic resin film layer (inner layer) such as polypropylene belonging to the adherend, which is used as a lithium ion secondary Packaging materials for batteries (packaging materials for battery cases).

The adhesive layer of the above-mentioned laminate, for example, proposes an adhesive layer that contains: a modified polyolefin resin and a multifunctional isocyanate compound; and the modified polyolefin resin is a homopolymer of propylene or propylene and It is obtained by graft-polymerizing an ethylenically unsaturated carboxylic acid or an anhydride thereof to a copolymer of ethylene, and has a carboxyl group (for example, refer to Patent Document 1).

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

However, there is a problem that the adhesive layer described in Patent Document 1 cannot fully satisfy the above-mentioned requirements for electrolyte solution resistance and adhesive strength.

In view of such a problem, the applicant of the present application proposes an adhesive that is excellent in durability and can sufficiently suppress a decrease in adhesive strength, and a laminate including an adhesive layer formed of the adhesive (see Patent Document 2).

[Prior Art Literature] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2010-092703

Patent Document 2: International Publication No. 2014/123183

However, the requirements for heat resistance and electrolyte resistance of the above-mentioned adhesive layer are further improved, and it is known that if the conventional adhesive is partially stretched at room temperature during molding, there will be a problem of whitening of the stretched part.

The subject of the present invention is to provide a coating agent that has excellent heat resistance and electrolyte resistance, and can form a formable adhesive layer that does not cause whitening, cracking, or peeling. The film obtained from the coating agent contains A laminate of 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 intensive studies, the inventors of the present invention found that the above-mentioned problems can be solved by a coating agent having the following configuration, and thus completed the present invention. The configuration example of this invention is as follows.

[1] A coating agent comprising: an olefin polymer (A), an olefin polymer (B) and an organic solvent; wherein the above-mentioned olefin polymer (A) contains: a composition derived from propylene Units (a1) of 97 mol% to 100 mol%, and constituent units (a2) derived from α-olefins with 2 to 20 carbon atoms (excluding propylene) of 0 mol% to 3 mol% % or less (wherein, the total of the structural unit (a1) and the structural unit (a2) is 100 mole %); the above-mentioned olefin polymer (B) contains: the structural unit (b1) derived from propylene ) of more than 70 mol% and less than 97 mol%, and constituent units (b2) derived from α-olefins with 2 to 20 carbon atoms (except propylene) exceeding 3 mol% and less than 30 mol% (where the total of the structural unit (b1) and the structural unit (b2) is 100 mol%) olefin polymers; the content ratio system of the structural units derived from propylene with respect to the total amount of the total olefin polymers 89.0 mol% or more and 97.4 mol% or less; the melting point of the above-mentioned olefin polymer (A) is 150 to 170°C, and the melting point of the above-mentioned olefin polymer (B) is 70 to 145°C; the above-mentioned olefin polymer (A) is Contained in the state of being dispersed in an organic solvent.

[2] The coating agent according to item [1], wherein a part or all of the above-mentioned olefin polymer (A) or (B) is a modified olefin graft-modified with a monomer containing a polar group. Department of polymers.

[3] The coating agent according to item [2], wherein the modified olefin-based polymerization system 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 system 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], further comprising 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 aliphatic polyisocyanate and multimer of aliphatic polyisocyanate.

唑啉化合物所構成群組中選擇的至少1種化合物。 [7] The coating agent according to item [5], wherein the curing agent (C) contains epoxy compounds and

At least one compound selected from the group consisting of oxazoline compounds.

[8] The coating agent according to any one of items [5] to [7], further comprising 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 derived from ethylene or 1-butene unit.

[10] The coating agent according to any one of items [1] to [9] ^, further comprising a liquid or semisolid hydrocarbon (E ).

[11] The coating agent according to item [10], wherein the hydrocarbon (E) is a polymer of an olefin having 2 to 20 carbon atoms (the olefin polymers (A) and (B) are excluded).

[12] The coating agent as described in any one of items [1] to [10], wherein the total amount of the above-mentioned total olefin polymers is the sum of the above-mentioned olefin polymers (A) and the above-mentioned olefin polymers (B) total amount.

[13] The coating agent according to any one of items [1] to [12], which is an adhesive agent.

[14] A thin film obtained from the coating agent described in any one of items [1] to [13].

[15] The film according to item [14], wherein the elongation at break measured in accordance with JIS C2151 is 4.7% or more.

[16] A laminate comprising: a substrate; and a layer composed of the coating agent described in any one of items [1] to [13].

[17] A packaging material for a battery case, which is a laminate comprising sequentially laminated metal foil, an adhesive layer, and an adherend; the adhesive layer is described in any one of items [1] to [13] A layer composed of a coating agent.

[18] A method of manufacturing a packaging material for a battery case, comprising the following steps: coating the coating agent described in any one of items [1] to [13] on a metal foil, and then performing a burning treatment and a step of forming an adhesive layer; and a step of laminating an adherend on the surface of the adhesive layer opposite to the metal foil by extrusion lamination.

According to the present invention, it is possible to provide a coating agent that has excellent heat resistance and electrolyte solution resistance, and can form a formable adhesive layer that does not cause whitening, cracking, or peeling. Films, A laminate containing an adhesive layer obtained from the coating agent, and a packaging material for battery cases containing the laminate.

1‧‧‧Packaging materials for battery case

2‧‧‧Substrate (metal foil)

3‧‧‧Inner layer (adhesive)

4‧‧‧outer layer

5‧‧‧Inner bonding layer

6‧‧‧Outer bonding layer

10‧‧‧Battery

11‧‧‧Electrolyte

17‧‧‧positive electrode

18‧‧‧negative electrode

19‧‧‧partition

Fig. 1 is a schematic cross-sectional view of an embodiment of a battery using the packaging material for a battery case of the present 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; it is characterized in that the above-mentioned olefin polymer (A) contains: a structural unit (a1) derived from propylene More than 97 mol% and less than 100 mol%, and structural units (a2) derived from α-olefins with 2 to 20 carbon atoms (excluding propylene) 0 mol% and less than 3 mol% (of which , taking the total of the constituent unit (a1) and the constituent unit (a2) as 100 mole %) of the olefin polymer; the above-mentioned olefin polymer (B) contains: 70 mole of the constituent unit (b1) derived from propylene % to less than 97 mol%, and constituent units (b2) derived from α-olefins with 2 to 20 carbons (except propylene) exceed 3 mol% to 30 mol% (among them, The total amount of the constituent unit (b1) and the constituent unit (b2) is 100 mol%) Olefin polymer; the content ratio of the constituent unit derived from propylene is 89.0 mol% with respect to the total amount of the olefin polymer Above and below 97.4 mol%; the melting point of the above-mentioned olefin polymer (A) is 150-170°C, and the melting point of the above-mentioned olefin polymer (B) is 70-145°C; the above-mentioned olefin polymer (A) is dispersed in organic The state in the solvent contains.

In addition, the coating agent of the present invention may further contain a curing agent (C) and/or a liquid or semi-solid hydrocarbon (E) with a kinematic viscosity at 200°C of 10-100,000 mm ² /s if necessary; In the case of the above curing agent (C), a 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 above-mentioned olefin polymer (A) is more than 97 mole % and less than 100 mole %, preferably more than 97.5 mole % and less than 100 mole %, more preferably more than 98 mole % and less than 100 mole % Contains the above constituent unit (a1) in an amount of 0 mol% to less than 3 mol%, preferably 0 mol% to 2.5 mol%, and most preferably 0 mol% to 2 mol%. The above-mentioned structural unit (a2) is contained in an amount of mol% or less (where the total of the structural unit (a1) and the structural unit (a2) is 100 mol%).

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

Furthermore, the above-mentioned olefin polymer (B) is more than 70 mole % and less than 97 mole %, preferably more than 71 mole % and less than 97 mole %, more preferably more than 72 mole % and The above constituent unit (b1) is contained in an amount of not more than 97 mol%, and is more than 3 mol% and not more than 30 mol%, preferably more than 3 mol% and not more than 29 mol%, more preferably more than The above-mentioned structural unit (b2) is contained in an amount of 3 mol% to 28 mol% or less (where the total of the structural unit (b1) and the structural unit (b2) is 100 mol%).

Accordingly, the above-mentioned olefin polymer (B) is a copolymer of propylene and α-olefins with 2 to 20 carbons (except propylene), which can be a random copolymer or a block copolymer, preferably random copolymers.

The α-olefins with 2 to 20 carbon atoms (excluding propylene) that form the above-mentioned constituent units (a2) and (b2) include, for example, ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. , Among these, ethylene and 1-butene are preferred. These may be used individually by 1 type, and may use 2 or more types together. In addition, the above-mentioned 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.

烯、5-乙烯基-2-降

烯、5-亞甲基-2-降

烯、2,5-降

二烯等非共軛多烯類。 The above-mentioned olefin polymers (A) and (B) may also contain unsaturated monomers other than propylene and α-olefins with 2 to 20 carbons (except propylene) within the scope of not damaging the effect of the present invention. (hereinafter referred to as "other unsaturated monomers") derived structural units. Other unsaturated monomer systems can include, for example: butadiene, isoprene and other conjugated polyenes; or 1,4-hexadiene, 1,7-octadiene, dicyclopentadiene, 5- Ethylene-2-nor

ene, 5-vinyl-2-nor

alkenes, 5-methylene-2-nor

alkenes, 2,5-nor

Non-conjugated polyenes such as dienes.

In the coating agent of the present invention, relative to the total amount of the total olefin polymers, the content ratio of the structural units derived from propylene is not less than 89.0 mol% and not more than 97.4 mol%, preferably not less than 90.0 mol% and not more than 97.4 mol%. Mole % or less. By setting the content ratio of the structural units derived from propylene within the above range, an adhesive layer excellent in heat resistance, electrolyte solution resistance, and formability can be formed. In addition, in one aspect of the present invention, the total amount of the above-mentioned total olefin polymers is the total amount of the above-mentioned propylene polymers (A) and the above-mentioned propylene polymers (B).

The melting point (Tm) of the above-mentioned olefin polymer (A) is 150-170°C, preferably 150-165°C, more preferably 155-160°C. On the other hand, the melting point (Tm) of the above-mentioned olefin polymer (B) is 70-145°C, preferably 75-145°C, more preferably 75-100°C. Accordingly, by using the above-mentioned olefin polymer (A) that is a high-melting point component and the above-mentioned olefin polymer (B) that is a low-melting point component in combination, it is possible to form an adhesive that is excellent in heat resistance, electrolyte solution resistance, and formability. layer.

In the present invention, Tm is obtained by differential scanning calorimetry (DSC measurement) according to JIS K7122. Specifically, after heating up from 30° C. to 180° C. at 10° C./min, the temperature is maintained for 3 minutes, and then , lower the temperature at 10°C/min to 0°C, hold at this temperature for 3 minutes, and then raise the temperature to 150°C at 10°C/min again, from the thermal analysis diagram at the second temperature rise, according to JIS K7122 ask for.

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

The above-mentioned olefin polymers (A) and (B) are measured by gel permeation chromatography (GPC), and the weight average molecular weight (Mw) in terms of standard polystyrene is, for example, not less than 10,000 and not more than 1,000,000, and, The molecular weight distribution (degree of dispersion) is, for example, 1 or more and 3 or less. In addition, the molecular weight distribution is a ratio (Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn).

The above-mentioned olefin polymers (A) and (B) are in the presence of known solid-state Ti catalysts or metallocene catalysts commonly used in the production of α-olefin polymers, by making the carbon number 2 to 20 It can be obtained by polymerizing α-olefins. The metallocene catalyst system can be exemplified by metallocene compounds such as rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)} zirconium dichloride, and Catalysts for organoaluminum oxy compounds such as aluminoxane and organoaluminum compounds such as triisobutylaluminum. More specific methods for producing the above-mentioned olefin polymers (A) and (B) include, for example, the method described in International Publication No. 2004/87775.

In the present invention, part or all of the above-mentioned olefin polymer (A) or (B) may be a modified olefin-based polymer grafted and modified by a polar group-containing monomer. By containing the modified olefin-based polymer, the adhesive force of the adhesive layer to the substrate (such as aluminum foil, etc.) can be further improved, and the electrolyte resistance can be improved.

The above-mentioned polar group-containing monomer system can be, for example: ethylenically unsaturated compounds containing hydroxyl groups, ethylenically unsaturated compounds containing amino groups, ethylenically unsaturated compounds containing epoxy groups, unsaturated carboxylic acids and their anhydrides and their derivatives Compounds, vinyl ester compounds, vinyl chloride, etc., preferably unsaturated carboxylic acids and their anhydrides.

烯、羥基苯乙烯、N-羥甲基丙烯醯胺、2-(甲基)丙烯醯氧乙基酸性磷酸酯、甘油單烯丙醚、烯丙醇、烯丙氧基乙醇、2-丁烯-1,4-二醇、甘油單醇等。 Examples of ethylenically unsaturated compounds containing hydroxyl groups include: hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (meth) 2-Hydroxy-3-phenoxypropyl acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, pentaerythritol mono(meth)acrylate, trihydroxy Methylpropane Mono(meth)acrylate, Tetramethylolethane Mono(meth)acrylate, Butylene Glycol Mono(meth)acrylate, Polyethylene Glycol Mono(meth)acrylate, Acrylic- Hydroxyl-containing (meth)acrylates such as 2-(6-hydroxyhexyloxy)ethyl ester; and 10-undecen-1-ol, 1-octen-3-ol, 2-methanol

olefin, hydroxystyrene, N-methylolacrylamide, 2-(meth)acryloxyethyl acid phosphate, glycerol monoallyl ether, allyl alcohol, allyloxyethanol, 2-butene -1,4-diol, monoglycerol, etc.

The amino group-containing ethylenically unsaturated compound is, for example, a vinyl monomer having at least one of an amino group or a substituted amino group represented by the following formula.

-NR ₁ R ₂

In the formula, _R1 is a hydrogen atom, methyl or ethyl; _R2 is a hydrogen atom, a carbon number of 1 to 12 and preferably an alkyl group with a carbon number of 1 to 8, and a carbon number of 8 to 12 and is preferably a 6~ 9 cycloalkyl. In addition, the above-mentioned alkyl group and cycloalkyl group may further have a substituent.

Such amine-containing ethylenically unsaturated compounds include, for example, amine methyl (meth)acrylate, propylamine ethyl (meth)acrylate, dimethylaminoethyl methacrylate, (meth) ) Alkyl ester derivatives of acrylic acid or methacrylic acid such as aminopropyl acrylate, phenylaminomethyl methacrylate, cyclohexylaminoethyl methacrylate, etc.; N-vinyldiethylamine, N-acetyl Vinylamine and other vinylamine derivatives; acrylamide, methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, N,N-dimethylaminopropyl Acrylamide-based derivatives such as acrylamide and other imides.

As the epoxy group-containing ethylenically unsaturated compound, a monomer having at least one polymerizable unsaturated bond group and an epoxy group in one molecule can be used.

Such epoxy group-containing ethylenically unsaturated compounds can be exemplified by glycidyl acrylate, glycidyl methacrylate and other unsaturated carboxylic acid glycidyl esters; or maleic acid, transbutylene Acenoic 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-methyl-2,3-dicarboxylic acid (methyl nadic acid ^TM ) and other monoepoxides of unsaturated dicarboxylic acids Propyl ester (in the case of monoglycidyl ester, the alkyl carbon number is 1~12); alkyl glycidyl ester, allyl glycidyl ether, 2-methallyl ring of styrene carboxylic acid Oxypropyl 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, ethylene monoxide cyclohexene, and the like.

烯二羧酸、雙環[2,2,1]庚-2-烯-5,6-二羧酸等不飽和羧酸或該等的衍生物(例如：酸酐、醯鹵、醯胺、醯亞胺、酯等)。 Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid,

Alkenedicarboxylic acid, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid and other unsaturated carboxylic acids or their derivatives (for example: acid anhydride, amide halide, amide, amide amines, esters, etc.).

Derivatives of unsaturated carboxylic acids include, for example, maleyl chloride, maleimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2, 2,1] Hept-2-ene-5,6-dicarboxylic anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, fumaric acid Diethyl ester, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, dimethyl bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylate , Hydroxyethyl (meth)acrylate, Hydroxypropyl (meth)acrylate, Glycidyl (meth)acrylate, Aminoethyl methacrylate, Aminopropyl methacrylate, etc.

Examples of vinyl ester compounds include: vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl isobutyrate, trimethyl vinyl acetate, vinyl caproate, vinyl neodecanoate, vinyl laurate ester, vinyl stearate, vinyl benzoate, vinyl salicylate, vinyl cyclohexanecarboxylate, etc.

These polar group-containing monomer systems may be used singly or in plural.

The above-mentioned modified olefin-based polymerization system preferably contains 0.1-15% by mass, more preferably 0.2-10% by mass, and most preferably 0.5-5% by mass, and contains constituent units derived from the above-mentioned polar group-containing monomers .

The content rate (modified amount) of these polar group-containing monomers can be adjusted according to the loading ratio when the olefin polymer and the polar group-containing monomer are reacted in the presence of a radical initiator or the like. In addition, the above-mentioned modified mass system can be obtained by known means such as ¹ H NMR measurement. Specific NMR measurement conditions can be exemplified as follows.

For ¹ H NMR measurement, use the ECX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., and the solvent is deuterated o-dichlorobenzene, the sample concentration is 20mg/0.6mL, the measurement temperature is 120°C, and the observation nucleus is ¹ H (400MHz ), the sequence is a single pulse, the pulse width is 5.12 μ seconds (45° pulse), the repetition time is 7.0 seconds, and the number of integration times is more than 500 times. The standard chemical shift is based on the hydrogen of tetramethylsilane being 0 ppm. For example, even if the peak of residual hydrogen originating from deuterated o-dichlorobenzene is set at 7.10 ppm as the standard value of the chemical shift, the same can be obtained result. Sharp peaks derived from ¹ H etc. of functional group-containing compounds can be specified by conventional methods.

Furthermore, when the above-mentioned polar group-containing monomer system uses monomers with acidic functional groups such as the above-mentioned unsaturated carboxylic acids and their anhydrides, the target amount of functional groups introduced into the modified olefin polymer can also be Use eg acid value. Here, the measuring method of an acid value is mentioned below, for example.

(Determination of acid value)

The basic operating system is based on JIS K2501-2003.

Correctly measure about 10g of the modified olefin polymer, and throw it into a 200mL tall beaker. 150 mL of a mixed solvent obtained by mixing xylene and dimethylformamide at a ratio of 1:1 (volume ratio) was added thereto as a titration solvent. A few drops of 1 w/v% phenolphthalein ethanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was dropped as an indicator, and the liquid temperature was heated to 80° C. to dissolve the sample. After the liquid temperature was stabilized at 80° C., titration was performed using a 0.1 mol/L potassium hydroxide solution in 2-propanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the acid value was determined from the titrated amount.

Calculation formula: acid value (mgKOH/g)=(EP1-BL1)×FA1×C1/SIZE

Among them, in the above calculation formula, "EP1" means the titer (mL), "BL1" means the blank value (mL), "FA1" means the factor of the titrant (1.00), and "C1" means the concentration conversion value (5.611mg/mL: equivalent to 0.1mol/L KOH 1mL of potassium hydroxide), "SIZE" means the sample collection amount (g).

This measurement was repeated 3 times, and the average value was set as the acid value.

The acid value of the modified olefin polymer is preferably 0.1-100 mgKOH/g, more preferably 0.5-60 mgKOH/g, and most preferably 0.5-30 mgKOH/g. Here, when a modified olefin polymer composition is formed by mixing a graft modified olefin polymer with an unmodified olefin polymer, it is preferable that the whole modified olefin polymer composition has The above-mentioned general acid value.

Furthermore, when maleic anhydride is used for the above-mentioned polar group-containing monomer system, an infrared spectrophotometer can also be used to calculate the grafting amount according to the carboxyl absorption of maleic anhydride detected around 1790 cm ⁻¹ .

As a method of graft-copolymerizing the polar group-containing monomer on the above-mentioned olefin polymer (A) and/or the above-mentioned olefin polymer (B), various methods can be cited. For example, dissolving the unmodified olefin polymer in an organic solvent, adding a polar radical-containing monomer and a free radical polymerization initiator, and heating and stirring to perform a graft copolymerization reaction; In the melt obtained by heating and melting the olefin polymer, add a monomer containing a polar group and a free radical polymerization initiator, and carry out graft copolymerization by stirring; the unmodified olefin polymer, containing polar The radical monomer and the radical polymerization initiator are mixed, and then the obtained mixture is supplied to the extruder, and the graft copolymerization reaction is carried out while performing heating and kneading; the unmodified olefin polymer is impregnated with After the solution formed by dissolving the polar group-containing monomer and the radical polymerization initiator in the organic solvent, it is heated to the highest temperature at which the unmodified olefin polymer will not dissolve, and the graft copolymerization reaction is carried out, etc.

The reaction temperature is preferably above 50°C, more preferably in the range of 80-200°C, and the reaction time is about 1 minute to 10 hours.

The reaction mode can be any one of batch type and continuous type, but in order to carry out graft copolymerization uniformly, batch type is preferred.

The free radical polymerization initiator used is not limited on the premise that it can promote the reaction between the unmodified olefin polymer and the polar group-containing monomer, especially organic peroxides and organic peroxyesters.

Specifically, there are: benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxide Oxybenzoate) hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauryl peroxide, tert-butyl peroxyacetate, 2,5-dimethyl- 2,5-bis(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, tert-butyl benzoate, per Tertiary butyl oxyphenyl acetate, tertiary butyl peroxyisobutyrate, tertiary butyl peroxycaprylate, tertiary butyl peroxytrimethylacetate, cumylperoxytrimethylacetate And tertiary butyl peroxy diethyl acetate; and other azo compounds, such as: azobisisobutyronitrile, dimethyl azoisobutyronitrile.

Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxy)hexyne-3, 2 , Dialkyl peroxides such as 5-dimethyl-2,5-di(tert-butylperoxy)hexane, 1,4-bis(tert-butylperoxyisopropyl)benzene, etc.

The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass relative to 100 parts by weight of the unmodified olefin polymer.

The grafting reaction is as described above, and can be carried out in an organic solvent or without a solvent. When the reaction is carried out in an organic solvent, the same or other organic solvent can be added directly or further to prepare a coating agent. When the grafting reaction is performed without using an organic solvent, the coating agent of the present invention is prepared by adding an organic solvent in advance. In addition, when the grafted modified olefin polymer is mixed with the unmodified olefin polymer system, it can be mixed in advance and then used in the preparation of the coating agent, or it can be mixed in a solvent during the preparation of the coating agent .

According to this, when carrying out the reaction or adding after the reaction, the organic solvent used to prepare the coating agent of the present invention is not particularly limited, for example: aromatic hydrocarbons such as benzene, toluene, xylene; hexane, heptane, etc. Aliphatic hydrocarbons such as alkane, octane, decane; cyclohexane, cyclohexene, methylcyclohexane, ethylcyclohexane, decahydronaphthalene and other alicyclic hydrocarbons; methanol, ethanol, isopropanol, butane Alcohols such as alcohol, pentanol, hexanol, propylene glycol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, isophorone, and acetophenone; Base cellosu and other cellosulfones; methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate and other esters; trichloroethylene, dichloroethylene, chlorobenzene and other halogenated hydrocarbons, etc. Among them, aromatic hydrocarbons, aliphatic hydrocarbons, and ketones are preferable. These can be used individually by 1 type or in combination of 2 or more types.

In the present invention, such a graft-modified olefin-based polymerization system may be used alone or in combination of two or more.

<Hardener (C)>

The coating agent of the present invention may optionally contain a curing agent (C) 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 are advantages in that the strength of the coating film is improved, and the adhesiveness, heat resistance, and chemical resistance are more excellent.

The curing agent (C) is not particularly limited, and examples thereof include polyisocyanate monomers and modified polyisocyanates. Among them, the polyisocyanate monomer system is a monomeric compound having multiple isocyanate groups in one molecule. Examples of such polyisocyanate monomer system include aromatic polyisocyanate, aromatic aliphatic polyisocyanate, and aliphatic polyisocyanate.

Here, examples of the aromatic polyisocyanate series include: cresyl diisocyanate (2,4- or 2,6-cresyl diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate ( m-, p-diisocyanate phenylene or mixtures 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), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate and other aromatic diisocyanates isocyanates and more.

Examples of araliphatic polyisocyanates include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), diisocyanate Tetramethylxylylene (1,3- or 1,4-tetramethylxylylene diisocyanate or mixtures thereof) (TMXDI), ω,ω'-diisocyanate-1,4- Araliphatic diisocyanates such as diethylbenzene, etc.

Examples of aliphatic polyisocyanates include: trimethylene diisocyanate, 1,2-propylidene diisocyanate, butyl diisocyanate (tetramethylene diisocyanate, 1,2-diisocyanate butylene ester, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate Aliphatic diisocyanates such as isocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylhexanoate, etc.

烷二異氰酸酯(各種異構物或其混合物)(NBDI)、雙(異氰酸基甲基)環己烷(1,3-或1,4-雙(異氰酸基甲基)環己烷、或該等的混合物)(H₆XDI)等脂環族二異氰酸酯。 In addition, the aliphatic polyisocyanate system includes alicyclic polyisocyanate. The alicyclic polyisocyanate series can be exemplified: 1,3-cyclopentyl diisocyanate, 1,3-cyclopentenyl diisocyanate, cyclohexyl diisocyanate (1,4-diisocyanate Cyclohexyl diisocyanate, cyclohexyl diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate ) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate), trans-trans forms of these, trans-cis or cis-cis, or a mixture thereof) (H ₁₂ MDI), methyl cyclohexyl diisocyanate (methyl-2,4-cyclohexyl diisocyanate, methyl- 2,6-diisocyanate cyclohexyl), nor

Alkane diisocyanate (various isomers or mixtures thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane , or mixtures thereof) (H ₆ XDI) and other alicyclic diisocyanates.

These polyisocyanate monomeric systems can be used individually or in combination of 2 or more types.

On the other hand, the polyisocyanate modified system can be, for example, a modified body formed by the reaction between the above-mentioned polyisocyanate monomers, and a modified body formed by the reaction of the above-mentioned polyisocyanate monomers with other compounds. Usually, it can be used Those with an average functional base of more than 2. The so-called "other compounds" here refer to compounds other than the above-mentioned polyisocyanate monomers, which can react with the above-mentioned polyisocyanate monomers. Polyols"), compounds with active hydrogen such as amines and water, and carbon dioxide.

Here, examples of monoalcohols usable in the present invention include butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecanol Alcohol, Myristyl Alcohol (Myristyl Alcohol), Pentadecyl Alcohol, Cetyl Alcohol (Cetyl Alcohol), Heptadecanyl Alcohol, Stearyl Alcohol (Stearyl Alcohol, Octadecanol), Nonadecanyl Alcohol, and Isomers of These (including 2-methyl-1-propanol (isobutanol)), and other alkanols (C20~50 alcohols); and enols such as oleyl alcohol, alkadienols such as octadienol, such as Aliphatic monoalcohols such as polyethylene butylene monoalcohol. Moreover, examples of the monoalcohol include alicyclic monoalcohols such as cyclohexanol and methylcyclohexanol, araliphatic monoalcohols such as benzyl alcohol, and the like.

In addition, polyols that can be used in the present invention include, for example, compounds having two or more hydroxyl groups generally used in the field of urethane resins, and may have a monomeric form or a polymeric form.

Among them, examples of polyhydric alcohols in the form of monomers include alkanediols such as ethylene glycol and propylene glycol; cyclohexanediol; dihydric alcohols such as cyclohexanedimethanol and benzenedimethanol; Triols such as methylolmethane, trimethylolethane, and trimethylolpropane; and alcohols having four or more hydroxyl groups, such as pentaerythritol and dipentaerythritol. In addition, in this specification, the polyol which has such a monomeric form is also called "low molecular weight polyol".

On the other hand, polyols having a polymer form include, for example, polyester polyols, polyether polyols, and polymer polyols generally used in the field of urethane resins.

二

三酮改質體、羰二醯亞胺改質體、脲二酮改質體、及脲酮亞胺改質體等。 Specific examples of such polyisocyanate modifiers include, for example, multimers of the above-mentioned polyisocyanate monomers, allophanate modifiers, polyol modifiers, biuret modifiers, and urea modifiers. plastid,

two

Modified triketone, modified carbonyl imide, modified uretdione, modified uretonimine, etc.

二

二酮改質體。 Here, examples of the above-mentioned multimer include, for example, dimers, trimers, pentamers, heptamers, etc. of polyisocyanate monomers. Among them, examples of trimers of polyisocyanate monomers include: modified isocyanurate, imine

two

Diketone modifier.

Furthermore, examples of the above-mentioned allophanate modified products include, for example, ureido groups produced by the reaction of the above-mentioned polyisocyanate monomers with monoalcohols (for example, the monoalcohols exemplified above such as stearyl alcohol). Formate modifier, etc.

The above-mentioned polyol modifying system can be, for example, a polyol modified product (alcohol adduct) formed by the reaction of polyisocyanate monomer and low molecular weight polyol (such as trihydric alcohol, etc.).

The above-mentioned biuret-modified system can be, for example, a biuret-modified body produced by the reaction of the above-mentioned polyisocyanate monomer with water or amines.

The above-mentioned urea-modified system can be, for example, a urea-modified product formed by the reaction of the above-mentioned polyisocyanate monomer and diamine.

二

三酮改質體係可舉例如：由上述聚異氰酸酯單體與碳酸氣體的反應，而生成之

二

三酮等。 the above

two

The triketone modification system can be, for example, formed by the reaction of the above-mentioned polyisocyanate monomer with carbon dioxide gas

two

Triketone etc.

The above-mentioned carbodiimide modified system may, for example, be a carbodiimide modified body produced by the decarbonation condensation reaction of the above-mentioned polyisocyanate monomer.

In addition, the polyisocyanate modified system can also mention, for example: polymethylene polyphenyl polyisocyanate (crude MDI, polymeric MDI) etc. besides the above.

In the present invention, among the above-mentioned polyisocyanate monomers and modified polyisocyanates, aliphatic polyisocyanates and multimers thereof are particularly preferably used. That is, in a preferred aspect of the present invention, the curing agent (C) is an aliphatic polyisocyanate or a multimer of aliphatic polyisocyanate.

These can be used individually by 1 type or in combination of 2 or more types.

In the coating agent of the present invention, when the curing agent (C) contains a polyisocyanate monomer or a modified polyisocyanate, the amount of the curing agent (C) added is relative to the above-mentioned olefin polymers (A) and (B), It is preferably 2 to 30 parts by mass for a total of 100 parts by mass of hydrocarbons (E) described later.

唑啉化合物中選擇的至少1種化合物。此情況，本發明塗佈劑，較佳係上述烯烴聚合體(A)及/或(B)至少含有1種上述改質烯烴系聚合體。藉此，可獲得硬化時的體積變化小、能依低溫進行硬化的塗佈劑，特別係可獲得接著強度優異的接著劑層。 The above-mentioned hardener (C) can also be used by epoxy compound and

At least one compound selected from oxazoline compounds. In this case, the coating agent of the present invention preferably contains at least one modified olefin polymer described above in the olefin polymer (A) and/or (B). Thereby, a coating agent capable of curing at a low temperature with a small volume change during curing can be obtained, and in particular an adhesive layer excellent in adhesive strength can be obtained.

或乙內醯脲等含雜環的環氧樹脂。 The said epoxy compound is a crosslinkable compound which has 2 or more epoxy groups in 1 molecule. Such epoxy compounds can be exemplified: bisphenol type epoxy resins such as bisphenol A type epoxy resin (different from hydrogenated bisphenol A type epoxy resin), bisphenol F type epoxy resin; hydrogenated bisphenol type epoxy resin Oxygen resin; Novolak type epoxy resin; Biphenyl type epoxy resin; Stilbene type epoxy resin; Hydroquinone type epoxy resin; Naphthalene skeleton type epoxy resin; Tetrahydroxyphenylethane type epoxy resin; Benzene type epoxy resin; dicyclopentadiene phenol type epoxy resin; 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, 2,2-bis( Cycloaliphatic epoxy resins such as 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of hydroxymethyl)-1-butanol; diepoxy resins of hexahydrophthalic anhydride Polyglycidyl ester of polybasic acid such as propyl ester; polyglycidyl ether of sorbitol, polyglycidyl ether of sorbitan, polyglycidyl ether of pentaerythritol, polyglycidyl ether of trimethylolpropane, polyglycidyl ether of poly Propylene Glycol Diglycidyl Ether, Diglycerol Polyglycidyl Ether, Glycerin Polyglycidyl Ether, Hexylene Glycol Diglycidyl Ether, Hydrogenated Bisphenol A Diglycidyl Ether and Cyclohexanedimethanol Diglycidyl Ether Glycidyl ether such as ether; diene polymer epoxy resin such as polybutadiene or polyisoprene; tetraglycidyl diaminodiphenylmethane, tetraglycidyl diaminomethylcyclohexyl Glycidylamine-type epoxy resins such as alkane, diglycidylaniline, tetraglycidyl m-xylylenediamine, etc.; three

Or epoxy resins containing heterocycles such as hydantoin.

Among the above-mentioned epoxy compounds, the bisphenol A type is preferable from the viewpoint of being able to obtain more excellent adhesive strength, especially an aluminum foil layer and a thermoplastic resin film layer such as polypropylene, and an adhesive layer that can be bonded with higher strength. Liquid epoxy resin, cycloaliphatic epoxy compound, trimethylolpropane polyglycidyl ether.

The bisphenol A type liquid epoxy resin is not particularly limited as long as it is a liquid resin at normal temperature (25° C.), and a commercially available one can also be used.

Examples of such commercially available systems include: EPICLON840, 840-S, 850, 850-S, EXA-850CRP, 850-LC (manufactured by DIC (stock)); jER828EL, 827 (manufactured by Mitsubishi Chemical (stock)); EPOMIC R -140P (manufactured by Mitsui Chemicals Co., Ltd.).

The above-mentioned alicyclic epoxy compound refers to a compound with at least one epoxy cycloalkyl group or epoxy cycloalkenyl group in the molecule, or at least one ring with at least one ring bonded by a single bond on the alicyclic ring in the molecule. Oxygen-based compounds.

烷、己二酸雙(3,4-環氧環己基甲酯)、二氧化乙烯環己烯、己二酸雙(3,4-環氧-6-甲基環己基甲酯)、3,4-環氧-6-甲基環己基-3,4-環氧-6-甲基環己烷羧酸酯、亞甲基雙(3,4-環氧環己烷)、二環戊二烯二環氧化物、乙二醇二(3,4-環氧環己基甲基)醚、乙烯雙(3,4-環氧環己烷羧酸酯)、1,2,8,9-二環氧檸檬烯、2,2-雙(羥甲基)-1-丁醇之1,2-環氧-4-(2-環氧乙烷基)環己烷加成物、日本專利特開2008-214555號公報所記載的化合物。 The above alicyclic epoxy compounds can be exemplified as: 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, 3',4'-epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloctyl-3,4-epoxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexane Hexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-di

Alkane, bis(3,4-epoxycyclohexylmethyl) adipate, ethylene dioxide cyclohexene, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3, 4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene ethylene diepoxide, ethylene glycol bis(3,4-epoxycyclohexylmethyl) ether, ethylene bis(3,4-epoxycyclohexanecarboxylate), 1,2,8,9-di Epoxylimonene, 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, Japanese Patent Laid-Open 2008 - Compounds described in Gazette No. 214555.

The above-mentioned alicyclic epoxy compounds can also use commercially available products, such as CELLOXIDE 2021P, EHPE3150, EHPE3150CE, EPOLEAD GT401 (all of which are manufactured by Daicel Co., Ltd.).

The aforementioned alicyclic epoxy compound is preferably 1,2-epoxy-4-( 2-oxiranyl) cyclohexane adduct.

Examples of the above-mentioned trimethylolpropane polyglycidyl ether system include trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, and mixtures thereof.

As the above-mentioned trimethylolpropane polyglycidyl ether system, a commercially available product can be used, and the commercially available product system includes, for example, EX-321L (manufactured by Nagase ChemteX Co., Ltd.).

唑啉化合物係1分子中具有2個以上

唑啉基 之可交聯的化合物。此種

唑啉化合物係可舉例如：含

唑啉基單體的聚合體、含

唑啉基單體與其他單體的共聚合體等含

唑啉基聚合物。 the above

The oxazoline compound has 2 or more in 1 molecule

An oxazoline-based cross-linkable compound. this kind

The oxazoline compound series can be for example: containing

Polymers of oxazoline-based monomers, containing

Copolymers of oxazoline-based monomers and other monomers, etc.

Azoline-based polymers.

唑啉基單體係可舉例如：2-乙烯基-2-

唑啉、2-乙烯基-4-甲基-2-

唑啉、2-乙烯基-5-甲基-2-

唑啉、2-異丙烯基-2-

唑啉、2-異丙烯基-4-甲基-2-

唑啉、2-異丙烯基-5-乙基-2-

唑啉、2-異丙烯基-2-

唑啉、2-異丙烯基-4,4-二甲基-2-

唑啉。該等係可單獨使用1種、或使用2種以上。 The above contains

The oxazoline-based monomer system can be exemplified by: 2-vinyl-2-

Azoline, 2-vinyl-4-methyl-2-

Azoline, 2-vinyl-5-methyl-2-

Azoline, 2-isopropenyl-2-

Azoline, 2-isopropenyl-4-methyl-2-

Azoline, 2-isopropenyl-5-ethyl-2-

Azoline, 2-isopropenyl-2-

Azoline, 2-isopropenyl-4,4-dimethyl-2-

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

Other monomer systems mentioned above can be exemplified: (meth)acrylic acid alkyl ester (alkyl carbon number is about 1~14); acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, Unsaturated carboxylic acids such as crotonic acid, styrenesulfonic acid and their salts (sodium salt, potassium salt, ammonium salt, tertiary amine salt, etc.); unsaturated nitriles such as acrylonitrile and methacrylonitrile; (meth)acrylic acid Amide, N-alkyl(meth)acrylamide, N,N-dialkyl(meth)acrylamide, (alkyl: methyl, ethyl, n-propyl, isopropyl, n-butyl base, isobutyl, tertiary butyl, 2-ethylhexyl, cyclohexyl, etc.) and other unsaturated amides; vinyl acetate, vinyl propionate and other vinyl esters; methyl vinyl ether, ethyl vinyl ether Vinyl ethers, etc.; α-olefins such as ethylene and propylene; halogen-containing α, β-unsaturated monomers such as vinyl chloride, vinylidene chloride, and vinyl fluoride; α, β, such as styrene and α-methylstyrene - unsaturated aromatic monomers. These may be used individually by 1 type, and may use 2 or more types.

唑啉化合物從能獲得接著強度更優異的接著劑層等觀點，較佳係含有2-異丙烯基-2-

唑啉的

唑啉化合物。市售物係可舉例如日本觸媒(股)製「EPOCROS」系列。 the above

The oxazoline compound preferably contains 2-isopropenyl-2-

oxazoline

Azoline compounds. Examples of commercially available products include the "EPOCROS" series manufactured by Nippon Shokubai Co., Ltd.

唑啉化合物的

唑啉當量，從能獲得接著強度及耐藥性、耐電解液性更優異的接著劑 層等觀點，較佳係100g/eq以上、更佳係125g/eq以上，且較佳係1,600g/eq以下、更佳係500g/eq以下。 The epoxy equivalent of above-mentioned epoxy compound and

of oxazoline compounds

The oxazoline equivalent is preferably 100 g/eq or more, more preferably 125 g/eq or more, and more preferably 1,600 g/eq from the viewpoint of obtaining an adhesive layer with better adhesive strength, chemical resistance, and electrolyte resistance. Below eq, more preferably below 500g/eq.

The said equivalent system can be measured based on JISK7236.

唑啉化合物中選擇的至少1種化合物的情況，該硬化劑(C)係相對於硬化劑(C)中的環氧基與

唑啉基當量/烯烴聚合體(A)及(B)中的環氧基或

唑啉基，反應性官能基的當量較佳係0.01以上、更佳係0.1以上，且較佳係50以下、更佳係30以下、特佳係20以下、最佳係10以下的方式調配。若硬化劑(C)的調配量在上述範圍內，便可獲得接著強度及耐藥性、耐電解液性更優異的接著劑層。 The coating agent of the present invention, when the curing agent (C) contains epoxy compound and

In the case of at least one compound selected from oxazoline compounds, the curing agent (C) is based on the epoxy group in the curing agent (C) and

Azoline group equivalent/epoxy group in olefin polymer (A) and (B) or

For the oxazoline group, the equivalent weight of the reactive functional group is preferably 0.01 or more, more preferably 0.1 or more, and is preferably 50 or less, more preferably 30 or less, most preferably 20 or less, most preferably 10 or less. When the compounding quantity of a hardening|curing agent (C) exists in the said range, the adhesive agent layer more excellent in adhesive strength, chemical resistance, and electrolytic solution resistance can be obtained.

<Catalyst (D)>

唑啉化合物中選擇的至少1種化合物。 The coating agent of this invention may contain the catalyst (D) whose pKa is 11 or more. In this case, the coating agent of the present invention preferably contains the above-mentioned curing agent (C), more preferably the above-mentioned curing agent (C) is obtained from epoxy compounds and

At least one compound selected from oxazoline compounds.

By using the above-mentioned catalyst (D), the cross-linking reaction can be efficiently promoted even at low temperature, and an adhesive layer with excellent chemical resistance and electrolyte resistance can be formed, so that an aluminum foil layer with excellent adhesive strength can be obtained. Adhesive layer that can be bonded with a thermoplastic resin film layer such as polypropylene with high strength.

The catalyst (D) may be used alone or in combination of two or more.

The above-mentioned catalyst (D) is not particularly limited on the premise that the pKa is 11 or more. It is preferably a compound that can promote the cross-linking reaction of the above-mentioned hardener (C). Such a compound can be for example: 1,8 - Strongly basic tertiary amines such as diazabicyclo[5.4.0]myrcene-7 (DBU), 1,6-diazabicyclo[3.4.0]nonene-5; phosphorus with phosphazene base Nitrile catalyst, preferably DBU, phosphazene catalyst.

In addition, the above-mentioned pKa is an acid dissociation constant at 25° C. in an aqueous solution. Also, for example, phosphoric acid has three pKas, namely pKa ₁ , pKa ₂ and pKa ₃ , pKa in the present invention refers to pKa ₁ , namely the first acid dissociation constant).

The compounding amount of the above-mentioned catalyst (D) is preferably 1 ppm or more, more preferably 100 ppm or more, and more preferably 1 mass % relative to 100 mass % of the non-volatile content (components other than the solvent) of the coating agent of the present invention. At most, more preferably at most 0.3% by mass. When the compounding amount of the catalyst (D) is within the above-mentioned range, a coating agent with excellent curing speed can be obtained, and an adhesive layer with excellent chemical resistance, electrolyte 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 with higher adhesive strength can be obtained.

The above-mentioned hydrocarbon (E) is not particularly limited under the premise of satisfying the above-mentioned kinematic viscosity, and is preferably a polymer of olefins with 2 to 20 carbon atoms (wherein, the above-mentioned olefin polymers (A) and (B) )except). Among them, it is preferable to use an oligomer or a polymer obtained by polymerizing an olefin having 2 to 20 carbon atoms alone, or an oligomer or a polymer obtained by copolymerizing an arbitrary mixture of two or more such olefins. .

The above-mentioned olefins with 2-20 carbon atoms are preferably used, for example, ethylene, propylene, 1-butene, isobutene, 1-octene, 1-decene, and 1-dodecene.

Specific examples of the above-mentioned hydrocarbon (E) include, for example, ethylene-propylene copolymers, isobutylene-1-butene copolymers, polyisobutylene, and the like.

The content of the above-mentioned hydrocarbon (E) in the coating agent of the present invention is preferably 1 to 15 parts by mass, more preferably 100 parts by weight of the total of the above-mentioned olefin polymers (A) and (B) and the above-mentioned hydrocarbon (E). The best is 2~10 parts by mass. When the hydrocarbon (E) content is within the above range, it tends to be excellent in adhesiveness and stability over time, 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, the coating agent of the present invention may contain other olefin-based resins (F) in addition to the above-mentioned components (A) to (E), within the range that does not impair the effects of the present invention. The "other olefin-based resin (F)" is not particularly limited as long as it does not belong to any of the above-mentioned olefin polymers (A) and (B), and the above-mentioned hydrocarbon (E), for example: Homopolymers of polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene; α-olefins such as ethylene, propylene, 4-methyl-1-pentene, etc. Regular or block copolymers; ethylene-propylene copolymers, ethylene-octene copolymers, propylene-octene copolymers, ethylene-propylene-1-butene copolymers, ethylene-propylene-terpolymers, cyclic polymers Olefin, ethylene-vinyl acetate, copolymer of ethylene-unsaturated carboxylic acid, ethylene-vinyl alcohol, ionomer resin, etc.

Furthermore, if necessary, transition metal compounds such as titanium oxide (rutile type), zinc oxide, etc.; pigments such as carbon black; thixotropic agents, tackifiers, tackifiers, etc. Additives for coatings such as additives, defoamers, surface conditioners, anti-sedimentation agents, antioxidants, weather resistance agents, heat stabilizers, light stabilizers, pigment dispersants, and antistatic agents.

<Use of Coating Agent>

The coating agent of the present invention is suitable as a primer or coating, an adhesive (such as a hot melt adhesive, an adhesive for dry lamination), an anchor coating agent for extrusion into a film, an adhesive film, an adhesive film, an adhesive piece.

[laminated body]

The laminate of the present invention (hereinafter also referred to as "this laminate") is not particularly limited as long as it contains a substrate and a layer composed of the coating agent of the present invention (hereinafter also referred to as "this coating agent") , may contain layers other than these. In addition, in the following descriptions in this specification, the layer composed of this coating agent is referred to as a "coating film" in view of its shape, and is referred to as an "adhesive layer" in view of its function. .

In this laminate, the above-mentioned coating film (adhesive layer) may exist on one side of the substrate, may exist on both sides, may exist on the entire surface of these surfaces, or may exist on a part.

The thickness of the above-mentioned coating film (adhesive layer) can be appropriately selected as long as it matches the desired application, etc., and there is no special limitation, such as 0.2 μm or more, preferably 1 μm or more, and for example, 100 μm or less, preferably 20 μm the following.

In addition, in order to obtain a coating film (adhesive layer) that can be formed without whitening, cracking or peeling, etc., the elongation at break of the film formed by this coating agent is preferably 4.7% or more, and more Better than 5.0%.

The above-mentioned base material is not particularly limited, and there is no special limit on the premise that the base material for forming the above-mentioned coating film (adhesive layer) is not particularly limited. For example, polyolefins such as polyethylene and polypropylene, or ABS resin , polycarbonate (PC), PET and other polyester resins, or polyphenylene sulfide (PPS), nylon and other polyamide resins, or acrylic resins and other resins composed of resin substrates; transparent evaporation PET and other barriers Films; metal foils made of metals such as ED steel sheets, Mg alloys, SUS (stainless steel), aluminum, and aluminum alloys; inorganic substrates made of inorganic materials such as the above metals or glass; substrates composed of the above resins and inorganic materials ; and decorative films, etc. Among these, metal foil, a polyolefin substrate, and a decorative film are preferable, and aluminum foil and a polyolefin substrate are more preferable.

In addition, for the surface of the substrate adjacent to the coating film (adhesive layer), in order to improve the adhesive strength, conventionally known surface treatment such as corona treatment may also be performed.

The above-mentioned decorative film can be, for example, a known design film, specifically, for example: a film that has previously been printed, painted, and vapor-deposited to decorate the above-mentioned resin substrate or metal foil; the design film and the above-mentioned Resin substrates or laminates of metal foils, etc.

Here, the designable film system includes, for example, acrylic film, PET film, PC film, COC (cyclic olefin copolymer) film, vinyl chloride film, ABS film, etc., which impart designability to thermoplastic films. In addition, designability can also be imparted to the above-mentioned coating film (adhesive layer) by a conventionally known method.

The method of imparting design (method of implementing decoration) is, for example, the existing vacuum forming methods such as vacuum forming method and pressure vacuum forming method, insert molding method, in-mold molding method, and the use of Japanese Patent No. 3733564. Describes the TOM method performed by the "vacuum forming device", etc. According to these methods, even a laminate having a complicated three-dimensional structure can be provided with design.

The thickness of the base material is preferably at least 1 μm, more preferably at least 5 μm, and is preferably at most 500 μm, more preferably at most 100 μm.

This laminate is usually used by adhering the desired adherend on the adhesive layer. That is, this laminated body may be an adhesive body in which a base material, an adhesive layer, and an adherend are sequentially laminated. The above-mentioned adherend can be, for example, the same thing as the above-mentioned base material.

The method for producing this laminate is not particularly limited, and a conventionally known method suitable for the intended use can be used.

This laminated system can be used, for example, in automotive interior and exterior components; various front panels of AV equipment, etc.; surface decoration materials such as buttons and signs; frames of information appliances such as mobile phones and cameras; housings, display windows, and buttons. various parts; exterior materials for furniture; interior materials for construction such as bathroom surfaces, walls, ceilings, and floors; exterior materials for construction such as exterior walls, fences, roofs, doors, and barge boards Interior materials such as window frames, doors, handrails, thresholds, lintels, surface cosmetic materials for furniture, etc.; optical components such as various displays, lenses, mirrors, goggles, window glass, etc.; Components for interior and exterior decoration of tools; various containers such as bottles, cosmetic containers, and storage compartments; packaging materials; and various other items.

<Packaging material for battery case>

A packaging material for a battery case which is one embodiment of the laminate of the present invention is a laminate comprising a metal foil, an adhesive layer, and an adherend laminated in this order, and the adhesive layer is a layer composed of the present coating agent.

Since the said packaging material for battery cases has the said adhesive layer, it is excellent in the adhesive strength between an adherend and a metal foil, and is excellent in electrolytic solution resistance. Therefore, even if the battery case packaging material is used for a long period of time, it can still effectively prevent the adhesive strength between the adherend and the metal foil from decreasing, and a battery case packaging material with excellent long-term reliability can be obtained.

There is no special limitation on the premise that the packaging material for the battery case is laminated in the order of metal foil, adhesive layer and adherend, and conventionally known layers can also be used between these layers or on the surface of the laminated body. 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. 1 .

As shown in FIG. 1 , a battery 10 includes a battery case packaging material 1 and an electrolytic solution 11 packaged in the battery case packaging material 1 . Moreover, the battery 10 is equipped with the positive electrode 17, the negative electrode 18, and the separator 19 accommodated in the packaging material 1 for battery cases. In this battery, the packaging material 1 for the battery case is formed into a bag shape in such a way that the inner surface of the inner layer 3 of the packaging material 1 for the battery case is in contact with the electrolyte solution 11, and the packaging material 1 for the battery case is sequentially A laminate consisting of an inner layer 3, an inner adhesive layer 5, a substrate 2, an outer adhesive layer 6, and an outer layer 4. The inner adhesive layer 5 corresponds to the adhesive layer of the laminate.

The above-mentioned inner layer 3 corresponds to the adherend of this laminate, which is the same as the specific example of the above-mentioned adherend, but in order to impart chemical resistance (electrolyte solution property), heat sealability, etc. to the battery case packaging material, it is relatively It is best to use thermoplastic polyolefin films such as unstretched polypropylene film, propylene‧ethylene copolymer film, or extruded polyolefin layer.

The above-mentioned base material 2 is a metal foil corresponding to this laminate, and the above-mentioned metal foil is, for example, aluminum foil and SUS foil. Moreover, chemical conversion treatment may also be given to the surface of a metal foil from a viewpoint, such as corrosion resistance.

The above-mentioned outer adhesive layer 6 is a layer as long as it can bond the outer layer 4 and the base material 2 (metal foil). A layer obtained by conventionally known adhesives such as adhesives and non-solvent type adhesives.

The above-mentioned outer layer 4 is not particularly limited. In order to impart heat resistance in the heat-sealing step during battery manufacture, formability during processing, pinhole resistance, insulation during distribution, etc., it is preferable to use a polyester film, Stretched or unstretched films such as polyamide films and polypropylene films, or multi-layer films with two or more layers laminated.

The electrolytic solution 11 is not particularly limited, and examples thereof include electrolytic solutions containing ethylene carbonate, diethyl carbonate, dimethyl carbonate, and lithium salts such as lithium hexafluorophosphate.

The thickness of the battery case packaging material is, for example, not less than 40 µm and not more than 160 µm.

<Manufacturing method of packaging material for battery case>

The manufacturing method of the packaging material for the battery case of the present invention comprises the steps of: coating the coating agent on the metal foil, drying, and forming an adhesive layer by performing a burning treatment; and forming an adhesive layer on the above adhesive layer. The step of laminating the adherend on the surface opposite to the above-mentioned metal foil by extrusion lamination. In addition, it also includes: after applying this coating agent, without passing through the baking step, on the surface of the above-mentioned adhesive layer opposite to the above-mentioned metal foil, laminated by extrusion lamination. step of the object.

The method of coating this coating agent on the metal foil is not particularly limited, and conventional known methods can be used, such as: die coating method, flow coating method, spray coating method, bar coating method, gravure coating method, Gravure reverse coating, contact reverse coating, micro gravure coating, roll coating, knife coating, rod coating, knife roll coating, air knife coating, batch Roll coating method, reverse roll coating method, transfer roll coating method, contact roll coating method, curtain coating method, printing method and other coating methods.

The method of performing a burning treatment on the coating agent coated on the metal foil, for example, is in the range of 180~250°C, preferably 190~250°C, more preferably 200~240°C. The adhesiveness of the adhesive layer to the metal foil can be improved by applying heating at the temperature in the above-mentioned range to perform the baking treatment on the coating agent.

The method of laminating the adherend by extrusion lamination is not particularly limited, for example, extruding the adherend using a known extruder on the adhesive layer formed on the metal foil, and then using a rubber roller A method of lamination by nip-pressing with cooling rolls.

[Example]

Hereinafter, the present invention will be described in more detail according to the embodiments, but the present invention is not limited by these embodiments.

1. Physical properties of polymers

The physical properties of the olefin polymers synthesized in Production Examples 1-1 to 1-4 and the hydrocarbon (E-1) synthesized in Production Example 2-1 were measured in the following manner.

<Content ratio of constituent units derived from propylene, ethylene, and 1-butene>

The content ratios of constituent units derived from propylene, ethylene, and 1-butene in the polymers obtained in the following production examples were determined by 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 was raised from 30°C to 180°C at 10°C/min, kept at 180°C for 3 minutes, and then cooled to 0°C at 10°C/min, and again The temperature was raised to 150° C. at 10° C./min. During the process, the melting point was determined according to JIS K 7122 from the thermogram at the second temperature rise. The results are shown in Table 1.

<Determination of Grafting Amount (Modified Amount) of Polar Group-Containing Monomer>

It can be obtained by measuring with ¹ H-NMR. The specific method is as mentioned above. The results are shown in Table 1.

<Measurement of weight average molecular weight (Mw)>

The weight average molecular weight (Mw) was measured on the following conditions using a gel permeation chromatography analyzer (manufactured by Shimadzu Corporation; LC-10 series).

‧Detector: Shimadzu Corporation; C-R4A

‧Tube string: TSKG 6000H-TSKG 4000H-TSKG 3000H-TSKG 2000H (manufactured by Tosoh Corporation)

‧Mobile phase: tetrahydrofuran

‧Temperature: 40℃

‧Flow rate: 0.8ml/min

Mw was calculated using a calibration curve made with monodisperse standard polystyrene.

2. Manufacture of polymer <Production Example 1-1> Synthesis of Olefin Polymer (A-1)

In an autoclave with an internal volume of 1.5L equipped with a stirrer, put 100 parts by mass of propylene polymer with 100 mol% of propylene unit and 435 parts by mass of toluene, and heat up to 140°C under stirring to completely dissolve the propylene polymer . This solution was kept in a state of 140° C., and 16 parts by mass of maleic anhydride and 1.5 parts by mass of dicumyl peroxide were dropped simultaneously over 4 hours while stirring. After completion of the dropping, the mixture was further stirred at 140° C. for 1 hour, and post-reacted to obtain an olefin polymer (A-1). Next, the solution containing the olefin polymer (A-1) 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 grafted maleic anhydride 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)

Except that 100 parts by mass of propylene polymer with 100 mol% of propylene units is changed to 100 parts by mass of propylene‧ethylene copolymer with 99.25 mol% of propylene units and 0.75 mol% of ethylene units, the rest are the same as Production Example 1- 1 Obtain an olefin polymer (A-2) in the same manner. The amount of grafted maleic anhydride 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)

In addition to changing 100 parts by mass of propylene polymer with 100 mol% of propylene units to 100 parts by mass of propylene‧ethylene copolymer with 96.5 mol% of propylene units and 3.5 mol% of ethylene units, and 16 parts by mass of maleic anhydride Except that the parts were changed to 30 parts by mass, the olefin polymer (B-1) was obtained in the same manner as in Production Example 1-1. The amount of grafted maleic anhydride 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)

In a 2-liter autoclave fully replaced by nitrogen, fill 900ml of hexane and 80g of 1-butene, and then add 1 millimole of triisobutylaluminum. After raising the temperature to 70°C, supply propylene so that the total pressure becomes 7kg/cm ² G, add methylalumoxane 0.30mmol, rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride Zr The atomic conversion was 0.001 millimole, propylene was continuously supplied, and the total pressure was maintained at 7 kg/cm ² G, and polymerization was carried out for 30 minutes. After polymerization, degassing was carried out, and the polymer was recovered in a large amount of methanol, and then 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 aforementioned propylene/1-butene copolymer was added to 10 L of toluene, and the temperature was raised to 145° C. under a nitrogen atmosphere to dissolve the copolymer in toluene. This solution was maintained at 145°C, and 382 g of maleic anhydride and 175 g of di-tert-butyl peroxide were dropped simultaneously over 4 hours while stirring, and then further stirred at 145°C for 2 hours. After cooling, a large amount of acetone was thrown in, the modified copolymer was precipitated, filtered, washed with acetone, and dried to recover the olefin polymer (B-2).

The amount of grafted maleic anhydride 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)

In a continuous polymerization reactor fully replaced by nitrogen and with stirring blades, add 1 liter of dehydrated and refined hexane, and then continuously supply ethyl aluminum sesquichloride adjusted to 96mmol/L according to the amount of 500ml/h ( Al(C ₂ H ₅ ) _1.5 ‧Cl _1.5 ) hexane solution for 1 hour, then continuously supply 500ml/h of VO(OC ₂ H ₅ )Cl ₂ adjusted to 16mmol/L as catalyst Hexane solution, and continuously supply hexane according to the amount of 500ml/h. On the other hand, from the upper part of the polymerizer, the polymerization liquid was continuously drawn out so that the polymerization liquid in the polymerization liquid container was always maintained at 1 liter. Next, ethylene gas was supplied in an amount of 47 L/h, propylene gas was supplied in an amount of 47 L/h, and hydrogen gas was supplied in an amount of 20 L/h using a bubbling pipe. The copolymerization reaction was carried out in a state maintained at 35° C. by circulating a refrigerant through a jacket installed outside the polymerizer. After the obtained polymerization solution was deashed with hydrochloric acid, a large amount of methanol was thrown in to precipitate, and then dried under reduced pressure at 130° C. for 24 hours.

The ethylene content of the obtained ethylene/propylene copolymer (hydrocarbon (E-1)) was 53 mol %, the weight average molecular weight was 14,000, the dynamic viscosity at 40°C was 37,500 cSt, and the dynamic viscosity at 200°C was 132 cSt.

3. Preparation of coating material

The coating materials used in the examples were prepared in the following manner. Table 2 shows the composition (parts by mass) of each coating material.

<Manufacturing Example 3-1> Preparation of Coating Material X

In an autoclave equipped with a stirrer, put 25 g of the olefin polymer (A-1) and 75 g of toluene, and heat to 130° C. to completely dissolve the olefin polymer. Then, while stirring, the temperature was lowered to 95° C. at a cooling rate of 25° C./hour, 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 with a solid content of 25% by mass.

<Manufacturing Example 3-2> Preparation of Coating Material Y

Put 5.5 g of olefin polymer (A-2), 12.5 g of olefin polymer (B-1), and 82 g of toluene into an autoclave equipped with a stirrer, and heat to 130° C. to completely dissolve the olefin polymer. Then, while stirring, the temperature was lowered to 85° C. at a cooling rate of 25° C./hour, 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 with a solid content of 18% by mass.

<Manufacturing Example 3-3> Preparation of Coating Material Z

16 g of olefin polymer (B-2) and 4 g of hydrocarbon (E-1) were dissolved in 80 g of toluene at 100° C. to obtain coating material Z of a transparent solution with a solid content of 20%.

4. Manufacture of composite film (laminate) [Example 1]

On the treated surface of a 40 μm thick aluminum foil that has undergone chemical conversion treatment on one side, the coating material Y is coated by the gravure roll coating method, and then formed by passing through a hot air drying oven at 200°C to form an adhesive layer with a coating amount of 2g/ ^m2 agent layer. Next, the propylene-ethylene copolymer resin was laminated on the adhesive layer with a thickness of 40 μm by extrusion lamination to obtain a composite film.

[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 blend of coating material X: 85 parts by mass and coating material Z: 15 parts by mass.

[Example 3]

Except that coating material Y is changed into coating material X: 80 mass parts and coating material Z: the blend of 20 mass parts, all the other are all obtained composite film in the same way as embodiment 1.

[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 blend of coating material X: 70 parts by mass and coating material Z: 30 parts by mass.

[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 blend of coating material X: 60 parts by mass and coating material Z: 40 parts by mass.

[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 blend of coating material X: 90 parts by mass and coating material Z: 10 parts by mass.

[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 blend of coating material X: 50 parts by mass and coating material Z: 50 parts by mass.

[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 coating material Z.

5. Evaluation [Evaluation of Adhesive Layer (Coating Film)] <Measurement of elongation at break>

The coating materials and coating material blends used in Examples 1-5 and Comparative Examples 1-4 were transferred into respective Teflon (registered trademark) petri dishes, and dried at 200°C. After cooling to room temperature, the dried coating film was taken out from the Teflon (registered trademark) petri dish, and the elongation at break of the coating film was measured at a chuck speed of 10 mm/min using a universal tensile measuring device according to JIS C2151. The results are shown in Table 3.

[Evaluation of composite film]

The composite films obtained in Examples 1-5 and Comparative Examples 1-4 were evaluated according to the following methods. The results are shown in Table 4.

<Normal bonding strength>

The composite film was cut out into a size of 60 mm in length and 15 mm in width to prepare a test piece. The test piece was subjected to a 180° peel test at a chuck speed of 50 mm/min using a universal tensile measuring device to measure the initial bonding strength of the composite film. In addition, in accordance with the measured initial bonding strength, evaluation was performed based on the following criteria.

(evaluation criteria)

◎: 12N/15mm or more

○: More than 9N/15mm and less than 12N/15mm

△: More than 7N/15mm, less than 9N/15mm

×: Less than 7N/15mm

<Strength after electrolyte resistance test>

For the mixed solvent mixed with ethyl carbonate and diethyl carbonate at a volume ratio of 3:7, a simulated electrolyte in which phosphorus hexafluoride lithium salt is added in a concentration of 1 mol/L, further Add 1000 ppm of distilled water, dip the composite film test piece cut into a width of 15 mm, and store it in an oven at 85° C. for 1 week. After taking out the test piece, use a universal tensile measuring device to implement a 180° peel test at a chuck speed of 50 mm/min to measure the bonding strength of the composite film. In addition, in accordance with the measured adhesive strength, evaluation was performed based on the following criteria.

(evaluation criteria)

◎: 11N/15mm or more

○: More than 9N/15mm and less than 11N/15mm

△: More than 7N/15mm, less than 9N/15mm

×: Less than 7N/15mm

<Heat Resistance Adhesion Strength>

The composite film was cut into a size of 60 mm in length and 15 mm in width to prepare a test piece. A universal tensile measuring device was used for the test piece, and a 180° peel test was carried out at a chuck speed of 50 mm/min in an environment of 100° C. to measure the heat-resistant adhesive strength of the composite film. In addition, in accordance with the measured heat-resistant adhesive strength, evaluation was performed based on the following criteria.

(evaluation criteria)

◎: 11N/15mm or more

○: More than 9N/15mm and less than 11N/15mm

△: More than 7N/15mm, less than 9N/15mm

×: Less than 7N/15mm

<formability>

For each composite film, under the environment of 23°C, using an Izod tester, visually observe the appearance of the coated surface with a ridge of 5 mm from the adherend side, and evaluate according to the following criteria.

(evaluation criteria)

○: Whitening of the coating film was not observed at all

△: Slight decrease in transparency was observed in a part of the coating film

×: Whitening was observed in the coating film

Claims (18)

A coating agent comprising: an olefin polymer (A), an olefin polymer (B) and an organic solvent; wherein the olefin polymer (A) contains: a structural unit derived from propylene (a1 ) from 97 mol% to 100 mol%, and the constituent units (a2) derived from α-olefins with 2 to 20 carbon atoms (excluding propylene) from 0 mol% to 3 mol% ( Among them, the total of the structural unit (a1) and the structural unit (a2) is set to 100 mol%) of the olefin polymer; the above-mentioned olefin polymer (B) contains: 70 mol of the structural unit (b1) derived from propylene More than 97 mole % and less than 97 mole %, and more than 3 mole % and less than 30 mole % of structural units (b2) derived from α-olefins with 2 to 20 carbon atoms (except propylene) (among them, The total amount of the constituent unit (b1) and the constituent unit (b2) is 100 mole %) of the olefin polymer; the content ratio of the constituent unit derived from propylene is 89.0 mole relative to the total amount of the total olefin polymer % and less than 97.4 mol%; the melting point of the above-mentioned olefin polymer (A) is 150~170°C, and the melting point of the above-mentioned olefin polymer (B) is 70~145°C; the above-mentioned olefin polymer (A) is dispersed in Contained in the state in an organic solvent. The coating agent according to claim 1, wherein a part or all of the above-mentioned olefin polymer (A) or (B) is a modified olefin-based polymer modified by grafting with a monomer containing a polar group. The coating agent according to claim 2, wherein the above-mentioned modified olefin-based polymerization system contains constituent units derived from the above-mentioned polar group-containing monomer in an amount of 0.1-15% 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 anhydrides. The coating agent according to claim 1 or 2, further comprising a hardener (C). The coating agent according to claim 5, wherein the curing agent (C) contains at least one selected from the group consisting of aliphatic polyisocyanate and multimer of aliphatic polyisocyanate. Such as the coating agent of claim 5, wherein the above-mentioned curing agent (C) contains epoxy compounds and

At least one compound selected from the group consisting of oxazoline compounds. The coating agent according to claim 5, further comprising a catalyst (D) having a pKa of 11 or more. The coating agent according to claim 1 or 2, 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 claim 1 or 2, further comprising a liquid or semi-solid hydrocarbon (E) with a kinematic viscosity at 200°C of 10 to 100,000 mm ² /s. The coating agent according to claim 10, wherein the above-mentioned hydrocarbon (E) is a polymer of olefins with 2 to 20 carbon atoms (wherein, the above-mentioned olefin polymers (A) and (B) are excluded). The coating agent according to claim 1 or 2, wherein the total amount of the above-mentioned olefin polymers is the total amount of the above-mentioned olefin polymers (A) and the above-mentioned olefin polymers (B). The coating agent as claimed in claim 1 or 2 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 in accordance with JIS C2151 is 4.7% or more. A laminate comprising: a substrate, and a layer composed of the coating agent according to any one of claims 1 to 13. A packaging material for a battery case, which is a laminate containing sequentially laminated metal foil, an adhesive layer, and an adherend; the adhesive layer is made of any one of claims 1-13. The layer composed of cloth agent. A method for manufacturing a packaging material for a battery case, comprising the steps of forming an adhesive layer by performing a burning treatment after coating the coating agent according to any one of Claims 1 to 13 on a metal foil; And a step of laminating an adherend on the surface of the adhesive layer opposite to the metal foil by extrusion lamination.

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