Adhesive composition, laminate, packaging material, and packaging material for battery case

Abstract

To provide an adhesive composition having excellent adhesion at a low temperature, a laminate provided with an adhesive layer comprising a dried product of the adhesive composition, a packaging material provided with the laminate and a packaging material for a battery case provided with the packaging material.SOLUTION: There is provided an adhesive composition comprising a crystalline modified olefin polymer, a non-crystalline modified hydrocarbon-based polymer, a cross-linking agent and a catalyst. The crystalline modified olefin polymer is obtained by modifying a crystalline α-olefin polymer having 2 to 20 carbon atoms with a monomer. The heat of melting of the crystalline modified olefin polymer as measured according to JIS K7122 is 1 J / g or more and 50 J / g or less. The non-crystalline modified hydrocarbon-based polymer is obtained by modifying a non-crystalline hydrocarbon-based polymer with a monomer. The monomer has a functional group reactive with an epoxy group or an oxazoline group. The kinematic viscosity of the amorphous hydrocarbon-based polymer at 200°C is 1 cSt or more and 100000 cSt or less. The crosslinking agent contains an epoxy compound and / or an oxazoline compound.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an adhesive composition, a laminate, a packaging material, and a packaging material for battery cases; more specifically, to an adhesive composition, a laminate including an adhesive layer made of a dried product of the adhesive composition, a packaging material including the laminate, and a packaging material for battery cases including the packaging material. [Background technology]

[0002] In recent years, from the viewpoint of achieving thinner designs, lithium batteries have been used as batteries for personal computers, portable terminal devices, etc. The lithium batteries are sealed, for example, in packaging.

[0003] Such a packaging material can be obtained, for example, by bonding an aluminum foil layer and a polypropylene film with an adhesive.

[0004] As such an adhesive, for example, a composition containing a modified olefin polymer (crystalline with a specific heat of fusion peak) modified with a monomer having a functional group reactive to an epoxy group or an oxazoline group, a hydrocarbon synthetic oil, a crosslinking agent, and a catalyst has been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2017 / 126520 Brochure Summary of the Invention [Problem to be solved by the invention]

[0006] On the other hand, from the viewpoint of improving productivity, such adhesives are required to have adhesion at low temperatures.

[0007] The present invention provides an adhesive composition that has excellent adhesion at low temperatures, a laminate that includes an adhesive layer made of a dried product of the adhesive composition, a packaging material that includes the laminate, and a packaging material for battery cases that includes the packaging material. [Means for solving the problem]

[0008] The present invention [1] is an adhesive composition comprising a crystalline modified olefin polymer, a non-crystalline modified hydrocarbon polymer, a crosslinking agent, and a catalyst, wherein the crystalline modified olefin polymer is a crystalline α-olefin polymer having 2 to 20 carbon atoms modified with a monomer having a functional group reactive with an epoxy group or an oxazoline group, and the crystalline modified olefin polymer has a heat of fusion of 1 J / g or more and 50 J / g or less, as measured in accordance with JIS K7122, and the non-crystalline modified hydrocarbon polymer is a non-crystalline hydrocarbon polymer modified with a monomer having a functional group reactive with an epoxy group or an oxazoline group, and the kinematic viscosity of the non-crystalline hydrocarbon polymer at 200°C is 1 cSt or more and 100,000 cSt or less, and the crosslinking agent comprises an epoxy compound and / or an oxazoline compound.

[0009] The present invention [2] further includes the adhesive composition according to the above [1], which contains a non-crystalline hydrocarbon polymer having a kinematic viscosity at 200°C of 1 cSt or more and 100,000 cSt or less.

[0010] The present invention [3] includes the adhesive composition according to the above [2], in which the mass ratio of the amorphous hydrocarbon polymer to the amorphous modified hydrocarbon polymer is 0.05 or more and 19 or less.

[0011] The present invention [4] includes the adhesive composition according to the above [2] or [3], wherein the amorphous hydrocarbon polymer is a polymer of an olefin having 2 to 20 carbon atoms.

[0012] The present invention [5] includes the adhesive composition according to any one of the above [1] to [4], wherein the content of the structural units derived from the monomer in the amorphous modified hydrocarbon polymer is 0.1 mass % or more and 15 mass % or less.

[0013] The present invention [6] includes the adhesive composition according to any one of the above [1] to [5], wherein the functional group is a carboxyl group or an acid anhydride group.

[0014] The present invention [7] includes a laminate having, in order toward one side in the thickness direction, a first adhesive layer made of a dried product of the adhesive composition described in any one of [1] to [6] above and a substrate.

[0015] The present invention [8] includes a packaging material having an inner layer and the laminate described in [7] above, arranged in this order toward one side in the thickness direction.

[0016] The present invention [9] includes a packaging material for battery cases, which comprises the packaging material described in [8] above, a second adhesive layer, and an outer layer in this order toward one side in the thickness direction. [Effects of the Invention]

[0017] The adhesive composition of the present invention contains a crystalline modified olefin polymer and a non-crystalline modified hydrocarbon polymer, and since it contains the non-crystalline modified hydrocarbon polymer, it has excellent adhesion at low temperatures.

[0018] The laminate of the present invention has a first adhesive layer made of a dried product of the adhesive composition of the present invention, and therefore has excellent adhesion at low temperatures.

[0019] The packaging material of the present invention includes the laminate of the present invention, and therefore has excellent adhesion at low temperatures.

[0020] The battery case packaging material of the present invention includes the packaging material of the present invention, and therefore has excellent adhesion at low temperatures. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic diagram showing one embodiment of the laminate of the present invention. [Figure 2] 2A and 2B show one embodiment of the method for producing a laminate of the present invention. Fig. 2A shows the first step of preparing a substrate. Fig. 2B shows the second step of arranging (forming) a first adhesive layer on the other surface of the substrate in the thickness direction. [Figure 3] FIG. 3 is a schematic diagram showing one embodiment of the packaging material of the present invention. [Figure 4] FIG. 4 is a schematic diagram showing one embodiment of a battery case packaging material of the present invention and a battery using this battery case packaging material. DETAILED DESCRIPTION OF THE INVENTION

[0022] The adhesive composition includes a crystalline modified olefin polymer, a non-crystalline modified hydrocarbon polymer, a crosslinking agent, and a catalyst.

[0023] <Crystalline modified olefin polymer> The crystalline modified olefin polymer is obtained by modifying a crystalline α-olefin polymer having 2 to 20 carbon atoms with a monomer having a functional group capable of reacting with an epoxy group or an oxazoline group.

[0024] [Crystalline α-olefin polymers having 2 to 20 carbon atoms] A crystalline α-olefin polymer having 2 to 20 carbon atoms is an olefin polymer containing structural units derived from an α-olefin having 2 to 20 carbon atoms, which can form a crystalline polymer. That is, a crystalline α-olefin polymer having 2 to 20 carbon atoms is obtained by polymerizing an α-olefin having 2 to 20 carbon atoms. Here, crystalline is defined as a solid state at 23°C and having a melting point with a heat of fusion of 1 J / g or more.

[0025] Examples of α-olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0026] The structural units derived from an α-olefin having 2 to 20 carbon atoms preferably include structural units derived from propylene and structural units derived from 1-butene. In other words, the crystalline polymer of an α-olefin having 2 to 20 carbon atoms is preferably a propylene / 1-butene copolymer.

[0027] The type and content of the structural unit derived from an α-olefin having 2 to 20 carbon atoms are selected so that the olefin polymer is crystalline.

[0028] Specifically, when the structural units derived from an α-olefin having 2 to 20 carbon atoms include structural units derived from propylene and structural units derived from 1-butene, the content of the structural units derived from propylene relative to 100 mol% of the total amount of the structural units derived from propylene and 1-butene is, for example, 50 mol% or more, preferably 60 mol% or more, and for example, 95 mol% or less, preferably 80 mol% or less. Furthermore, the content of the structural units derived from 1-butene relative to 100 mol% of the total amount of the structural units derived from propylene and 1-butene is, for example, 5 mol% or more, preferably 20 mol% or more, and for example, 50 mol% or less, preferably 40 mol% or less.

[0029] When the content ratio of the propylene-derived structural unit and the content ratio of the 1-butene-derived structural unit are equal to or greater than the above lower limit and equal to or less than the above upper limit, the adhesiveness at low temperatures is excellent.

[0030] The above content ratio may be, for example, 13 This can be confirmed by known means such as C-NMR measurement (the same applies below).

[0031] Crystalline α-olefin polymers having 2 to 20 carbon atoms can be obtained by, for example, the methods described in Japanese Patent No. 3939464 and International Publication No. 2004 / 87775. Specifically, crystalline α-olefin polymers having 2 to 20 carbon atoms can be obtained by polymerizing an α-olefin having 2 to 20 carbon atoms in the presence of a metallocene catalyst.

[0032] The heat of fusion of the crystalline α-olefin polymer having 2 to 20 carbon atoms, measured in accordance with JIS K7122, is, for example, 1 J / g or more, preferably 10 J / g or more, more preferably 20 J / g or more, and for example, 50 J / g or less, preferably 40 J / g or less.

[0033] When the heat of fusion is equal to or greater than the above lower limit and equal to or less than the above upper limit, the adhesiveness at low temperatures is excellent.

[0034] The melting point of the crystalline α-olefin polymer having 2 to 20 carbon atoms is, for example, 40°C or higher, or preferably 60°C or higher, and, for example, 100°C or lower.

[0035] The melting point can be measured by a differential scanning calorimeter (the same applies hereinafter).

[0036] The crystalline α-olefin polymer having 2 to 20 carbon atoms has a weight average molecular weight measured by GPC of, for example, 100,000 or more, preferably 200,000 or more, and for example, 1,000,000 or less, preferably 500,000 or less.

[0037] The crystalline α-olefin polymers having 2 to 20 carbon atoms can be used alone or in combination of two or more kinds.

[0038] [Monomer] The monomer has a functional group that can react with an epoxy group or an oxazoline group.

[0039] Such functional groups include, for example, a hydroxyl group, an amino group, a carboxyl group, an acid anhydride group, an ester group, and a thiol group.

[0040] The monomer is a compound having the above-mentioned functional group, and examples thereof include hydroxyl group-containing ethylenically unsaturated compounds, amino group-containing ethylenically unsaturated compounds, unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, vinyl ester compounds, and thiol group-containing ethylenically unsaturated compounds.

[0041] The hydroxyl group-containing ethylenically unsaturated compound has a hydroxyl group as the functional group. Examples of the hydroxyl group-containing ethylenically unsaturated compound include hydroxyl group-containing (meth)acrylic acid esters. Examples of the hydroxyl group-containing (meth)acrylic acid esters include 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate.

[0042] The amino group-containing ethylenically unsaturated compound has an amino group as the functional group. Examples of the amino group-containing ethylenically unsaturated compound include aminomethyl (meth)acrylate and propylaminoethyl (meth)acrylate.

[0043] The unsaturated carboxylic acid has a carboxyl group as the functional group. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid.

[0044] The unsaturated carboxylic acid anhydride has an acid anhydride group as the functional group. Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride.

[0045] The vinyl ester compound has an ester group as the functional group, and examples of the vinyl ester compound include vinyl acetate, vinyl propionate, and vinyl n-butyrate.

[0046] The thiol group-containing ethylenically unsaturated compound has a thiol group as the functional group. Examples of the thiol group-containing ethylenically unsaturated compound include allyl mercaptan and 2-vinylbenzyl mercaptan.

[0047] The monomer preferably includes a carboxyl group-containing monomer and an acid anhydride group-containing monomer. That is, the functional group preferably includes a carboxyl group and an acid anhydride group. If the functional group is a carboxyl group or an acid anhydride group, the pot life and adhesion of the formulation can be improved.

[0048] As the monomer, more preferably, an unsaturated carboxylic acid anhydride is used, and even more preferably, maleic anhydride is used.

[0049] The monomers can be used alone or in combination of two or more kinds.

[0050] [Production of crystalline modified olefin polymer] The crystalline modified olefin polymer can be obtained by modifying a crystalline α-olefin polymer having 2 to 20 carbon atoms with a monomer.

[0051] To modify a crystalline α-olefin polymer having 2 to 20 carbon atoms with a monomer, for example, the crystalline α-olefin polymer having 2 to 20 carbon atoms is first dissolved in a known organic solvent (for example, toluene).

[0052] Next, the monomer and the radical polymerization initiator are added, and the mixture is heated and stirred.

[0053] The modification amount (introduction amount) of the monomer in the crystalline α-olefin polymer having 2 to 20 carbon atoms, i.e., the content ratio of the structural units derived from the monomer in the crystalline α-olefin polymer having 2 to 20 carbon atoms, is, for example, 0.1 mass% or more, preferably 0.5 mass% or more, and for example, 15 mass% or less, preferably 10 mass% or less, more preferably 5 mass% or less, even more preferably 4 mass% or less, and particularly preferably 2 mass% or less, relative to the crystalline α-olefin polymer having 2 to 20 carbon atoms.

[0054] When the modification amount is equal to or greater than the lower limit and equal to or less than the upper limit, the pot life and adhesion can be improved.

[0055] The above-mentioned modification amount is, for example, 1 This can be confirmed by known means such as H-NMR measurement (the same applies below).

[0056] Examples of the radical polymerization initiator include organic peroxides and organic peresters.

[0057] Examples of organic peroxides include dicumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and tert-butyl peroxybenzoate. Examples of organic peresters include tert-butyl peracetate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert-butyl persec-octoate, tert-butyl perpivalate, cumyl perpivalate, and tert-butyl perdiethyl acetate. Further, other azo compounds such as azobis-isobutylnitrile and dimethylazoisobutylnitrile may also be used as the radical polymerization initiator.

[0058] Of the radical polymerization initiators, preferred are organic peroxides, and more preferred is di-tert-butyl peroxide.

[0059] The mixing ratio of the radical polymerization initiator relative to 100 parts by mass of the crystalline α-olefin polymer having 2 to 20 carbon atoms is, for example, 0.001 parts by mass or more and, for example, 10 parts by mass or less.

[0060] The radical polymerization initiators can be used alone or in combination of two or more kinds.

[0061] The heating temperature is, for example, 50° C. or higher, preferably 80° C. or higher, and, for example, 250° C. or lower. The reaction time is, for example, 1 minute or longer and 10 hours or shorter.

[0062] In this way, the crystalline α-olefin polymer having 2 to 20 carbon atoms is modified with the monomer, and a crystalline modified olefin polymer (a crystalline modified olefin polymer varnish) is obtained.

[0063] The crystalline modified olefin polymer is crystalline. Therefore, it is distinguished from the amorphous modified hydrocarbon polymer described below. Specifically, the crystalline modified olefin polymer has a predetermined heat of fusion (described below) and a predetermined melting point (described below), whereas the amorphous modified hydrocarbon polymer does not have a predetermined heat of fusion or a predetermined melting point.

[0064] The heat of fusion of the crystalline modified olefin polymer, measured according to JIS K7122, is 1 J / g or more, preferably 10 J / g or more, more preferably 20 J / g or more, and 50 J / g or less, preferably 40 J / g or less.

[0065] When the heat of fusion is equal to or greater than the above lower limit and equal to or less than the above upper limit, the adhesiveness at low temperatures is excellent.

[0066] The melting point of the crystalline modified olefin polymer is, for example, 40°C or higher, preferably 60°C or higher, and, for example, 100°C or lower.

[0067] The weight average molecular weight of the crystalline modified olefin polymer measured by GPC is, for example, 10,000 or more, preferably 50,000 or more, and for example, 500,000 or less, preferably 150,000 or less.

[0068] <Amorphous modified hydrocarbon polymer> A non-crystalline modified hydrocarbon polymer is obtained by modifying a non-crystalline hydrocarbon polymer with a monomer having a functional group capable of reacting with an epoxy group or an oxazoline group. Amorphous is defined as a property of a compound in which neither a melting point nor a crystallization temperature having a heat of fusion of 1 J / g or more can be detected.

[0069] [Non-crystalline hydrocarbon polymer] The amorphous hydrocarbon polymer is a polymer containing structural units derived from hydrocarbons. As the hydrocarbon, an olefin having 2 to 20 carbon atoms is preferably used from the viewpoints of low-temperature adhesion and adhesion to olefin substrates. That is, the amorphous hydrocarbon polymer is preferably an olefin polymer containing structural units derived from an olefin having 2 to 20 carbon atoms. That is, the amorphous hydrocarbon polymer is preferably obtained by polymerizing an olefin having 2 to 20 carbon atoms.

[0070] Examples of olefins having 2 to 20 carbon atoms include ethylene, propylene, 1-butene, cis-2-butene, trans-2-butene, isobutylene (isobutene), 1-pentene, cis-2-pentene, trans-2-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene, 1-hexene, 2-hexene, 3-hexene, 2,3-dimethyl-2-butene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Preferred examples include ethylene, propylene, and isobutylene. More preferred examples include a combination of ethylene and propylene, or the sole use of isobutylene. In other words, more preferred examples of amorphous hydrocarbon polymers include ethylene / propylene copolymers and polyisobutylene.

[0071] The type and content of the hydrocarbon-derived structural unit are selected so that the hydrocarbon polymer is non-crystalline.

[0072] Specifically, when the hydrocarbon-derived structural units include ethylene-derived structural units and propylene-derived structural units, the content of the ethylene-derived structural units relative to 100 mol% of the total of the ethylene-derived structural units and the propylene-derived structural units is, for example, 40 mol% or more, preferably 50 mol% or more, and for example, 80 mol% or less, preferably 60 mol% or less. Furthermore, relative to 100 mol% of the total of the ethylene-derived structural units and the propylene-derived structural units, the content of the propylene-derived structural units is, for example, 20 mol% or more, preferably 40 mol% or more, and for example, 60 mol% or less, preferably 50 mol% or less.

[0073] When the content ratio of the ethylene-derived structural unit and the content ratio of the propylene-derived structural unit are equal to or greater than the above lower limit and equal to or less than the above upper limit, the adhesiveness at low temperatures is excellent.

[0074] The non-crystalline hydrocarbon polymer can be produced by the same method as the method for producing the crystalline α-olefin polymer having 2 to 20 carbon atoms exemplified above as the crystalline modified olefin polymer.

[0075] The kinematic viscosity of the amorphous hydrocarbon polymer at 200°C is 1 cSt or more and 100,000 cSt or less. Furthermore, amorphous hydrocarbon polymers can be distinguished into amorphous hydrocarbon synthetic oils and amorphous hydrocarbon semi-solid resins based on the kinematic viscosity. Specifically, amorphous hydrocarbon polymers having a kinematic viscosity of 1 cSt or more, preferably 10 cSt or more, more preferably 100 cSt or more, and for example, 10,000 cSt or less, preferably 1,000 cSt or less, more preferably 500 cSt or less, are amorphous hydrocarbon synthetic oils. Furthermore, amorphous hydrocarbon polymers having a kinematic viscosity of more than 10,000 cSt, preferably 30,000 cSt or more, and 100,000 cSt or less, preferably 60,000 cSt or less, are amorphous hydrocarbon semi-solid resins.

[0076] Furthermore, as will be described in detail later, the amorphous hydrocarbon polymer is modified with a monomer to become an amorphous modified hydrocarbon polymer. A non-crystalline hydrocarbon polymer can also be used in combination with such an amorphous modified hydrocarbon polymer. In such a case, examples of combinations of an amorphous hydrocarbon polymer and an amorphous modified hydrocarbon polymer include a combination of an amorphous hydrocarbon synthetic oil and an amorphous modified hydrocarbon synthetic oil (an amorphous modified hydrocarbon synthetic oil obtained by modifying an amorphous hydrocarbon synthetic oil with a monomer), a combination of an amorphous hydrocarbon synthetic oil and an amorphous modified hydrocarbon semi-solid resin (an amorphous modified hydrocarbon semi-solid resin obtained by modifying an amorphous hydrocarbon semi-solid resin with a monomer), a combination of an amorphous hydrocarbon semi-solid resin and an amorphous modified hydrocarbon synthetic oil, and a combination of an amorphous hydrocarbon semi-solid resin and an amorphous modified hydrocarbon synthetic oil. Examples of suitable combinations include a combination of a non-crystalline hydrocarbon-based synthetic oil with a non-crystalline modified hydrocarbon-based synthetic oil, a non-crystalline hydrocarbon-based semi-solid resin, and a combination of a non-crystalline hydrocarbon-based synthetic oil with a non-crystalline modified hydrocarbon-based semi-solid resin; preferably, a combination of a non-crystalline hydrocarbon-based synthetic oil with a non-crystalline modified hydrocarbon-based synthetic oil, a combination of a non-crystalline hydrocarbon-based synthetic oil with a non-crystalline modified hydrocarbon-based semi-solid resin, or a combination of a non-crystalline hydrocarbon-based semi-solid resin with a non-crystalline modified hydrocarbon-based synthetic oil; more preferably, a combination of a non-crystalline hydrocarbon-based synthetic oil with a non-crystalline modified hydrocarbon-based synthetic oil, or a combination of a non-crystalline hydrocarbon-based semi-solid resin with a non-crystalline modified hydrocarbon-based synthetic oil.

[0077] If the kinematic viscosity at 200°C is equal to or higher than the above lower limit and equal to or lower than the above upper limit, the adhesiveness at low temperatures can be improved.

[0078] The kinematic viscosity at 200°C can be measured based on JIS K 2283 (the same applies hereinafter).

[0079] The weight average molecular weight of the amorphous hydrocarbon polymer measured by GPC is, for example, 5,000 or more, preferably 10,000 or more, and for example, 150,000 or less, preferably 50,000 or less, more preferably 20,000 or less.

[0080] The amorphous hydrocarbon polymers can be used alone or in combination of two or more kinds.

[0081] [Monomer] The monomer has a functional group capable of reacting with an epoxy group or an oxazoline group. Examples of such a monomer include the monomers exemplified in the above-mentioned crystalline modified olefin polymer, and preferably include a carboxyl group-containing monomer and an acid anhydride group-containing monomer. That is, the functional group is preferably a carboxyl group or an acid anhydride group. If the functional group is a carboxyl group or an acid anhydride group, the pot life and low-temperature adhesion can be improved.

[0082] The monomers can be used alone or in combination of two or more kinds.

[0083] [Production of amorphous modified hydrocarbon polymers] The amorphous modified hydrocarbon polymer can be obtained by modifying an amorphous hydrocarbon polymer with a monomer.

[0084] To modify an amorphous hydrocarbon polymer with a monomer, for example, the amorphous hydrocarbon polymer is first dissolved in a known organic solvent (for example, toluene).

[0085] Next, the monomer and the radical polymerization initiator are added, and the mixture is heated and stirred.

[0086] The amount of modification (introduction amount) of a monomer in a non-crystalline hydrocarbon polymer, i.e., the content ratio of structural units derived from a monomer in a non-crystalline hydrocarbon polymer, is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and for example, 15% by mass or less, preferably 10% by mass or less, more preferably 6% by mass or less, even more preferably 4% by mass or less, relative to the non-crystalline hydrocarbon polymer.

[0087] When the amount of modification is equal to or greater than the lower limit and equal to or less than the upper limit, adhesion at low temperatures can be improved.

[0088] Examples of the radical polymerization initiator include the radical polymerization initiators exemplified for the above-mentioned crystalline modified olefin polymer, preferably organic peroxides, more preferably di-tert-butyl peroxide.

[0089] The mixing ratio of the radical polymerization initiator relative to 100 parts by mass of the amorphous hydrocarbon polymer is, for example, 0.001 parts by mass or more and, for example, 10 parts by mass or less.

[0090] The radical polymerization initiators can be used alone or in combination of two or more kinds.

[0091] The heating temperature and reaction time are the same as those exemplified for the crystalline modified olefin polymer described above.

[0092] In this way, the amorphous hydrocarbon polymer is modified with the monomer, and an amorphous modified hydrocarbon polymer (amorphous modified hydrocarbon polymer varnish) is obtained.

[0093] The kinematic viscosity of the amorphous modified hydrocarbon polymer at 200°C is the same as that of the amorphous hydrocarbon polymer described above.

[0094] The weight average molecular weight of the amorphous modified hydrocarbon polymer measured by GPC is, for example, 1,000 or more, preferably 5,000 or more, and for example, 30,000 or less, preferably 10,000 or less.

[0095] <Crosslinking agent> The crosslinking agent includes an epoxy compound and / or an oxazoline compound.

[0096] Examples of epoxy compounds include bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resins, bisphenol F-type epoxy resins), novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, cresol novolac-type epoxy resins), aliphatic-type epoxy resins, alicyclic-type epoxy resins, hydrogenated bisphenol-type epoxy resins, and amine-type epoxy resins, and preferably, novolac-type epoxy resins, and more preferably, phenol novolac-type epoxy resins.

[0097] Examples of the oxazoline compound include an oxazoline group-containing polymer, such as a homopolymer of an oxazoline group-containing monomer and a copolymer of an oxazoline group-containing monomer and another monomer copolymerizable with the oxazoline group-containing monomer.

[0098] Examples of oxazoline group-containing monomers include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and 2-isopropenyl-4,4-dimethyl-2-oxazoline.

[0099] Other monomers copolymerizable with the oxazoline group-containing monomer include, for example, (meth)acrylic acid alkyl esters, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid), unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile), unsaturated amides (e.g., (meth)acrylamide), vinyl esters (e.g., vinyl acetate, vinyl propionate), vinyl ethers (e.g., methyl vinyl ether, ethyl vinyl ether), α-olefins (e.g., ethylene, propylene), and unsaturated aromatic monomers (e.g., styrene, α-methylstyrene).

[0100] The oxazoline compound is preferably a copolymer of an oxazoline group-containing monomer and another monomer copolymerizable with the oxazoline group-containing monomer, and more preferably an oxazoline group-containing polystyrene.

[0101] The crosslinking agent preferably contains an epoxy compound or an oxazoline compound, and more preferably contains an epoxy compound but does not contain an oxazoline compound, from the viewpoint of improving adhesion at low temperatures.

[0102] The crosslinking agents can be used alone or in combination of two or more.

[0103] <Catalyst> The catalyst is added to promote the crosslinking reaction of the crosslinking agent. Examples of the catalyst include a strongly basic tertiary amine (e.g., 1,8-diazabicyclo[5.4.0]undecene-7(DBU) or 1,6-diazabicyclo[3.4.0]-5-nonene), and a phosphazene catalyst having a phosphazene base, preferably a strongly basic tertiary amine, more preferably DBU.

[0104] The catalysts can be used alone or in combination of two or more.

[0105] <Preparation of Adhesive Composition> To prepare the adhesive composition, a crystalline modified olefin polymer, a non-crystalline modified hydrocarbon polymer, a crosslinking agent, and a catalyst are mixed together.

[0106] The content of the crystalline modified olefin polymer is, from the viewpoint of improving adhesion at low temperatures, for example, 40 parts by mass or more, preferably 60 parts by mass or more, more preferably 70 parts by mass or more, and even more preferably 80 parts by mass or more, relative to 100 parts by mass of the total amount of the crystalline modified olefin polymer and the non-crystalline modified hydrocarbon polymer. Also, from the viewpoint of improving adhesion at low temperatures, the content is, from the viewpoint of improving adhesion at low temperatures, for example, 99 parts by mass or less, preferably 97 parts by mass or less, and more preferably 93 parts by mass or less.

[0107] The content of the non-crystalline modified hydrocarbon polymer is, from the viewpoint of improving adhesion at low temperatures, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 7 parts by mass or more, relative to 100 parts by mass of the total amount of the crystalline modified olefin polymer and the non-crystalline modified hydrocarbon polymer. Also, from the viewpoint of improving adhesion at low temperatures, the content is, from the viewpoint of improving adhesion at low temperatures, for example, 60 parts by mass or less, preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less.

[0108] The content of the crosslinking agent is, for example, 1 part by mass or more, preferably 10 parts by mass or more, and for example, 30 parts by mass or less, preferably 15 parts by mass or less, more preferably 0.5 parts by mass or less, per 100 parts by mass of the total amount of the crystalline modified olefin polymer and the non-crystalline modified hydrocarbon polymer.

[0109] The catalyst content is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 5 parts by mass or less, preferably 1.5 parts by mass or less, and more preferably 1.2 parts by mass or less, per 100 parts by mass of the total amount of the crystalline modified olefin polymer and the non-crystalline modified hydrocarbon polymer.

[0110] In the above preparation, the adhesive composition preferably further contains a non-crystalline hydrocarbon polymer. That is, the adhesive composition preferably contains a non-crystalline hydrocarbon polymer. The non-crystalline hydrocarbon polymer is not modified by the above monomer, that is, it is a non-crystalline unmodified hydrocarbon polymer.

[0111] Examples of such amorphous hydrocarbon polymers include polymers containing the same hydrocarbon-derived structural units as the amorphous hydrocarbon polymers exemplified above. Specifically, the type of amorphous hydrocarbon polymer is the same as or different from the hydrocarbon polymer before modification in the amorphous modified hydrocarbon polymer, and preferably different from the viewpoint of improving adhesion at low temperatures. When the type of amorphous hydrocarbon polymer is different from the hydrocarbon polymer before modification in the amorphous modified hydrocarbon polymer, examples of combinations of the amorphous modified hydrocarbon polymer and the amorphous hydrocarbon polymer include a combination of a maleic anhydride-modified ethylene / propylene copolymer and polyisobutylene, a combination of a maleic anhydride-modified polyisobutylene and an ethylene / propylene copolymer, and more preferably a combination of a maleic anhydride-modified ethylene / propylene copolymer and polyisobutylene.

[0112] The kinematic viscosity of the amorphous hydrocarbon polymer at 200°C is, for example, 1 cSt or more and, for example, 100,000 cSt or less. Specifically, it is the same as the kinematic viscosity at 200°C of the amorphous hydrocarbon polymers exemplified above.

[0113] The weight average molecular weight of the non-crystalline hydrocarbon polymer measured by GPC is the same as the weight average molecular weight of the non-crystalline hydrocarbon polymer exemplified above measured by GPC.

[0114] When the adhesive composition contains a non-crystalline hydrocarbon polymer, the content of the crystalline modified olefin polymer is, from the viewpoint of improving adhesion at low temperatures, for example, 60 parts by mass or more, preferably 70 parts by mass or more, and more preferably 75 parts by mass or less, relative to 100 parts by mass of the total amount of the crystalline modified olefin polymer, the non-crystalline modified hydrocarbon polymer, and the non-crystalline hydrocarbon polymer; and, from the viewpoint of improving adhesion at low temperatures, for example, 95 parts by mass or less.

[0115] The content of the non-crystalline modified hydrocarbon polymer is, from the viewpoint of improving adhesion at low temperatures, for example, 1 part by mass or more, preferably 3 parts by mass or more, more preferably 6 parts by mass or more, relative to 100 parts by mass of the total amount of the crystalline modified olefin polymer, the non-crystalline modified hydrocarbon polymer, and the non-crystalline hydrocarbon polymer. Also, from the viewpoint of improving adhesion at low temperatures, the content is, from the viewpoint of improving adhesion at low temperatures, for example, 20 parts by mass or less, preferably 15 parts by mass or less.

[0116] The content of the non-crystalline hydrocarbon polymer is, from the viewpoint of improving adhesion at low temperatures, for example, 5 parts by mass or more, preferably 10 parts by mass or more, relative to 100 parts by mass of the total amount of the crystalline modified olefin polymer, the non-crystalline modified hydrocarbon polymer, and the non-crystalline hydrocarbon polymer. Also, from the viewpoint of improving adhesion at low temperatures, the content is, from the viewpoint of improving adhesion at low temperatures, for example, 25 parts by mass or less, preferably 20 parts by mass or less, more preferably 17 parts by mass or less, and even more preferably 14 parts by mass or less.

[0117] Furthermore, the mass ratio of the non-crystalline hydrocarbon polymer to the non-crystalline modified hydrocarbon polymer (non-crystalline hydrocarbon polymer / non-crystalline modified hydrocarbon polymer) is, from the viewpoint of improving adhesion at low temperatures, for example, 0.05 or more, preferably 0.5 or more, more preferably 1 or more, more preferably 1.3 or more, and, from the viewpoint of improving adhesion at low temperatures, for example, 19 or less, preferably 10 or less, more preferably 5 or less, even more preferably 3 or less, and particularly preferably 2 or less.

[0118] The content of the crosslinking agent is, for example, 1 part by mass or more, preferably 5 parts by mass or more, and for example, 20 parts by mass or less, preferably 15 parts by mass or less, per 100 parts by mass of the total amount of the crystalline modified olefin polymer, the non-crystalline modified hydrocarbon-based polymer, and the non-crystalline hydrocarbon-based polymer.

[0119] The catalyst content is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, and for example, 5 parts by mass or less, preferably 1 part by mass or less, per 100 parts by mass of the total amount of the crystalline modified olefin polymer, the non-crystalline modified hydrocarbon polymer, and the non-crystalline hydrocarbon polymer.

[0120] In the above preparation, a crystalline modified olefin polymer (that is, a crystalline α-olefin polymer having 2 to 20 carbon atoms) before modification can also be blended in an appropriate ratio with the adhesive composition.

[0121] In the preparation, additives may be blended into the adhesive composition in an appropriate ratio, such as leveling agents, antifoaming agents, antioxidants, heat stabilizers, ultraviolet absorbers, plasticizers, surfactants, pigments, thixotropic agents, thickeners, tackifiers, surface conditioners, antisettling agents, weathering agents, pigment dispersants, antistatic agents, fillers, antifungal agents, and silane coupling agents.

[0122] This prepares an adhesive composition.

[0123] The acid value of the adhesive composition is, for example, 0.5 KOHmg / g or more, preferably 1.0 KOHmg / g or more, more preferably 1.3 KOHmg / g or more, and for example, 5 KOHmg / g or less, preferably 2.2 KOHmg / g or less, more preferably 1.8 KOHmg / g or less.

[0124] The method for measuring the acid value will be described in detail in the Examples below.

[0125] The adhesive composition may also be diluted with a known organic solvent during and / or after the preparation.

[0126] When the adhesive composition is diluted, the solid content concentration is, for example, 10% by mass or more and, for example, 70% by mass or less.

[0127] <Action and effect> The adhesive composition contains a crystalline modified olefin polymer and a non-crystalline modified hydrocarbon polymer. The non-crystalline modified hydrocarbon polymer improves adhesion at low temperatures, from the viewpoint of improving tackiness and reactivity with a curing agent.

[0128] On the other hand, for example, the composition of Patent Document 1 does not contain a non-crystalline modified hydrocarbon polymer, and therefore, from the viewpoint of improving tackiness and reactivity with a curing agent, it is not possible to improve adhesion at low temperatures.

[0129] The adhesive composition has excellent adhesion at low temperatures and can therefore be suitably used, for example, as an adhesive (dry lamination adhesive) for various components (e.g., electronic components, optical components, and battery components), and in particular, as an adhesive for packaging materials for battery cases.

[0130] In the following description, a laminate having an adhesive layer made of a dried product of the adhesive composition, a packaging material having the laminate, and a packaging material for a battery case having the packaging material will be described in detail.

[0131] <Laminate> An embodiment of the laminate of the present invention will be described with reference to FIG.

[0132] In Figure 1, the up-down direction of the paper surface is the up-down direction (thickness direction), and the upper side of the paper surface is the upper side (one side in the thickness direction), and the lower side of the paper surface is the lower side (the other side in the thickness direction). Also, the left-right direction and the depth direction of the paper surface are surface directions perpendicular to the up-down direction. Specifically, they conform to the directional arrows in each figure.

[0133] The laminate 10 has a film shape (including a sheet shape) with a predetermined thickness. The laminate 10 extends in a plane direction perpendicular to the thickness direction. The laminate 10 has a flat upper surface and a flat lower surface.

[0134] The laminate 10 includes a first adhesive layer 1 and a base material 2 in this order toward one side in the thickness direction. Specifically, the laminate 10 includes the first adhesive layer 1 and the base material 2 that is placed directly on the upper surface of the first adhesive layer 1 (one side in the thickness direction).

[0135] There are no particular limitations on the thickness of the laminate 10. The thickness of the laminate 10 is, for example, 10 μm or more and, for example, 150 μm or less.

[0136] [First adhesive layer] The first adhesive layer 1 is an adhesive layer for bonding any adherend to a substrate 2. The first adhesive layer 1 is made of a dried adhesive composition.

[0137] Next, to arrange (form) the first adhesive layer 1, an adhesive composition (varnish of the adhesive composition) is applied to the other surface in the thickness direction of the substrate 2, and heated and dried as necessary, as described in detail below. In this way, the first adhesive layer 1 is arranged (formed).

[0138] The thickness of the first adhesive layer 1 is, for example, 1 μm or more and, for example, 50 μm or less.

[0139] [Base material 2] The substrate 2 has a film shape (including a sheet shape) with a predetermined thickness.

[0140] The material of the substrate 2 is not particularly limited. Examples of materials for the substrate 2 include polymeric materials and metal materials. Examples of polymeric materials include olefin resins (e.g., polyethylene and polypropylene), acrylic resins, polyester resins, polycarbonate resins, acrylonitrile-styrene-butadiene copolymer resins (ABS resins), polyamide resins (e.g., nylon), and polyphenylene sulfide resins. Examples of metal materials include aluminum, gold, silver, copper, nickel, zinc, titanium, cobalt, indium, and chromium.

[0141] There is no particular limitation on the thickness of the substrate 2. The thickness of the substrate 2 is, for example, 10 μm or more and, for example, 100 μm or less.

[0142] [Laminate manufacturing] An embodiment of a method for manufacturing a laminate will be described with reference to FIGS. 2A and 2B.

[0143] The method for manufacturing the laminate 10 includes a first step of preparing a substrate 2, and a second step of applying an adhesive composition (varnish of the adhesive composition) to the other thickness-wise surface of the substrate 2 and arranging (forming) a first adhesive layer 1 on the other thickness-wise surface of the substrate 2.

[0144] In the first step, a substrate 2 is prepared as shown in FIG. 2A.

[0145] In the second step, as shown in FIG. 2B, the first adhesive layer 1 is disposed (formed) on the other surface of the substrate 2 in the thickness direction.

[0146] To dispose (form) the first adhesive layer 1 on the other surface of the substrate 2 in the thickness direction, an adhesive composition (varnish of the adhesive composition) is applied to the other surface of the substrate 2 in the thickness direction.

[0147] In order to apply the adhesive composition (varnish of the adhesive composition) to the other surface in the thickness direction of the substrate 2, first, the other surface in the thickness direction of the substrate 2 is subjected to a surface treatment, if necessary.

[0148] Examples of the surface treatment include corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment, and preferably corona treatment.

[0149] Next, the adhesive composition (varnish of the adhesive composition) is applied to the other surface in the thickness direction of the substrate 2 by a known method, and is dried by heating if necessary.

[0150] The heating temperature is, for example, 50° C. or more, preferably 80° C. or more, and for example, 120° C. or less. The heating time is, for example, 10 seconds or more, and for example, 120 seconds or less.

[0151] As a result, the first adhesive layer 1, which is a dried product of the adhesive composition, is disposed (formed) on the other surface in the thickness direction of the substrate 2. In this way, the laminate 10 is produced.

[0152] Such a laminate 10 includes a first adhesive layer 1 made of a dried adhesive composition. Therefore, when this laminate 10 is bonded to any adherend via the first adhesive layer 1, it exhibits excellent adhesion at low temperatures.

[0153] <Packaging material> An embodiment of the packaging material of the present invention will be described with reference to FIG.

[0154] The packaging material 20 has a film shape (including a sheet shape) with a predetermined thickness. The packaging material 20 extends in a plane direction perpendicular to the thickness direction. The packaging material 20 has a flat upper surface and a flat lower surface.

[0155] The packaging material 20 includes an inner layer 3 and a laminate 10 (a laminate 10 including a first adhesive layer 1 and a base material 2 in that order toward one side in the thickness direction) in that order toward one side in the thickness direction. Specifically, the packaging material 20 includes the inner layer 3 and the laminate 10 that is placed directly on the upper surface of the inner layer 3 (one side in the thickness direction).

[0156] There are no particular limitations on the thickness of the packaging material 20. The thickness of the packaging material 20 is, for example, 15 μm or more and, for example, 300 μm or less.

[0157] Inner Layer The inner layer 3 is a layer that becomes the inside when the packaging material 20 is made into a bag shape.

[0158] The material of the inner layer 3 is appropriately selected depending on whether the packaging material 20 has heat sealing properties and the type of contents to be contained in the bag when the packaging material 20 is formed into a bag. As will be described in detail later, when the contents to be contained are an electrolyte solution, a polyolefin film is selected.

[0159] There are no particular limitations on the thickness of the inner layer 3. The thickness of the inner layer 3 is, for example, 30 μm or more and, for example, 600 μm or less.

[0160] [Packaging manufacturing] To manufacture the packaging material 20, the inner layer 3 is placed on the other surface in the thickness direction of the laminate 10 (the other surface in the thickness direction of the first adhesive layer 1), and the first adhesive layer 1 is cured. This causes the first adhesive layer 1 to harden, bonding the inner layer 3 and the laminate 10 together. In this way, the packaging material 20 is manufactured.

[0161] The curing temperature is low because the packaging material 20 includes the laminate 10. Specifically, the temperature is 20° C. or higher, preferably 40° C. or higher, and, for example, 80° C. or lower. The curing time is, for example, 1 day or longer, and, for example, 7 days or shorter, preferably 5 days or shorter.

[0162] The packaging material 20 includes the laminate 10. Therefore, the packaging material 20 has excellent adhesion at low temperatures.

[0163] <Battery case packaging and batteries> Referring to FIG. 4, one embodiment of the battery case packaging material of the present invention and a battery using this battery case packaging material will be described.

[0164] The battery 30 includes a battery case packaging material 31 and an electrolyte 32 packaged in the battery case packaging material 31. The battery 30 also includes a positive electrode 33, a negative electrode 34, and a separator 35 housed in the battery case packaging material 31.

[0165] [Battery case packaging material] The battery case packaging material 31 is configured in a bag shape so that the inner layer 3 of the battery case packaging material 31 comes into contact with the electrolyte solution 32. Specifically, the battery case packaging material 31 packages the electrolyte solution 32 so that the inner layer 3 comes into contact with the electrolyte solution 32.

[0166] 4A, the battery case packaging material 31 includes a packaging material 20 (the packaging material 20 including an inner layer 3, a first adhesive layer 1, and a base material 2, in that order toward one side in the thickness direction), a second adhesive layer 4, and an outer layer 5, in that order toward one side in the thickness direction. Specifically, the battery case packaging material 31 includes the packaging material 20, the second adhesive layer 4 disposed directly on the upper surface (one side in the thickness direction) of the packaging material 20, and the outer layer 5 disposed directly on the upper surface (one side in the thickness direction) of the second adhesive layer 4.

[0167] As described above, the packaging material 20 includes the inner layer 3, the first adhesive layer 1, and the base material 2, arranged in this order toward one side in the thickness direction. In the battery case packaging material 31, a polyolefin film is selected for the inner layer 3 from the viewpoint of chemical resistance (electrolyte resistance) to the electrolyte solution 32. Examples of polyolefin films include polyethylene-based films and polypropylene-based films. Examples of polyethylene-based films include low-density polyethylene films (LDPE) and linear low-density polyethylene films (LLDPE). Examples of polypropylene-based films include oriented polypropylene films (CPP films), uniaxially oriented polypropylene films, and biaxially oriented polypropylene films (OPP films). Preferably, the polyolefin film is a polypropylene-based film, more preferably an oriented polypropylene film (CPP film).

[0168] In the battery case packaging material 31, the material of the substrate 2 is preferably a metal material, more preferably aluminum.

[0169] The second adhesive layer 4 is formed from a known adhesive. Alternatively, the above adhesive composition may be used instead of the known adhesive.

[0170] There are no particular limitations on the thickness of the second adhesive layer 4. The thickness of the inner layer 3 is, for example, 1 μm or more and, for example, 50 μm or less.

[0171] The outer layer 5 is a layer that forms the outside of the battery case packaging material 31 .

[0172] Examples of materials for the outer layer 5 include the polymer materials exemplified for the substrate 2 described above, preferably polyamide resin, and more preferably nylon.

[0173] There are no particular limitations on the thickness of the outer layer 5. The thickness of the outer layer 5 is, for example, 10 μm or more and, for example, 100 μm or less.

[0174] The packaging material 31 for the battery case is manufactured by disposing the outer layer 5 on one thickness-wise surface of the packaging material 20 (one thickness-wise surface of the substrate 2) via a second adhesive layer 4 formed by applying a known adhesive (or adhesive composition).

[0175] The battery case packaging material 31 includes the packaging material 20. Therefore, it has excellent adhesion at low temperatures.

[0176] In addition, in FIG. 4, both ends (opposing inner layers 3) of the battery case packaging material 31 are sealed by heat sealing to form a bag.

[0177] [Electrolyte] The electrolyte solution 32 is not particularly limited, and may contain, for example, ethylene carbonate, diethyl carbonate, dimethyl carbonate, and a lithium salt such as lithium hexafluorophosphate.

[0178] The positive electrode 33 and the negative electrode are disposed facing each other with a gap therebetween so as to be in contact with the electrolyte solution 32. The separator is disposed so as to be sandwiched between the positive electrode 33 and the negative electrode .

[0179] The battery 30 described above is used as, for example, a lithium ion secondary battery. In such a case, the battery case packaging material 31 is used as a lithium ion secondary battery case packaging material. [Example]

[0180] Next, the present invention will be described based on examples and comparative examples, but the present invention is not limited to the following examples. Note that "parts" and "%" are by mass unless otherwise specified. Furthermore, specific numerical values ​​such as blending ratios (content ratios), physical property values, and parameters used in the following description can be substituted with the corresponding upper limit values ​​(numeric values ​​defined as "equal to or less than") or lower limit values ​​(numeric values ​​defined as "equal to or more than" or "exceeding") of the blending ratios (content ratios), physical property values, parameters, etc. described in the above "Modes for Carrying Out the Invention."

[0181] <Ingredient details> The trade names and abbreviations of the components used in each Production Example, each Example, and each Comparative Example are described in detail below. Oppanol B15SFN: Amorphous hydrocarbon polymer, polyisobutylene, weight average molecular weight: 106,000, kinematic viscosity at 200°C measured according to JIS K 2283: 52,000 cSt, manufactured by BASF jER152: Phenol novolac resin, manufactured by Mitsubishi Chemical Corporation RPS-1005: Oxazoline group-containing polystyrene, manufactured by Nippon Shokubai Co., Ltd. and Epocross Co., Ltd. DBU: 1,8-diazabicyclo[5.4.0]undecene-7, manufactured by San-Apro Co., Ltd.

[0182] <Production of crystalline modified olefin polymer> Manufacturing Example 1 [Production of crystalline α-olefin polymers having 2 to 20 carbon atoms] A 2-liter autoclave, the atmosphere of which had been thoroughly purged with nitrogen, was charged with 900 ml of hexane and 90 g of 1-butene. Then, 1 mmol of triisobutylaluminum was added, and the temperature was raised to 70°C. Propylene was then supplied to the autoclave to maintain a total pressure of 7 kg / cm. 2 The temperature was adjusted to G, 0.30 mmol of methylaluminoxane and 0.001 mmol of rac-dimethylsilylene-bis{1-(2-methyl-4-phenylindenyl)}zirconium dichloride (calculated as Zr atom) were added, and propylene was continuously supplied to maintain the total pressure at 7 kg / cm. 2 The mixture was polymerized for 30 minutes while maintaining the temperature at 50°C. This produced a propylene / 1-butene copolymer (a crystalline α-olefin polymer having 2 to 20 carbon atoms). After polymerization, the mixture was degassed and the propylene / 1-butene copolymer was recovered in a large amount of methanol and dried under reduced pressure at 110°C for 12 hours.

[0183] The melting point of the propylene / 1-butene copolymer was 78.3°C. The heat of fusion of the propylene / 1-butene copolymer, measured in accordance with JIS K7122, was 29.2 J / g. The weight average molecular weight of the propylene / 1-butene copolymer, measured by GPC, was 330,000. The propylene content of the propylene / 1-butene copolymer was 67.2 mol%.

[0184] [Production of crystalline modified olefin polymer] 3 kg of propylene / 1-butene copolymer was added to 10 L of toluene and heated to 145°C under a nitrogen atmosphere to dissolve the propylene / 1-butene copolymer in toluene. Furthermore, 382 g of maleic anhydride as a monomer and 175 g of di-tert-butyl peroxide as a radical polymerization initiator were added to the system under stirring over 4 hours, and the mixture was then stirred at 145°C for 2 hours. This produced a maleic anhydride-modified propylene / 1-butene copolymer. The mixture was then cooled, and a large amount of acetone was added to precipitate the maleic anhydride-modified propylene / 1-butene copolymer. The copolymer was then filtered, washed with acetone, and vacuum dried.

[0185] The melting point of the maleic anhydride-modified propylene / 1-butene copolymer was 75.8°C. The heat of fusion of the maleic anhydride-modified propylene / 1-butene copolymer, measured in accordance with JIS K7122, was 28.6 J / g. The weight-average molecular weight of the maleic anhydride-modified propylene / 1-butene copolymer, measured by GPC, was 110,000. In the maleic anhydride-modified propylene / 1-butene copolymer, the modification amount (introduction amount) of the monomer in the propylene / 1-butene copolymer was 1 mass%.

[0186] <Production of amorphous hydrocarbon polymer> Manufacturing Example 2 In a continuous polymerization reactor equipped with a stirrer and thoroughly purged with nitrogen, 1 liter of dehydrated and purified hexane was added, and ethylaluminum sesquichloride (Al(C2H5)1.5 Cl) adjusted to 96 mmol / L was added. 1.5 A hexane solution of VO(OC2H5)C (16 mmol / L) was continuously fed at a rate of 500 ml / h for 1 hour. l2 The hexane solution was continuously fed at 500 ml / hour, and hexane at 500 ml / hour. Meanwhile, the polymerization solution was continuously withdrawn from the top of the polymerization vessel so that the polymerization solution in the vessel was always 1 liter. Next, ethylene gas was fed at 47 L / hour, propylene gas at 47 L / hour, and hydrogen gas at 20 L / hour using a bubbling tube. The copolymerization reaction was carried out at 35°C by circulating a coolant through a jacket attached to the outside of the polymerization vessel. The obtained polymerization solution was deashed with hydrochloric acid, poured into a large amount of methanol for precipitation, and then dried under reduced pressure at 130°C for 24 hours. An ethylene / propylene copolymer was thus produced.

[0187] The ethylene / propylene copolymer had an ethylene content of 55.9 mol%. The ethylene / propylene copolymer had a weight average molecular weight of 14,000. The ethylene / propylene copolymer had a kinematic viscosity at 200°C of 132 cSt, measured in accordance with JIS K 2283.

[0188] <Production of amorphous modified hydrocarbon polymer> Manufacturing Example 3 3 kg of the ethylene / propylene copolymer of Production Example 2 was added to 10 L of toluene and heated to 145°C under a nitrogen atmosphere to dissolve the ethylene / propylene copolymer in toluene. Furthermore, 550 g of maleic anhydride as a monomer and 180 g of di-tert-butyl peroxide as a radical polymerization initiator were added to the system over 4 hours while stirring. Stirring was then carried out at 145°C for 2 hours. This produced a maleic anhydride-modified ethylene / propylene copolymer. The mixture was then cooled, and a large amount of acetone was added to precipitate the maleic anhydride-modified ethylene / propylene copolymer. The copolymer was then filtered, washed with acetone, and vacuum dried.

[0189] The maleic anhydride-modified ethylene / propylene copolymer had a weight average molecular weight of 7100 as measured by GPC. The maleic anhydride-modified ethylene / propylene copolymer had a kinematic viscosity of 27 cSt at 200°C as measured in accordance with JIS K 2283. In the maleic anhydride-modified ethylene / propylene copolymer, the modification amount (introduction amount) of the monomer in the ethylene / propylene copolymer was 5.0 mass%.

[0190] Production Example 4 A maleic anhydride-modified ethylene / propylene copolymer was produced according to the same procedure as in Production Example 3, except that the amount of maleic anhydride was changed to 400 g.

[0191] The maleic anhydride-modified ethylene / propylene copolymer had a weight average molecular weight of 7100 as measured by GPC. The maleic anhydride-modified ethylene / propylene copolymer had a kinematic viscosity of 370 cSt at 200°C as measured in accordance with JIS K 2283. In the maleic anhydride-modified ethylene / propylene copolymer, the modification amount (introduction amount) of the monomer in the ethylene / propylene copolymer was 3.0 mass%.

[0192] Manufacturing Example 5 A non-crystalline modified hydrocarbon polymer (maleic anhydride-modified polyisobutylene) was produced according to the same procedure as in Production Example 3. However, the ethylene / propylene copolymer in Production Example 2 was changed to Oppanol B15SFN manufactured by BASF.

[0193] The maleic anhydride-modified polyisobutylene had a weight average molecular weight of 85,000 as measured by GPC. The maleic anhydride-modified polyisobutylene had a kinematic viscosity of 46,000 cSt at 200°C as measured in accordance with JIS K 2283. In the maleic anhydride-modified polyisobutylene, the modification amount (introduction amount) of the monomer in the polyisobutylene was 4.3 mass%.

[0194] <Production of Adhesive Composition> Example 1 80 parts by mass of the crystalline modified olefin polymer of Production Example 1, 2 parts by mass of the amorphous modified hydrocarbon polymer of Production Example 3, and 18 parts by mass of the amorphous hydrocarbon polymer of Production Example 2 were heated and dissolved in 400 g of a mixed solvent of methylcyclohexane / ethyl acetate = 80 / 20. The mixture was then cooled and mixed with a crosslinker (50 g of a solution obtained by dissolving 10 g of jER152 in 40 g of ethyl acetate) and a catalyst (8.0 g of a solution obtained by dissolving 0.8 g of DBU in 7.2 g of ethyl acetate). This produced an adhesive composition.

[0195] Examples 2 to 9, Comparative Examples 1 and 2 An adhesive composition was produced according to the same procedure as in Example 1, except that the formulation was changed according to Table 1.

[0196] <Evaluation> [Acid value] A solution was prepared by adding 35 ml of toluene and 15 ml of n-butanol to an Erlenmeyer flask, followed by 0.8 g of a diluted solution prepared by diluting 0.1 g of special-grade bromothymol blue with 100 ml of 19% ethanol. Next, N / KOH-ethanol solution was added to this solution until the solution turned green, and then 5 g of each adhesive composition from each Example and Comparative Example was added and completely dissolved. The solution was then titrated with N / KOH-ethanol solution until the solution turned blue, the titer was measured, and the acid value was calculated based on the following formula (1). The results are shown in Table 1. Acid number (KOH mg / g) = (sample titration amount × factor × 5.61) / sample weight (1)

[0197] [Adhesion at low temperatures] The adhesive composition of each Example and Comparative Example was applied to the other thickness-wise surface of the aluminum foil and dried at 100°C for 1 minute (dry film thickness: approximately 3 μm). As a result, a first adhesive layer was disposed (formed) on the other thickness-wise surface of the aluminum foil. Next, a 30 μm-thick CPP film (one-sided corona-treated) was disposed on the other thickness-wise surface of the first adhesive layer (the other thickness-wise surface of the first adhesive layer was bonded to the corona-treated surface of the CPP film). Thereafter, it was aged at 60°C for 3 days. As a result, a laminate was produced.

[0198] The resulting laminate was cut into a 15 mm wide test piece, and a 180° peel test was performed on this test piece using a universal tensile tester at a crosshead speed of 50 mm / min to measure the peel strength of the aluminum foil / CPP. The results are shown in Table 1.

[0199] The adhesion at low temperatures was evaluated based on the following criteria, and the results are shown in Table 1. [standard] ⊚: The peel strength of aluminum foil / CPP was 11 N / 15 mm or more. Good: The peel strength of aluminum foil / CPP was 9 N / 15 mm or more and less than 11 N / 15 mm. ×: The peel strength of aluminum foil / CPP was less than 9 N / 15 mm.

[0200] [Table 1] [Explanation of symbols]

[0201] 1 First adhesive layer 2 Base material 3 Inner layer 4 Second adhesive layer 5 Outer layer 10 Laminate 20 Packaging material 31 Packaging material for battery cases

Claims

1. a crystalline modified olefin polymer; an amorphous modified hydrocarbon polymer; an amorphous hydrocarbon polymer having a kinematic viscosity at 200°C of 1 cSt or more and 100,000 cSt or less; a cross-linking agent; a catalyst; The crystalline modified olefin polymer is obtained by modifying a crystalline α-olefin polymer having 2 to 20 carbon atoms with a monomer having a functional group reactive with an epoxy group or an oxazoline group, the crystalline modified olefin polymer has a heat of fusion measured in accordance with JIS K7122 of 1 J / g or more and 50 J / g or less; the amorphous modified hydrocarbon polymer is obtained by modifying an amorphous hydrocarbon polymer with a monomer having a functional group reactive with an epoxy group or an oxazoline group; the non-crystalline hydrocarbon polymer has a kinematic viscosity at 200°C of 1 cSt or more and 100,000 cSt or less; The adhesive composition, wherein the crosslinking agent comprises an epoxy compound and / or an oxazoline compound.

2. 2. The adhesive composition according to claim 1, wherein a mass ratio of the amorphous hydrocarbon polymer to the amorphous modified hydrocarbon polymer is 0.05 or more and 19 or less.

3. 3. The adhesive composition according to claim 1, wherein the amorphous hydrocarbon polymer is a polymer of an olefin having 2 to 20 carbon atoms.

4. 4. The adhesive composition according to claim 1, wherein the content of the structural units derived from the monomer in the amorphous modified hydrocarbon polymer is 0.1% by mass or more and 15% by mass or less.

5. the functional group possessed by the monomer that modifies the crystalline α-olefin polymer having 2 to 20 carbon atoms is a carboxyl group or an acid anhydride group, 5. The adhesive composition according to claim 1, wherein the functional group possessed by the monomer that modifies the amorphous hydrocarbon polymer is a carboxyl group or an acid anhydride group.

6. A laminate comprising, in order toward one side in the thickness direction, a first adhesive layer made of a dried product of the adhesive composition according to any one of claims 1 to 5 and a substrate.

7. A packaging material comprising an inner layer and the laminate according to claim 6 in this order toward one side in the thickness direction.

8. A packaging material for a battery case, comprising the packaging material according to claim 7, a second adhesive layer, and an outer layer, arranged in this order toward one side in a thickness direction.

Images