CN114854332A - Adhesive composition, lithium battery packaging material, and lithium battery - Google Patents
Adhesive composition, lithium battery packaging material, and lithium battery Download PDFInfo
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- CN114854332A CN114854332A CN202110153872.1A CN202110153872A CN114854332A CN 114854332 A CN114854332 A CN 114854332A CN 202110153872 A CN202110153872 A CN 202110153872A CN 114854332 A CN114854332 A CN 114854332A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/10—Homopolymers or copolymers of propene
- C09J123/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/06—Polyethene
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
- H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a binder composition, and a lithium battery pack and a lithium battery manufactured using the binder composition. The invention aims to provide an adhesive composition having both adhesive force and adhesive reliability. Embodiments of the present invention include an adhesive composition including (a) a polyvinyl compound, (B) a polypropylene compound, (C) a polyolefin elastomer, (D) a rubber elastomer; the components (A) and (B) are modified and/or unmodified compounds, and the adhesive composition of the invention has excellent adhesive force and adhesive reliability.
Description
Technical Field
The present invention relates to an adhesive, and further, to an adhesive for a lithium battery. The invention also relates to a lithium battery packaging material and a lithium battery using the adhesive.
Background
Polypropylene materials are resistant to high temperatures, stable in chemical properties, and good in mechanical strength, and are suitable for use as adhesives with long required service life and high application environment temperature, and meanwhile, polypropylene has good water vapor barrier properties and mechanical properties, but poor barrier properties to oxygen. Polypropylene is often combined with metal, nylon, or EVOH into a composite to meet both barrier and strength requirements.
Dry compounding or thermal compounding of polypropylene based adhesives are two commonly used compounding methods. However, the composite strength and reliability obtained by the two composite methods are limited, and the composite method is especially not suitable for being used in media with strong corrosiveness. These disadvantages limit the use of such composites in highly corrosive environments such as power cell packaging.
The adhesive used for dry lamination generally has polyurethane as a resin matrix. Polyurethanes hydrolyze under either acidic or basic conditions, resulting in degradation and adhesive failure. The polypropylene-based adhesive is generally resistant to hydrolysis but has low adhesive force, so that the adhesive force between the polypropylene-based adhesive and a polar substrate reported in the literature is low, and the polypropylene-based adhesive is easy to separate from the interface between the polypropylene-based adhesive and the polar substrate under the action of stress and a medium.
In certain environments, such as applications where the chemical environment is complicated, such as lithium batteries, the binder inevitably comes into contact with the electrolyte and is thus subject to corrosion. While adhesion is difficult to improve without dry lamination with polyurethane or a component of similar nature. That is, the adhesive in the related art has difficulty in both adhesion and adhesion reliability.
Patent document 1(US10,777,785) has a problem that the adhesion reliability is not satisfactory to some extent when the olefin-based component is laminated and an epoxy or isocyanate-based curing agent is further added, but the adhesion is not sufficient.
In patent document 2(US7,485,393), some embodiments use a urethane dry-laminated adhesive and may lower the adhesion reliability, and some embodiments use a modified polypropylene for the inner layer of the adhesive, but the adhesive of the formulation still has room for improvement.
Patent document 3(US10,703,944) uses acid-modified polyolefin as an adhesive inner layer, patent document 4(US10,766,229) is an adhesive using polyurethane in large quantities, and patent document 5(US7,041,380) is an adhesive layer based on polypropylene. These documents, although making some improvements to the conventional polyolefin adhesives, have room for improvement in adhesion and adhesion reliability as also described above.
Disclosure of Invention
The invention aims to provide an adhesive which has excellent adhesive force and adhesive reliability. Another object of the present invention is to provide a lithium battery pack and a lithium battery using the binder.
The inventors of the present invention have found that the adhesion can be greatly improved by using a conventional nonpolar (or less polar) adhesive component such as polyethylene, polypropylene and elastomer in combination and adding a rubber elastomer thereto at the same time, and thus have completed the present invention.
The present invention includes an adhesive composition comprising the following components (a) to (D):
(A) a polyvinyl compound,
(B) A polypropylene compound,
(C) A polyolefin elastomer,
(D) A rubber elastomer;
the components (A) and (B) are modified and/or unmodified compounds.
In a preferred embodiment, nano-inorganic particles of the component (E) are further added.
In a preferred embodiment, the nano inorganic particles are fumed silica, aluminum trioxide or talc, and the content of the nano inorganic particles is 3 to 15 mass%; the content of the rubber elastomer is 15 mass% or more.
In a preferred embodiment, the rubber elastomer is any one or more of the following (a) to (d):
(a) an elastomer obtained by mixing and dispersing rubber particles in a matrix,
(b) An elastomer prepared by melting a rubber component and a matrix,
(c) An elastomer synthesized by using a rubber component as one of the copolymerization components,
(d) An elastomer having an island-in-sea structure.
In a preferred embodiment, the rubber elastomer is an elastomer obtained by dispersing a rubber component in a styrene-based compound.
In a preferred embodiment, the components (a) to (D) include:
(A) 6-25 mass% of modified polyethylene and/or modified ethylene copolymer,
(B1) 10-30% by mass of modified polypropylene and/or modified propylene copolymer,
(B2) Polypropylene and/or propylene copolymer: the balance of,
(C) 10-25% by mass of a polyolefin elastomer,
(D) 8-30% by mass of a rubber elastomer.
In a preferred embodiment, the modification is an acid or anhydride modification.
In a preferred embodiment, the adhesion to aluminum is above 400N/25mm in a 180 peel test.
The invention also comprises a packaging material for lithium batteries, which contains the adhesive composition.
The invention also comprises a lithium battery which contains the packing material.
The adhesive of the present invention can provide excellent adhesion by itself without adding a polar component or dry-compounding with other polar components (e.g., polyurethane, etc.), and thus can improve adhesion (e.g., adhesion of 400N/25mm or more to aluminum) and at the same time, can provide good chemical resistance, i.e., high adhesion reliability.
The binder of the present invention is particularly suitable for use as a packing material for lithium batteries, and further, a lithium battery having excellent durability can be obtained.
Detailed Description
Hereinafter, a specific embodiment of the present invention will be described. These embodiments and examples are merely for convenience of illustration and are not to be construed as limitations of the invention.
In the present invention, "%" of each component means "% by mass" unless otherwise specified.
In the present invention, the modification means acid or acid anhydride modification unless otherwise specified.
In the present invention, when a numerical range, or "upper limit" or "lower limit" is used, it is to be understood that the numerical range includes the number. That is, for example, 1 to 10% is understood to include both 1% and 10%, and a description with an upper limit of 1% and a lower limit of 5% is understood to include both 1% and 5%.
(adhesive component)
The adhesive of the present invention comprises the following components (a) to (D): (A) a polyethylene compound, (B) a polypropylene compound, (C) a polyolefin elastomer, and (D) a rubber elastomer.
(component A)
The polyvinyl compound used in the present invention is preferably a modified polyvinyl compound, and more preferably an acid-modified or acid anhydride-modified polyvinyl compound. It is also possible to use a mixture of a modified polyvinyl compound and an unmodified polyvinyl compound.
When the modified product and the unmodified product are used in combination, the proportion of the modified polyvinyl compound is preferably more than 50% by mass, more preferably more than 60% by mass, still more preferably more than 70% by mass, most preferably more than 80% by mass, for example, 90% by mass or 95% by mass, and may be 100% by mass, from the viewpoint of improving the adhesive force. While also depending on the particular component ratios used and the requirements for other functions, in general, the modification can improve adhesion.
In the present invention, the acidic substance used as the graft is not particularly limited as long as it is an acidic organic acidic substance which can be generally used in the graft reaction for modification, and for example, an organic acid or an organic acid anhydride may be used.
Examples of organic acids or organic acid anhydrides for modification include, but are not limited to, generally small-molecule α, β -unsaturated carboxylic acids or anhydrides: acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, and mixtures of two or more thereof. Acrylic acid and maleic anhydride are preferred. These acidic materials are readily available and have a high grafting yield. The amount of the modifying acid or acid anhydride added to the total weight of the modified polyvinyl compound is generally 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total weight of the modified polyvinyl compound; the amount of the carboxyl group contained in the acid is preferably 0.1 to 5% by weight, more preferably 0.2 to 2% by weight, and particularly preferably 0.4 to 1% by weight.
The polyethylene compound in the present invention can be used as one of the components constituting the binder base resin (blended with the polypropylene matrix), and the content thereof is not particularly limited, but is generally 1 mass% or more, more preferably 6 mass% or more, further preferably 10 mass% or more, and most preferably 15 mass% or more, based on 100 mass% of the total binder. In the component (A), other components may be used in addition to the polyvinyl compound to improve the adhesion. The upper limit of the polyvinyl compound is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, most preferably 25% by mass or less, for example 20% by mass.
The polyvinyl compound in the present invention may be an ethylene homopolymer or a copolymer of ethylene and other components.
Examples of the polyethylene include high-density polyethylene, medium-density polyethylene, low-density polyethylene, and linear low-density polyethylene.
When a copolymer is used, examples of the component copolymerizable with ethylene include α -olefins such as styrene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1, 5-hexadiene, and combinations thereof.
The ethylene copolymer preferably has an ethylene unit content of 40% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, most preferably 80% by mass or more, for example 90% by mass or 95% by mass.
The polyvinyl compound used in the present invention can be synthesized by a known method, or a commercially available product can be used.
(component B)
The polypropylene-based compound used in the present invention may be a modified or unmodified polypropylene-based compound, and from the viewpoint of achieving both adhesion and adhesion reliability, it is preferable to use both of them in combination. The modified polypropylene-based compound is preferably an acid-modified or acid anhydride-modified polypropylene-based compound.
When both are used together, the ratio (modified/unmodified) is generally 1/10-10/1, preferably 1/5-5/1, more preferably 1/3-3/1, most preferably 1/2-2/1, for example 1.5/1-1/1.5 or 1.2/1-1/1.2, or 1: 1. In a preferred embodiment, the modified material may be slightly more than the unmodified material, for example, 1.5/1 or 1.2/1, in which case both adhesion and adhesion reliability can be better achieved.
Examples of the acid or acid anhydride for modification and the modification ratio are the same as those listed in the above section relating to the component (A).
The content of the polypropylene-based compound in the present invention as the adhesive base component is not particularly limited, and is generally 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and most preferably 20% by mass or more; in the component (B), various other components may be used in combination in addition to the polypropylene-based compound to improve the adhesion. The upper limit of the amount of the polypropylene-based compound is preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and most preferably 55% by mass or less, for example, 40% by mass or 50% by mass.
The polypropylene compound in the present invention may be a propylene homopolymer or a copolymer of propylene and other components. For example, the polypropylene may be any 1 or more selected from homopolypropylene, copolypropene, and branched polypropylene.
When a copolymer is used, examples of the component copolymerizable with ethylene include α -olefins such as styrene, ethylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, 1, 5-hexadiene, and combinations thereof.
The propylene copolymer preferably has a propylene unit content of 40% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, most preferably 80% by mass or more, for example, 90% by mass or 95% by mass.
The polypropylene compound used in the present invention can be synthesized by a known method, or a commercially available product can be used.
(component C)
In the adhesive composition, a polyolefin elastomer is further included to improve adhesion. The polyolefin elastomer is used as the adhesive base component, and the content is not particularly limited. The content is generally 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, for example, 12% by mass or 15% by mass, based on 100% by mass of the total amount of the binder; however, in view of the marginal effect of the polyolefin content and the balance with the content of other components required for maintaining the adhesive properties, the upper limit of the content of the polyolefin elastomer is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, for example 16% by mass or 18% by mass.
The polyolefin elastomer used in the present invention can be synthesized by a known method, and a commercially available product can be used. Examples thereof include common ethylene- α -olefin copolymers, propylene- α -olefin copolymers, butene homopolymers and copolymers, metallocene-catalyzed propylene- α -olefin copolymers, ethylene-octene copolymers, ethylene-2-butene copolymers, ethylene-hexene copolymers, and the like. Examples of the α -olefin include 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, norbornene, 1-decene, and 1, 5-hexadiene.
(component D)
The present inventors have found that the adhesion of polyolefins, particularly polypropylene/polyethylene adhesives, can be greatly improved by adding a rubber elastomer without impairing the adhesion reliability.
The rubber elastomer used in the present invention may be, for example, a saturated rubber elastomer or an unsaturated rubber elastomer. Specifically, an elastomer containing any one of natural rubber, isoprene rubber, polybutadiene rubber, styrene-butadiene rubber, nitrile rubber, chloroprene rubber, butyl rubber, halogenated butyl rubber (e.g., chlorinated butyl rubber, brominated butyl rubber), ethylene-propylene-diene rubber, and ethylene-propylene-diene rubber as a rubber component is exemplified.
The rubber elastomer in the present invention is not particularly limited in content. It is generally 2% by mass or more, more preferably 5% by mass or more, still more preferably 8% by mass or more, most preferably 10% by mass or more, for example, 15% by mass. However, in view of the marginal effect of the content of the rubber elastomer and the balance with the content of other components necessary for maintaining the adhesive properties, the upper limit of the content of the rubber elastomer is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, most preferably 30% by mass or less, for example, 20% by mass or 25% by mass.
The rubber elastomer of the present invention preferably contains styrene such as general-purpose styrene, high molecular weight styrene, heat-resistant styrene, high-fluidity styrene, high-impact styrene, and the like. Styrene is preferably used as a matrix or as one of the copolymeric (e.g. graft or block copolymeric) components.
The rubber elastomer of the present invention is preferably used in such a manner that the rubber component is dispersed in the matrix. The form of dispersion is not particularly limited as long as the rubber component can be dispersed in the matrix. It is preferable to select a suitable rubber component and a matrix to mix them so that the rubber component has a sea-island structure.
As a mixing method, for example, rubber particles are added to a matrix and mixed, or a rubber component may be melt-mixed with the matrix, or the rubber component may be added to an elastomer by copolymerization (e.g., graft copolymerization or block copolymerization).
The rubber elastomer used in the present invention can be synthesized by a known method, and a commercially available product can be used.
(other Components)
The binder composition of the present invention may further contain component (E), i.e., nano inorganic particles, as necessary. For the adhesive composition of the present invention, the addition of nano inorganic particles can further improve the adhesion. The inorganic nanoparticles are not particularly limited and may be, for example, fumed silica, aluminum trioxide or talc, nano metal oxides such as nano Ti0 2 、Al 2 O 3 、ZrO 2 Etc., non-metal oxides, e.g. nano SiO 2 Metal hydroxides, e.g. nano Co (OH) 2 、La(OH) 3 And the like, as well as metal sulfides such as silver sulfide, tin sulfide, nano nitrides, and the like. Fumed silica, aluminum trioxide or talc are preferred.
The fumed silica generally has an average particle diameter of 5 to 15nm and a specific surface area of 2 to 200m 2 Properties of/g, bulk density 20-150g/l, e.g. EVONIK Aerosil 200, Aerosil 300, Aerosil 380 etc
The lower limit of the content of the nano inorganic particles may be 1 mass%, 2 mass%, 5 mass%, or 10 mass%, and the upper limit thereof may be 30 mass%, 25 mass%, 20 mass%, or 15 mass%, based on 100 mass% of the total amount of the binder.
The adhesive of the present invention may further contain functional additives such as an antioxidant, a stabilizer, an initiator, and a modifier (a modifier other than the above-mentioned acid). These additives may be selected from known additives according to the desired function, as long as the object of the present invention is not impaired. Although the amount of the additives having different functions is different, the content of the functional additives is preferably 0.1% to 5%, more preferably 0.5 to 2%, and the functional additives can exert the corresponding functions at such a content without adversely affecting the adhesive body.
The polymer raw material of the present invention preferably contains no or little additive having poor chemical resistance as an auxiliary additive or modifier other than the propylene compound, and is suitable for an acid-base environment.
(Properties of adhesive)
The adhesive of the present invention is more excellent as the adhesive strength is larger, and is generally easy to be 300N/25mm or more, preferably 400N/25mm or more, and more preferably 500N/25mm, to an aluminum sheet, while ensuring the adhesion reliability.
The reason why the adhesion to an aluminum sheet is used as a criterion is that when the adhesive is used for applications such as a lithium battery, at least one side of the adhesive is generally adhered to an aluminum foil as one layer of an adhesive package, and the adhesion to aluminum is high, the adhesion to the aluminum is considered to be high.
(method for producing adhesive)
In the present invention, the method for producing the adhesive is not particularly limited as long as the components can be uniformly mixed, and for example, the mixing can be performed at a high temperature by an extruder.
The mixing temperature is not particularly limited and generally depends on the melting temperature of the adhesive component, but is generally 80 ℃ or higher, preferably 100 ℃ or higher, more preferably 120 ℃ or higher, for example 150 ℃, and the upper limit thereof is preferably 500 ℃ or lower, more preferably 400 ℃ or lower, most preferably 300 ℃ or lower, for example 200 ℃ or 250 ℃.
(lithium cell and its packaging material)
The adhesive can be used as one layer of adhesive of a lithium battery packaging material and used for manufacturing a lithium battery.
Examples
(preparation of adhesive)
The adhesive of the present invention can be prepared by the following steps, but can be prepared by other known methods.
Step 1: preparation of adhesive composition
The components are uniformly dispersed physically according to the formula proportion recorded in the table, and are subjected to blending extrusion at the temperature of 180 ℃ by a double-screw extruder, underwater cooling and grain cutting.
And a step 2: preparation of peeled specimens
Placing a proper amount of adhesive particles between two pieces of 0.2mm aluminum sheets, heating to 190 ℃ for 5 minutes, pressurizing and compounding to form a sample strip with the thickness of 1.0mm, and putting the sample strip into water to quench to room temperature. The bars were cut into 25mm wide peel test bars.
In the present invention, the adhesive force of the adhesive was evaluated by the following peel strength test.
(evaluation of adhesive force)
Aluminum sheets at two ends of the sample strip are fixed on a universal tensile tester, and 180-degree stripping tensile test is carried out, wherein the test speed is 100 mm/min. The peel force (unit: N/25mm) was recorded.
The materials used in the present invention are as follows:
a1: acid-modified Polymer: mPE (acid or acid anhydride modified polyethylene, which takes metallocene catalyzed polyethylene as raw material, the target modification rate is 0.2 to 1.0 mass percent, the melt index is 1.0 to 3.0 g/10 mm @190 ℃ and is 2.16Kg),
B1: mPP (acid or anhydride modified polypropylene, using ethylene propylene random copolymer as raw material, target modification rate 0.2-1.0 mass%, melt index 10-50 g/10 mm @190 ℃ 2.16Kg) B2: polypropylene: SK R140H.
Polyolefin elastomer:
c1: dow chemical Engage 8200,
C2: the Dow chemical Engage 8677XLT,
C3: mobil Vistamaxx 3980fl,
C4: mofu Vistamaxx 3020
Rubber elastomer:
D1：Kraton G1643 SEBS、
D2：Taipol 6014、
d3: 622P butyl rubber Dispersion
Nano modified particles:
e1: gas phase nano SiO 2 。
The adhesion measurement results of the formulation components and the adhesives of the examples and comparative examples are given in the following table. The numerical values of the contents of the components in the tables are mass%.
Example 1
Example 2
Example 3
As described above, in examples 1 to 3 containing all of the components A to D of the present invention, sufficient adhesiveness was obtained even without using a polar component such as polyurethane. In example 3, when 3% or more of nanoparticles and 15% or more of a rubber elastomer were added simultaneously, the adhesive strength was further improved to 500N/25mm or more.
Comparative example 1
Comparative example 1 shows the case where component A, D was not added, and it was found that the adhesion was significantly insufficient in this case.
Comparative example 2
Comparative example 3
Comparative examples 2 and 3 show cases where component A, C was not added or component D was not added, and although they have some preliminary practical utility, the adhesive strength was still insufficient.
Comparative example 4
In comparative example 4, the polyolefin elastomer and the rubber elastomer were added, but it was found that the improvement of the adhesive force was significantly insufficient depending on only the polypropylene substrate itself without using the mixture of polyethylene and polypropylene as the substrate.
Comparative example 5
Comparative example 6
In comparative examples 5 and 6, the addition of the rubber elastomer was found to be insufficient for the improvement of the adhesive strength, since only the rubber elastomer was added and the polyolefin elastomer was not added.
Claims (10)
1. An adhesive composition comprising the following components (A) to (D):
(A) a polyvinyl compound,
(B) A polypropylene compound,
(C) A polyolefin elastomer,
(D) A rubber elastomer;
the components (A) and (B) are modified and/or unmodified compounds.
2. The adhesive composition according to claim 1, further added with ingredient (E) nano inorganic particles.
3. The adhesive composition according to claim 2, wherein the nano inorganic particles are fumed silica, aluminum trioxide or talc, and the content of the nano inorganic particles is 3 to 15 mass%; the content of the rubber elastomer is 15 mass% or more.
4. The adhesive composition according to claim 1, wherein the rubber elastomer is any one or more of the following (a) to (d):
(a) an elastomer obtained by mixing and dispersing rubber particles in a matrix,
(b) An elastomer prepared by melting a rubber component and a matrix,
(c) An elastomer synthesized by using a rubber component as one of the copolymerization components,
(d) An elastomer having an island-in-sea structure.
5. The adhesive composition according to claim 4, wherein the rubber elastomer is an elastomer obtained by dispersing a rubber component in a styrene compound.
6. The adhesive composition according to claim 1, wherein the components (A) to (D) comprise:
(A) 6-25 mass% of modified polyethylene and/or modified ethylene copolymer,
(B1) 10-30% by mass of modified polypropylene and/or modified propylene copolymer,
(B2) Polypropylene and/or propylene copolymer: the balance of,
(C) 10-25% by mass of a polyolefin elastomer,
(D) 8-30% by mass of a rubber elastomer.
7. The adhesive composition of any one of claim 1, the modification being an acid or anhydride modification.
8. The adhesive composition according to any one of claims 1 to 7, which has an adhesion to aluminum of 400N/25mm or more in a 180 ° peel test.
9. A packaging material for a lithium battery, comprising the binder composition according to any one of claims 1 to 8.
10. A lithium battery comprising the packing material according to claim 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110153872.1A CN114854332A (en) | 2021-02-04 | 2021-02-04 | Adhesive composition, lithium battery packaging material, and lithium battery |
| PCT/CN2022/070505 WO2022166518A1 (en) | 2021-02-04 | 2022-01-06 | Adhesive composition, packaging material for lithium battery, and lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110153872.1A CN114854332A (en) | 2021-02-04 | 2021-02-04 | Adhesive composition, lithium battery packaging material, and lithium battery |
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| CN114854332A true CN114854332A (en) | 2022-08-05 |
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| CN202110153872.1A Pending CN114854332A (en) | 2021-02-04 | 2021-02-04 | Adhesive composition, lithium battery packaging material, and lithium battery |
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| CN (1) | CN114854332A (en) |
| WO (1) | WO2022166518A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378579A (en) * | 1999-09-03 | 2002-11-06 | 纳幕尔杜邦公司 | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| CN102844394A (en) * | 2010-03-12 | 2012-12-26 | 伊奎斯塔化学有限公司 | Adhesive composition |
| KR20170028588A (en) * | 2015-09-04 | 2017-03-14 | 태영화학공업 주식회사 | Polyolefin tape and manufacturing method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6184298B1 (en) * | 1998-06-19 | 2001-02-06 | E. I. Du Pont De Nemours And Company | Adhesive compositions based on blends of grafted polyethylenes and non-grafted polyethylenes and styrene container rubber |
| JP4972284B2 (en) * | 2002-10-15 | 2012-07-11 | エクソンモービル・ケミカル・パテンツ・インク | Multiple catalyst systems for olefin polymerization and polymers produced therefrom |
| US10081212B2 (en) * | 2014-07-03 | 2018-09-25 | Bostik, Inc. | Cohesively failing, non-staining hot melt adhesives |
| CN107083213B (en) * | 2017-05-26 | 2018-12-28 | 新乡市华洋粘合剂有限公司 | A kind of dairy products adhesive for packaging and preparation method thereof |
-
2021
- 2021-02-04 CN CN202110153872.1A patent/CN114854332A/en active Pending
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2022
- 2022-01-06 WO PCT/CN2022/070505 patent/WO2022166518A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1378579A (en) * | 1999-09-03 | 2002-11-06 | 纳幕尔杜邦公司 | Low activation temperature adhesive composition with high peel strength and cohesive failure |
| CN102844394A (en) * | 2010-03-12 | 2012-12-26 | 伊奎斯塔化学有限公司 | Adhesive composition |
| KR20170028588A (en) * | 2015-09-04 | 2017-03-14 | 태영화학공업 주식회사 | Polyolefin tape and manufacturing method thereof |
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| WO2022166518A1 (en) | 2022-08-11 |
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