KR102336272B1 - Adhesive composition and packaging material for battery - Google Patents

Abstract

Disclosed are an adhesive composition including a base mixture containing an adhesiveness applying agent, an aromatic vinyl monomer, and an epoxy compound; and a packaging material for a battery including the adhesive composition. By using the adhesive composition, a polyolefin film and a metal foil can be easily and stably attached.

Description

Adhesive composition and battery packaging material {ADHESIVE COMPOSITION AND PACKAGING MATERIAL FOR BATTERY}

The present invention relates to an adhesive composition and a packaging material for a battery. More specifically, it relates to an adhesive composition comprising a resin component and a monomer component, and a battery packaging material comprising an adhesive layer formed therefrom.

Secondary batteries, which are easy to use and have excellent electrical characteristics, are being applied to portable devices and electric vehicles (EVs). Secondary batteries can reduce the use of fossil fuels, and are attracting attention as a next-generation energy source in terms of environment-friendliness and energy efficiency improvement.

Secondary batteries are classified into pouch type and can type according to the material of the battery case. The pouch type accommodates the electrode assembly in an atypical pouch made of metal foil and polymer. On the other hand, in the can type, the electrode assembly is accommodated in a can made of metal or the like.

The metal foil included in the pouch protects the battery cell composed of the electrode assembly and the electrolyte, and supplements the electrochemical properties of the battery cell. In addition, in order to suppress direct contact between the electrolyte and the metal foil, a sealant layer including a polypropylene (PP) resin, a polyethylene (PE) resin, etc. is laminated on the inner layer of the aluminum foil.

In order to laminate a sealant layer on one surface of the metal foil, an adhesive including a polyolefin-based resin may be used. For example, as an adhesive, polyolefins such as polyethylene (PE), cast polypropylene (CPP), or polypropylene (PP) or copolymers thereof have been used.

For example, Patent Document 1 discloses an adhesive composition containing acid-modified polypropylene (A), non-functionalized polypropylene (B) and polyethylene (C), and having a melting point of 70 to 140°C. The adhesive composition of Patent Document 1 has an advantage that it can provide a strong adhesive force. However, polypropylene contained in the adhesive composition is not easily dissolved, and there is a limitation in that molding is difficult.

Korean Patent Publication No. 2018-0075489

One object of the present invention is to provide an adhesive composition having improved adhesion and chemical reliability.

One object of the present invention is to provide a battery packaging material comprising an adhesive layer formed of the adhesive composition.

1. A base mixture and an initiator are included, wherein the base mixture comprises 10 to 50 parts by weight of a tackifier based on 100 parts by weight in total; 10 to 50 parts by weight of an aromatic vinyl monomer; and 10 to 40 parts by weight of an epoxy compound.

2. The adhesive composition according to the above 1, wherein the tackifier comprises at least one selected from the group consisting of polyterpene-based resins, rosin-based resins, and petroleum resins.

3. The method of 2 above, wherein the petroleum resin comprises at least one selected from the group consisting of an aliphatic petroleum resin, an alicyclic petroleum resin, a copolymer-based petroleum resin, and a hydrogenated petroleum resin, the adhesive composition.

4. The adhesive composition according to the above 1, wherein the base mixture further comprises an acrylic monomer.

5. The adhesive composition according to the above 4, wherein the content of the acrylic monomer is 30 parts by weight or less based on 100 parts by weight of the base mixture.

6. The adhesive composition according to the above 1, wherein the initiator includes a radical initiator and a cationic initiator.

7. The adhesive composition according to the above 6, wherein the content of the initiator is 0.1 to 5 parts by weight.

8. The adhesive composition according to 1 above, prepared in a solvent-free type.

9. The adhesive composition according to the above 1, wherein the base mixture does not contain a polypropylene-based resin.

10. sealant layer; a metal foil laminated on the sealant layer; and a first adhesive layer bonding the sealant layer and the metal foil to each other, wherein the first adhesive layer includes the adhesive composition according to 1 above.

11. The battery packaging material according to the above 10, wherein the sealant layer includes a polypropylene-based resin.

12. The above 10, laminated on the metal foil, polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate

A battery packaging material further comprising an exterior substrate layer comprising a tee or a mixture thereof.

Adhesive compositions according to embodiments of the present invention are prepared in a solvent-free type and do not include a polypropylene-based resin. Therefore, the content of the solute is not limited by the type of solvent, and an adhesive composition having improved adhesive strength can be provided.

In addition, the adhesive composition has a high content of a tackifier, an aromatic vinyl monomer, and an epoxy compound and is dense. Thus, it is possible to provide improved electrolytic resistance to the electrolyte solution for a battery.

In addition, the polymerization reaction of the adhesive composition is initiated by ultraviolet rays and/or heat, and a hot melt process for curing the adhesive composition is not accompanied. Accordingly, the manufacturing process is simple and improved formability can be provided.

In addition, the adhesive composition according to embodiments of the present invention may be used in a battery packaging material. For example, the adhesive composition may be used to laminate a metal foil to a sealant layer. In addition, the adhesive composition can further suppress separation of the sealant layer from the metal foil by providing improved adhesive strength.

In addition, since the adhesive composition has improved electrolytic resistance, it is possible to further delay exposure of the metal foil to an electrolyte for a battery. As a result, it is possible to delay the reduction of the battery life due to oxidation of the metal foil.

In addition, the adhesive composition is easy to mold and has excellent moldability, and the use of the adhesive composition can contribute to reduction of process cost and process time of a battery packaging material.

1 is a schematic cross-sectional view showing a battery packaging material including an adhesive composition according to exemplary embodiments.

Embodiments of the present invention provide an adhesive composition.

The present specification includes a base mixture and an initiator, and the base mixture includes 10 to 50 parts by weight of a tackifier based on 100 parts by weight in total; 10 to 50 parts by weight of an aromatic vinyl monomer; and 10 to 40 parts by weight of an epoxy compound.

In addition, the base mixture does not include a polypropylene-based resin. Excessive use of the solvent may be suppressed or the solvent may not be used by excluding the use of the polypropylene resin. For example, in exemplary embodiments, the adhesive composition is prepared in a solvent-free type.

The adhesive composition of the present invention can provide excellent adhesive strength without containing a liquid solvent. In addition, the adhesive composition according to the exemplary embodiments, unlike the adhesive composition including the polypropylene-based resin, is prepared by a radical polymerization reaction rather than a hot melt process, and can provide excellent moldability.

In addition, the present specification is a sealant layer; metal foil laminated on the sealant layer; and a first adhesive layer for bonding the sealant layer and the metal foil, wherein the first adhesive layer further discloses a battery packaging material comprising the adhesive composition according to 1 above. The sealant layer may include a polyolefin-based resin, and the polyolefin-based resin may be a polypropylene-based resin. Hereinafter, a battery packaging material will be described on the premise that the sealant layer is a polyolefin film including a polyolefin-based resin.

Hereinafter, the technical significance of each configuration will be described in more detail.

<Tackifier>

In exemplary embodiments, the base mixture includes a tackifier. The tackifier is applied between the sealant layer and the metal foil, and the sealant layer and the metal foil can be adhered by the tackifier. Unlike the prior invention, the tackifier of the present invention does not contain a polypropylene resin, and is one selected from the group consisting of polyterpene resin, rosin resin, and petroleum resin. may be more than

In addition, in each adhesive composition, the petroleum resin may be at least one selected from the group consisting of aliphatic petroleum resins, alicyclic petroleum resins, copolymer petroleum resins, and hydrogenated petroleum resins. .

Illustratively, the petroleum resin may be a polymer obtained by polymerizing an aliphatic compound and/or an alicyclic compound obtained from petroleum fraction. In addition, the monomer of the petroleum resin may include a C5 to C9 fraction which is a diolefin. For example, the petroleum resin may be prepared by polymerizing C5 to C9 under a cationic initiator (AlCl ₃ or BF ₃ ) atmosphere, and going through a decatalysis process, a washing process, and a resin separation process. As examples of commercially available petroleum resins, aromatic C9 petroleum resins (HIKOTACK ^® DP100, HIKOTACK ^® P120, manufactured by Kolon Industries), aromatic C8 to C9 petroleum resins (Kristalex F85, Eastman), and the like can be considered.

In some embodiments, the petroleum resin may be a copolymer-based petroleum resin or a hydrogenated petroleum resin. The copolymer-based petroleum resin may be a resin obtained by copolymerizing an aliphatic compound, an alicyclic compound, and/or an aromatic compound obtained from petroleum fractions. Moreover, hydrogenated petroleum resin is resin obtained by hydrogenating the petroleum resin containing one or more conjugated bonds in hydrogen atmosphere. As specific examples, ARCON (manufactured by Arakawa Chemical Industry Co., Ltd.), Hiretsu (manufactured by Mitsui Chemical Corporation), Quinton (manufactured by Nippon Zeon Corporation), Escorez (manufactured by Tonex Corporation) etc. may be considered.

In addition, in each adhesive composition, the rosin-based resin may include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, partially polymerized rosin, and modified rosin.

In some embodiments, the use of a rosin-based resin may be considered to improve adhesive strength, moldability, and electrolytic resistance, and a rosin-based resin may be used to improve electrolytic resistance.

In addition, the use of partially polymerized rosin may be considered from the viewpoint that compatibility with an aromatic vinyl monomer and an epoxy compound and improvement of electrolytic resistance can be pursued harmoniously.

<Aromatic Vinyl Monomer>

In embodiments, the base mixture includes an aromatic vinyl monomer. The aromatic vinyl monomer may be mixed with a tackifier, and may enhance the adhesion between the polyolefin film and the adhesive composition by strengthening the interaction (Π stacking) between multiple bonds.

The aromatic vinyl monomer is one that can achieve the above-described object, preferably an aromatic vinyl monomer having 4 to 20 carbon atoms, more preferably 6 to 15 carbon atoms. For example, styrene; methyl styrenes such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene and trimethyl styrene; alkyl styrenes such as o-ethyl styrene, m-propyl styrene, p-butyl styrene, α-pentyl styrene, β-hexyl styrene, diethyl styrene, triethyl styrene, and 4-t-butyl styrene; chlorostyrenes such as o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, and trichlorostyrene; bromostyrenes such as o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, and sabromostyrene; fluorostyrenes such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, and trifluorostyrene; nitro styrenes such as o-nitro styrene, m-nitro styrene, p-nitro styrene, dinitro styrene, and trinitro styrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, and trihydroxystyrene; divinylbenzenes such as o-divinylbenzene, m-divinylbenzene, and p-divinylbenzene; diisopropenyl benzenes such as o-diisopropenyl benzene, m-diisopropenyl benzene and p-diisopropenyl benzene; The use of one type or two or more types such as etc. may be considered.

In particular, the use of methyl styrene such as styrene, α-methyl styrene, p-methyl styrene, etc., alkyl styrene such as 4-t-butyl styrene, divinylbenzene monomer, or a mixture of divinylbenzene isomers improves adhesion and reduces production costs. It can be considered from the point of view that the harmonious pursuit of

<Epoxy compound>

In embodiments, the base mixture includes an epoxy compound. The epoxy compound can be mixed with the tackifier to improve the cohesive force of the tackifier, and add an interaction between oxygen atoms and metal atoms to improve the adhesion between the adhesive composition and the metal foil.

It is sufficient as long as it can achieve the objective mentioned above as an epoxy compound. For example, as an epoxy compound, Bisphenol-type epoxy compounds, such as a bisphenol A epoxy compound and a bisphenol F-type epoxy compound; novolac-type epoxy compounds such as phenol novolac-type epoxy compounds and cresol novolak-type epoxy compounds; Aliphatic epoxy compound, alicyclic epoxy compound, aromatic epoxy compound, naphthalene type epoxy compound, polyfunctional epoxy compound, biphenyl type epoxy compound, glycidyl ether type epoxy compound, glycidyl ester type epoxy compound, glycidyl amine type epoxy compounds; alcohol-type epoxy compounds such as hydrogenated bisphenol A-type epoxy compounds; halogenated epoxy compounds such as brominated epoxy compounds; Epoxy group-containing polymer resins such as rubber-modified urethane resins, urethane-modified epoxy compounds, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymers, epoxy group-containing polyester resins, epoxy group-containing polyurethane resins, and epoxy group-containing acrylic resins; Phenoxymethyloxetane, 3,3-bis(methoxymethyl)oxetane, 3,3-bis(phenoxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl- 3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, phenol novolac oxetane, 1,4-bis{[ Oxetanyl group-containing compounds such as (3-ethyl3-oxetanyl)methoxy]methyl}benzene may be considered, and these may be used alone or in combination of two or more.

Preferably, the use of an aliphatic epoxy compound, an alicyclic epoxy compound, or the like may be considered in terms of exhibiting excellent elastic modulus and adhesive strength. Specific examples of preferred aliphatic epoxy compounds include neopentyl glycol diglycidyl ether (Kukdo Fine Chem, LD204), 2-ethylhexyl glycidyl ether (Kukdo Fine Chem, ME102), 1,4-butanediol diglycy Dil ether (Aldrich), 1,6-hexanediol diglycidyl ether (Aldrich), 1,2-propanediol diglycidyl ether (Aldrich), etc. may be considered, and alicyclic epoxy Preferred examples of the compound include 1,4-cyclohexanedimethanol diglycidyl ether (Kukdo Fine Chem, DE204), (3',4'-epoxycyclohexane)methyl 3,4-epoxy cyclohexyl carboxylate (Daisel Corporation) , Celloxide 2021P), 1,2-epoxy-4-vinylcyclohexane (Daicel, Celloxide 2000), vinyl cyclohexane dioxide (Union Carbide, ERL-4206), nimonene diepoxide (Daisel's Celloxide 3000), di Glycidyl ester hexahydrophthalic anhydride (CY184 from Ciba-Geigy) and the like may be considered.

In preferred embodiments, the base mixture comprises a total of 100 parts by weight, including 10 to 50 parts by weight of a tackifier; 10 to 50 parts by weight of aromatic vinyl monomer (Vinyl monomer); and 10 to 40 parts by weight of an epoxy compound.

For example, when the tackifier is included in an amount of less than 10 parts by weight in the base mixture, the adhesive strength may be poor due to the insufficient content of the tackifier. As a result, the adhesive strength may be poor or, in severe cases, even the electrolytic resistance may be poor.

Accordingly, from the viewpoint of imparting good or excellent adhesive strength to the adhesive composition, the tackifier is preferably included in 10 to 50 parts by weight, 20 to 50 parts by weight, 10 to 40 parts by weight, or 20 to 40 parts by weight. It is more preferable to be included.

For example, when the aromatic vinyl monomer is contained in an amount of less than 10 parts by weight in the base mixture, the adhesive strength may be poor due to the insufficient content of the aromatic vinyl monomer, and even if the adhesive strength is good due to insufficient stress of the adhesive composition, the moldability is good. can be bad Conversely, when the aromatic vinyl monomer is included in more than 50 parts by weight in the base mixture, the adhesive strength of the adhesive composition to the metal foil may be reduced, and the adhesive strength may be poor.

Accordingly, from the viewpoint of imparting good or excellent adhesive strength to the adhesive composition, the aromatic vinyl monomer is preferably included in 10 to 50 parts by weight, and 20 to 50 parts by weight, 30 to 50 parts by weight, or 35 to 45 parts by weight. It is more preferable to be included.

For example, when the epoxy compound is included in an amount of less than 10 parts by weight in the base mixture, the metal foil and the adhesive composition may not be sufficiently adhered, so that the adhesive strength may be poor. Conversely, when the epoxy compound is contained in an amount exceeding 40 parts by weight in the base mixture, the adhesive strength between the polyolefin film and the adhesive composition is lowered, resulting in poor adhesive strength or poor moldability due to excessive aggregation of the tackifier.

Therefore, from the viewpoint of imparting good or excellent adhesive strength to the adhesive composition, the epoxy compound is preferably included in 10 to 40 parts by weight, and preferably in 20 to 40 parts by weight, 10 to 30 parts by weight, or 25 to 35 parts by weight. It is more preferable to be

<Acrylic Monomer>

In addition, in some embodiments, the base mixture may further include an acrylate monomer, and the amount of the acrylic monomer is preferably 30 parts by weight or less based on 100 parts by weight of the base mixture.

When the acrylic monomer is further included in the base mixture, the acrylic monomer may contribute to improving the adhesive strength between the adhesive composition and the polyolefin film or may contribute to improving the adhesive strength between the adhesive composition and the metal foil. As a result, the adhesive strength of the adhesive composition may be improved from good to excellent or from bad to good.

In some embodiments, the acrylic monomer may be an acrylic monomer containing a polar functional group. The acrylic monomer containing a polar functional group may further contribute to improving the adhesive strength between the adhesive composition and the metal foil. The polar functional group included in the acrylic monomer may be exemplified by epoxy, alkoxy, isocyanate, aziridine, and the like.

<Initiator>

The present invention is characterized in that a complicated hot melt process is not applied by promoting the curing of the adhesive composition through a radical polymerization reaction.

Further, in each adhesive composition, the initiator preferably contains a radical initiator and a cationic initiator. The radical initiator initiates the polymerization reaction through generation of radical ions. Similarly, cationic initiators initiate polymerization through the production of cations and include conventional Lewis acids.

In embodiments, 2,2-azobis-2,4-dimethylvaleronitrile (V-65, Wako (manufactured)), 2,2-azobisisobutyronitrile (V-60) as a thermal initiator , Wako (produced)) or 2,2-azobis-2-methylbutyronitrile (V-59, Wako (produced)) azo initiators; Dipropyl peroxydicarbonate (Peroyl NPP, NOF (produced)), diisopropyl peroxy dicarbonate (Peroyl IPP, NOF (produced)), bis-4-butylcyclohexyl peroxydicarbonate (Peroyl TCP, NOF (produced) )), diethoxyethyl peroxy dicarbonate (Peroyl EEP, NOF (agent)), diethoxyhexyl peroxy dicarbonate (Peroyl OPP, NOF (agent)), hexyl peroxy dicarbonate (Perhexyl ND, NOF (agent) ), dimethoxybutyl peroxy dicarbonate (Peroyl MBP, NOF carbonate compounds; Hexyl peroxypivalate (Perhexyl PV, NOF (available)), amyl peroxypivalate (Luperox 546M75, Atofina (available)), butyl peroxypivalate (Perbutyl, NOF (available)) or trimethylhexanoyl peroxide ( Peroyl 355, NOF (supplied), dimethyl hydroxybutyl peroxaneodecanoate (Luperox 610M75, Atofina™), amyl peroxy neodecanoate (Luperox 546M75, Atofina™), or butyl peroxy neo peroxyester compounds such as decanoate (Luperox 10M75, from Atofina); acyl peroxides such as 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide or dibenzoyl peroxide; ketone peroxide; dialkyl peroxide; peroxyketal; Alternatively, one or more than one type of peroxide initiator such as hydroperoxide may be used.

In addition, in embodiments, as the initiator by light (ultraviolet rays), a benzoin-based, hydroxy ketone-based, aminoketone-based or phosphine oxide-based photoinitiator may be used, and specifically, benzoin, benzoin methyl Ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin isobutyl ether, acetophenone, dimethyl anino acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio) Phenyl]-2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4 '-Diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethyl Thioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyldimethyl ketal, acetophenone dimethyl ketal, p-dimethylamino benzoic acid ester, oligo[2-hydroxy-2 -methyl-1-[4-(1-methylvinyl)phenyl]propanone] and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and the like can be used.

Also, in some embodiments, the radical initiator may be a peroxy ester-based compound including one or more tertiary carbons. For example, illustratively the peroxy ester may be one of amyl peroxy pivalate, t-butyl peroxy pivalate, hexyl peroxy pivalate, butyl peroxy pivalate, or amyl peroxy neodecanoate. have.

In embodiments, 0.1 to 5 parts by weight of the initiator is preferably included with respect to 10 to 50 parts by weight of the tackifier. When the initiator is included in an amount of less than 0.1 parts by weight, there is a fear that curing of the adhesive composition may not be sufficiently achieved. Conversely, when included in excess of 5 parts by weight, there is a fear that the formation of a homogeneous adhesive layer is limited. Therefore, it is preferable that 0.1 to 5 parts by weight of the initiator is included.

In addition, the present specification further discloses a battery packaging material. In exemplary embodiments, the battery packaging material includes a sealant layer; metal foil laminated on the sealant layer; and a first adhesive layer bonding the sealant layer to the metal foil, wherein the first adhesive layer includes the adhesive composition as described above.

For example, the sealant layer may include a polyolefin-based resin such as polyethylene (PE) or polypropylene (PP) or a copolymer thereof. Polyolefin-based resins or copolymers are excellent in heat preservation, moisture resistance, heat resistance, chemical resistance, and the like, and may provide advantages of easy processing.

In addition, the sealant layer primarily protects the metal foil from the electrolyte of the battery. The sealant layer having excellent moisture resistance may suppress moisture permeation of the electrolyte, and the sealant layer having excellent chemical resistance may not be decomposed by the electrolyte. For example, the sealant layer may include a polypropylene-based resin, and the form may be a film.

In addition, the adhesive compositions according to the exemplary embodiments have excellent electrolytic resistance even though they do not contain a polypropylene-based resin as an adhesive. Accordingly, the first adhesive layer including the adhesive composition as described above may secondaryly protect the metal foil from the electrolyte.

In addition, the battery packaging material may further include an exterior substrate layer laminated on the metal foil. In addition, a second adhesive layer may be formed to adhere the metal foil and the exterior substrate layer. Illustratively, the second adhesive layer may include a polyurethane-based adhesive.

In addition, the exterior substrate layer may have insulating properties. For example, the exterior substrate layer includes a polyester resin and a polyamide resin. In addition, the polyester resin includes polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, co-polyester, polycarbonate, and the like, and the polyamide resin includes nylon 6, nylon 66, and nylon 6 copolymers of nylon 66, and nylon 610.

Hereinafter, with reference to the drawings, the embodiments will be described in more detail. However, the following drawings attached to the present specification illustrate preferred embodiments, and serve to further understand the technical idea together with the content of the above-described invention, so that the present invention is limited only to the matters described in those drawings and interpreted is not

1 is a schematic cross-sectional view illustrating a battery packaging material including an adhesive composition according to exemplary embodiments.

Referring to FIG. 1 , the battery packaging material 1 to which the embodiment is applied includes an exterior substrate layer 2 , a sealant layer 3 , a metal foil 4 , a second adhesive layer 5 , and a first adhesive layer 6 . it can be seen that The adhesive composition is included in the first adhesive layer 6, the first adhesive layer 6 is located between the metal foil 4 and the sealant layer 3, and the metal foil 4 and the sealant layer 3 are the first adhesive layer (6) can be attached at the same time.

Hereinafter, preferred embodiments are presented to aid understanding, but these examples only illustrate the present invention and do not limit the appended claims, and various changes and modifications to the embodiments within the scope and spirit of the present invention It is obvious to a person skilled in the art that this is possible, and it goes without saying that such variations and modifications fall within the scope of the appended claims.

Examples and Comparative Examples

The adhesive composition of Example 1 was applied to one surface of an aluminum foil (manufactured by AA8079-O) with a gravure roll, and an unstretched polypropylene film having a thickness of 40 µm was laminated on the other surface of the adhesive composition. Then, the unstretched polypropylene was irradiated with ultraviolet rays (2J of high pressure mercury) toward one side to laminate an aluminum foil and a polypropylene film.

Specific compositions of the exemplary embodiments are shown in Table 1 below. For example, in Example 1, after mixing 30 parts by weight of DP100 (Kolong Industries), 40 parts by weight of aromatic vinyl monomer instyrene (TCI), and 30 parts by weight of epoxy compound ST3000 (Kukdo Chemical), a cationic initiator TTA UV-692 (Tetrachem) ) 3 parts by weight, and 1 part by weight of the radical initiator LUPEROX® 223M75 (ARKEMA).

In addition, specific compositions of the exemplary comparative examples are shown in Table 2 below.

In addition, the base mixtures included in each Example and Comparative Example were prepared by mixing for about 1 hour.

division Example One 2 3 4 5 6 7 8 9 10 11 12 13 Furtherance tackifier A 30 10 50 40 B 30 C 30 30 30 D 30 30 30 30 30 Aromatic vinyl monomer I 40 40 40 40 50 10 50 II 40 40 40 40 40 III 40 epoxy compound G 30 30 30 30 40 40 10 you 30 30 30 NS 30 20 20 Acrylic monomer It's 10 ii 10 cationic initiator X 3 3 3 3 3 3 3 3 3 3 3 3 3 radical initiator Y One One One One One One One One One One One One Z One

division comparative example One 2 3 4 5 Furtherance tackifier A 40 5 60 50 B C D 60 Aromatic vinyl monomer I 55 20 50 II III epoxy compound a 45 20 50 50 b c Acrylic monomer It's ii cationic initiator X 3 3 3 3 radical initiator Y One One One One Z

The abbreviations in Tables 1 and 2 above refer to the following resins or compounds.

A: DP100, petroleum resin, made by Kolon Industries

B: P120, petroleum resin, made by Kolon Industries

C: Kristalex F85, petroleum resin, made by Eastman

D: Poly-Pale, rosin-based resin, made by Eastman

I: Styrene, made by TCI

II: Vinyltoluene (m-,p-mixture), TCI agent

III: 4-tert-Butylstyrene, made by TCI

a: ST3000, made by Kukdo Chemical

b: LD203, made by Kukdo Fine Chem

c: DE204, made by Kukdo Fine Chem

i: 2-Hydroxyethylacrylate, TCI agent

ii: Glycidyl Methacrylate, TCI agent

X: TTA UV-692, made by Tetrachem

Y: LUPEROX® 223M75, di-2-ethylhexyl peroxydicarbonate, manufactured by ARKEMA

Z: LUPEROX® 546M75, tert-amyl peroxyneodecanoate, manufactured by ARKEMA

Experimental example

The physical properties of the adhesive layers prepared in Examples and Comparative Examples according to Tables 1 and 2 were measured in the following manner. The measurement results are shown in Table 3 below.

division Adhesive strength electrolytic resistance formability Example One ○ ◎ ○ 2 ○ ○ ◎ 3 ◎ ○ ○ 4 ○ ◎ ○ 5 ○ ○ ○ 6 ◎ ○ ◎ 7 ○ ◎ ○ 8 ◎ ○ ○ 9 ○ ○ ◎ 10 ◎ ◎ ○ 11 ○ ◎ ◎ 12 ◎ ○ ○ 13 ○ ○ ○ comparative example One X X ○ 2 X ○ ○ 3 X ○ ○ 4 X ○ ○ 5 ○ ○ X

(1) Adhesive strength evaluation

A specimen was prepared by cutting the laminate of aluminum and unstretched polypropylene prepared in Examples or Comparative Examples to have a width of 15 mm and a length of 100 m. Then, the T-Peel peel force of the specimen was measured using an autograph (AG-1S, SHIMADZU). The peeling speed was 24 m/min.

◎ (excellent): 8 N/15 mm or more

○ (Good): 6 N/15 mm to less than 8 N/15 mm

△ (less than): 4 N/15mm to less than 6 N/15mm

X (bad): less than 4 N/15mm

(2) Electrolytic resistance evaluation

Each of the Examples and Comparative Examples was 15 mm in length, cut to a length of 100 m to prepare a specimen, and immersed in an electrolyte solution (dimethyl carbonate: ethyl carbonate = 1: 2 + Li salt) in an atmosphere of 85 °C. Thereafter, for each specimen, the laminate strength between the core of the aluminum foil and the unstretched polypropylene film was measured immediately after immersion, 5 days after immersion, 10 days after immersion, and 14 days after immersion. Detailed evaluation criteria of the laminate strength are as follows.

◎ (Excellent): No change in laminate strength

○ (Good): Retention of laminate strength of 60% or more

△ (less than): 30% or more retention of laminate strength

X (bad): delamination

(3) Formability evaluation

The above Examples and Comparative Examples were molded into a blank shape of 110 mm × 180 mm, respectively. In detail, single-stage bulging molding was performed as a straight mold with a free molding height, and the moldability was compared by the molding height of each sample. Detailed evaluation criteria of molding height are as follows.

◎ (excellent): 7 mm or more

○ (Good): 6 mm to less than 7 mm

△ (less than): 5 mm to less than 6 mm

X (bad): less than 5 mm

In the above-described examples, the adhesive strength, the electrolytic resistance, and the moldability were all good or higher. In addition, most of the examples were found to be excellent in one or more items of adhesive strength, electrolytic resistance, and moldability.

In particular, Example 6 showed that both adhesive strength and moldability were excellent, Example 10 showed that both adhesive strength and electrolytic resistance were excellent, and Example 11 showed that both electrolytic resistance and moldability were excellent.

On the other hand, in the comparative example, at least one of adhesive strength, electrolytic resistance, and moldability was found to be poor.

1: Battery packaging material 2: Exterior material layer
3: Sealant 4: Metal foil
5: second adhesive layer 6: first adhesive layer

Claims (12)

Consists of a base mixture and an initiator,
The base mixture is 10 to 50 parts by weight of a total of 100 parts by weight of a tackifier comprising at least one selected from the group consisting of polyterpene-based resins, rosin-based resins, and petroleum resins; 10 to 50 parts by weight of an aromatic vinyl monomer; and 10 to 40 parts by weight of an epoxy compound,
The content of the initiator includes 0.1 to 5 parts by weight of the total 100 parts by weight of the composition,
The base mixture does not contain a polypropylene-based resin,
An adhesive composition for battery packaging materials, which is prepared in a solvent-free type.
delete According to claim 1,
The petroleum resin comprises at least one selected from the group consisting of an aliphatic petroleum resin, an alicyclic petroleum resin, a copolymer-based petroleum resin, and a hydrogenated petroleum resin, an adhesive composition.
According to claim 1,
The base mixture further comprises an acrylic monomer, the adhesive composition.
5. The method of claim 4,
The content of the acrylic monomer is 30 parts by weight or less based on 100 parts by weight of the base mixture, the adhesive composition.
According to claim 1,
The initiator comprises a radical initiator and a cationic initiator, the adhesive composition.
delete delete delete sealant layer;
a metal foil laminated on the sealant layer; and
a first adhesive layer bonding the sealant layer and the metal foil;
The first adhesive layer comprises the adhesive composition according to claim 1, a battery packaging material.
11. The method of claim 10,
The sealant layer comprises a polypropylene-based resin, a battery packaging material.
11. The method of claim 10,
A battery packaging material, which is laminated on the metal foil and further comprises an exterior substrate layer comprising polyamide resin, polyethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, or a mixture thereof.

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