KR20220094708A - Film for packaging polymer cell - Google Patents

Abstract

The present invention provides a film for packaging a cell, comprising: a first base layer; a metal layer disposed inside the first base layer; a second base layer disposed inside the metal layer; and an adhesive layer disposed between the metal layer and the second base layer, wherein the adhesive layer includes one or more acid-modified resins selected from the group consisting of an acid-modified polyolefin resin having a melting temperature (Tm) of 65 to 75 ℃. Therethrough, the present invention may provide the film for packaging the cell, which has high temperature (120℃ or more) stability, high strength and adhesive durability (Al/thermal bonding layer), gas barrier properties, sealing properties, pinhole resistance, chemical stress resistance and high barrier properties.

Description

Film for polymer battery packaging {FILM FOR PACKAGING POLYMER CELL}

The present invention relates to a packaging material for a polymer battery.

A polymer battery, also called a lithium secondary battery, is a battery that has a polymer electrolyte and generates an electric current by the movement of lithium ions.

The polymer battery is composed of a positive electrode current collector material/positive electrode active material layer/electrolyte layer/negative electrode active material layer/negative electrode current collector material and an exterior body for packaging them. As a packaging material for forming an exterior body, a metal tube obtained by press-working metal to form a container in a cylindrical shape or a rectangular parallelepiped shape has been used.

Since the outer wall of the container is hard and the shape of the battery itself is limited in such a metal tube, the degree of freedom of shape is low. For this reason, in recent years, a multilayer film is used as a packaging material.

In the case of a multilayer film, it consists of a base material layer, an aluminum layer, and a heat-adhesive resin layer at least. Such a multilayer film has been used by processing it into a desired shape using press working or the like. However, it has been pointed out that the multilayer film is weak in terms of durability. In particular, in the case of lithium ion polymer batteries, durability decreases due to temperature rise due to heat generation during axial/discharge, and strongly permeable solvents such as aprotic solvents such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, or ethyl methyl carbonate There was a durability problem due to external leakage of a highly active electrolyte containing

In Japanese Patent No. 4,559,547, acid-modified polyolefin resin is applied to improve adhesion between an aluminum layer with excellent gas barrier properties and a heat-adhesive resin layer, but the adhesive strength with the metal layer is not stable and the adhesive strength is not uniform. had a problem.

However, in the case of acid-modified polyolefin, the melting temperature is 90°C to 110°C. Therefore, there was a problem in terms of durability such as exfoliation and leakage of electrolyte due to not being able to withstand the high temperature (120°C or more) generated during charging/discharging of the battery.

In addition, there was a problem that the adhesive strength with the metal layer was not stable and uniform.

Japanese Patent No. 4,559,547

The technical tasks to be achieved by the present invention are high temperature (over 120 °C) stability, strength, adhesion durability (Al/heat adhesive layer), gas barrier properties, sealing properties, pinhole resistance, chemical stress resistance, And to provide a film for polymer battery packaging excellent in barrier properties (High barrier).

The present invention, as a means for solving the above problems,

a first base layer; a metal layer disposed inside the first base layer; a second base layer disposed inside the metal layer; and an adhesive layer disposed between the metal layer and the second base layer,

The adhesive layer consists of at least one essential acid-modified resin selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and optionally contains an acid-modified polyolefin resin It provides a film for battery packaging.

According to the present invention, one or more essential acid-modified resins selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and optionally acid-modified polyolefin resin High-temperature (over 120°C) stability through an adhesive layer containing It is possible to provide a film for battery packaging having high barrier properties and high barrier properties.

The present invention is a first base layer; a metal layer disposed inside the first base layer; a second base layer disposed inside the metal layer; and an adhesive layer disposed between the metal layer and the second base layer,

The adhesive layer consists of at least one essential acid-modified resin selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and optionally contains an acid-modified polyolefin resin It relates to a film for battery packaging.

The adhesive layer is a film for battery packaging that has excellent heat resistance, good pinhole resistance, and excellent adhesive strength with aluminum by processing the above-described acid-modified resin by T-die extrusion method or dry lamination method. can provide

Hereinafter, the battery packaging film of the present invention will be specifically described as follows.

In the present invention, the first base layer is a polyolefin resin such as polypropylene; aliphatic-aromatic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polyethylene naphthalate; Polycaprolactam (Nylon 6), polyhexamethylene adipate (Nylon 6.6), a copolymer of nylon 6 and nylon 6.6, polylauryllactam (Nylon 12), polyhexamethylene sebacamide (Nylon 6.10), or poly ( polyamide resins such as meta-xylene adipamide) (MXD6) and the like; And it may include any one or more selected from the group consisting of polycarbonate.

The first base layer may be laminated to improve required physical properties, for example, pinhole resistance and insulation properties. When the first base layer is laminated, the first base layer includes at least one resin layer of two or more layers, and the thickness of each layer is 5 μm or more, for example, 6 to 50 μm, 10 to 20 μm. have.

In one embodiment, the first base layer is a polyethylene terephthalate film, a film selected from the group consisting of a nylon film and a polypropylene film is formed as a single layer or a multi-layer. In this case, it is possible to improve external surface friction, heat resistance, flexibility, durability, bendability, and barrier properties, as well as improve mechanical properties.

In an embodiment, the first base layer may use a film obtained by biaxially stretching the base layer materials.

In the present invention, the metal layer is not particularly limited that it can impart gas barrier properties, for example, aluminum or copper can be suitably used. Among them, aluminum can be used in consideration of cost and workability such as bonding.

In one embodiment, if it is a metal excellent in barrier properties, pin hole resistance and workability, there is no particular suggestion, and general soft aluminum or aluminum having an iron content of 10 wt% or less may be used. In this case, when the iron content exceeds 10 wt%, workability may be deteriorated.

In addition, in the case of the aluminum layer, in order to prevent the problem of aluminum corrosion caused by hydrogen fluoride generated by electrolyte and moisture, if the aluminum layer is treated with either phosphate treatment, chromate treatment, zirconium treatment, or titanium treatment, corrosion is performed. can prevent

Furthermore, in order to further increase the adhesive strength between the aluminum layer and the heat bonding layer, an anchor coating agent of an organic titanium-based, isocyanate-based, polyurethane-based, amine-based, or polybutadiene-based anchor coating agent is used. can

The metal layer preferably has a thickness of 10 μm to 120 μm, and when the thickness of the metal layer is less than 10 μm, pinholes may occur.

In the present invention, the adhesive layer is made of one or more essential acid-modified resins selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and optionally acid-modified poly It may include an olefin resin.

인 것을 사용할 수 있고, 이러한 산변성 폴리올레핀 수지는 용융 온도(Tm)가 65 내지 75℃인 산변성 폴레올레핀 수지는 용융 온도(Tm)가 65 내지 75℃인 산변성 폴리프로필렌 또는 용융 온도(Tm)가 65 내지 75℃인 산변성 폴리에틸렌을 포함한다.In addition, in the present invention, the acid-modified polyolefin resin has a melting temperature (Tm) of 65 to 75

may be used, and the acid-modified polyolefin resin has a melting temperature (Tm) of 65 to 75° C. The acid-modified polyolefin resin has a melting temperature (Tm) of 65 to 75° C., acid-modified polypropylene or melting temperature (Tm) contains acid-modified polyethylene of 65 to 75 °C.

In addition, acid-modified butadiene rubber, acid-modified styrene (Styrene)-butadiene rubber is, for example, acid-modified acrylonitrile-butadiene rubber, acid-modified styrene (Styrene)- These include ethylene rubber, acid-modified Styrene-ethylene-butylene-styrene rubber, and Styrene-isoprene-styrene rubber.

In addition, the content of the polar acid component of the acid-modified resin is, for example, 0.01wt% to 15wt%, or 4wt% to 10wt%. When the content of the polar acid component is less than 0.01wt%, the adhesive strength between the metal layer and the second base layer may be weakened, and if it exceeds 15wt%, post-processability may be deteriorated.

In the present invention, acid modification is a graft copolymerization reaction of an unsaturated carboxylic acid or anhydride thereof such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, citraconic acid, citraconic anhydride, itaconic acid, or itaconic anhydride. can be introduced through

In another embodiment, acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and acid-modified polyolefin resin may be graft-modified in a solvent and acid-modified. That is, the solvent, the resin in the reactor. A liquid resin prepared by mixing the carboxylic acid or its anhydride, and a catalyst and uniformly grafting an acid toilet to the resin under an appropriate pressure and temperature may be used.

In this way, when the acid toilet is grafted in a solvent, the acid toilet is uniformly grafted in contrast to the conventional method in which the solid polymer is simply melted and mixed using heat (melting compounding). Therefore, there is an effect of uniformly and stably increasing the adhesive strength with the metal layer under the same conditions.

Examples of the solvent used in the reactor in the present invention include ethanol, methanol, cyclohexane, normal nucleic acid, toluene, benzene, pure water, and dichloroethylene. any one or more selected from the group consisting of dichloroethane, methanol, carbon tetrachloride, acetone, ortho-dichlorobenzene, methyl acetate, xylene, chlorobenzene, chloroform, tetrachloroethane, tetrachloroethylene and trichloroethylene, and uniform Toluene can be used in terms of making a liquid phase.

In particular, the acid-modified polyolefin in a solvent has a melting temperature (Tm) of 65 to 75° C., so it is distinguished from acid-modified polyolefin that has been acid-modified by melt mixing, or acid-modified polyolefin introduced with an acid group by graft copolymerization. .

In an embodiment, the acid-modified resin may be mixed with other resins as needed. Resins that can be mixed with the acid-modified resin include polyolefins such as polypropylene or polyethylene; α-olefin-acrylic acid ester copolymers such as propylene-acrylic acid ester copolymers; ?-olefin-methacrylic acid ester copolymers such as propylene-methacrylic acid ester copolymers; acetate copolymers such as ethylene vinyl acetate copolymer or ethylene butyl acetate copolymer (EBA); elastomers such as ethylene butyl rubber (EBR), ethylene acrylic acid copolymer (EAA), or ethylene methacrylic acid copolymer (EMAA); or an ionomer such as a zinc ionomer or a sodium ionomer, but is not limited thereto.

In the present invention, the second base layer may use the same resin as the above-described first base layer without limitation. polyolefin resins such as, for example, polypropylene resins or polyethylene resins; polyester resins such as polyethylene terephthalate and polyethylene naphthalate; and at least one resin selected from the group consisting of polyamide resins such as aliphatic polyamide or aromatic polyamide. In addition, similar to the first substrate, one or more films may be laminated and used as needed.

In the present invention, the adhesive layer/second base layer structure among the multilayer structure of the first base layer/metal layer/adhesive layer/second base layer is, for example, as follows 1) to 15).

One) Acid-modified nylon layer / polyethylene layer

2) Acid-modified nylon layer / polypropylene layer

3) Acid-modified nylon layer / Polyethylene and polypropylene mixed layer

4) Acid-modified PBT layer / polyethylene layer

5) Acid-modified PBT layer / polypropylene layer

6) Acid-modified PBT layer / Polyethylene and polypropylene mixed layer

7) Acid-modified PET layer / Polyethylene layer

8) Acid-modified PET layer / polypropylene layer

9) Acid-modified PET layer / Polyethylene and polypropylene mixed layer

10) Acid-modified polypropylene layer / polypropylene layer having a melting temperature (Tm) of 65 to 75°C

11) Acid-modified polypropylene layer / polyethylene layer having a melting temperature (Tm) of 65 to 75°C

12) Acid-modified polypropylene layer having a melting temperature (Tm) of 65 to 75°C / Polyethylene and polypropylene mixed layer

13) Acid-modified polyethylene layer / polypropylene layer having a melting temperature (Tm) of 65 to 75°C

14) Acid-modified polyethylene layer / polyethylene layer having a melting temperature (Tm) of 65 to 75°C

15) Acid-modified polyethylene layer having a melting temperature (Tm) of 65 to 75°C / Polyethylene and polypropylene mixed layer

In the present invention, it is possible to increase the barrier properties of the electrolyte solution and improve the pinhole resistance by additionally including an adhesion reinforcing layer between the adhesive layer and the second substrate.

In the present invention, the adhesion reinforcing layer may be, for example, an acid-modified polyolefin resin. In an embodiment, when acid-modified polypropylene or acid-modified polypropylene having a melting temperature (Tm) of 65 to 75° C. is used, heat resistance may be improved.

In the present invention, the multilayer structure of the adhesive layer/adhesion reinforcing layer/second base layer is as shown in 16) to 27) below, for example.

One) Acid-modified nylon layer/ Acid-modified PP layer/ Polyethylene layer

2) Acid-modified nylon layer / Acid-modified PP layer / Polypropylene layer

3) Acid-modified nylon layer / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

4) Acid-modified PBT layer / Acid-modified PP layer / Polyethylene layer

5) Acid-modified PBT layer / Acid-modified PP layer / Polypropylene layer

6) Acid-modified PBT layer / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

7) Acid-modified PET layer/ Acid-modified PP layer/ Polyethylene layer

8) Acid-modified PET layer / Acid-modified PP layer / Polypropylene layer

9) Acid-modified PET layer/ Acid-modified PP layer/ Polyethylene and polypropylene mixed layer

10) Acid-modified PP / acid-modified PP layer / polyethylene layer having a melting temperature (Tm) of 65 to 75 °C

11) Acid-modified PP / acid-modified PP layer / polypropylene layer having a melting temperature (Tm) of 65 to 75 °C

12) Acid-modified PP/acid-modified PP layer with a melting temperature (Tm) of 65 to 75°C/polyethylene and polypropylene mixed layer

13) Acid-modified Butadiene rubber/ Polyethylene and polypropylene mixed layer

14) Acid-modified Styrene-Butadiene Rubber/ Polyethylene and Polypropylene Mixed Layer

15) Acid-modified Butadiene rubber / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

31) Acid-modified Styrene-Butadiene rubber / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

In one embodiment, the battery packaging film of the present invention,

a first base layer in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed in a single layer or in multiple layers;

an aluminum layer disposed inside the first base layer;

a second base layer disposed inside the metal layer and including polypropylene or a mixture of polyethylene and polypropylene; and

and an adhesive layer disposed between the aluminum layer and the second base layer and including at least one acid-modified resin selected from the group consisting of acid-modified polyethylene terephthalate, acid-modified polybutylene terephthalate, and acid-modified nylon.

In another embodiment, the battery packaging film of the present invention,

a first base layer in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed in a single layer or in multiple layers;

an aluminum layer disposed inside the first base layer;

a second base layer disposed inside the metal layer and including polypropylene or a mixture of polyethylene and polypropylene; and

At least one selected from the group consisting of acid-modified polyethylene having a melting temperature (Tm) of 65 to 75°C and acid-modified polypropylene having a melting temperature (Tm) of 65 to 75°C, disposed between the aluminum layer and the second base layer and an adhesive layer comprising an acid-modified resin.

Here, several methods may be used for lamination of the metal layer and the adhesive layer of the present invention. The first method is a method of heat-sealing by applying pressure to the metal layer and the adhesive layer using a heated roll. The second method is to heat-seal the metal layer while extruding the adhesive layer resin with a T-die extruder. In addition, the metal layer and the adhesive layer film may be laminated through a dry lamination method.

In addition, the method of bonding the first base layer to the metal layer may be a one-component or two-component dry lamination method, but is not limited thereto.

The adhesive used in the dry lamination of the present invention is a cured polyurethane-based, polysilicon-based, acid-modified polypropylene, acid-modified polypropylene, or acid-modified polyolefin or polyacrylic-based adhesive grafted in a solvent. Adhesives may be used.

Hereinafter, the present invention will be described in more detail through Examples according to the present invention and Comparative Examples not according to the present invention, but the scope of the present invention is not limited by the Examples presented below.

[Examples 1 to 3, Comparative Examples 1 to 3]

In Examples 1 to 3 and Comparative Examples 1 to 3, films were prepared by bonding the components of each layer shown in Table 1 below in a 3-layer co-extrusion method or a T-die multi-layer co-extrusion method.

At this time, the first base layer was biaxially oriented nylon, and nylon 6.6 was used to a thickness of 15 μm, the metal layer had an iron content of 1% aluminum 40 μm, the adhesive layer had a thickness of 20 μm, and the second base layer was T-die cast. A film was prepared by laminating the processed polypropylene to a thickness of 40 μm.

In the present invention, it is possible to increase the barrier properties of the electrolyte solution and improve the pinhole resistance by additionally including an adhesion reinforcing layer between the adhesive layer and the second substrate.

In the present invention, the adhesion reinforcing layer may be, for example, an acid-modified polyolefin resin. In an embodiment, when acid-modified polypropylene or acid-modified polypropylene having a melting temperature (Tm) of 65 to 75° C. is used, heat resistance may be improved.

In the present invention, the multilayer structure of the adhesive layer/adhesion reinforcing layer/second base layer is as shown in 16) to 27) below, for example.

One) Acid-modified nylon layer/ Acid-modified PP layer/ Polyethylene layer

2) Acid-modified nylon layer / Acid-modified PP layer / Polypropylene layer

3) Acid-modified nylon layer / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

4) Acid-modified PBT layer / Acid-modified PP layer / Polyethylene layer

5) Acid-modified PBT layer / Acid-modified PP layer / Polypropylene layer

6) Acid-modified PBT layer / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

7) Acid-modified PET layer/ Acid-modified PP layer/ Polyethylene layer

8) Acid-modified PET layer / Acid-modified PP layer / Polypropylene layer

9) Acid-modified PET layer/ Acid-modified PP layer/ Polyethylene and polypropylene mixed layer

10) Acid-modified PP / acid-modified PP layer / polyethylene layer having a melting temperature (Tm) of 65 to 75 °C

11) Acid-modified PP / acid-modified PP layer / polypropylene layer having a melting temperature (Tm) of 65 to 75 °C

12) Acid-modified PP/acid-modified PP layer with a melting temperature (Tm) of 65 to 75°C/polyethylene and polypropylene mixed layer

13) Acid-modified Butadiene rubber/ Polyethylene and polypropylene mixed layer

14) Acid-modified Styrene-Butadiene Rubber/ Polyethylene and Polypropylene Mixed Layer

15) Acid-modified Butadiene rubber / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

31) Acid-modified Styrene-Butadiene rubber / Acid-modified PP layer / Polyethylene and polypropylene mixed layer

In one embodiment, the battery packaging film of the present invention,

a first base layer in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed in a single layer or in multiple layers;

an aluminum layer disposed inside the first base layer;

a second base layer disposed inside the metal layer and including polypropylene or a mixture of polyethylene and polypropylene; and

and an adhesive layer disposed between the aluminum layer and the second base layer and including at least one acid-modified resin selected from the group consisting of acid-modified polyethylene terephthalate, acid-modified polybutylene terephthalate, and acid-modified nylon.

In another embodiment, the battery packaging film of the present invention,

a first base layer in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed in a single layer or in multiple layers;

an aluminum layer disposed inside the first base layer;

a second base layer disposed inside the metal layer and including polypropylene or a mixture of polyethylene and polypropylene; and

At least one selected from the group consisting of acid-modified polyethylene having a melting temperature (Tm) of 65 to 75°C and acid-modified polypropylene having a melting temperature (Tm) of 65 to 75°C, disposed between the aluminum layer and the second base layer and an adhesive layer comprising an acid-modified resin.

Here, several methods may be used for lamination of the metal layer and the adhesive layer of the present invention. The first method is a method of heat-sealing by applying pressure to the metal layer and the adhesive layer using a heated roll. The second method is to heat-seal the metal layer while extruding the adhesive layer resin with a T-die extruder. In addition, the metal layer and the adhesive layer film may be laminated through a dry lamination method.

In addition, the method of bonding the first base layer to the metal layer may be a one-component or two-component dry lamination method, but is not limited thereto.

The adhesive used in the dry lamination of the present invention is a cured polyurethane-based, polysilicon-based, acid-modified polypropylene, acid-modified polypropylene, or acid-modified polyolefin or polyacrylic-based adhesive grafted in a solvent. Adhesives may be used.

Hereinafter, the present invention will be described in more detail through Examples according to the present invention and Comparative Examples not according to the present invention, but the scope of the present invention is not limited by the Examples presented below.

[Examples 1 to 3, Comparative Examples 1 to 3]

In Examples 1 to 3 and Comparative Examples 1 to 3, films were prepared by bonding the components of each layer shown in Table 1 below in a 3-layer co-extrusion method or a T-die multi-layer co-extrusion method.

At this time, the first base layer was biaxially oriented nylon, and nylon 6.6 was used to a thickness of 15 μm, the metal layer had an iron content of 1% aluminum 40 μm, the adhesive layer had a thickness of 20 μm, and the second base layer was T-die cast. A film was prepared by laminating the processed polypropylene to a thickness of 40 μm.

first base layer metal layer adhesive layer adhesive reinforcing layer 2nd base layer Adhesive method Example 1 Biaxially Stretched Nylon AL acid-modified nylon Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Example 2 Biaxially Stretched Nylon AL Acid-modified PBT Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Example 3 Biaxially Stretched Nylon AL Acid-modified PET Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Example 12 Biaxially Stretched Nylon AL Acid Modified Butadiene Rubber Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Example 13 Biaxially Stretched Nylon AL Acid Modified Styrene-Butadiene Rubber Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Example 14 Biaxially Stretched Nylon AL Acid-modified Styrene-Butadiene rubber: 70%
Acid-modified polypropylene having a melting temperature (Tm) of 65 to 75°C: 30% Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Comparative Example 1 Biaxially Stretched Nylon AL polyethylene Adhesive Strengthener polypropylene T-Dies multi-layer co-extruder Comparative Example 2 Biaxially Stretched Nylon AL Acid-modified polyethylene polypropylene T-Dies multi-layer co-extruder Comparative Example 3 Biaxially Stretched Nylon AL Acid-modified polypropylene polypropylene T-Dies multi-layer co-extruder Biaxially Stretched Nylon Nylon 66 Resin (Product Name: Kolon Plastic KP3355) AL Aluminum with 1% iron content Acid-modified PBT A product obtained by grafting 5% maleic anhydride to polybutylene terephthalate (trade name: Kolon Plastic KP513) with a twin compound device. Acid-modified PET A product obtained by grafting 5% maleic anhydride to polyethylene terephthalate (brand name: SK Chemicals BB8055) using a twin compound device. acid-modified nylon A product obtained by grafting 5% maleic anhydride to Nylon 66 (product name: Kolon Plastics KP3355) with a twin compound device. Adhesive Strengthener A product obtained by grafting 2% maleic anhydride to polypropylene (product name: Lotte Chemical SFC-550) polyethylene Linear low-density polyepylene (product name: Lotte Chemical UF315) acid-modified polyethylene
A product obtained by grafting 5% maleic anhydride to a linear low-density polyepylene (product name: Lotte Chemical UF315) using a twin compound device.
Acid-modified polypropylene: A product obtained by grafting 5% maleic anhydride to homopolypropylene (product name: Lotte Chemical SFC-550) using a twin compound device. Acid Modified Butadiene Rubber A product obtained by grafting 5% maleic anhydride to a product with a pattern viscosity of 43 using a twin compound device. acid metamorphosis
Styrene-Butadiene Rubber A product obtained by grafting 5% maleic anhydride to a product with a styrene content of 23.5% using a twin compound device. Acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75°C Polypropylene (PP) and α-olefine, random copolymer having a molecular weight of 50000-100000 were grafted by reacting 5 parts by weight of maleic anhydride compared to the polymer in a solution reaction method in a cyclohexane solvent.

- My Pinhole -

After applying stress (folding and unfolding) 100 times at room temperature (23°C), pinhole resistance (number of pinholes per 1m2 of coated area) was measured and shown in Table 2.

- Peeling Temperature -

The peeling temperature between the metal layer and the second base layer was measured while the temperature was raised at 5° C. intervals through an aging oven, and the results are shown in Table 2.

division pinhole resistance peeling temperature Example 1 0 195℃ Example 2 0 185℃ Example 3 0 200℃ Example 12 0 210℃ Example 13 0 210℃ Example 14 0 200℃ Comparative Example 1 100 120℃ Comparative Example 2 10 120℃ Comparative Example 3 15 145℃

As shown in Table 2, acid-modified nylon, acid-modified PBT resin, acid-modified PET, acid-modified butadiene rubber, and acid-modified styrene-butadiene rubber were heat-bonded with aluminum. In Examples 1 to 3, 12, 13, and 14, pinholes did not appear at all, whereas in Comparative Examples 1 to 3 using acid-modified ethylene, acid-modified polyethylene, and acid-modified polypropylene, 100, 10, and 15 pinholes were It was found that the pinhole resistance was significantly reduced.

In addition, in the peeling temperature, the peeling temperatures of Examples 1 to 3, 12, 13, and 14 were maintained at 180°C or higher, whereas in Comparative Examples 1 to 3, the peeling occurred when the peeling temperature was 150°C or higher.

-Measurement of barrier properties of organic solvents (water vapor permeability)-

The barrier properties (moisture permeability) of the organic solvent were measured for the second base layer not including the metal layer by the ASTM E96 CaCl ₂ method, and the results are shown in Table 3.

division Thickness (㎛) ethyl acetate methyl ethyl ketone
(MEK) n-nucleic acid carbon tetrachloride Example 1 70 2.5 1.0 0.2 0.1 Example 2 75 1.5 2.0 0.3 0.2 Example 3 75 1.0 1.5 0.2 0.15 Example 12 75 35 30 45 47 Example 13 75 30 25 40 42 Example 14 75 40 35 80 100 Comparative Example 1 85 350 230 2370 4150 Comparative Example 2 85 357 235 2385 4165 Comparative Example 3 80 76.6 55.4 785 2030

As shown in Table 3, it was found that the organic solvent barrier properties of Examples 1 to 3 exhibited very excellent organic solvent barrier properties (permeability) compared to Comparative Examples 1 to 3, 12, 13, and 14.

- Adhesive strength of metal layer/adhesive layer -

The aluminum layer was fixed to the shaft, and the adhesive strength (N/15 mm) was measured by pulling the heat-adhesive layer film at a speed of 50 mm per minute, and the results are shown in Table 4 below.

-Deep drawing-

Specimen: After taking horizontal * vertical = 140mm * 170mm

Pressure/Time = 0.382MPA/5sec to measure the increased depth.

division Adhesive strength of aluminum/heat adhesive layer
(N/15mm) formability
(deep drawing) Example 1 35 6.7 or higher Example 2 31 6.7 or higher Example 3 33 6.7 or higher Example 12 30 7.0 or higher Example 13 31 7.0 or higher Example 14 29 7.0 or higher Comparative Example 1 0.5 5.0 Comparative Example 2 25 6.0 Comparative Example 3 20 6.0

As shown in Table 4, Examples 1 to 3, 12, 13, and 14 were found to have an adhesive strength of at least 50% or more compared to Comparative Examples 1 to 3, and in Comparative Example 1 using a polyethylene resin, the metal layer and It can be seen that the adhesive strength of

Formability It was also found that Examples 1 to 3, 12, 13, and 14 improved the formability by 10% or more compared to Comparative Examples 1 to 3. Also, Examples 12, 13, 14 rather than Examples 1 to 3 It was confirmed that the moldability was better.

[Examples 1 to 3, Comparative Examples 1 to 3]

In Examples 1 to 3 and Comparative Examples 1 to 3, films were prepared by bonding the components of each layer shown in Table 5 below by a dry lamination method or a T-die multi-layer coextrusion method.

At this time, the first base layer was biaxially oriented nylon, and nylon 66 was used to a thickness of 15 μm, the metal layer was 40 μm aluminum with 1% iron content, the adhesive layer had a thickness of 20 μm, and the second base layer was T-die cast. A film was prepared by laminating the processed polypropylene to a thickness of 40 μm.

[Examples 4 to 7, 15, 16, 17 and Comparative Example 4]

In Examples 4 to 7, 15, 16, 17 and Comparative Example 4, the components of each layer shown in Table 5 below were adhered to each other by a dry lamination method or a T-die multi-layer co-extrusion method to prepare a film.

At this time, the thickness of the polyethylene terephthalate used for the first base layer is 12 μm, the thickness of the biaxially stretched nylon is 15 μm, and the metal has a thickness of 40 μm After bonding the first base layer and the metal layer through a dry lamination process. , the metal layer and the second base layer were T-die thermally bonded. In this case, the product thickness of the adhesive layer and the second base layer used in Examples 4 and 5 was processed to a thickness of 70 μm.

first base layer metal layer adhesive layer adhesive reinforcement layer 2nd base layer Extrusion method
(AL layer/heat adhesive layer/
Adhesive layer/most resistant resin layer)
Example 4 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% nylon adhesive layer Polyethylene and polypropylene each 50% mixed layer T-Dies
Extrusion processing Example 5 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% PBT adhesive layer Polyethylene and polypropylene each 50% mixed layer T-Dies
Extrusion processing Example 6 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75°C - Polyethylene and polypropylene each 50% mixed layer Dry lamination Example 7 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75°C adhesive layer Polyethylene and polypropylene each 50% mixed layer T-Dies extrusion Example 15 Biaxially Stretched Nylon AL Acid Modified Butadiene Rubber adhesive layer Polyethylene and polypropylene each 50% mixed layer T-Dies extrusion Example 16 Biaxially Stretched Nylon AL Acid Modified Styrene-Butadiene Rubber - Polyethylene and polypropylene each 50% mixed layer Dry lamination Example 17 Biaxially Stretched Nylon AL Acid-modified Styrene-Butadiene rubber: 70%
Acid-modified polypropylene having a melting temperature (Tm) of 65 to 75°C: 30% - Polyethylene and polypropylene each 50% mixed layer Dry lamination Comparative Example 4 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% polypropylene adhesive layer Polyethylene and polypropylene each 50% mixed layer T-Dies extrusion Acid-modified 5% PBT A product obtained by grafting 5% maleic anhydride to polybutylene terephthalate (product name: Kolon Plastic KP513) using a twin compound device. Acid-modified 5% PET A product obtained by grafting 5% maleic anhydride to polyethylene terephthalate (brand name: SK Chemicals BB8055) using a twin compound device. acid-modified nylon A product obtained by grafting 5% maleic anhydride to Nylon 66 (product name: Kolon Plastics KP3355) with a twin compound device. Acid-modified polypropylene A product obtained by grafting 5% maleic anhydride to homopolypropylene (product name: Lotte Chemical SFC-550) using a twin compound device. adhesive layer A polypropylene product obtained by grafting 5% maleic anhydride from homoPP (brand name: Lotte Chemical SFC-750) with a melt index of 8 using a twin compound device. Acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75°C Polypropylene (PP) and α-olefine, random copolymer having a molecular weight of 50000-100000 were grafted by reacting 5 parts by weight of maleic anhydride compared to the polymer in a solution reaction method in a cyclohexane solvent. polyethylene Linear low-density polyepylene (product name: Lotte Chemical UF315) polypropylene Homopolypropylene (product name: Lotte Chemical SFC-550) Acid Modified Butadiene Rubber A product obtained by grafting 5% maleic anhydride to a product with a pattern viscosity of 43 using a twin compound device. Acid Modified Styrene-Butadiene Rubber A product obtained by grafting 5% maleic anhydride to a product with a styrene content of 23.5% using a twin compound device.

- Environmental stress resistance-

In order to evaluate the environmental stress resistance, ESCR (Environmental Stress Cracking Resistance), ethylene carbonate, which is used as a secondary battery electrolyte, was prepared in a constant temperature bath to a temperature of 40 °C, and aluminum and After impregnating the heat-sealed Examples 4 to 7, 15, 16, and 17 Comparative Examples 1 and 4, the time for 50% peeling was measured, and the results are shown in Table 6.

division chemical stress resistance
(ESCR) Comparative Example 1 24hr Comparative Example 4 540hr Example 4 over 920hr Example 5 over 920hr Example 6 over 920hr Example 7 over 920hr Example 15 over 920hr Example 16 over 920hr Example 17 900hr

As shown in Table 6, Examples 4 to 7, 15, 16 using acid-modified nylon, acid-modified polybutylene terephthalate, and acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75° C. as adhesive layers, respectively , 17 compared to Comparative Examples 1 and 4 using acid-modified polypropylene, it can be confirmed that it has a maximum environmental stress resistance of 38 times or more.

In addition, Examples 6 and 7 using acid-modified 5% polypropylene having an acid-modified melting temperature (Tm) of 65 to 75° C., which were acid-modified in a solvent, were about 1.7 times compared to Comparative Example 4 using general acid-modified polypropylene. It was confirmed that the environmental stress resistance of

[Example 8]

After mixing 15 parts by weight of an ethylene acrylic acid copolymer (EXXON's trade name: ESCOR 5100) to 80 parts by weight of polybutylene terephthalate (PBT) resin grafted with maleic anhydride (MAH) at 5 wt%, an extruder (twin extruder) After making a thin film by using a T-die extruder, it was peeled off to prepare a heat-adhesive layer film having a thickness of 80 μm.

[Example 9]

Example 8 except that maleic anhydride (MAH) was prepared by mixing 15 parts by weight of EMMA (methyl methacrylate-ethylene copolymer) with 80 parts by weight of a 5 wt% grafted nylon (polyamide) resin to prepare a thin film A film was prepared in the same manner as described above.

[Comparative Example 5]

A film was prepared in the same manner as in Example 7, except that a thin film was prepared by extruding 1.5 wt% of maleic anhydride (MAH) grafted acid-modified polyethylene resin (LLDPE).

[Comparative Example 6]

A film was prepared in the same manner as in Example 7, except for preparing a thin film by extruding 5 wt% of maleic anhydride (MAH) grafted acid-modified polyethylene resin (HDPE).

- Gas barrier properties (gas permeability)-

For the films prepared in Examples 8 and 9, Comparative Examples 5 and 6, a gas permeability measuring device (S-69 type 160 ml) manufactured by Shibata Kagaku Kogyou Co., Ltd. was used. (Method for measuring oxygen permeability according to ASTM D 3985), and measured at a temperature of 23° C., the results are shown in Table 7.

Comparative Example/Example thickness Gas permeability (cc/m2/atm/24hr) Oxygen nitrogen carbon dioxide MEK (methyl ethyl ketone) Comparative Example 5 80㎛ 4500 800 17000 4500 Comparative Example 6 80㎛ 2100 420 8300 2100 Example 8 80㎛ 35 15 200 35 Example 9 80㎛ 40 20 250 40 This is a measure of gas barrier properties (gas permeability) by processing only the adhesive layer into a film.

As shown in Table 7, Examples 8 and 9 containing polybutylene terephthalate (PBT) or nylon (polyamide resin) as the adhesive layer according to the present invention were acid-modified polyethylene resin films (LLDPE) as adhesive layers. It can be seen that both gas barrier properties and organic solvent (MEK) barrier properties are about 40 times or more superior to those of Comparative Example 5, and it can be confirmed that they are very excellent compared to Comparative Example 6, which is an acid-modified polyethylene resin film (HDPE) as an adhesive layer. .

Therefore, when the film in which the metal layer and the adhesive layer or the second base layer are bonded according to the present invention is used as a packaging material for a polymer battery, a product having durability during long-term use can be provided.

[Examples 10 to 11]

In Examples 10 and 11, a packaging material was prepared in the same manner as in Example 4, except that acid-modified nylon having an acid-modified content of 5 parts by weight shown in Table 8 was used as the adhesive layer, and in Example 10, a metal layer A packaging material was prepared in the same manner as in Example 9, except that epoxy silane (trade name: GLYMO) was anchor-coated as an anchor coating agent.

first base layer metal layer adhesive layer adhesive reinforcing layer 2nd base layer Extrusion method Example 10 PET/Biaxially Stretched Nylon AL layer Acid-modified 5% nylon 50% each of polyolefin and polypropylene mixed layer Example 11 PET/Biaxially Stretched Nylon AL layer + anchor coating treatment Acid-modified 5% nylon 50% each of polyolefin and polypropylene mixed layer acid-modified nylon 5% maleic anhydride grafted to nylon 6.6 product (product name: Kolon Plastic KP3355)

division pinhole resistance
(100 times) Aluminum/Inner Layer Adhesive Strength
(N/15mm) Example 10 0 34 Example 11 0 38

Table 8 is the result of measuring the pinhole resistance and the adhesive strength between the aluminum/inner layer for Examples 10 and 11, and the method for measuring the pinhole resistance and the adhesive strength is the same as described above. As shown in Table 9, it can be seen that the adhesive strength is further improved by 10% when the aluminum is subjected to anchor coating.

Although the above has been described with reference to the preferred embodiment of the present invention, those skilled in the art can variously modify and change the present invention within the scope without departing from the spirit and scope of the present invention described in the claims below. You will understand that it can be done.

- Electrolyte resistance test -

To measure the electrolyte resistance, a pouch specimen was collected with a width of 15 mm and a length of 150 mm, impregnated with a standard electrolyte, and then the adhesive strength between aluminum and the adhesive layer was measured at 65℃ for one week.

Measure the T-type peel strength using UTM at a speed of 300 mm/min.

The evaluation method was measured by ASTM D1876, and the results are shown in Table 10.

division Aluminum/adhesive layer electrolyte resistance strength (N/15mm) 1Days 7Days Example 1 10.9 10.8 Example 2 11.2 10.9 Example 3 9.5 9.0 Example 12 14.5 14.8 Example 13 15.0 15.1 Example 14 14.0 14.0 Comparative Example 1 0.2 0.0 Comparative Example 2 5.0 4.0 Comparative Example 3 9.8 9.5

As shown in Table 10, Examples 1 to 3, 12, 13, and 14 had an electrolyte-resistant adhesive strength of at least 2 times or more at least 60% compared to Comparative Examples 1 to 3, 12, 13, and 14. , It was found that the electrolyte resistance strength was improved by about 40% in Examples 12, 13, and 14 than in Examples 1, 2, and 3, and moreover, it was confirmed that the strength of the electrolyte resistance did not decrease and was continuously maintained as time passed. have.

Claims (14)

a first base layer;
a metal layer disposed inside the first base layer;
a second base layer disposed inside the metal layer; and
An adhesive layer disposed between the metal layer and the second base layer,
The adhesive layer is composed of at least one essential acid-modified resin selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and optionally contains an acid-modified polyolefin resin film for battery packaging.
The method of claim 1,
The acid-modified polyolefin resin has a melting temperature (Tm) of 65 to 75°C for battery packaging.
The method of claim 1,
The first base layer is a battery packaging film comprising at least one selected from the group consisting of a polyolefin resin, an aliphatic-aromatic polyester resin, a polyamide resin, and a polycarbonate.
The method of claim 1,
The first base layer is a film for battery packaging in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed as a single layer or a multilayer.
The method of claim 1,
A film for battery packaging whose metal layer is an aluminum layer.
6. The method of claim 5,
The aluminum layer is a film for battery packaging treated with anti-corrosion treatment or anchor coating treatment.
The method of claim 1,
The adhesive layer is a copolymer of acid-modified polyethylene terephthalate, acid-modified polybutylene terephthalate, acid-modified polytrimethylene terephthalate, acid-modified polyethylene naphthalate, acid-modified nylon 6, acid-modified nylon 6.6, acid-modified nylon 6 and nylon 6.6. , acid-modified nylon 12, acid-modified nylon 6.10, or acid-modified polymetaxylene idipamide (MXD6), acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, Acid-modified acrynitrile-Butadiene rubber, Acid-modified Styrene-Butadiene Styrene rubber, Acid-modified Styrene-ethylene-butylene-styrene rubber, Styrene-isoprene-styrene rubber Film for battery packaging.
The method of claim 1,
The acid content of the acid-modified resin is 0.01wt% to 15wt% of the film for battery packaging.
The method of claim 1,
Acid-modified resin is a film for battery packaging in which the acid component is graft-modified in a solvent.
The method of claim 1,
The adhesive layer may include polyolefin, α-olefin-acrylic acid ester copolymer, α-olefin-methacrylic acid ester copolymer, acetate copolymer, and elastomer; Or a film for battery packaging further comprising an ionomer.
The method of claim 1,
The second base layer is a battery packaging film comprising at least one resin selected from the group consisting of polyolefin resin, polyester resin, and polyamide resin.
The method of claim 1,
A battery packaging film further comprising an adhesive reinforcing layer disposed between the second base layer and the adhesive layer.
The method of claim 1,
The adhesive reinforcing layer is a battery packaging film comprising an acid-modified polyolefin.
a first base layer in which a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film is formed in a single layer or in multiple layers;
an aluminum layer disposed inside the first base layer;
a second base layer disposed inside the metal layer and including polypropylene or a mixture of polyethylene and polypropylene; and
It is disposed between the aluminum layer and the second base layer,
It contains at least one essential acid-modified resin selected from the group consisting of acid-modified butadiene rubber, acid-modified styrene-butadiene rubber, and having a melting temperature (Tm) of 65 to 75° C. A battery packaging film comprising an adhesive layer comprising at least one acid-modified resin selected from the group consisting of acid-modified polyethylene and acid-modified polypropylene having a melting temperature (Tm) of 65 to 75°C.