KR101406982B1 - Film for packaging polymer cell - Google Patents

Abstract

The present invention provides a film for packaging cells. The film for packaging cells includes a first substrate layer; a metal layer which is placed inside the first substrate layer; a second substrate layer which is placed inside the metal layer; and an adhesive layer which is placed between the metal layer and the second substrate layer. The adhesive layer includes one or more types of acid-denatured resin among a group of acid-denatured polyester resin, acid-denatured polyamide resin, and acid-denatured polyolefin resin having a melting temperature (Tm) between 65 and 75°C. The film for packaging cells has high strength, adhesion stability, adhesion durability (Al/heat sealing layer), gas barrier properties, sealability, pin-hole resistance, chemical stress resistance, and high barrier properties.

Description

{FILM FOR PACKAGING POLYMER CELL}

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

Polymer batteries, also called lithium secondary batteries, are cells that have a polymer electrolyte and generate electric current by the movement of lithium ions.

The polymer battery is composed of a positive electrode current collector / a positive electrode active material layer / an electrolyte layer / a negative electrode active material layer / a negative electrode current collector and an external body for packing them. As a packaging material for forming an external body, a metal pipe having conventionally metal pressed into a cylindrical shape or a rectangular parallelepiped shape has been used.

Such a metal pipe has a reduced degree of freedom in its shape because the shape of the battery itself is limited because the outer wall of the container is hard. For this reason, multilayer films have recently been used as a packaging material.

In the case of a multilayer film, at least a base layer, an aluminum layer, and a thermally adhesive resin layer are formed. Such a multilayer film has been used by processing into a desired shape using a 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 a lithium ion polymer battery, the durability of the lithium ion polymer cell due to heat generation due to heat generation during shaft / discharge is lowered, and a strong permeation solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, There is a durability problem due to the outflow of the highly active electrolyte including the electrolyte.

Japanese Patent No. 4,559,547 discloses an acid-modified polyolefin resin in order to improve the adhesion between the aluminum layer and the heat-bonding resin layer, which is excellent in gas barrier property, but the bonding strength with the metal layer is not stable and the bonding strength is not uniform There was a problem.

Japanese Patent No. 4,559,547

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to provide a method of manufacturing a semiconductor device, which is excellent in strength, adhesion uniformity, adhesion persistence (Al / thermal adhesion layer), gas barrier property, sealing property, barrier film for packaging a polymer battery.

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,

Wherein the adhesive layer comprises at least one acid-modified resin selected from the group consisting of an acid-modified polyester resin, an acid-modified polyamide resin and an acid-modified polyolefin resin.

According to the present invention, by using at least one acid-modified resin selected from the group consisting of an acid modified polyester resin, an acid modified polyamide resin and an acid modified polyolefin resin as an adhesive layer, a high strength and adhesion persistence (Al / It is possible to provide a film for packaging a battery having excellent adhesion uniformity, excellent gas barrier property, sealing property, pinhole property, chemical resistance, and barrier property.

1 is a graph of an acid-denatured 5% polypropylene obtained by graft-modifying an acid in a solvent and measuring the acid-denatured content by differential scanning calorimetry (DSC).
2 is a graph of an acid-modified 5% polypropylene having an acid group introduced by graft copolymerization measured by differential scanning calorimetry (DSC).

The present invention relates to a liquid crystal display 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 comprises at least one acid-modified resin selected from the group consisting of an acid-modified polyester resin, an acid-modified polyamide resin and an acid-modified polyolefin resin.

The adhesive layer is prepared by processing the above-mentioned acid-modified resin by a T-die extrusion method or a dry lamination method to produce a battery packaging film having excellent heat resistance, good pinhole property, .

Hereinafter, the battery packaging film of the present invention will be described in detail.

In the present invention, the first base layer may be a polyolefin resin such as polypropylene; Aliphatic-aromatic polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate or polyethylene naphthalate; (Nylon 6), polyhexamethylene adipate (Nylon 6.6), copolymers of Nylon 6 and Nylon 6.6, polylauryl lactam (Nylon 12), polyhexamethylene Cevacamide (Nylon 6.10), or poly Meta-xylylene adipamide) (MXD6), and the like; And a polycarbonate. The term " a "

The first base layer may be laminated in order to improve the required physical properties such as pinhole resistance and insulation. When the first base layer is laminated, it is preferable that the first base layer contains at least one resin layer of two or more layers and the thickness of each layer is at least 5 탆, for example, 6 to 50 탆 and 10 to 20 탆 have.

In one embodiment, the first substrate layer is formed as a single layer or multiple layers of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film, and a polypropylene film. In this case, it is possible not only to improve external surface friction, heat resistance, flexibility, durability, bending property and barrier property, but also to improve mechanical properties.

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

In the present invention, the metal layer is not particularly limited as long as gas barrier properties can be imparted. For example, aluminum or copper can be suitably used. Among them, aluminum can be used in consideration of workability such as price and bonding.

In one specific example, no special proposal is made if the metal is superior in terms of barrier property, pin hole property and workability, and aluminum having general soft aluminum or iron content of 10 wt% or less can be used. At this time, when the iron component content exceeds 10 wt%, the workability may be deteriorated.

In order to prevent aluminum corrosion caused by hydrogen fluoride generated by electrolytes and moisture in the case of aluminum layer, when the aluminum layer is treated with aluminum by selecting one of phosphate treatment, chromate treatment zirconium treatment, or titanium nitride treatment, Can be prevented.

Further, in order to further increase the bonding strength between the aluminum layer and the thermal adhesive layer, anchor coating treatment is performed using an organic titanium, isocyanate, polyurethane, amine or polybutadiene anchor coating agent .

The thickness of the metal layer is preferably in the range of 10 to 120 탆. When the thickness of the metal layer is less than 10 탆, pinholes are likely to occur. If the thickness is more than 120 탆, the workability is deteriorated and the material cost burden may increase.

In the present invention, the adhesive layer may include at least one selected from the group consisting of an acid-modified polyester resin, an acid-modified polyamide resin and an acid-modified polyolefin resin.

The acid-modified polyester resin includes acid-modified aliphatic-aromatic polyester resins such as acid-modified polyethylene terephthalate, acid-modified polybutylene terephthalate, acid-modified polytrimethylene terephthalate or acid-modified polyethylene naphthalate . Acid modified nylon 6, acid denaturated nylon 6.6, acid denaturated nylon 6 and nylon 6.6, acid denaturated nylon 12, acid denaturated nylon 6.10, acid denatured polyamide resin, Adipamide) (MXD6), and the like.

In the present invention, the acid-modified polyolefin resin having a melting temperature (Tm) of 65 to 75 ° C can be used. The acid-modified polyolefin resin having a melting temperature (Tm) of 65 to 75 ° C has a melting temperature (Tm) Modified polypropylene having a melting temperature (Tm) of 65 to 75 占 폚 or an acid-modified polyethylene having a melting temperature (Tm) of 65 to 75 占 폚.

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

In the present invention, the acid modification is carried out by graft copolymerization of an unsaturated carboxylic acid or an anhydride thereof such as maleic acid, maleic anhydride, acrylic acid, methacrylic acid, citraconic acid, citraconic anhydride, itaconic acid, As shown in FIG.

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

In the case of grafting the acid toilet bowl in the solvent, the acid toilet bowl is uniformly grafted in comparison with the grafting of the toilet bowl by melting and mixing the polymer by using the conventional solid state polymer Therefore, it is effective to uniformly and stably increase the bonding 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, dichloroethylene. At least one selected from the group consisting of dichloroethane, methanol, carbon tetrachloride, acetone, ortho-dichlorobenzene, methyl acetate, xylene, chlorobenzene, chloroform, tetrachloroethane, tetrachlorethylene and trichlorethylene, Toluene can be used to make one liquid phase.

Particularly, polyolefins which have undergone acid modification in a solvent are distinguished from acid-modified polyolefins which have been acid-modified by melting and mixing in terms of having a melting temperature (Tm) of 65 to 75 ° C or acid-modified polyolefins into which acid groups have been introduced by graft copolymerization .

In the specific examples, the acid-modified resin may be mixed with other resins as needed. Resins that can be used in admixture with the acid-modified resin include polyolefins such as polypropylene or polyethylene; Alpha -olefin-acrylic acid ester copolymers such as propylene-acrylic acid ester copolymers; Alpha -olefin-methacrylic acid ester copolymer such as propylene-methacrylic acid ester copolymer; Acetate copolymers such as ethylene vinyl acetate copolymers or ethylene butyl acetate copolymers (EBA); An elastomer 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 the present invention is not limited thereto.

For example, an acid-modified 5% polypropylene having a melting temperature (Tm) of 65 to 75 ° C is prepared by reacting a polypropylene having a molecular weight of 50000 to 100000 in a cyclohexane solvent with 5 parts by weight of maleic anhydride relative to the polymer .

FIG. 1 is a graph of an acid-denatured 5% polypropylene obtained by graft-modifying an acid in a solvent by differential scanning calorimetry (DSC), and FIG. 2 is a graph showing an acid-denatured 5% polypropylene obtained by introducing an acid group by graft- And a differential scanning calorimetry (DSC).

As shown in Fig. 1, the melting temperature (Tm) of an acid-denatured 5% polypropylene prepared by grafting 5 parts by weight of maleic anhydride to the polymer in a polypropylene having a molecular weight of 50000 to 100000 in cyclohexane solvent by a solution reaction method, As shown in Fig. 2, 5% of anhydrous maleic anhydride was grafted onto an acid-modified polypropylene homopolypropylene (trade name: Lotte Chemical H3400) with an acid denatured 5% poly The melting temperature (Tm) of propylene was 162.37 ° C.

Therefore, polyolefins subjected to acid modification in a solvent are distinguished from acid-modified polyolefins obtained by melt-mixing and acid-modified polyolefins or acid-modified polyolefins obtained by graft copolymerization with acidic groups and having a melting temperature (Tm) of 65 to 75 ° C can confirm.

In the present invention, the same resin as the above-described first base layer can be used for the second base layer without limitation. Polyolefin resins such as polypropylene resin or polyethylene resin; Polyester resins such as polyethylene terephthalate or polyethylene naphthalate; And a polyamide resin such as an aliphatic polyamide or an aromatic polyamide. Further, similar to the first substrate, one or more films may be laminated and used if necessary.

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

1) 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) An acid-modified polypropylene layer having a melting temperature (Tm) of 65 to 75 占 폚 / polypropylene layer

11) An acid-modified polypropylene layer / polyethylene layer having a melting temperature (Tm) of 65 to 75 占 폚

12) An acid-modified polypropylene layer having a melting temperature (Tm) of 65 to 75 DEG C / polyethylene and a polypropylene mixed layer

13) An acid-modified polyethylene layer having a melting temperature (Tm) of 65 to 75 占 폚 / polypropylene layer

14) An acid-modified polyethylene layer / polyethylene layer having a melting temperature (Tm) of 65 to 75 占 폚

15) an acid-modified polyethylene layer having a melting temperature (Tm) of 65 to 75 DEG C / polyethylene / polypropylene mixed layer

In the present invention, an adhesion strengthening layer may be additionally provided between the adhesive layer and the second substrate to improve the barrier property of the electrolyte solution and improve the pinhole resistance.

In the present invention, for example, an acid-modified polyolefin resin may be used as the adhesive strengthening layer. In the specific examples, when acid-modified polypropylene or acid-modified polypropylene having a melting temperature (Tm) of 65 to 75 占 폚 is used, the heat resistance can be increased.

In the present invention, the multi-layer structure of the adhesive layer / adhesive strengthening layer / second base layer is as shown in the following 16) to 27), for example.

16) Acid denaturated nylon layer / Acid denaturated PP layer / Polyethylene layer

17) Acid-modified nylon layer / acid-modified PP layer / polypropylene layer

18) Acid-denatured nylon layer / Acid denaturated PP layer / Polyethylene and polypropylene mixed layer

19) Acid-modified PBT layer / acid denatured PP layer / polyethylene layer

20) acid-modified PBT layer / acid-modified PP layer / polypropylene layer

21) acid-modified PBT layer / acid-modified PP layer / polyethylene-polypropylene mixed layer

22) Acid denatured PET layer / acid denatured PP layer / polyethylene layer

23) acid-denatured PET layer / acid denatured PP layer / polypropylene layer

24) acid-denatured PET layer / acid denatured PP layer / polyethylene-polypropylene mixed layer

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

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

27) an acid-modified PP / acid-denatured PP layer having a melting temperature (Tm) of 65 to 75 DEG C / a polypropylene mixed layer

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

A first base layer formed of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film and a polypropylene film formed as a single layer or a multilayer;

An aluminum layer disposed inside the first base layer;

A second base layer disposed inside the metal layer, the second base layer comprising 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 comprises

A first base layer formed of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film and a polypropylene film formed as a single layer or a multilayer;

An aluminum layer disposed inside the first base layer;

A second base layer disposed inside the metal layer, the second base layer comprising polypropylene or a mixture of polyethylene and polypropylene; And

An acid-modified polyethylene having a melting temperature (Tm) of 65 to 75 DEG C and an acid-modified polypropylene having a melting temperature (Tm) of 65 to 75 DEG C, arranged between the aluminum layer and the second base layer, And an adhesive layer containing an acid-modified resin.

Here, several methods can be used for laminating the metal layer and the adhesive layer of the present invention. The first method is a method in which heat is applied by applying a pressure to the metal layer and the adhesive layer using a heated roll. The second method is a method of thermally fusing the adhesive layer resin with a metal layer while extruding the adhesive layer resin with a T-die extruder. The other metal layer and the adhesive layer film can also be laminated by a dry lamination method.

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.

Examples of the adhesive used in the dry lamination of the present invention include a cured polyurethane system, a polysilicon system, an acid-modified polypropylene obtained by acid-grafting in a solvent, or an acid-modified polyolefin obtained by acid- Adhesive can be used.

[Example]

Hereinafter, the present invention will be described in more detail with reference to Examples of the present invention and Comparative Examples which are not based on the present invention, but the scope of the present invention is not limited by the following Examples.

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

In Examples 1 to 3 and Comparative Examples 1 to 3, the components of each layer shown in the following Table 1 were bonded by a 3-layer co-extrusion method or a T-die multilayer co-extrusion method to produce a film.

At this time, the first base layer was a biaxially stretched nylon, Nylon 6.6 having a thickness of 15 mu m, the metal layer having an iron content of 1% of aluminum of 40 mu m, the adhesive layer of 20 mu m thick, Was laminated to a thickness of 40 탆 to prepare a film.

The first substrate layer Metal layer Adhesive layer Adhesion strengthening layer The second substrate layer Adhesion method Example 1 Biaxially oriented nylon AL Acid-denatured nylon Adhesion Enhancer Polypropylene T-Dies multilayer co-extruder Example 2 Biaxially oriented nylon AL Acid-modified PBT Adhesion Enhancer Polypropylene T-Dies multilayer co-extruder Example 3 Biaxially oriented nylon AL Acid-modified PET Adhesion Enhancer Polypropylene T-Dies multilayer co-extruder Comparative Example 1 Biaxially oriented nylon AL Polyethylene Adhesion Enhancer Polypropylene T-Dies multilayer co-extruder Comparative Example 2 Biaxially oriented nylon AL Acid denatured polyethylene Polypropylene T-Dies multilayer co-extruder Comparative Example 3 Biaxially oriented nylon AL Acid-modified polypropylene Polypropylene T-Dies multilayer co-extruder Biaxially oriented nylon Nylon 66 resin (trade name: KOLON PLASTIC KP3355) AL Aluminum with an iron content of 1% Acid-modified PBT A product obtained by grafting 5% of maleic anhydride to polybutylene terephthalate (trade name: KOLON PLASTIC KP513) by Twin Compound equipment Acid-modified PET A product obtained by grafting 5% of maleic anhydride to a polyethylene terephthalate (trade name: SK Chemicals BB8055) by a twin compound apparatus Acid-denatured nylon 5% of maleic anhydride was grafted onto a Nylon 66 product (trade name: KOLON PLASTIC KP3355) with a twin compound device Adhesion Enhancer A product obtained by grafting 2% maleic anhydride on polypropylene (trade name: Lotte Chemical SFC-550) Polyethylene Product of Linear Low Density Polyethylene (product name: Lotte Chemical UF315) Acid-modified polyethylene A product obtained by grafting 5% of anhydrous maleic anhydride in a linear low-density polyethylene (product name: Lotte Chemical UF315) with a twin compound device Acid-modified polypropylene: 5% of maleic anhydride was grafted onto homopolypropylene (trade name: Lotte Chemical H3400) with a twin compound device

- My pinholes -

The pinhole resistance (number of pinholes per 1 m 2 of coated area) was measured at room temperature (23 ° C) after 100 times stress (repeated folding and folding), and is shown in Table 2.

- Peeling temperature -

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

division Pinhole Peeling temperature Example 1 0 195 ℃ Example 2 0 185 ℃ Example 3 0 200 ℃ Comparative Example 1 100 120 DEG C Comparative Example 2 10 120 DEG C Comparative Example 3 15 145 ° C

As shown in Table 2, pinholes were not observed at all in Examples 1 to 3 in which acid-denatured nylon, acid-modified PBT resin and acid-modified PET were thermally adhered to aluminum, while acid-denatured ethylene, acid-modified polyethylene, In Comparative Examples 1 to 3, 100, 10 and 15 pinholes were found, respectively, indicating that the pinhole resistance greatly decreased.

In addition, at the peeling temperature, the peeling temperature of Examples 1 to 3 was maintained at 180 占 폚 or more, whereas in Comparative Examples 1 to 3, peeling occurred at 150 占 폚 or more.

- Barrier measurement of organic solvent (moisture permeability) -

The second substrate layer not containing the metal layer was measured for barrier property (moisture permeability) of the organic solvent 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 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, the organic solvent barrier properties of Examples 1 to 3 were superior to those of Comparative Examples 1 to 3 in terms of barrier properties (water permeability).

- Adhesion strength of metal layer / adhesive layer

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

division Adhesion strength of aluminum / heat adhesive layer
(N / 15 mm) Example 1 35 Example 2 31 Example 3 33 Comparative Example 1 0.5 Comparative Example 2 25 Comparative Example 3 20

As shown in Table 4, Examples 1 to 3 showed an adhesive strength of at least 50% or more as compared with Comparative Examples 1 to 3, and in Comparative Example 1 using polyethylene resin, the adhesive strength to the metal layer was remarkably Can be confirmed.

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

In Examples 1 to 3 and Comparative Examples 1 to 3, the components of each layer shown in Table 5 below were bonded by a dry lamination method or a Ti-die multilayer co-extrusion method to produce a film.

At this time, the first base layer was biaxially stretched nylon, and Nylon 66 was used as a thickness of 15 占 퐉. The metal layer had an aluminum content of 1% aluminum of 40 占 퐉 and an adhesive layer of 20 占 퐉. Was laminated to a thickness of 40 탆 to prepare a film.

[Examples 4 to 7 and Comparative Example 4]

In Examples 4 to 7 and Comparative Example 4, the components of each layer shown in Table 5 below were bonded by a dry lamination method or a Ti-die multilayer co-extrusion method to produce a film.

At this time, after the first base layer and the metal layer were bonded to each other through the dry lamination process, the thickness of the polyethylene terephthalate used for the first base layer was 12 μm, the thickness of the biaxially oriented nylon was 15 μm, and the thickness of the metal was 40 μm , And Ti-die thermally adhered to the metal layer and the second base layer. In this case, the adhesive layers of Examples 4 and 5 and the product thicknesses of the second base layer were combined to a thickness of 70 탆.

The first substrate layer Metal layer Adhesive layer Adhesion strengthening layer The second substrate layer Extrusion method
(AL layer / thermal adhesive layer /
Adhesive layer / innermost layer)
Example 4 PET / biaxially oriented nylon AL layer Acid denatured 5% nylon Adhesive layer Polyethylene and polypropylene 50% mixed layer T-Dies
Extrusion processing Example 5 PET / biaxially oriented nylon AL layer Acid denatured 5% PBT Adhesive layer Polyethylene and polypropylene 50% mixed layer T-Dies
Extrusion processing Example 6 PET / biaxially oriented nylon AL layer Modified 5% polypropylene having a melting temperature (Tm) of 65 to 75 占 폚 - Polyethylene and polypropylene 50% mixed layer Dry lamination Example 7 PET / biaxially oriented nylon AL layer Modified 5% polypropylene having a melting temperature (Tm) of 65 to 75 占 폚 Adhesive layer Polyethylene and polypropylene 50% mixed layer T-Dies
Extrusion processing Comparative Example 4 PET / biaxially oriented nylon AL layer Acid modified 5% polypropylene Adhesive layer Polyethylene and polypropylene 50% mixed layer T-Dies
Extrusion processing Acid denatured 5% PBT A product obtained by grafting 5% maleic anhydride in polybutylene terephthalate (trade name: KOLON PLASTIC KP513) with a twin compound device Acid denatured 5% PET A product obtained by grafting 5% of maleic anhydride to a polyethylene terephthalate (trade name: SK Chemicals BB8055) by a twin compound apparatus Acid-denatured nylon 5% of maleic anhydride was grafted onto a Nylon 66 product (trade name: KOLON PLASTIC KP3355) with a twin compound device Acid-modified polypropylene Homopolypropylene (trade name: Lot 5), which is obtained by grafting 5% of anhydrous maleic anhydride in Lot Compound (H3400) with a twin compound Adhesive layer A polypropylene product with a melt index of 8 (PP (trade name: Lotte Chemical SFC-750) grafted with 5% maleic anhydride using a twin compound device Modified 5% polypropylene having a melting temperature (Tm) of 65 to 75 占 폚 Polypropylene having a molecular weight of 50000-100000 is grafted by reacting maleic anhydride with 5 parts by weight of polymer in a cyclohexane solvent by a solution reaction method. Polyethylene Product of Linear Low Density Polyethylene (product name: Lotte Chemical UF315) Polypropylene Homopolypropylene (trade name: Lotte Chemical H3400)

- Environmental stress -

Environmental Stress In order to evaluate the ESCR (Environmental Stress Cracking Resistance) property, an ethylene carbonate (ethylene carbonate) used as a secondary battery electrolyte was made into a thermostatic bath at a temperature of 40 ° C, After impregnating the thermally fusible examples 4 to 7, comparative example 1 and comparative example 4, the time for peeling 50% was measured, and the results are shown in Table 6.

division Chemical Stress Resistance
(ESCR property) Comparative Example 1 24hr Comparative Example 4 540hr Example 4 920hr or more Example 5 920hr or more Example 6 920hr or more Example 7 920hr or more

As shown in Table 6, in Examples 4 to 7, in which the adhesive layer was composed of acid denatured nylon, acid denatured polybutylene terephthalate and acid denatured 5% polypropylene having a melting temperature (Tm) of 65 to 75 ° C, It can be confirmed that it has an environmental stress of at least 38 times higher than that of Comparative Example 1 and Comparative Example 4 using propylene.

In addition, in Examples 6 and 7 in which acid-denatured 5% polypropylene having acid-denaturation in a solvent at a melting temperature (Tm) of 65 to 75 ° C was used, the acid-modified polypropylene was 1.7 times It was confirmed that the resin had an internal environmental stress.

[Example 8]

15 parts by weight of an ethylene acrylic acid copolymer (trade name: ESCOR 5100, manufactured by EXXON) was mixed with 80 parts by weight of a polybutylene terephthalate (PBT) resin having 5 wt% of maleic anhydride (MAH) grafted therein, (AL) layer prepared above was thermally fused by using a T-Dies extruder and then peeled to prepare a thermally adhesive layer film having a thickness of 80 탆.

[Example 9]

Except that 80 parts by weight of a polyamide resin in which 5 wt% of maleic anhydride (MAH) was grafted was mixed with 15 parts by weight of EMMA (methyl methacrylate-ethylene copolymer) to prepare a thin film. And the film was prepared in the same manner as in (1).

[Comparative Example 5]

A film was prepared in the same manner as in Example 7, except that an acid-modified polyethylene resin (LLDPE) in which maleic anhydride (MAH) was grafted at 1.5 wt% was extruded to prepare a thin film.

[Comparative Example 6]

A film was prepared in the same manner as in Example 7, except that an amino-modified polyethylene resin (HDPE) having 5 wt% of maleic anhydride (MAH) was grafted to prepare a thin film.

- Gas barrier property (gas permeability) -

Gas permeability measurement apparatus (S-69 type 160 ml) manufactured by Shibata Kagaku Kogyo Co., Ltd. was applied to the films prepared in Example 8, Example 9 and Comparative Example 5 and Comparative Example 6 (Measurement method of oxygen permeability according to ASTM D 3985) at a temperature of 23 캜, and the results are shown in Table 7.

Comparative Example / Example thickness Gas permeability (cc / m 2 / atm / 24 hr) Oxygen nitrogen carbon dioxide MEK (methyl ethyl ketone) Comparative Example 5 80 탆 4500 800 17000 4500 Comparative Example 6 80 탆 2100 420 8300 2100 Example 8 80 탆 35 15 200 35 Example 9 80 탆 40 20 250 40 Gas barrier property (gas permeability) measured by processing only adhesive layer.

As shown in Table 7, in Examples 8 and 9 including polybutylene terephthalate (PBT) or nylon (polyamide resin), which is an adhesive layer according to the present invention, an acid-modified polyethylene resin film (LLDPE) It was confirmed that both the gas barrier property and the organic solvent (MEK) barrier property were superior to those of Comparative Example 5 by about 40 times or more, and that the adhesive layer was also superior to Comparative Example 6 which was an acid-modified polyethylene resin film (HDPE) .

Therefore, when a film to which the metal layer and the adhesive layer or the second base layer according to the present invention are bonded is used as a packaging material for a polymer battery, a product having durability in 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 an acid-modified nylon having an acid denaturation content of 5 parts by weight shown in the following Table 8 was used as an adhesive layer. In Example 10, Was prepared in the same manner as in Example 9, except that an anchor coating agent, anoxosilane (trade name GLYMO) was anchor-coated.

The first substrate layer Metal layer Adhesive layer Adhesion strengthening layer The second substrate layer Extrusion method Example 10 PET / biaxially oriented nylon AL layer Acid denatured 5% nylon 50% polyolefin and polypropylene mixed layer Example 11 PET / biaxially oriented nylon AL layer + anchor coating treatment Acid denatured 5% nylon 50% polyolefin and polypropylene mixed layer Acid-denatured nylon A product obtained by grafting 5% of maleic anhydride to a nylon 6.6 product (trade name: KOLON PLASTIC KP3355)

division Pinhole
(100 times) Aluminum / Inner layer adhesive strength
(N / 15 mm) Example 10 0 34 Example 11 0 38

Table 8 shows the results of measurement of the pinhole resistance and the bonding strength between the aluminum and the inner layer for Examples 10 and 11, and the methods for measuring the pinhole resistance and the bonding strength are as described above. As shown in Table 9, it can be seen that the adhesive strength is improved by 10% when anchor coating is applied to aluminum.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention as defined by the following claims It can be understood that

Claims (15)

A first base layer;
A metal layer disposed inside the first base layer;
A second base layer disposed inside the metal layer; And
And an adhesive layer disposed between the metal layer and the second base layer,
Wherein the adhesive layer comprises at least one acid-modified resin selected from the group consisting of an acid-modified polyester resin, an acid-modified polyamide resin and an acid-modified polyolefin resin.
The method according to claim 1,
The acid-modified polyolefin resin has a melting temperature (Tm) of 65 to 75 캜.
The method according to claim 1,
Wherein the first base layer comprises 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 according to claim 1,
Wherein the first base layer is formed of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film and a polypropylene film as a single layer or a multilayer.
The method according to claim 1,
Wherein the metal layer is an aluminum layer.
6. The method of claim 5,
Aluminum layer is a film for packaging of batteries which is treated with an anti-corrosion treatment or an anchor coating.
The method according to claim 1,
The adhesive layer may be formed of a copolymer of acid denatured polyethylene terephthalate, acid denatured polybutylene terephthalate, acid denatured polytrimethylene terephthalate, acid denatured polyethylene naphthalate, acid denatured nylon 6, acid denatured nylon 6.6, acid denatured nylon 6 and nylon 6.6 , Acid denaturated nylon 12, acid denaturated nylon 6.10, or acid denaturated polymethylaniledi adipamide (MXD6).
The method according to claim 1,
The acid-dense content of the acid-modified resin is 0.01 wt% to 15 wt%.
The method according to claim 1,
Wherein the acid-modified resin is graft-modified with an acid component in a solvent.
The method according to claim 1,
The adhesive layer may be formed of a polyolefin, an? -Olefin-acrylic acid ester copolymer, an? -Olefin-methacrylic acid ester copolymer, an acetate copolymer, an elastomer; Or an ionomer.
The method according to claim 1,
And the second base layer comprises at least one resin selected from the group consisting of a polyolefin resin, a polyester resin and a polyamide resin.
The method according to claim 1,
And further comprising an adhesive strengthening layer disposed between the second base layer and the adhesive layer.
The method according to claim 1,
Wherein the adhesive reinforcing layer comprises an acid-modified polyolefin.
A first base layer formed of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film and a polypropylene film formed as a single layer or a multilayer;
An aluminum layer disposed inside the first base layer;
A second substrate layer disposed inside the aluminum layer, the second substrate layer comprising 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 denatured polyethylene terephthalate, acid denatured polybutylene terephthalate, and acid denatured nylon. film.
A first base layer formed of a film selected from the group consisting of a polyethylene terephthalate film, a nylon film and a polypropylene film formed as a single layer or a multilayer;
An aluminum layer disposed inside the first base layer;
A second substrate layer disposed inside the aluminum layer, the second substrate layer comprising polypropylene or a mixture of polyethylene and polypropylene; And
An acid-modified polyolefin disposed between the aluminum layer and the second base layer and having a melting temperature (Tm) of 65 to 75 DEG C and an acid-modified polypropylene having a melting temperature (Tm) of 65 to 75 DEG C. And an adhesive layer containing an acid-modified resin as described above.

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