KR102097599B1 - Impact-resistant adhesive composition for fixing batteries and a pressure sensitive adhesive double-coated tape - Google Patents

Abstract

An adhesive composition of the present invention comprises: one or two or more rubber selected from the group consisting of nitrile rubber, natural rubber, styrene-butadiene rubber, butyl rubber, nitrile butadiene rubber, and styrene isoprene styrene rubber; 3 to 10 parts by weight of tackifier; 5 to 10 parts by weight of resin having a hydroxyl group; 1 to 5 parts by weight of phenol resin; 10 to 20 parts by weight of oxidation stabilizer; and 1 to 10 parts by weight of fine particles, with respect to 100 parts by weight of the rubber. The adhesive composition and double-sided tape for fixing a battery of the present invention are excellent in adhesion to an aluminum laminate sheet used as a battery pouch, are not only useful for fixing a battery, but also have excellent reliability, such as maintaining the adhesive performance for a certain period of time even under a high temperature and high humidity environment, and have improved impact resistance and durability.

Description

An adhesive composition for fixing a battery having excellent impact resistance and a double-sided tape comprising the adhesive composition {Impact-resistant adhesive composition for fixing batteries and a pressure sensitive adhesive double-coated tape}

The present invention relates to a rubber-based pressure-sensitive adhesive composition having excellent impact resistance and a double-sided tape for fixing a battery using the same, and more specifically, by adding a tackifier, a resin having a hydroxyl group, and a phenol resin to the rubber-based pressure-sensitive adhesive, a battery that is difficult to adhere to The present invention relates to a double-sided tape for fixing a battery having improved impact resistance by including fine particles in an adhesive composition and an adhesive layer and an adhesive layer having enhanced adhesion to an exterior material.

In the related art, a removable battery is mainly used for detachable batteries, and since a detachable battery must freely separate the battery from a mobile phone device, additional parts such as a battery separator and a cover are required to increase the manufacturing cost and detach the battery from the mobile phone device. Since a space portion that can be added has to be added, there is a problem of increasing the volume of the mobile phone and limiting the design of the mobile phone.

In addition, since the removable battery requires frequent opening of the mobile phone cover to replace the battery, a mobile phone cover having excellent mechanical strength must be applied, which causes a problem of limiting the material of the mobile phone. In other words, as a material for a mobile phone device, a material having excellent elasticity such as plastic is easy to apply, but a material having low elasticity such as metal is limited in application because deformation may occur when the process of opening and closing the cell phone case is repeated.

In order to solve the above problem, recently, an integral battery in which a battery is semi-permanently interposed in a mobile phone device, rather than a removable type, has been used. Conventionally, a double-sided tape commonly used to fix the integral battery to a mobile phone device is used. have.

On the other hand, the battery can be classified into a pouch-type battery, a cylindrical battery, a square battery, and the like, and the double pouch-type battery stores the electrode assembly assembled by interposing a separator between the positive electrode and the negative electrode in a pouch-shaped laminate sheet as a battery case. , After injecting the electrolyte, it is manufactured by sealing it. At this time, the pouch-shaped laminate sheet is a polyolefin-based resin layer / aluminum layer / sheet made of an insulating polymer layer is often used, the material of the insulating polymer layer is usually a nylon-based material.

However, when the insulating polymer layer located on the outermost surface is a nylon material, the adhesive performance is poor as a general point adhesive due to material characteristics, and in particular, the adhesive strength and impact resistance are deteriorated in a high temperature and high humidity environment. It can cause problems.

Accordingly, there is a need to develop technology for an adhesive composition for fixing a battery and an adhesive tape having excellent adhesion to a laminate sheet of a battery pouch and maintaining adhesion even under a high temperature and high humidity environment.

Korean Patent Registration No. 10-1417188 (20140630)

An object of the present invention is to provide a composition of an adhesive tape for fixing a battery and a double-sided tape using the same, which improves impact resistance and adhesion, and maintains adhesive performance even in a high temperature and high humidity environment.

The adhesive composition of the present invention for solving the above problems includes one or two or more rubbers selected from the group consisting of nitrile rubber, natural rubber, styrene butadiene rubber, butyl rubber, nitrile butadiene rubber, and styrene isoprene styrene rubber; Tackifier 3 to 10 parts by weight based on 100 parts by weight of the rubber; 5 to 10 parts by weight of a resin having a hydroxyl group; 1 to 5 parts by weight of phenol resin; Oxidizing stabilizer 10 to 20 parts by weight; And 1 to 10 parts by weight of fine particles.

In one embodiment of the present invention, the rubber is a mixture of styrene isoprene styrene rubber and styrene butadiene rubber in a weight ratio of 7: 3 to 5: 5, and the tackifier is hydrogenated styrene-methyl styrene-indene It is a polymer.

In addition, the double-sided tape for fixing the battery of the present invention, the base layer; It includes an adhesive layer formed on both sides of the base layer, the base layer includes polyurethane and fine particles, and the adhesive layer includes the adhesive composition.

In one embodiment of the present invention, the base layer has a thickness of 20 to 50 μm, and the adhesive layer has a thickness of 20 to 50 μm.

In one embodiment of the present invention, the base layer contains 2 to 20 parts by weight of the fine particles with respect to 100 parts by weight of polyurethane.

In one embodiment of the present invention, the adhesive composition and the fine particles contained in the base layer are talc, silicon beads, glass beads, calcium carbonate, silica, acrylic resin in powder form, and one selected from the group consisting of thermally expandable microspheres Or a mixture of two or more.

The adhesive composition of the present invention and the double-sided tape for fixing a battery are excellent in adhesion with an aluminum laminate sheet used as a battery pouch, and are useful not only for fixing a battery, but also maintains adhesion performance in a high temperature and high humidity environment for a certain period of time. It has excellent reliability, and has the effect of improving impact resistance and durability.

1 is a cross-sectional view of a double-sided tape for fixing a battery according to the present invention.
Figure 2 shows the method of the Dupont shear test.

Hereinafter, the preferred embodiment of the present invention and the physical properties of each component will be described in detail, but it is intended to be described in detail so that a person skilled in the art to which the present invention pertains can easily implement the invention. This does not mean that the technical spirit and scope of the present invention is limited.

The pouch-type battery is manufactured by storing an electrode assembly including an anode / separator / cathode in a pouch-shaped exterior material of an aluminum laminate sheet, and then injecting an electrolyte to seal the exterior material. And the laminate sheet is composed of a plurality of layers, the outermost layer is a polymer resin having insulating properties is used.

However, when the insulating polymer resin layer constituting the outermost layer of the laminate sheet is a nylon-based material, there is a problem in that the adhesive strength and the heterogeneous material are low due to the material characteristics of nylon. That is, the conventional adhesive for fixing the battery has a low adhesion to the adherend when the nylon-based material is an adherend, and furthermore, the adhesion is significantly reduced under a high temperature and high humidity environment, resulting in battery detachment during external shock or negative performance of electronic devices such as mobile phones. There was a fear of influence. Accordingly, the present invention was devised to improve the above problems.

Rubber, which is a main component constituting the pressure-sensitive adhesive of the present invention, has not only been used as a pressure-sensitive adhesive for a long time, but has been widely used to date. The rubber softens when heated, but does not melt completely, and its relatively cohesive properties are strong but not sticky, making it difficult to react with other reactors on the surface of the adherend. That is, since the rubber itself has poor adhesiveness, generally, a tackifier or tackifier resin is added to increase the tackiness, which is a property that the surface of the adherend and the surface of the adhesive adhere.

The adhesive composition according to the present invention selects a rubber having good impact resistance as a basic resin, adds an tackifier to improve the adhesive strength of the rubber, as well as an adhesive to improve the adhesive strength of the battery exterior material with nylon By introducing a resin having a hydroxyl group and a phenol resin into the component, the hydrogen bonding strength between the hydroxyl group and the electronegative group of nylon is improved, and the hydrogen bonding strength between the -OH group of the phenol resin and the active hydrogen of nylon is improved. It is characterized by providing sufficient adhesion when fixing the battery and improving reliability by preventing deterioration of adhesion even under high temperature and high humidity environments.

In addition, the adhesive composition according to the present invention is characterized in that the fine particles are added to the adhesive composition to improve impact resistance.

An adhesive composition having improved adhesive strength, reliability and impact resistance according to the present invention includes rubber; Tackifier 3 to 10 parts by weight based on 100 parts by weight of the rubber; 5 to 10 parts by weight of a resin having a hydroxyl group; 1 to 5 parts by weight of phenol resin; Oxidizing stabilizer 10 to 20 parts by weight; And 1 to 10 parts by weight of fine particles.

The rubber is preferably one or a mixture of two or more selected from the group consisting of nitrile rubber, natural rubber, styrene-butadiene rubber, butyl rubber, nitrile butadiene rubber, styrene-isoprene-styrene rubber.

Among them, styrene-isoprene-styrene rubber and styrene-butadiene are selected, and when the mixing ratio thereof is a weight ratio of 7: 3 to 5: 5, the effect of improving elasticity and impact resistance is best exhibited.

The styrene-isoprene-styrene (SIS) rubber and styrene-butadiene rubber (SBR) have low glass transition temperature (Tg), are composed only of hydrocarbons, and have very low surface energy. It has an excellent advantage. In addition, the styrene-isoprene-styrene (SIS) rubber is a type of isoprene rubber, and has superior elasticity and softness compared to other rubbers.

The weight average molecular weight of the styrene-isoprene-styrene rubber and styrene butadiene rubber is preferably 5,000 to 200,000, and more preferably 10,000 to 170,000, but is not limited thereto. At this time, when the weight average molecular weight is less than 5,000, there is a weak problem in heat resistance, and when the weight average molecular weight exceeds 200,000, there is a problem that the elasticity of the rubber falls and the peeling force and the wetting property are low.

The styrene content of the styrene-isoprene-styrene (SIS) rubber and styrene butadiene rubber is preferably 15 to 30% by weight, respectively, but is not limited thereto. At this time, when the styrene content is less than 15% by weight, the cohesive force becomes insufficient, the hardness (hardness) is low, there is a problem that the high-temperature durability is lowered, when the styrene content exceeds 30% by weight, the peel strength is reduced, such as adhesiveness There is a problem that this becomes insufficient.

The conventionally used styrene-isoprene-styrene rubber and styrene-butadiene rubber are characterized by being cured. The cured styrene-isoprene-styrene rubber and styrene-butadiene rubber have a degree of curing (gel content) of about 80% to about 99. %to be. The cured styrene-isoprene-styrene rubber and styrene-butadiene rubber have a problem of insufficient elasticity and lack of wettability due to their high degree of curing (gel content), so that the styrene-isoprene-styrene rubber and styrene-butadiene rubber of the present invention Is preferably non-curable.

The pressure-sensitive adhesive composition of the present invention includes a tackifier to improve adhesion. If the tackifier of the present invention is excellent in compatibility with the rubber, the type is not limited, but rosin resins derived from rosin, terpene resins derived from terpenes such as pinene, aliphatic hydrocarbons derived from petroleum distillation Gina aromatic hydrocarbon resins can be used, and specific examples of the aliphatic hydrocarbon resins or aromatic hydrocarbon resins derived from the petroleum distillation are preferably hydrogenated styrene-methyl styrene-indene copolymers. The hydrogenated styrene-methyl styrene-indene copolymer has a weight average molecular weight of 600 to 1100, preferably 750 to 900, a number average molecular weight of 400 to 800, preferably 500 to 700, more preferably It may be 550 to 650.

The tackifier is preferably 3 to 10 parts by weight based on 100 parts by weight of the rubber. If the tackifier is out of the above range and is less than 3 parts by weight, the adhesive strength may decrease, and when it exceeds 10 parts by weight, the content of the resin or phenol resin having a hydroxyl group, which will be described later, is reduced, and the aluminum laminate sheet is a battery storage container. It is not preferable because the point adhesive force with and may decrease.

In the adhesive composition of the present invention, in order to improve the adhesive strength with the nylon-based material constituting the aluminum laminate sheet as an adherend, 5 to 10 parts by weight of a resin having a hydroxyl group with respect to 100 parts by weight of the rubber; 1 to 5 parts by weight of phenol resin is added.

Since the resin having the hydroxyl group improves the hydrogen bonding strength of the nylon electronegativity group, the resin group is advantageous in improving the adhesion due to the electronegativity with the adherend.

The type of the resin having the hydroxyl group is not limited as long as it is excellent in compatibility with rubber, but a xylene-modified polyol is preferred. The xylene-modified polyol may function to improve the adhesive strength of the pressure-sensitive adhesive composition of the present invention, as well as improving the point adhesion with the adherend, and also being resistant to moisture. The viscosity of the xylene-modified polyol may be about 50 to 1000 mPa · s at 75 ° C., and more preferably 100 to 500 mPa · s.

The resin having a hydroxyl group is preferably 5 to 10 parts by weight based on 100 parts by weight of rubber, and exhibits the best adhesion performance when the above range is satisfied. If it is less than 5 parts by weight, reliability in a humid environment may be deteriorated, and when it is more than 10 parts by weight, the wettability of the pressure-sensitive adhesive may be reduced, which is not preferable.

The phenol resin is also added to improve the adhesive strength with the nylon material when the adherend is a nylon-based material, such as the resin having the hydroxyl group. The phenol resin of the present invention has the adhesive property of the resin itself, and functions to increase heat resistance. Therefore, the pressure-sensitive adhesive composition of the present invention to which the phenol resin is added can function to improve reliability under a high temperature environment.

Phenolic resin is a synthetic resin obtained by condensation reaction of phenols and aldehydes, and is divided into branches of novolac prepared under an acid catalyst as a reaction product of phenol and formaldehyde, and Resol prepared from an alkali catalyst. The phenol resin is preferably a resol resin.

The melting point of the phenol resin is preferably 100 to 145 ° C, and more preferably 115 to 130 ° C.

It is preferable that the phenol resin of this invention is 1-5 weight part with respect to 100 weight part of rubber. If it is less than 1 part by weight, there is a concern that high temperature reliability may be deteriorated, and when it exceeds 5 parts by weight, the wettability of the pressure-sensitive adhesive may be reduced, which is not preferable.

Examples of the oxidation stabilizer of the present invention include products of BASF, such as Irganox 1010, Irganox 1035, Irganox 1076, or Irganox 1222. It is not limited.

The adhesive composition of the present invention, in order to improve the impact resistance, contains fine particles, the fine particles of the present invention is a group consisting of talc, silicone beads, glass bis, calcium carbonate, silica, acrylic resin in powder form and thermally expandable microhollows A mixture of one or two or more selected from is preferred, and a mixture of acrylic resin and silica in powder form, and a thermally expandable microhollow body expanding at 100 to 140 ° C is preferred.

In the adhesive composition of the present invention, the content of the fine particles is 1 to 10 parts by weight based on 100 parts by weight of the rubber. When the content of the fine particles is less than the above range, it is not preferable in terms of impact resistance, and when it exceeds the above range, it is not preferable in terms of adhesion performance.

Hereinafter, a double-sided tape for fixing a battery of the present invention manufactured using the adhesive composition will be described in detail.

1, the double-sided tape 100 for fixing a battery of the present invention, the base layer 120; It includes an adhesive layer 110 formed on both sides of the base layer, the base layer includes polyurethane and fine particles, and the adhesive layer includes the adhesive composition.

The base layer is a layer that serves as a base for the double-sided tape and serves to maintain the shape of the double-sided tape from external stress or impact. It is preferable that the base layer has a thickness of 20 to 50 µm. When the thickness of the substrate layer is less than 20 μm, it is not preferable in terms of impact resistance, and when the thickness of the substrate layer exceeds 50 μm, the thickness of the double-sided tape becomes thicker, making it difficult to apply to electronic devices that are in recent trend of miniaturization and thinning. There is a risk of falling.

The material constituting the base layer may be made of one selected from the group consisting of polyurethane, polyethylene naphthalate, polyethylene terephthalate, polyphenylene sulfide and ethylene-methacrylic acid copolymer, from the viewpoint of properties such as elastic elongation recovery rate Polyurethane is most preferred.

Polyurethane is generally a resin comprising a soft segment composed of a polyol monomer unit and a hard segment composed of a polyfunctional isocyanate compound or a low molecular weight glycol monomer unit.

Polyols used in the production of polyurethanes are compounds having two or more hydroxyl groups. For example, it is preferable that the number of hydroxyl groups of the polyol is close to 2 from the viewpoint of enhancing properties such as rubber elastic elongation recovery rate. Specifically, the number of hydroxyl groups of the polyol is preferably 2 to 3, and more preferably 2. As the polyol, for example, polyester polyol, polyether polyol, polycaprolactone polyol, polycarbonate polyol, castor oil-based polyol can be used, and two or more kinds of polyols may be used in combination.

As the polyfunctional isocyanate compound used in the production of polyurethane, for example, a polyfunctional aliphatic isocyanate compound, a polyfunctional alicyclic isocyanate compound, and a polyfunctional aromatic isocyanate compound can be used. Further, trimethylolpropane adducts of these compounds, burettes reacted with water, and trimers having an isocyanurate ring can also be used. You may use together 2 or more types of polyfunctional isocyanate compounds.

The polyurethane of the present invention can be obtained by curing a composition containing the polyol described above and a polyfunctional isocyanate compound.

The substrate layer of the present invention is characterized by including fine particles to improve elasticity and impact resistance. The content of the fine particles is 2 to 20 parts by weight, more preferably 5 to 15 parts by weight, and most preferably 7 to 12 parts by weight with respect to 100 parts by weight of polyurethane. When the content of the fine particle powder is less than 2 parts by weight, there is a problem in that it is difficult to achieve an effect of increasing the tensile strength and elongation of the double-sided tape due to a slight elasticity effect of the base layer, and when the content of the fine particle powder exceeds 20 parts by weight There is a problem of increasing the weight and manufacturing cost of the base layer.

The adhesive layer constituting the double-sided tape of the present invention is formed on the upper / lower surface of the base layer, and the thickness of the upper adhesive layer and the lower adhesive layer may have a thickness of 20 to 50 micrometers, respectively. For the formation of the adhesive layer, for example, a method of applying a material containing the rubber-based adhesive composition on the substrate layer (coating method), a method of adhering a film containing the rubber-based adhesive composition on the substrate (dry laminating) Law).

In order to improve impact resistance, the base layer and the adhesive layer of the present invention include fine particles, wherein the fine particles are made of talc, silicon beads, glass bis, calcium carbonate, silica, acrylic resin in powder form, and thermally expandable microhollows. One or two or more mixtures selected from are preferred.

The thermally expandable microspheres mean particles in which hydrocarbons are contained in a spherical polymer shell. In the heat-expandable microspheres that can be used in the present invention, when heated, the softening of the shell starts, and at the same time, the hydrocarbons contained therein start to gasify and the microspheres expand as the internal pressure increases. When the microspheres expand by heating, the internal pressure and the tension and external pressure of the shell polymer are balanced to maintain the expanded state. In addition, the feature is that it is designed to cause shrinkage because the tension and the external pressure of the thinned shell increase when heating is continued. Since the shell itself has ductility, it may have a property that rupture does not occur.

As a substance that is easily expanded by heating, for example, propane, propylene, butene, normal butane, isobutane, isopentane, neopentane, normal pentane, normal hexane, isohexane, heptane, octane, petroleum ether, halogen of methane Low-boiling liquids such as cargo and tetraalkylsilanes; And azodicarbonamide gasified by pyrolysis.

Examples of the material constituting the shell include nitrile monomers such as acrylonitrile, methacrylonitrile, α-chloracrylonitrile, α-ethoxyacrylonitrile, and fumaronitrile; Carboxylic acid monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and citraconic acid; Vinylidene chloride; Vinyl acetate; Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclo (Meth) acrylic acid esters such as hexyl (meth) acrylate, benzyl (meth) acrylate, and β-carboxyethyl acrylate; Styrene monomers such as styrene, α-methylstyrene, and chlorostyrene; And polymers composed of amide monomers such as acrylamide, substituted acrylamide, methacrylamide, and substituted methacrylamide. The polymer composed of these monomers may be either a homopolymer or a copolymer. As said copolymer, for example, vinylidene chloride-methyl methacrylate-acrylonitrile copolymer, methyl methacrylate-acrylonitrile-methacrylonitrile copolymer, methyl methacrylate-acrylonitrile copolymer, And an acrylonitrile-methacrylonitrile-itaconic acid copolymer.

In particular, the thermally expandable microspheres of the present invention are preferably expanded at a drying temperature of 100 to 140 ° C, as will be described later.

When the thermal expansion start temperature of the thermally expandable microsphere is less than 100 ° C, it is not preferable in terms of adhesive strength of the double-sided tape, and when the thermal expansion start temperature exceeds 140 ° C, it is not preferable in terms of impact resistance.

The particle diameter before expansion of the thermally expandable microspheres is preferably 0.1 μm to 100 μm, more preferably 2 μm to 50 μm, still more preferably 5 μm to 30 μm, particularly preferably 10 μm to 15㎛. Therefore, when the particle size before heating of the thermally expandable microspheres is average particle diameter, it is preferably 3 µm to 50 µm, more preferably 10 µm to 40 µm. The particle diameter and the average particle diameter are values obtained by a particle size distribution measurement method in a laser scattering method.

The thickness of the shell of the thermally expandable microspheres may be 2 to 15 μm, and more preferably 3 to 10 μm. Further, it is preferable that the pressure resistance of the thermally expandable microspheres has a mechanical strength of 300 kg / cm 2 or more.

It is preferable that the thermally expandable microspheres have a moderate strength that does not rupture until the volume expansion rate is preferably 5 times or more, more preferably 7 times or more, and even more preferably 10 times or more.

The glass bead is a special glass egg, which is not broken by impact and can maintain abrasion resistance, and can withstand internal stress and impact resistance, and thus is applied to the base layer and adhesive layer of a double-sided tape for fixing a battery having excellent impact resistance according to the present invention It has the effect of improving the mechanical strength.

The talc, silicon beads, calcium carbonate and silica play an important role in improving the strength and heat insulation effect, and at the same time, they also contain minerals, and thus also serve as flame retardants.

Among them, a mixture of acrylic resin and silica in powder form is preferable, and a preferable range of the mixing ratio of acrylic resin and silica is 3: 1 to 1: 1.

Hereinafter, specific examples of the present invention will be described. The specific examples of the following examples are only examples and the scope of the present invention is not limited to the following examples.

<Example 1>

Preparation of polyurethane base layer composition

The base layer is prepared by mixing 5 parts by weight of fine particles with 100 parts by weight of polyurethane (noru paint NEM-390) having a weight average molecular weight of 580,000, and a viscosity of 25 ° C of 3,000 to 4,000 cps, and the fine particles are made of acrylic resin. Powder (LP-4100, manufacturer: Mitsubishi rayon) and silica (AEROSIL 200, manufacturer: EVONIK) were used in a weight ratio of 2: 1.

Preparation of rubber-based adhesive layer composition

As a rubber-based adhesive, styrene-isoprene-styrene rubber (weight average molecular weight is 170,000, viscosity 200 cps, trade name: Hanwha RB745) and styrene-butadiene rubber (weight average molecular weight 120,000, viscosity 800 cps) are mixed at a weight ratio of 6: 4. Prepared, compared to 100 parts by weight of the rubber mixture, 5 parts by weight of fine particles, 7 parts by weight of a tackifier (Regalite R1100, manufacturer ETSMAN), 7 parts by weight of a resin having a hydroxyl group (K-100, manufacturer: FUDOW) , Phenolic resin (KC4001, manufacturer: Gangnam Hwaseong) 3 parts by weight, an oxidation stabilizer (Iganox 1010, manufacturer: BASF) 15 parts by weight of the mixture was mixed. As the fine particles, an acrylic resin powder (LP-4100, manufacturer: Mitsubishi rayon) and silica (AEROSIL 200, manufacturer: EVONIK) were used in a weight ratio of 2: 1.

Production of double-sided tape for fixing batteries

On one side of the peeling treatment surface of a 50 µm thick polyester film (Toray Co., trade name XP-3BR) treated with a silicone-based release treatment agent, the above-described polyurethane-based composition was applied so that the final thickness was 20 µm. It was applied to form a coating layer. On the upper surface of the continuously applied polyurethane-based composition, a rubber-based adhesive layer composition was applied with an applicator to be 40 μm to form an adhesive layer. A rubber-based adhesive layer composition was applied to the lower surface of the polyuritene-based composition with an applicator to form 40 μm to form an adhesive layer. Finally, a double-sided tape with a thickness of 100 μm was prepared.

<Example 2>

In manufacturing the double-sided tape for fixing the battery in Example 1, except that the thickness of the base layer was changed to 30㎛, each thickness of the upper and lower adhesive layer to each 35㎛, in the same manner as in Example 1 above. Double-sided tape was prepared.

<Example 3>

In manufacturing the double-sided tape for fixing a battery in Example 1, the thickness of the base layer was changed to 40 µm, and each thickness of the upper and lower adhesive layers was changed to 30 µm, respectively. Double-sided tape was prepared.

<Example 4>

In manufacturing the double-sided tape for fixing a battery in Example 1, except that the thickness of the base layer was changed to 50 μm and each thickness of the upper and lower adhesive layers to 25 μm, respectively, in the same manner as in Example 1 above. Double-sided tape was prepared.

<Comparative Example 1>

When preparing the composition of the rubber-based adhesive layer in Example 1, the double-sided tape was prepared in the same manner as in Example 1, except that the tackifier, the resin having a hydroxyl group, the phenol resin, and the oxidation stabilizer were not added. It was prepared.

<Comparative Example 2>

When preparing the composition of the rubber-based adhesive layer in Example 2, the double-sided tape was prepared in the same manner as in Example 2, except that the tackifier, the resin having a hydroxyl group, the phenol resin, and the oxidation stabilizer were not added. It was prepared.

<Comparative Example 3>

When preparing the composition of the rubber-based adhesive layer in Example 3, the double-sided tape was prepared in the same manner as in Example 3, except that the tackifier, the resin having a hydroxyl group, the phenol resin, and the oxidation stabilizer were not added. It was prepared.

<Comparative Example 4>

When preparing the composition of the rubber-based adhesive layer in Example 4, the double-sided tape was prepared in the same manner as in Example 4, except that the tackifier, the resin having a hydroxyl group, the phenol resin, and the oxidation stabilizer were not added. It was prepared.

Experimental Example 1: Adhesion test

As an adherend, a laminate sheet base material and a SUS substrate of PE / AL / Nylon, which are battery storage case materials, were prepared. The double-sided tapes of Examples and Comparative Examples were attached on the laminate sheet substrate and the SUS substrate. At this time, the nylon constituting the laminate sheet is attached to face the double-sided tape. Thereafter, the double-sided tape was peeled from the adherend at a peeling rate of 20 mm / min, and the force (gf / inch) when peeled between the adherend and the double-sided tape was measured and the results are shown in Tables 1 and 2.

Experimental Example 2: Push-out test

To compare the adhesive strength of the double-sided tape, the extrusion strength was measured and evaluated. Specifically, a laminate sheet of PE / AL / Nylon having a hole in the center was prepared as the first sheet, and a magnesium sheet was prepared as the second sheet. The double-sided tape was cut into a rectangular rim shape having a band width of 3 mm, and the outer dimension of the rectangular ring was 15.5 mm × 15.5 mm (horizontal × length). The second sheet was adhered to the center of the first sheet using a cut double-sided adhesive tape, and then stored at room temperature (25 ° C) for 3 days. Then, when the second sheet is pressed through a hole in the first sheet at a constant strain rate of 20 mm / min using a universal testing machine (UTM), the maximum strength of pushing the maximum force when both sheets are adhered to each other As recorded.

For each case after storing the specimen with double-sided tape at low temperature (0 ℃) for 72 hours, storing it at 85 ℃ 85% RH environment for 72 hours, and storing it for 72 hours after thermal shock, the Dupont type as above The results of the test are shown in Tables 1 and 2 below.

Experimental Example 3: Dupont impact test (vertical) test

The double-sided tapes of Examples and Comparative Examples were measured using a Dupont type impact tester.

Specifically, in a magnesium sheet having a size of 50 mm × 50 mm × 2 mm with a hole having a diameter of 10 mm formed in the center, PE of 20 mm × 20 mm × 3 mm via the double-sided tape of the examples and comparative examples Laminate specimens were prepared by attaching a laminate sheet of / AL / Nylon. At this time, the laminated sheet and the double-sided tape were adhered so that the nylon layer of the laminate sheet faced the double-sided tape. After the laminate specimen was stored at 25 ° C for 72 hours, the glass and double-sided adhesive tapes were detached while dropping 100 g of weight from the height of 50 mm to 500 mm sequentially at a position of 50 mm from the laminate sheet surface of the laminated specimen. It was observed whether or not the fall impact test was conducted. At this time, when the glass and the double-sided adhesive tape were not detached, a fall impact test was performed while increasing the weight of the weights to 150g, 200g, 300g and 400g until they were detached, and 350 when the weight was 150g In the case of ~ 500mm, 200g, 400 ~ 500mm, 300g, and 400g, they were dropped at a position raised by 50mm sequentially within a height of 350 ~ 500mm.

Accordingly, for each double-sided tape according to the above Examples and Comparative Examples

Impact strength was calculated from the weight and height of the weight when the laminate sheet and the double-sided tape were detached, and the results are shown in Tables 1,2.

For each case after storing the specimen with double-sided tape at low temperature (0 ℃) for 72 hours, storing it at 85 ℃ 85% RH environment for 72 hours, and storing it for 72 hours after thermal shock, the Dupont type as above The results of the test are shown in Tables 1 and 2 below.

Experimental Example 4: Dupont shear test

2 schematically shows a method of measuring the shear strength (Dupont Shear). Referring to Figure 2, for the adhesive tape (C) of the Examples and Comparative Examples, after preparing a specimen having a frame shape of 1mm width, a laminate of PE / AL / Nylon of a size corresponding to the size of the frame shape A sheet (A) and a magnesium sheet (B) were prepared and specimens were attached therebetween. Then, as shown in FIG. 2, the PE / AL / Nylon laminate sheet (A) and magnesium sheet (B) were pushed at the speed of 6 mm / min in the direction of the arrow to measure shear strength. The results are shown in Table 1 below. , 2.

For the above experiment, after storing the specimen with double-sided tape at low temperature (0 ℃) for 72 hours, storing it at 85 ℃ 85% RH environment for 72 hours, and storing it for 72 hours after applying thermal shock, It was carried out each, and the results are shown in Tables 1 and 2 below.

Example 1 Example 2 Example 3 Example 4 Adhesion (gf / in) PE / AL / Nylon laminate sheet 1548 1246 1145 1053 SUS 2850 2424 1874 1540 Push-out (kgf) Room temperature 72hr 8.9 8.7 8.8 8.9 Low temperature 72hr 10.0 9.9 9.7 9.9 85 ℃ 85% R.H 72hr 8.6 8.9 8.8 9.1 Thermal shock 72hr 9.5 9.3 9.1 9.2 Dupont impact (kgf) Room temperature 72hr 210.7 210.7 205.8 171.5 Low temperature 72hr 161.7 151.9 156.8 151.9 85 ℃ 85% R.H 72hr 215.6 220.5 215.6 181.3 Thermal shock 72hr 235.2 235.2 240.1 210.7 Dupont shear (kgf) Room temperature 72hr 372.4 362.6 382.2 313.6 Low temperature 72hr 313.6 303.8 323.4 235.2 85 ℃ 85% R.H 72hr 323.4 323.4 313.6 333.2 Thermal shock 72hr 401.8 401.8 411.6 362.6

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Adhesion (gf / in) PE / AL / Nylon laminate sheet 947 746 542 340 SUS 1829 1452 1164 975 Push-out (kgf) Room temperature 72hr 6.3 6.6 6.8 6.6 Low temperature 72hr 7.5 7.2 7.5 7.4 85 ℃ 85% R.H 72hr 6.9 6.9 7.2 7.3 Thermal shock 72hr 7.3 7.0 7.3 6.7 Dupont impact (kgf) Room temperature 72hr 122.5 114.3 114.3 122.5 Low temperature 72hr 91.7 95.7 93.5 91.7 85 ℃ 85% R.H 72hr 95.7 91.7 98.0 95.7 Thermal shock 72hr 98 138.8 179.7 98 Dupont shear (kgf) Room temperature 72hr 163.3 204.2 232.8 163.3 Low temperature 72hr 81.7 122.5 138.8 81.7 85 ℃ 85% R.H 72hr 114.3 122.5 147.0 114.3 Thermal shock 72hr 196.0 204.2 204.2 196.0

As shown in Tables 1 and 2, the double-sided tapes according to Examples 1 to 4 of the present invention have excellent adhesion to the aluminum laminate sheet, which is a battery pouch material, compared to the double-sided tapes of Comparative Examples 1 to 4, and Push- Out, Dupont impact, and Dupont shear tests show much better adhesion performance.

This is considered to be because the adhesive layer composition of the double-sided tape of the present invention improved the adhesion to the aluminum laminate sheet.

As described above, the double-sided tape of the present invention is excellent in impact resistance, adhesive strength, durability, and reliability, so it will be very useful as a battery fixing tape.

100: double-sided tape for fixing the battery
110: adhesive layer
120: base layer

Claims (6)

Rubber in which styrene isoprene styrene rubber and styrene butadiene rubber are mixed in a weight ratio of 7: 3 to 5: 5;
Tackifier 3 to 10 parts by weight based on 100 parts by weight of the rubber; 5 to 10 parts by weight of a resin having a hydroxyl group; 1 to 5 parts by weight of phenol resin; Oxidizing stabilizer 10 to 20 parts by weight; And 1 to 10 parts by weight of fine particles,
The tackifier is a hydrogenated styrene-methyl styrene-indene copolymer,
The resin having a hydroxyl group is a xylene-modified polyol, the adhesive composition for fixing a battery, characterized in that. delete Base layer;
Includes an adhesive layer formed on both sides of the base layer,
The base layer includes polyurethane and fine particles, and contains 2 to 20 parts by weight of the fine particles with respect to 100 parts by weight of the polyurethane,
The adhesive layer includes the adhesive composition of claim 1,
The fine particles, a double-sided tape for fixing the battery, characterized in that a mixture of acrylic resin and silica in a 3: 1 to 1: 1 mixture. According to claim 3,
The base layer has a thickness of 20 to 50 μm, and the adhesive layer has a thickness of 20 to 50 μm. delete delete

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