BRPI0912720B1 - adhesive film - Google Patents

Description

ADHESIVE FILM

TECHNICAL FIELD OF THE INVENTION [001] The present invention relates to an adhesive film. For example, an adhesive film formed in a tape-like format, which can preferably be used in an indicator film in which the letters or figures are indicated on a surface of an adhesive film, or adhesive tape to join cables or wires electrical equipment, such as trays for wiring an automobile.

BACKGROUND OF THE INVENTION [002] In the quality of the adhesive film of various types of insulating tapes such as those used in various electrical instruments in automobiles, railways, airplanes, ships, homes, factories and the like, a vinyl chloride adhesive film is used in which an adhesive agent is applied to one side of a base material using a resin composition, including vinyl chloride resin as a raw material, as it has the appropriate degree of flexibility and elongation, and is excellent at retarding flame, mechanical resistance, heat deformation capacity, electrical insulating capacity, and moldability, as well as relatively inexpensive.

[003] Typically, a plasticizer is formulated into the base material of the adhesive film to soften the base material. However, as time passes, there are cases in which plasticizers move from the base material to the adhesive layer. When the plasticizer moves to the adhesive layer, the adhesive agent is softened, and its stickiness and squeezing onto a side surface of the rolled roll (adhesive side) occurs, and the cohesive strength or adhesive strength of the adhesive is reduced, to in this way, cause the adhesive film to peel off the substrate. In addition, in a case where the adhesive film is peeled off

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2/29 of the substrate, there are situations in which a part of the adhesive and plasticizer remains attached to the substrate, and therefore, contaminating the substrate.

[004] As an adhesive film intended to inhibit this type of movement of the plasticizer, it has been proposed to provide an adhesive film with a first curable layer between a base material and an adhesive layer (for example, Patent Document 1 and Document of Patent 2). However, in cases where these films are wound in a rolled format, if a paste surface is not protected by a separator of the base material or a back surface (a surface that does not form a paste surface) of a base material it is not treated superficially, the surface of the adhesive layer of an adhesive film that is superimposed is in direct contact with the posterior surface of the other adhesive film, and therefore, the movement of the plasticizer occurs between the adhesive film. Therefore, there is a problem in which the movement of the plasticizer cannot be sufficiently prevented, unless the paste or back surface is further protected.

Patent Document 1: Publication of the unexamined Japanese patent application η- H11-263946; and

Patent Document 2: Publication of unexamined Japanese patent application No. 2002-146274.

DESCRIPTION OF THE INVENTION [005] The present invention aims to provide an adhesive film in which the movement of the plasticizer from the base material to the adhesive agent is reduced, its adhesive strength, unwinding force and holding power are excellent, and deposits of adhesive on the substrate are reduced.

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3/29 [006] The present invention is one that achieves the aforementioned objectives, and the following text is a summary of the invention:

(1) an adhesive film consisting of a base material consisting of a vinyl chloride resin composition, and an adhesive layer formed on at least one side of the base material, the adhesive layer including:

(i) a base adhesive agent consisting of natural rubber and / or styrene butadiene rubber;

(ii) a grafted polymer in which a (meta) acrylic acid ester with an alkyl group is polymerized as a graft in a natural rubber and / or styrene butadiene rubber; and (iii) a plasticizer; wherein (A) the plasticizer is formulated at 3% by weight to 4% by weight with respect to the adhesive agent that constitutes the adhesive layer, (B) the grafted polymer is formulated to 10 parts by weight to 50 parts by weight with respect to to 100 parts by weight of the base adhesive consisting of natural rubber and / or styrene butadiene rubber, and (C) the Mooney viscosity of the grafted polymer is a Mooney viscosity of 60 Ms 1 + 4 (100 ° C) at 90 Ms 1 + 4 (100 ° C) as described in JIS K 6300.

(2) the adhesive film, according to the aforementioned item (1), in which the vinyl chloride resin composition includes at least 50% by weight of the vinyl chloride resin in relation to the total quantity of the resin components .

(3) the adhesive film, according to the item (1) above, in which the grafted polymer comprises 60% by weight to 80% by weight of rubber.

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4/29 styrene and butadiene, and 20% by weight to 40% by weight of the (meta) acrylic acid ester with a polymerized alkyl group as a graft.

(4) the adhesive film, according to item (1) above, in which the (meta) acrylic acid ester with an alkyl group is one selected from the group consisting of (meta) methyl acrylate, (meta) acrylate of n-butyl, 2-ethyl (meta) acrylate, and a mixture of them.

(5) the adhesive film, according to item (1) above, in which the plasticizer is diisononyl phthalate.

(6) the adhesive film, according to item (1) above, in which 15% by weight to 45% by weight of the plasticizer are included in the base material in relation to the total amount of resin components of the resin composition of the like vinyl chloride.

[007] According to the present invention, an adhesive film can be provided in which the movement of the plasticizer from the base material to the adhesive agent is reduced, the resistance of the adhesive, the unwinding force and the holding power are excellent, and adhesive deposits are reduced.

MODE FOR CARRYING OUT THE INVENTION [008] The adhesive film of the present invention is an adhesive film consisting of a base material that includes a vinyl chloride resin composition, and an adhesive layer formed on at least one side of the base material. mentioned above, in which the aforementioned adhesive layer is made of an adhesive agent that includes 0.3% by weight to 4% by weight of a plasticizer in relation to the adhesive agent, and a grafted polymer in which an ester of (meta) acrylic acid with an alkyl group and polymerized as a graft in a natural rubber and / or styrene butadiene.

I. Base Material

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5/29 [009] The vinyl chloride type resin composition that constitutes the base material is not specifically limited in any specific way, as long as a vinyl chloride resin is included as the main constituent of the resin components. The vinyl chloride resin is a homopolymer resin, which is a monopolymer of a conventionally known vinyl chloride, or several conventionally known copolymer resins, and therefore, is not particularly limited in any way.

[010] As the aforementioned copolymer resin, a known copolymer can be employed, with a copolymer resin of a vinyl chloride and a vinyl ester, such as a vinyl acetate and vinyl chloride copolymer resin, or a vinyl chloride copolymer resin and vinyl propionate; an acrylic acid ester copolymer resin such as vinyl chloride and butyl acrylate copolymer resin, or vinyl chloride copolymer resin and 2-ethylhexyl acrylate; a vinyl chloride and an olefin copolymer resin, such as a vinyl chloride and ethylene copolymer resin, or a vinyl chloride and propylene copolymer resin; and vinyl chloride and acrylonitrile copolymer resin, and the like, typically being exemplified. However, the use of a homopolymer resin which is a vinyl chloride monopolymer, a vinyl chloride and ethylene copolymer resin, and a vinyl chloride and vinyl acetate copolymer resin are particularly preferable. The co-monomer content in the copolymer resin is not particularly limited in any way, as long as it can be determined according to the desired moldability quality, and the like.

[011] The ratio of vinyl chloride resin to the total amount of resin components of the vinyl chloride type resin composition is, for example, not less than 50% by weight, more preferably not less than 80 % by weight, and even more preferably 90% by weight at

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100% by weight. In addition, a flame retardant, a stabilizing agent, an antioxidant, a pigment, or an inorganic filler, or the like, can be added when needed.

[012] As a vinyl chloride resin, a vinyl chloride resin can preferably be used. As a flexible vinyl chloride resin, one can be exemplified in which a sufficient amount of a stabilizing agent, or plasticizer and the like, is added to the vinyl chloride resin with a degree of polymerization at an average viscosity of 900 to 1,300. When the aforementioned degree of polymerization of vinyl chloride resin is below 900, there are cases in which the base material is softened and the thermal resistance is reduced. On the other hand, when the degree of polymerization mentioned above exceeds 1,300, there are cases in which the dispersion capacity of additives in the vinyl chloride type resin composition is decreased, and the flexibility of the adhesive film is decreased. The degree of polymerization mentioned above is calculated using the JIS K6720-2 standard, dissolving 200 g of resin in 50 ml of nitrobenzene and measuring the specific viscosity of the polymer solution in a tank at a constant temperature of 30 ° C, using an Ubbelohde viscometer.

Plasticizer [013] To soften the base material, a plasticizer can be formulated into the base material. The type of plasticizer that can be used in the base material is not particularly limited, as long as a known plasticizer can be employed. A dibasic acid ester, such as DOP (dioctyl phthalate), DINP (diisononyl phthalate), DINA (diisononyl adipate), DBP (dibutyl phthalate), TOTM (tris-2-ethylhexyl trimellitate), and DIDP (diisodecyl phthalate) described in the “Handbook of Adhesives (Japan Adhesive Tape Manufacturer's Association, 3- Edition, P-69); a liquid rubber such as liquid polyisobutylene, a liquid isoprene, and a liquid butene; an aromatic processing oil, a naphthenic processing oil, an oil

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7/29 paraffinic processing, castor oil, pine oil, can be exemplified as a typical plasticizer. They can be used alone or in combinations of two or more. The ratio of the plasticizer to the total amount of resin components of the vinyl chloride type resin composition is preferably. 15% by weight to 45% by weight, and even more preferably 15% by weight to 30% by weight. When the plasticizer mentioned above has a weight percentage less than 15%, there are cases in which the base material is hardened. On the other hand, when the weight percentage exceeds 45%, there are cases in which problems such as contraction of the base material or rupture of the base material occur at the time of production of the base material.

[014] The thickness of the base material is by no means particularly limited, provided that it is preferably 10 pm to 500 pm, more preferably 12 pm to 200 pm, and even more preferably 15 pm to 100 pm. In addition, the base material can exist in the form of a single layer, or it can exist in the form of a plurality of layers.

[015] The base material can also be subjected to various processes, such as posterior surface treatment, antistatic treatment, and osmotic conditioning treatment, when necessary.

II. Adhesive Layer [016] The adhesive agent to form the adhesive layer of the present invention includes 0.3% by weight to 4% by weight of a plasticizer relative to the adhesive agent, and a grafted polymer in which an acid ester (meta) acrylic with an alkyl group is polymerized as a graft in a natural rubber and / or a styrene and butadiene rubber (hereinafter referred to as “SBR”).

Base Adhesive Agent

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8/29 [017] The adhesive agent includes a natural rubber and / or a styrene butadiene rubber as the base adhesive agent.

[018] Natural rubber is widely used as a basis for an adhesive composition. In addition, SBR is a representative generic rubber, which is excellent in its resistance to aging, its resistance to corrugation, and its resistance to plasticizers, and the like. Natural rubbers and SBRs available on the market can be used.

[019] As a SBR, a conventionally used SBR can be employed. Furthermore, the proportion of styrene and butadiene as monomeric components of SBR is by no means particularly limited. The type and degree of SBR is by no means particularly limited, and therefore, various types and degrees of SBR can be employed.

Plasticizer [020] As a plasticizer that can be formulated in the adhesive layer, the aforementioned known plasticizers can be used in a similar way to those usable in a base material.

[021] The percentage content of the plasticizer in the adhesive layer is 0.3% by weight to 4% by weight, and preferably 1% by weight to 3% by weight with respect to the adhesive agent. When the percentage content of the plasticizer is less than 0.3% by weight, in some cases, the movement of the plasticizer from the base material that constitutes the vinyl chloride type resin composition is not impeded and the resistance to cohesion of the agent adhesive is decreased, and in cases where the adhesive strength increases with the time of lamination and adhesive deposits are generated when the adhesive film is peeled off. On the other hand, when the percentage content of the aforementioned plasticizer exceeds 4% by weight, there are cases in which there is an insufficiency in the initial cohesive resistance of the adhesive agent that is not

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9/29 related to the time passing, and adhesive deposits are generated when the adhesive film is peeled. Having the plasticizer present in the adhesive agent in the quantity specified above, the movement of the plasticizer from the base material to the adhesive agent can be prevented by the chemical equilibrium principle.

[022] The content of the plasticizer of the present invention was measured by the method mentioned below:

Device Name: Gas chromatography (GC Japan Electron Optics Laboratories, Ltd.)

Test Method: Adhesive agent of the adhesive film was measured by peeling with n-hexane, extracted, and dried at 40 ° C.

Grafted Polymer [023] The grafted polymer of the present invention demonstrates an effect in which the deterioration of adhesive properties rarely occurs so as to be excellent in anti-plasticizing properties, and a decrease in the cohesive resistance of the adhesive agent is prevented further by the movement of the plasticizer. In addition, as the (meta) acrylic acid ester with an alkyl group is grafted, improvements in adhesion properties to various substrates and in unwinding strength can be achieved, as well as the functionality efficiency at low temperatures. The formulated amount of the grafted polymer is from 10 parts by weight to 50 parts by weight, and preferably 20 parts by weight to 50 parts by weight with respect to 100 parts by weight, the base adhesive consisting of natural rubber and / or SBR. When the grafted polymer is less than 10 parts by weight, there are cases in which the appropriate adhesive strength for various substrates, and the appropriate unwinding force cannot be obtained. On the other hand, when the grafted polymer exceeds 50 parts by weight, there are cases in which the polymer

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10/29 grafted is super hardened, and therefore, it cannot be used as an adhesive agent.

[024] The grafted polymer is capable of exerting a high degree of unwinding strength, and allowing adhesion to substrates that are difficult to affix an adhesive film, providing a low molecular weight polar component (natural rubber, SBR) and a polar component high molecular weight (ester of (meta) acrylic acid with an alkyl group) within the molecular structure of the aforementioned grafted polymer. Consequently, as both molecular components need to be properly distributed, it is preferable that 60% by weight to 80% by weight of natural rubber and / or SBR, and 20% by weight to 40% by weight of the (meth) acrylic acid ester with an alkyl group are polymerized in the grafted polymer. It is even more preferable that 65% by weight to 75% by weight of natural rubber and / or SBR, and 25% by weight to 35% by weight of the (meth) acrylic acid ester with an alkyl group are polymerized.

[025] As the (meta) acrylic acid ester with an aforementioned alkyl group, methyl (meta) acrylate (hereinafter referred to as “MMA”), (meta) ethyl acrylate, (meta) acrylate can be exemplified npropyl, isopropyl (meta) acrylate, n-butyl (meta) acrylate, 2-ethylhexyl acrylate, (meta) benzyl acrylate, (meta) cyclohexyl acrylate, (meta) acrylate isooctyl, (meta) n-octyl acrylate, (meta) nonyl acrylate, (meta) isononyl acrylate, (meta) undecyl acrylate, (meta) isoundecyl acrylate, (meta) dodecyl acrylate, (meta) acrylate of isotridecyl, (meth) tetradecyl acrylate. And similar, whether they are used alone or in combinations of two or more. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferably employed.

[026] The Mooney viscosity of the grafted polymer of the present invention is 60 Ms 1 + 4 (100 ° C) to 90 Ms 1 + 4 (100 ° C), and preferably 70 Ms 1 + 4 (100 ° C) at

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Ms 1 + 4 (100 ° C). When the Mooney viscosity is less than 60 Ms 1 + 4 (100 ° C), there are cases in which the fluidity of the adhesive is weakened, and a high degree of cohesive strength cannot be achieved. On the other hand, when the Mooney viscosity exceeds 90 Ms 1 + 4 (100 ° C), there are cases in which the cohesive resistance of the adhesive is too high. As a method of regulating Mooney viscosity, any known method can be exemplified, and so the method itself is by no means particularly limited. For example, a method for chewing with an open Banbury cylinder mixer, and a kneader can be exemplified. Particularly, from the point of view of being able to easily regulate Mooney viscosity, it is preferable that the method of chewing is by an open cylinder. Mooney viscosity measurement is based on the JIS K-6300.

Additive [027] Several known additives, for example, a plasticizer; an ultraviolet absorber; a stabilizing agent such as an antioxidant; a catching agent; a load; a coloring agent; an antistatic agent; a foaming agent; and a surfactant, for example, can also be formulated into the adhesive when necessary.

[028] The sticky resin used as a sticky agent can be selected taking into account the compatibility between each component, and the softening point, and the like. For example, a terpenic resin, a rosin resin, a hydrogenated rosin resin, a coumarone-indene resin, a styrene resin, a petroleum resin, such as an aliphatic or alicyclic type, a terpene resin phenol, a xylene resin, and another aliphatic hydrocarbon resin or aromatic hydrocarbon resin can be exemplified. The softening point of the handle resin is 65 ° C to 170 ° C, and preferably 80 ° C to 150 ° C. The formulated amount of handle resin is in the range of 50 parts by weight to 200 parts in

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12/29 weight, and preferably in the range of 100 parts by weight to 150 parts by weight, relative to 100 parts by weight of the adhesive. When the amount of sticky resin is too low, there are cases in which a high degree of adhesive strength cannot be applied to the adhesive film. On the other hand, when the amount of sticky resin is too high, there are cases where the adhesive strength of the adhesive film is too high.

III. Adhesive Film [029] The adhesive film of the present invention consists of a base material consisting of a resin composition of the vinyl chloride type, and an adhesive layer formed on at least one side of the aforementioned base material. Normally, an adhesive layer that is formed on only one side of a base material can also be formed on both sides of it. The adhesive film can be produced by forming an adhesive layer on at least one side of a base material, using a conventional method such as a coating method. In addition, the adhesive layer can also be protected by the release base material (release liner). In addition, the adhesive film may also include another layer (for example, an intermediate layer, and a coating and a paint base), as long as the effects of the present invention are not compromised.

[030] The medium for forming the base material is by no means particularly limited, as long as it allows the formulation of each of the above materials, using a conventional kneading and melting device, or various formulation devices (for example, a single-screw or double-screw extruder, cylinder, Banbury mixer, and several kneaders), in such a way that each component is uniformly dispersed, the transformation of the aforementioned mixture into a base material by means of a calender molding apparatus, and the cut to the desired width of the tape. For example, the cylinder configuration in the mold of the

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13/29 calender can employ a known configuration, such as an L shape, an inverse L shape, and a Z shape, and the cylinder temperature can be adjusted in a conventional range of 150 ° C to 200 ° C, and preferably in a range of 160 ° C to 180 ° C.

[031] The means for applying the adhesive that forms the adhesive layer on the base material is by no means particularly limited. For example, a Gravure cylinder coating applicator, an inverse cylinder coating applicator, a submerged cylinder coating applicator, a bar coating applicator, a blade coating applicator, a spray coating applicator, and the like can be employed. Although the thickness of the adhesive layer after drying can be properly selected within a range in which its adhesive properties and handling properties are not compromised, the thickness of the adhesive layer is, for example, 5 pm to 100 pm, and preferably 10 pm to 50 pm. When it is thinner than this, the adhesive strength and unwinding force are decreased. On the other hand, when it is thicker than this, its coating power is decreased, and adhesive deposits are easily formed.

[032] The adhesive film of the present invention can be produced as an adhesive tape (adhesive film wound in a rolled format), having a state or configuration in which it is wound in a rolled shape by means of its winding in a rolled shape, and in cases where it is not wound in a rolled format, it can be produced as an adhesive sheet.

[033] Applying a release agent on a posterior surface (a surface that does not form a paste-like surface) of the adhesive film to provide a surface layer with subsequent treatment when the adhesive film is being transformed into the adhesive tape, preventing the movement of the plasticizer between the adhesive film can be even more

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14/29 insured if the tape is wound in a rolled format. Similarly, having the release surface of the release liner in contact and laminated on the surface of the adhesive layer, the release liner is sandwiched between the surface of the adhesive layer of an adhesive film and the back surface of another adhesive film, and so being. , preventing the plasticizer from moving between the adhesive film can be further ensured.

Examples [034] In this specification, the present invention will be explained in more detail on the basis of Examples and Comparative Examples. However, the present invention is not specifically limited to these examples.

[035] The materials used in the examples are those indicated below, respectively:

(1) a vinyl chloride resin: TH-1000 (manufactured by Taiyo Enbi Co., Ltd .; with a degree of polymerization of 1,100), and TH-1300 (manufactured by Taiyo Enbi Co., Ltd .; with a degree of polymerization of 1,300);

(2) a plasticizer: DINP (manufactured by DIC);

(3) a catching agent: a C5C9 petroleum resin (manufactured by Exxon Chemical Co., Ltd .; with a softening point of 94 ° C);

(4) a stabilizing agent: Ca-Zn stabilizing agent (manufactured by Mizusawa Industrial Chemicals, Ltd.);

(5) a modifier: MBS (copolymer of methyl methacrylate, butadiene and styrene) (manufactured by Japan Synthetic Rubber Co., Ltd.);

(6) a grafted polymer in which MMA is polymerized as a graft in a natural rubber: MEGAPOLY 30 (manufactured by Asiatic; a polymer

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15/29 grafted in which 30% by weight of MMA are grafted in 70% by weight of natural rubber);

(7) a grafted polymer in which MMA is polymerized as a graft in a natural rubber: MEGAPOLY 50 (manufactured by Asiatic; a grafted polymer in which 50% by weight of MMA is polymerized as a graft in 50% by weight of natural rubber);

(8) a grafted polymer in which MMA is polymerized as a graft in an SBR: SGMM-30 (manufactured by Denki Kagaku Kogyo Co., Ltd .; a grafted polymer in which 30% by weight of MMA is polymerized as a 70% graft by weight of SBR);

(9) a grafted polymer in which butyl methacrylate is polymerized as a graft in an SBR: SGBM-30 (manufactured by Denki Kagaku Kogyo Co., Ltd .; a grafted polymer in which 30% by weight of butyl methacrylate is polymerized as grafting in 70% by weight of SBR); and (10) a grafted polymer in which butyl acrylate is polymerized as a graft in an SBR: SGBA-30 (manufactured by Denki Kagaku Kogyo Co., Ltd .; a grafted polymer in which 30% by weight of butyl acrylate is polymerized as a graft in 70% by weight of SBR).

Table 1

Examples 1 2 3 4 5 Material of Base PVC TH1000 (degree of Polim. 100 100 100 100 100

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1,100) TH1300 (Polymers Degree 1.300) - - - - - Plasticizer DINP% by weight 25 25 25 25 25 Adhesive agent Eraser Natural Ms 1 + 4 (100 ° C): 45 100 100 100 100 100 SBR Ms 1 + 4 (100 ° C): 30 - - - - - MEGAPOLY 30 Ms 1 + 4 (100 ° C): 80 20 50 - - - MEGAPOLY 50 Ms 1 + 4 (100 ° C): 90 - - 20 - - SGMM-30 Ms 1 + 4 (100 ° C): 80 - - - 20 - SGBM-30 Ms 1 + 4 - - - - 20

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(100 ° C): 70 SGBA-30 Ms 1 + 4 (100 ° C): 60 - - - - - Plasticizer content DINP% by weight 2 0.6 1.9 2.3 2.3 Characteristic value Initial adhesive strength (N / 10 mm) About SUS 2 3 1.8 3 3 About PE 1.7 1.6 1.5 1.7 1.7 About PVC 1.7 2 1.6 2.7 2.7 About PET 2.5 2.7 2.4 3.2 3.2 Change in adhesive strength over time in relation to SUS (N / 10 mm) Initial (30 min after attachment) 2 3 1.8 3 3 One month after attachment 2.1 3 1.9 3 3.2 -20 ° C (30 min later 2.5 2.8 2.6 3.2 3.5

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annexation) Adhesion power Weight drop time (min) 300 350 350 400 350 Unwinding force (N / 10 mm) 7 days after production 6.2 7 6 6 6 SUS stripping Presence or absence of initial peeling Favorable Favorable Favorable Favorable Favorable After a month Favorable Favorable Favorable Favorable Favorable SUS adhesive deposits 30 min after attachment Favorable Favorable Favorable Favorable Favorable One month after annexation Favorable Favorable Favorable Favorable Favorable

Table 1 Continuation

Examples

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6 7 8 9 Base material PVC TH-1000 (degree of Polimer. 1,100) 100 100 100 - TH-1300 (Degree of polymer. 1,300) - - - 100 Plasticizer % by weight of Dl NP 25 25 25 30 Adhesive agent Eraser Natural Ms 1 + 4 (100 ° C): 45 100 - 50 100 SBR Ms 1 + 4 (100 ° C): 30 - 100 50 - MEGAPOLY 30 Ms 1 + 4 (100 ° C): 80 - 20 20 20 MEGAPOLY 50 Ms 1 + 4 (100 ° C): 90 - - - SGMM-30 Ms 1 + 4 (100 ° C): 80 - - - - SGBM-30 Ms 1 + 4 (100 ° C): 70 - - - - SGBA-30 Ms 1 + 4 (100 ° C): 60 20 - - - Content of Plasticizer % by weight of Dl NP 2.4 3 2.5 4

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Characteristic value Initial adhesive strength (N / 10 mm) Regarding SUS 3.5 1.7 1.9 2.1 Regarding PE 2 1.5 1.8 1.7 Regarding PVC 3 1.6 1.8 1.9 Regarding PET 3.5 2 2.7 2.7 Change in adhesive strength over time in relation to SUS (N / 10 mm) Initial (30 min after attachment) 3.5 1.7 1.9 2.1 One month after annexation 3.7 2.1 2.3 2.5 -20 ° C (30 min after attachment) 4.1 2.3 2.8 2.5 Holding power Time to drop weight (min) 350 350 320 280 Unrolling force (N / 10 mm) 7 days after production 6 6 6.6 6.5 Peel and SUS nto Presence or absence of initial peeling Favor vel Favorable Favorable Favorable

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After a month Favor vel Favorable hey Favorable hey Favorable hey Deposits 30 min after attachment Favor vel Favorable hey Favorable hey Favorable hey SUS sticker One month after annexation Favor vel Favorable hey Favorable hey Favorable hey

Table 2

Comparative Examples 1 2 3 Base Material PVC TH-1000 (Degree of Polim. 1100) 100 100 100 Plasticizer % by weight of Dl NP 25 25 25 Adhesive agent Natural rubber Ms 1 + 4 (100 ° C): 45 100 100 100 SBR Ms 1 + 4 (100 ° C): 30 - - - MEGAPOLY 30 Ms 1 + 4 (100 ° C): 50 - - - MEGAPOLY Ms 1 + 4 (100 ° C): 80 - 8 60

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30 MEGAPOLY 30 Ms 1 + 4 (100 ° C): 95 - - - Content of Plasticizer % by weight of Dl NP 6 4 2 Characteristic value Initial adhesive strength (N / 10 mm) Regarding SUS 0.5 0.7 4.5 Regarding PE 0.2 0.3 4 Regarding PVC 0.5 0.7 4.2 Regarding PET 0.5 0.7 4.8 Change in adhesive strength over time in relation to SUS (N / 10 mm) Initial (30 min after attachment) 0.5 0.7 4.5 One month after annexation 3.2 3.5 4.7 -20 ° C (30 min after annexation) 0.8 1.2 5 Holding power Weight drop time (min) 30 100 400 Unrolling force 7 days after production 2 3 15

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nto (N / 10 mm) Peeling of SUS Presence or absence of initial peeling Unfavorable Unfavorable Favorable After a month Favorable Unfavorable Favorable SUS adhesive deposits 30 min after attachment Unfavorable Unfavorable Favorable One month after annexation Unfavorable Unfavorable Favorable

Table 2 Continuation

Comparative Examples 4 5 6 Base material PVC TH-1000 (Degree of polymer. 1,100) 100 100 100 Plasticizer % by weight of DINP 25 25 25 Adhesive agent Natural rubber Ms 1 + 4 (100 ° C): 45 100 100 100

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SBR Ms 1 + 4 (100 ° C): 30 - - - MEGAPOLY 30 Ms 1 + 4 (100 ° C): 50 20 - - MEGAPOLY 30 Ms 1 + 4 (100 ° C): 80 - - 20 MEGAPOLY 30 Ms 1 + 4 (100 ° C): 95 - 20 - Content of Plasticizer % by weight of DINP 2.5 1.8 6 Characteristic value Initial adhesive strength (N / 10 mm) Regarding SUS 2.5 1.8 1.5 Regarding PE 2 1.6 1.5 Regarding PVC 2 2 1.7 Regarding PET 2.4 2 1.8 Change in adhesive strength over time in relation to SUS Initial (30 min after attachment) 2.5 1.8 1.5 One month after annexation 5 2 3

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(N / 10 mm) -20 ° C (30 min after attachment) 3 2.2 3.5 Holding power Time to drop weight (min) 200 400 10 Unrolling force (N / 10 mm) 7 days after production 9 5 4 Peel and SUS nto Presence or absence of initial peeling Favorable Unfavorable Favorable After a month Favorable Unfavorable Unfavorable SUS adhesive deposits 30 min after attachment Unfavorable Favorable hey Unfavorable One month after annexation Unfavorable Favorable hey Unfavorable

[036] The “initial adhesive strength” in Tables 1 and 2 was measured according to JIS Z 0237. After allowing the adhesive film to rest for at least hours in the evaluation test room with the temperature set at 23 ± 2 ° C and humidity adjusted to 50 ± 5% RH, the adhesive film was applied on various substrates (SUS (stainless steel), PE (polyethylene), PVC (poly (chloride of

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26/29 vinyl)), and PET (poly (ethylene terephthalate)) by rolling a 2,000 g roll back and forth twice, and peeling resistance at 180 degrees (N / 10 mm) was measured after 30 minutes. A peeling resistance of 1 N / 10 mm or more was favorable.

[037] The “change in adhesive strength over time in relation to SUS” in Tables 1 and 2 was measured according to JIS Z 0237. After the adhesive film was allowed to rest for at least 24 hours in the assessment test room with the temperature set at 23 ± 2 ° C and the relative humidity set at 50 ± 5% RH, the adhesive film was applied over a SUS 304 steel sheet by rolling a 2,000 g roll back and forth twice, and then the peeling resistance at 180 degrees (N / 10 mm) was measured in 30 minutes and one month after that. After the adhesive film was allowed to rest for at least 24 hours in the assessment test room with the temperature set at -20 ± 2 ° C, the adhesive film was applied to a SUS 304 steel sheet by rolling a 2000 g roll to back and forth twice, and then the peel strength at 180 degrees (N / 10 mm) was measured 30 minutes after that. In any case, 1 N / 10 mm or more was favorable.

[038] The “holding power” in Tables 1 and 2 was measured according to JIS Z 0237. After the adhesive film was allowed to rest for at least 24 hours in the assessment test room with the temperature set at 23 ± 2 ° C and the relative humidity adjusted to 50 ± 5% RH, the adhesive film was applied on a SUS 304 steel plate, used as a substrate, and 20 mm χ 20 mm adhesive film were attached to it. Then, a load of 500 g was loaded in the direction of gravity and a weight drop time (min) of it was measured at n = 3 or more under an atmosphere of 40 ° C. The values in the aforementioned tables were average values. A fall time of 300 min was favorable.

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27/29 [039] The “unwinding force” in Tables 1 and 2 was measured according to JIS Z 0237. After the adhesive film was allowed to rest for at least 24 hours in the temperature test room adjusted at 23 ± 2 ° C and the relative humidity adjusted at 50 ± 5% RH, the value was measured at n = 3 or more by unrolling an adhesive film for about three seconds at a speed of 15.8 m / min. The values in the aforementioned tables are average values. A value within the range of 6 N / 10 min to 8 N / 10 min was favorable.

[040] The “peeling of SUS” in Tables 1 and 2 was measured according to the JIS G 4305 standard. After the adhesive film was allowed to rest for at least 24 hours in the evaluation test room with the temperature set at 23 ± 2 ° C, and the relative humidity adjusted to 50 ± 5% RH, the adhesive film was adhered by pressure on a SUS 304 steel plate, and its adhesive state was visually observed after the initial 30 minutes and, again, 7 days later , and then its superiority or inferiority was evaluated according to the following criteria. The pressure adhesion method employed a 200 g cylinder to adhere under pressure, moving back and forth once at a speed of 5 mm / s, according to JIS K 6253.

Favorable: No stripping

Unfavorable: Some peeling [041] The “SUS adhesive deposits” in Tables 1 and 2 were measured according to JIS G 4305. After the adhesive film was allowed to rest for at least 24 hours in the temperature test room set at 23 ± 2 ° C and the relative humidity set at 50 ± 5% RH, the adhesive film was adhered under pressure to a SUS 304 steel sheet, the adhesive film was peeled at a peeling speed of 300 mm / min and a peeling angle of 180 degrees after the initial 30 minutes and again after a month, the surface of the SUS 304 steel plate was visually observed after peeling, and then its

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28/29 superiority or inferiority was assessed according to the following criteria. The pressure bonding method employed a 200 g cylinder to adhere under pressure, moving back and forth once at a speed of 5 mm / s, according to JIS K 6253.

Favorable: No deposit of adhesive present

Unfavorable: Adhesive deposits present

Example 1 (i) One hundred parts by weight of vinyl chloride resin (manufactured by Taiyo Enbi Co., Ltd .; TH-1000) with a degree of polymerization of 1,100, 25 parts by weight of DINP (manufactured by DIC) as plasticizer, 10 parts by weight of C5C9 petroleum resin (manufactured by Exxon Chemical Co., Ltd .; with a softening point of 94 ° C) as a tacking agent, 2 parts by weight MBS (manufactured by Japan Synthetic Rubber Co. , Ltd.) as a modifier, 2 parts by weight of Ca-Zn stabilizing agent (manufactured by Mizusawa Industrial Chemicals, Ltd.) as a stabilizing agent, 0.2 parts by weight of St acid (NOF Corporation), and 2 parts by weight from MMA (Kanegabuchi Chemical Industries Co., Ltd.) were formulated with a Henschel mixer; and transformed into a sheet with a thickness of 120 pm through calender molding (the temperature of the cylinder was from 145 ° C to 180 ° C). The aforementioned sheet was rolled up to a predetermined length (20 m) and annealed for 8 hours at 120 ° C to obtain the base material.

(ii) One hundred parts by weight of natural rubber (Mooney viscosity = 45), 20 parts by weight of a grafted polymer (Mooney viscosity = 80) in which 30% by weight of MMA are polymerized as a graft in 70% by weight of rubber natural (manufactured by Asiatic; MEGAPOLY 30), and 2% by weight of DINP (manufactured by DIC) were formulated in a mixture; 100 parts by weight of a terpenic resin (manufactured by Yasuhara Chemical Co., Ltd .; YS PX-1000 resin) as a handle resin, and 2 parts by weight of 4-ethyl-6-t-butyl

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29/29 phenol (Kawaguchi Chemical Industry, Co., Ltd .; Antage W-500) as an antioxidant was formulated therein after being dissolved in toluene to form a base of 30% by weight; in order to obtain the adhesive agent.

(iii) the adhesive agent was applied on a surface of the base material with a coating applicator with inverse cylinders, and went through a drying process, an adhesive layer was formed with a thickness after drying of 20 pm, and cut into a 25 mm wide tape to obtain an adhesive film.

Examples 2 to 9:

[042] With the exception of the various base materials and adhesive agent compositions that were modified as indicated in Table 1, the adhesive film was produced based on Example 1.

Comparative Examples 1 to 6:

[043] With the exception of the various adhesive agent compositions that were modified as indicated in Table 2, the adhesive film was produced based on Example 1.

[044] As is evident from Tables 1 and 2, according to the present invention, the initial adhesive resistance (30 minutes after being attached) of various substrates (SUS, PE, PVC, and PET) is superior. In addition, even with respect to changes in the adhesive strength of SUS over time (initial 30 minutes after a month, and at a low temperature of -20 ° C), the high degree of adhesive strength is maintained. For this reason, it should be understood that an adhesive film in which the movement of the plasticizer from the base material to the adhesive agent is reduced, and the adhesive strength, unwinding force and holding power are superior, and deposits of adhesive on the substrate are reduced, can be easily obtained.

Claims (5)

1. Adhesive film comprising a base material consisting of a resin composition of the vinyl chloride type, and an adhesive layer formed on at least one side of the base material, the adhesive layer characterized by the fact that it comprises: (i) a base adhesive agent consisting of natural rubber and / or styrene butadiene rubber; (ii) a grafted polymer in which a (meta) acrylic acid ester with an alkyl group is polymerized as a graft in a natural rubber and / or styrene butadiene rubber; and (iii) a plasticizer; where (A) the plasticizer is composed of 0.3% by weight to 4% by weight in relation to the adhesive agent that constitutes the adhesive layer, (B) the grafted polymer is composed of 10 parts by weight to 50 parts by weight with respect to 100 parts by weight of the base adhesive composed of natural rubber and / or styrene butadiene rubber, and (C) the Mooney viscosity of the grafted polymer is a Mooney viscosity of 60 Ms 1 + 4 (100 ° C) at 90 Ms 1 + 4 (100 ° C), as described in the JIS K 6300 standard, and 15% by weight to 45% by weight of the plasticizer are included in the base material in relation to the total amount of resin components of the vinyl chloride type resin composition. 2. Adhesive film according to claim 1, characterized by the fact that the vinyl chloride resin composition comprises at least Petition 870180133319, of 9/24/2018, p. 39/41 2/2 50% by weight of the vinyl chloride resin in relation to the total quantity of the resin components. 3. Adhesive film according to claim 1, characterized in that the polymer comprises 60% by weight to 80% by weight of styrene butadiene rubber, and 20% by weight to 40% by weight of the acid ester ( meta) acrylic with a polymerized alkyl group as a graft. 4. Adhesive film according to claim 1, characterized by the fact that the ester of (meta) acrylic acid with an alkyl group is one selected from the group consisting of (meta) methyl acrylate, (meta) acrylate of n -butyl, 2-ethyl (meta) acrylate, and a mixture of these. 5. Adhesive film, according to claim 1, characterized by the fact that the plasticizer is diisononyl phthalate.