JP5339052B2 - Adhesive laminate - Google Patents

Description

  The present invention relates to a pressure-sensitive adhesive laminate, and more specifically, a bonded surface by adhering to a bonded surface having a low surface roughness, such as a molded product such as metal, glass, and plastic, a processed product, and a coated product It is related with the adhesive laminated body which protects the damage | wound and dirt of this, and can be easily peeled off at the time of use.

  In the present specification, “ratio”, “part”, “%” and the like indicating the composition are based on mass unless otherwise specified, and the “/” mark indicates that they are integrally laminated. “LDPE” is an abbreviation, functional expression, common name, or industry term for “low density polyethylene” and “MFR” for “melt flow rate”.

  (Main use) The main use of the adhesive laminate of the present invention is to adhere to the surface of products such as building materials, daily necessities, stationery, home appliances, automobiles, various displays, packaging materials, cushioning materials, heat insulating materials, It is used as a soundproofing material. However, it is not particularly limited as long as it is used as a packaging material, a cushioning material, a heat insulating material, a soundproofing material, etc., in close contact with the surface of the product.

(Background Art) Conventionally, foams have a wide variety of uses such as packaging materials, cushioning materials, heat insulating materials, and soundproofing materials. Adhesive is applied to the surface of the foam to make an adhesive-processed foam product, or a foamed layer and an adhesive layer are laminated by coextrusion to make an adhesive laminate. It is also used for surface protection of metal plates and glass plates. However, in the production of the adhesive laminate, the conventional production method in which it is applied after being dissolved in an organic solvent has a large fire risk and environmental burden. Therefore, it is preferable that the production can be carried out by extrusion molding without using a solvent and having few production steps, excellent molding processability and excellent economic efficiency. Moreover, since it is consumed in large quantities and is peeled off and discarded after use, it can be manufactured at a low cost, and it is also required to have a low environmental load even if it is incinerated after use. Furthermore, if an adhesive layer with good adhesion is used, it is usually manufactured and used in a wound state, so that wrinkles are generated at the time of manufacture, or it is rewound from the wound state at the time of use, so that it is wound and in contact with the adhesive layer. Difficult to peel off from the back layer (referred to as blocking phenomenon), difficult to rewind, and in severe cases, transfer to the surface on the back layer side where the adhesive layer contacts and remain, or the adhesive laminate breaks or supplies Becomes unstable, and there is a problem that workability and machine suitability deteriorate. Furthermore, although the adhesive and the adhesive layer have good adhesion to the surface, there are problems in that the heat resistance (heat aging resistance), weather resistance, etc. are poor and the adhesive force varies.
Therefore, the pressure-sensitive adhesive laminate can be manufactured by extrusion molding which does not use a solvent, has few manufacturing processes, is excellent in molding processability and is excellent in economic efficiency, and can be manufactured and post-processed in a wound state, and can be stored and stored. It can be easily rewound even after being distributed, can be attached to the adherend with good adhesion, has excellent workability and mechanical suitability during use, and can be easily peeled off when there is little change in adhesive strength over time. Is required.

(Prior Art) Conventionally, a pressure-sensitive adhesive layer is provided on one surface of a porous substrate, and a specific polyalkylene-based laminate material (a), a laminate material (b), and a release agent are sequentially laminated on the other surface. An adhesive tape is known (for example, see Patent Document 1). However, adhesive coating uses a solvent at the time of manufacture, so there are environmental problems, and there are many manufacturing processes, so the cost is high. In coating type adhesive products, the adhesive remains on the adherend, etc. There is also a problem that there is a problem of contamination.
Further, a conjugated diene of a polymer mainly composed of a conjugated diene compound having a vinyl bond content of 65 to 85% is formed on the smooth surface of the base material layer (c) having a smooth layer (b) on at least one surface of the foam (a). There is known a pressure-sensitive adhesive laminate obtained by laminating a pressure-sensitive adhesive layer (e) made of a hydrogenated diene polymer (d) in which a partial double bond is saturated by 80% or more (see, for example, Patent Document 2). ). However, a laminate in which an adhesive layer consisting of a foamed layer and a hydrogenated diene copolymer is laminated by coextrusion technology has problems in heat resistance stability, weather resistance, etc., and the adhesive strength increases with time, making peeling difficult There is a drawback of becoming.

JP-A-63-33485 JP-A-11-61066

  In order to solve the above-described problems, the present inventors have made extensive studies and have completed the present invention. Its purpose is that it does not use a solvent, has few manufacturing processes, is excellent in molding processability, and can be manufactured by extrusion molding, and can be manufactured and post-processed in a wound state, stored and distributed. It can be easily rewound afterwards, can be attached to the adherend with good adhesion, has excellent workability and mechanical suitability during use, and has little change in adhesive strength over time even when attached to the adherend. It is to provide an adhesive laminate that can be easily peeled off when it is desired to peel off.

In order to solve the above problems, the pressure-sensitive adhesive laminate according to the invention of claim 1 is a pressure-sensitive adhesive laminate in which a back layer, a foam layer and an pressure-sensitive adhesive layer are sequentially laminated. The adhesive layer is made of an ethylene-α-olefin copolymer polymerized under a metallocene catalyst and a styrene thermoplastic elastomer, and conforms to the JIS-Z-0237 adhesive tape / adhesive sheet test method The unwinding force between the back surface layer and the adhesive layer measured by the test method is 0.1 N / 25 mm or less.
In the pressure-sensitive adhesive laminate according to the invention of claim 2, the styrenic thermoplastic elastomer is a hydrogenated diene copolymer, the vinyl aromatic compound polymer block (A), the conjugated diene polymer or the vinyl aromatic compound A random copolymer block (B) of a conjugated diene, and at least a block (A) and a block (B) of a taper block (C) in which the vinyl aromatic compound gradually increases among the vinyl aromatic compound and the conjugated diene (A) (A) )-(B) block copolymer, (A)-(B)-(A) block copolymer, (A)-(B)-(C) block copolymer One or a plurality of hydrogenated diene copolymers which are added to saturate 80% or more of the double bonds of the conjugated diene.
The pressure-sensitive adhesive laminate according to the invention of claim 3 is such that the styrenic thermoplastic elastomer is a styrene-isobutylene block copolymer in which the hard segment is a polystyrene compound and the soft segment is polyisobutylene. It is.
In the pressure-sensitive adhesive laminate according to the invention of claim 4, the foam layer is formed by foaming a composition comprising a thermoplastic resin and a chemical foaming agent simultaneously with the film formation by the multilayer coextrusion method, and the foaming ratio is 1.1 to 3.0 times.
The pressure-sensitive adhesive laminate according to the invention of claim 5 is such that the total thickness of the pressure-sensitive adhesive laminate is 200 to 500 μm, and the thickness of the pressure-sensitive adhesive layer is 5 to 30% of the total thickness of the pressure-sensitive adhesive laminate. It is a thing.

According to the first aspect of the present invention, no solvent is used, the number of manufacturing steps is small, the molding processability is excellent, and it is possible to manufacture by extrusion molding that is also excellent in economic efficiency. Can be easily rewound after storage and distribution, can be attached to the adherend with good adhesion, has excellent workability and mechanical suitability during use, and is easy to peel when there is little change in adhesive strength over time An adhesive laminate that can be peeled is provided.
According to the second aspect of the present invention, in addition to the effect of the first aspect, there is provided a pressure-sensitive adhesive laminate that can be easily peeled off when it is desired to peel with little change in adhesive force over time.
According to the third aspect of the present invention, in addition to the effect of the first aspect, there is provided a pressure-sensitive adhesive laminate that can be easily peeled off when it is desired to peel with little change in adhesive force over time.
According to the fourth aspect of the present invention, in addition to the effects of the first to third aspects, a pressure-sensitive adhesive laminate having more excellent buffering properties is provided.
According to this invention of Claim 5, in addition to the effect of Claims 1-4, the adhesion laminated body which has moderate rigidity is provided.

Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view of an adhesive laminate showing one embodiment of the present invention.

  (Adhesive Laminate) As shown in FIG. 1, the adhesive laminate 10 of the present invention has a back layer 11, a foam layer 13 and an adhesive layer 19 laminated in this order. The pressure-sensitive adhesive laminate 10 is formed by a multilayer coextrusion molding method. The adhesive layer 19 is made of an ethylene-α-olefin copolymer and a styrene thermoplastic elastomer polymerized under a metallocene catalyst.

  By doing in this way, the unwinding force between the back surface layer 11 and the adhesion layer 19 can be 0.1 N / 25mm or less. The rewinding force between the back layer 11 and the adhesive layer 19 is the rewinding force between the first back layer 11 and the second adhesive layer 1919 using the two adhesive laminates 10. It was measured by a test method based on the JIS-Z-0237 adhesive tape / adhesive sheet test method. For this reason, even if the adhesive layer 19 with good adhesion is used or manufactured and used in a wound state, winding wrinkles are unlikely to occur during manufacturing. Even in use, even if the pressure-sensitive adhesive laminate is overlapped in a wound state, the front and back surfaces do not adhere (blocking phenomenon), and the wound pressure-sensitive adhesive laminates 10 can be separated. For this reason, since the adhesive laminate itself is not cut and can be easily rewound, the supply is stable, and workability and mechanical suitability can be improved.

  (Back layer) As the back layer 11, a thermoplastic resin, that is, a resin that reversibly softens at a high temperature can be applied. The thermoplastic resin is not particularly limited, and specific examples include, for example, polyolefin resins such as polyethylene and polypropylene, polyamide resins, polyester resins such as polybutylene terephthalate and polyethylene terephthalate, vinyl chloride, polyphenylene ether, Examples thereof include polyphenylene ether resins such as modified polyphenylene ether, styrene resins such as polystyrene and heat-resistant polystyrene, acrylic resins, acrylonitrile / butadiene / styrene resins, and polycarbonate. These resins may be used alone or in combination of two or more. Preferably, polyethylene resins such as low density polyethylene and ethylene copolymer having extrudability and moderate rigidity are preferable. Moreover, it is preferable also from the point of the prevention of a spear which will be described later.

  (Foaming layer) The foaming layer 13 is formed by foaming a composition comprising a thermoplastic resin and a foaming agent, preferably a chemical foaming agent, simultaneously with the film formation by the multilayer coextrusion method, and the foaming ratio is 1.1. ˜3.0 times.

  (MFR of foam layer) The foam layer 13 in the pressure-sensitive adhesive laminate of the present invention is constituted by adding a foaming agent to a base resin made of a thermoplastic resin. The base resin preferably has a low MFR exhibiting high melt strength and melt elasticity, and preferably has an MFR of 0.5 to 10.0 g / 10 min. If the MFR is less than this range, the expansion ratio cannot be obtained, and if it exceeds this range, the bubble shape becomes poor.

  (Foaming agent) The chemical foaming agent is preferably an inorganic foaming agent. Organic foaming agents are undesirable because they generate decomposition gases such as ammonia gas, nitrogen gas, and carbon monoxide gas, and decomposition residues and sublimation substances cause contamination and corrosion of processing machines and metal products. . As the inorganic foaming agent used in the present invention, a foaming agent composed of sodium hydrogen carbonate whose generated gas is carbon dioxide and water vapor is suitable.

  (Addition amount) In the present invention, the above foaming agent is added in the range of 0.1 to 2.0% by mass. More preferably, it is 0.2 to 1.0 mass% addition. If the amount is less than 0.1% by mass, the dispersion is poor and sufficient foaming cannot be obtained. If the amount exceeds 2.0% by mass, fine foaming cannot be realized, and may not easily occur during production. By adding 0.1 to 2.0% by mass of a foaming agent to the above base resin, a foamed layer having a foaming ratio of 1.1 to 3.0 times can be obtained. If the expansion ratio is less than this range, the buffering property is insufficient, and if it exceeds this range, it is difficult to obtain closed cells and the surface state is deteriorated. By setting the expansion ratio to 1.1 to 3.0 times, a buffer function, handling suitability, and strength can be realized.

  (Meani) Extrusion molding method has a defect that when it is extruded from a die, resinous deposits (Mayani) such as extruded resin composition and its oxide are generated at the outlet (die lip) of the die. Must. By providing the back surface layer 11, it is possible to prevent the occurrence of resinous deposits on the die lip at the time of molding, and the productivity can be improved.

  The foaming agent is generally added using a high-concentration master batch and mixed with the base resin to obtain a desired addition concentration. What is necessary is just to determine suitably the density | concentration of a masterbatch so that the foaming agent density | concentration in the foaming layer 13 may become the range of 0.1-2.0 mass%. Further, any of the back layer 11, the foam layer 13 and the adhesive layer 19 may be used within a range that does not affect the function, for example, a lubricant, a plasticizer, a filler, an antistatic agent, an antiblocking agent, a crosslinking agent, and an antioxidant. Additives such as ultraviolet absorbers, light stabilizers, colorants such as dyes and pigments, and others may be added.

  (Adhesion layer) The adhesion layer 19 is an ethylene-α-olefin copolymer polymerized under a metallocene catalyst and a styrene thermoplastic elastomer.

  (Ethylene-α-olefin copolymer) The ethylene-α-olefin copolymer is a copolymer of ethylene and α-olefin produced in the presence of a metallocene catalyst. Preferably, it is a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and specific examples include linear low density polyethylene (LLDPE).

  (Elastomer) Hydrogenated diene copolymer includes vinyl aromatic compound polymer block (A), conjugated diene polymer or random copolymer block of vinyl aromatic compound and conjugated diene (B), vinyl aromatic compound And (A)-(B) block copolymer comprising at least block (A) and block (B) of a tapered block (C) in which vinyl aromatic compounds gradually increase among conjugated dienes, (A)-(B )-(A) block copolymer, (A)-(B)-(C) block copolymer The selected block copolymer was hydrogenated to saturate more than 80% of the conjugated diene double bonds. One or a plurality of hydrogenated diene copolymers are used. The styrene-isobutylene block copolymer is a styrene-isobutylene block copolymer in which the hard segment is a polystyrene compound and the soft segment is polyisobutylene.

The vinyl aromatic compound used in the hydrogenated diene copolymer of the present invention is styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N— Examples include diethyl-p-aminoethyl styrene and vinyl pyridine, and styrene and α-methyl styrene are particularly preferable. Conjugated dienes are 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5- Examples include diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene, etc. In order to obtain a hydrogenated diene copolymer excellent in physical properties, 1,3-butadiene, isoprene 1,3-pentadiene is preferred.

  The hydrogenated diene copolymer includes the vinyl aromatic compound polymer block (A), a conjugated diene polymer, or a random copolymer block (B) of a vinyl aromatic compound and a conjugated diene, and a vinyl aromatic compound. The conjugated diene is obtained by hydrogenating a diene block copolymer containing at least (A) and (B) of the tapered block (C) in which the vinyl aromatic compound gradually increases. Here, the diene block copolymer preferably has a configuration of (A)-(B), (A)-(B)-(A), or (A)-(B)-(C). Further, the block (A) and the block (B) do not necessarily need to be clearly distinguished, and a tapered portion where the vinyl aromatic compound gradually decreases as the block (A) shifts to the block (B). A configuration having

  Furthermore, in the hydrogenated diene copolymer of the present invention, 80% or more, preferably 90% or more of the conjugated diene portion of the block (B) needs to be hydrogenated and saturated. Here, when the hydrogenation rate is 80% or less, the heat resistance and weather resistance are poor. In the styrene-isobutylene block copolymer of the present invention, the hard segment is composed of a polystyrene compound and the soft segment is composed of polyisobutylene, and the soft segment does not contain a double bond by using isobutylene. The styrene-isobutylene block copolymer includes a styrene polymer block (A), an isobutylene polymer block, a random copolymer block (B) of styrene and isobutylene, and a random copolymer of styrene and isobutylene. (A)-(B) block copolymer, (A)-(B)-(A) block comprising at least block (A) and block (B) of tapered block (C) in which styrene gradually increases in the coalescence A copolymer and a block copolymer (A)-(B)-(C) can be used.

  Polystyrene compounds of the styrene-isobutylene block copolymer include styrene, o-, m-, p-methylstyrene, α-methylstyrene, β-methylstyrene, 2,6-dimethylstyrene, 2,4-dimethyl. Styrene, α-methyl-o-methylstyrene, α-methyl-m-methylstyrene, α-methyl-p-methylstyrene, β-methyl-o-methylstyrene, β-methyl-m-methylstyrene, β-methyl -P-methylstyrene, 2,4,6-trimethylstyrene, α-methyl-2,6-dimethylstyrene, α-methyl-2,4-dimethylstyrene, β-methyl-2,6-dimethylstyrene, β- Examples include methyl-2,4-dimethylstyrene. These may be used alone or in combination of two or more.

  It is well known that a compound containing a double bond is decomposed or aged by heat or aging, and particularly a raw rubber containing a lot of double bonds is aged rapidly. That is, heat resistance stability (heat aging resistance), weather resistance, and the like are deteriorated, and the adhesive force varies. However, since the adhesive layer 19 of the present invention has few or no double bonds, it is compared with conventional unsaturated or hydrogenated adhesives such as styrene-butadiene-styrene and styrene-isoprene-styrene block copolymers. Excellent heat resistance and weather resistance. Furthermore, excellent properties such as flexibility, vibration damping properties, and gas barrier properties derived from polyisobutylene can be imparted.

  (Manufacturing method) As a manufacturing method of the adhesion laminated body 10, there exist an inflation film forming method, a T-die film forming method, etc. If multilayer coextrusion molding is possible, it will not specifically limit.

  (Thickness) The pressure-sensitive adhesive laminate 10 has a three-layer structure of a back layer 11 / a foam layer 13 / an adhesive layer 19, and a thickness of 200 μm to 500 μm is suitable. If it is less than 200 μm, the amount of bubbles contained is small, and the foaming feeling is insufficient. The thickness of the adhesive layer 19 is preferably in the range of 5 to 30% of the total thickness of the adhesive laminate 10. If the thickness of the pressure-sensitive adhesive layer 19 is less than 5% of the total thickness, the pressure-sensitive adhesiveness may be insufficient and the back layer 11 / foamed layer 13 may not be supported, which is not preferable. On the other hand, if it exceeds 30%, the rigidity of the pressure-sensitive adhesive laminate is insufficient.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it is not limited to this. In addition, except a solvent, each composition of each layer is a mass part of solid content conversion.

(Example 1) As the back layer 11, the foam layer 13, and the adhesive layer 19, the following compositions were used, respectively, by a three-layer multilayer coextrusion molding, an air-cooled top blown film forming method, and a film forming temperature of 230 ° C. The adhesive layered product of Example 1 in which the back layer 11 is 15 μm / the foam layer 13 is 235 μm / the adhesive layer 19 is a total thickness of 300 μm consisting of three layers, and the foam layer 13 has an expansion ratio of 2.0 times. Manufactured.
As the (back layer 11), 100 parts by mass of a low density polyethylene resin, Sumikasen G201F manufactured by Sumitomo Chemical Co., Ltd. (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) was adjusted.
As the (foaming layer 13), 97 parts by mass of low density polyethylene resin, Sumikasen G201F (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nitto Chemical Industries, Ltd. 3 parts by mass of a blowing agent master batch and fine blow S-20N (20% master batch) were prepared.
(Adhesion layer 19) 80 parts by mass of a linear low density polyethylene resin, Kernel KS340T (density = 0.880 g / cm ³ , MFR = 3.5 g / 10 min) manufactured by Nippon Polyethylene Co., Ltd., made by Kraton Polymer 20 parts by mass of Clayton MD6649 (MFR = 15 g / 10 min) was adjusted.

(Example 2) The pressure-sensitive adhesive laminate 10 of Example 2 was produced in the same manner as in Example 1 except that the following compositions were used as the back layer 11, the foam layer 13, and the pressure-sensitive adhesive layer 19, respectively.
As the (back layer 11), 100 parts by mass of a low density polyethylene resin, Sumikasen G201F manufactured by Sumitomo Chemical Co., Ltd. (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) was adjusted.
As the (foaming layer 13), 97 parts by mass of low density polyethylene resin, Sumikasen G201F (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nitto Chemical Industries, Ltd. 3 parts by mass of a blowing agent master batch and fine blow S-20N (20% master batch) were prepared.
(Adhesion layer 19) 90 parts by mass of a linear low density polyethylene resin, a kernel KS340T (density = 0.880 g / cm ³ , MFR = 3.5 g / 10 min) manufactured by Nippon Polyethylene Co., Ltd., manufactured by Kraton Polymer Clayton MD6649 (MFR = 15 g / 10 min) was adjusted to 10 parts by mass.

(Example 3) An adhesive laminate 10 of Example 3 was produced in the same manner as in Example 1 except that the following compositions were used as the back layer 11, the foam layer 13, and the adhesive layer 19, respectively.
As the (back layer 11), 100 parts by mass of a low density polyethylene resin, Sumikasen G201F manufactured by Sumitomo Chemical Co., Ltd. (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) was adjusted.
As the (foaming layer 13), 97 parts by mass of low density polyethylene resin, Sumikasen G201F (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nitto Chemical Industries, Ltd. 3 parts by mass of a blowing agent master batch and fine blow S-20N (20% master batch) were prepared.
(Adhesion layer 19) 80 parts by mass of a linear low density polyethylene resin, Kernel KF360T (density = 0.898 g / cm ³ , MFR = 3.5 g / 10 min) manufactured by Nippon Polyethylene Co., Ltd., manufactured by Kraton Polymer 20 parts by mass of Clayton MD6649 (MFR = 15 g / 10 min) was adjusted.

(Comparative Example 1) An adhesive laminate 10 of Comparative Example 1 was produced in the same manner as in Example 1 except that the following compositions were used as the back layer 11, the foam layer 13, and the adhesive layer 19, respectively.
As the (back layer 11), 100 parts by mass of a low density polyethylene resin, Sumikasen G201F manufactured by Sumitomo Chemical Co., Ltd. (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) was adjusted.
As the (foaming layer 13), 97 parts by mass of low density polyethylene resin, Sumikasen G201F (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nitto Chemical Industries, Ltd. 3 parts by mass of a blowing agent master batch and fine blow S-20N (20% master batch) were prepared.
As the (adhesive layer 19), 100 parts by mass of a linear low density polyethylene resin and a kernel KS340T (density = 0.880 g / cm ³ , MFR = 3.5 g / 10 min) manufactured by Nippon Polyethylene Co., Ltd. were adjusted.
The adhesive strength of the pressure-sensitive adhesive laminate 10 of Comparative Example 1 to the methacrylic resin surface and the unwinding force between the back surface layer 11 and the pressure-sensitive adhesive layer 19 were very weak and could not be measured due to peeling.

(Comparative Example 2) An adhesive laminate 10 of Comparative Example 2 was produced in the same manner as in Example 1 except that the following compositions were used as the back layer 11, the foam layer 13, and the adhesive layer 19, respectively.
(Back layer 11) was omitted.
As the (foaming layer 13), 97 parts by mass of low density polyethylene resin, Sumikasen G201F (density = 0.919 g / cm ³ , MFR = 2.0 g / 10 min) manufactured by Sumitomo Chemical Co., Ltd., manufactured by Nitto Chemical Industries, Ltd. 3 parts by mass of a blowing agent master batch and fine blow S-20N (20% master batch) were prepared.
(Adhesion layer 19) 80 parts by mass of a linear low density polyethylene resin, Kernel KS340T (density = 0.880 g / cm ³ , MFR = 3.5 g / 10 min) manufactured by Nippon Polyethylene Co., Ltd., made by Kraton Polymer 20 parts by mass of Clayton MD6649 (MFR = 15 g / 10 min) was adjusted.
In the production of the pressure-sensitive adhesive laminate 10 of Comparative Example 2, since there is no back layer, the foamed layer is exposed on the surface, a large amount of burrs are generated on the die lip, continuous film formation is not possible, and the surface of the pressure-sensitive adhesive laminate is extremely rough. It was not practical.

  (Evaluation method) Using the adhesive laminates 10 of Examples 1 to 3 and Comparative Examples 1 to 2, the buffer function was evaluated from the initial adhesive force, the unwinding force, and the expansion ratio. The results are shown in Table 1.

(Measurement method) Foaming magnification was determined by forming the pressure-sensitive adhesive laminates 10 of Examples and Comparative Examples and allowing them to stand at 23 ° C. for 1 day, then cutting in the thickness direction, photographing the cut surface with an optical microscope, and foaming. The expansion ratio was calculated from the area ratio of the foamed portion and the unfoamed portion of the layer 13. An expansion ratio of 1.1 to 3.0 times is regarded as acceptable and is represented by “◯”.
The initial adhesive force is a rubber roll (weight 2 kg, width 45 mm, roll diameter) defined in JIS-Z-0237, in which the adhesive layer 19 of the adhesive laminate 10 of Examples and Comparative Examples is stacked on a methacryl plate having a thickness of 3 mm. 95 mm, rubber hardness 80 ± 5 Hs), one reciprocal pressure bonding was performed, and after 1 hour, the peel strength at 180 ° peeling was measured at a pulling rate of 300 mm / min to determine the adhesive strength.
(Rewinding force) Cut out from the pressure-sensitive adhesive laminate 10 of Examples 1 and 2 with a width of 25 mm,
The two back layers 11 and the second pressure-sensitive adhesive layer 19 are overlapped, and the 180 ° peel strength is peeled by a test method in accordance with the JIS-Z-0237 pressure-sensitive adhesive tape / pressure-sensitive adhesive sheet test method. Was measured at a pulling speed of 300 mm / min, and the unwinding force between the back layer 11 and the adhesive layer 19 was determined. The unwinding force is an index of the unwinding property at the time of use. In order to easily unwind, it is necessary to set the unwinding force to 0.5 N / 25 mm or less, preferably 0.1 N / 25 mm or less.
The MFR is a measured value of the outflow amount for 10 minutes in a condition of 190 ° C. and a load of 21.2 N in accordance with JIS-K-7210.

(Evaluation results) In the pressure-sensitive adhesive laminates 10 of Examples 1 to 3, the production was satisfactory, the foaming ratio indicating buffering property was “◯”, and the adhesive strength was 2.9, 2.2, and 2.7, respectively. The rewinding force (rewinding force) was 0.1 N / 25 mm or less, and there was no problem in the manufacture, processing, and use in a wound form.
In Comparative Example 1, the initial adhesive force with respect to the methacrylic resin surface and the unwinding force between the back surface layer 11 and the adhesive layer 19 were very weak and were peeled off, so measurement was impossible. In the production of Comparative Example 2, since there is no back layer, the foam layer is exposed on the surface, a large amount of scum is generated on the die lip, continuous film formation is not possible, the surface of the adhesive laminate is extremely rough, and is not practical. And the product was not obtained.

It is sectional drawing of the adhesion laminated body which shows one Example of this invention.

Explanation of symbols

11: Back layer 13: Foam layer 19: Adhesive layer

Claims (5)

In the adhesive laminate in which the back layer, the foam layer and the adhesive layer are sequentially laminated,
A composition comprising a polyethylene-based resin reversibly softened at a high temperature, a thermoplastic resin having a melt flow rate (MFR) in the range of 0.5 to 10.0 g / 10 min, and a foaming agent, and a metallocene Preparing an ethylene-α-olefin copolymer polymerized under a catalyst and a styrenic thermoplastic elastomer;
Next, a thermoplastic resin and a foaming agent in which the polyethylene resin that is reversibly softened by the high temperature and the melt flow rate (MFR) are in the range of 0.5 to 10.0 g / 10 min. And a composition containing an ethylene-α-olefin copolymer polymerized under the above-mentioned metallocene catalyst and a styrene-based thermoplastic elastomer, and forming them by a multilayer coextrusion molding method. Foam at the same time as
Thermoplastic resin and foaming agent in which the back layer made of polyethylene resin that is reversibly softened by the high temperature and the melt flow rate (MFR) are in the range of 0.5 to 10.0 g / 10 min. And a pressure-sensitive adhesive laminate in which an adhesive layer made of a composition containing an ethylene-α-olefin copolymer polymerized under the above metallocene catalyst and a styrene-based thermoplastic elastomer is sequentially laminated. Consists of
Furthermore, using the two adhesive laminates described above, the first back layer and the second adhesive layer are stacked, and the test method conforms to the JIS-Z-0237 adhesive tape / adhesive sheet test method. The pressure-sensitive adhesive laminate is characterized in that the unwinding force between the back layer and the pressure-sensitive adhesive layer measured in the above is in the range of 0.1 N / 25 mm or less and 0.02 N / 25 mm. The styrenic thermoplastic elastomer is a hydrogenated diene copolymer and is a vinyl aromatic compound polymer block (A), a conjugated diene polymer or a random copolymer block of a vinyl aromatic compound and a conjugated diene (B), (A)-(B) block copolymer comprising at least block (A) and block (B) of a taper block (C) in which vinyl aromatic compounds gradually increase among vinyl aromatic compounds and conjugated dienes, A block copolymer selected from A)-(B)-(A) block copolymer and (A)-(B)-(C) block copolymer is hydrogenated to give 80 conjugated diene double bonds. 2. The pressure-sensitive adhesive laminate according to claim 1, wherein the pressure-sensitive adhesive laminate is one or more of hydrogenated diene copolymers saturated with at least%. 2. The pressure-sensitive adhesive laminate according to claim 1, wherein the styrene-based thermoplastic elastomer is a styrene-isobutylene block copolymer in which a hard segment is composed of a polystyrene-based compound and a soft segment is composed of polyisobutylene. The foam layer is formed by foaming a composition comprising a thermoplastic resin and a chemical foaming agent simultaneously with film formation by the multilayer coextrusion method, and the foaming ratio is 1.1 to 3.0 times. The pressure-sensitive adhesive laminate according to any one of claims 1 to 3. The total thickness of the said adhesive laminated body is 200-500 micrometers, and the thickness of the said adhesive layer is 5-30% of the total thickness of the said adhesive laminated body, The any one of Claims 1-2 characterized by the above-mentioned. The pressure-sensitive adhesive laminate according to item 1.

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