JP2019116554A - Composition, adhesive and adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition having a high initial adhesive force and suppressing a change with time of the adhesive force at a high temperature. The composition of the present invention is an amorphous olefin having a unit based on propylene and a unit based on at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. -Based copolymer, and acid or amine modification of a block copolymer having a segment based on an aromatic vinyl compound polymer and a segment based on a conjugated diene compound polymer or a hydrogenated product of the conjugated diene compound polymer The content of the amorphous olefin-based copolymer is 60 to 99.5 parts by mass based on 100 parts by mass of the total amount of the amorphous olefin-based copolymer and the acid- or amine-modified product. [Selection diagram] None

Description

  The present invention relates to a composition, an adhesive and an adhesive film.

  Conventionally, for self-adhesive type pressure-sensitive adhesives, ethylene-vinyl acetate copolymers, ethylene-α-olefin copolymers, ethylene-based copolymers, amorphous polyolefins, styrene elastomers, etc. Crystalline or amorphous polymers are used.

  Patent Document 1 discloses a surface protection film comprising a base material layer made of a polyolefin resin, and an adhesive layer made of an acid-modified product of a block copolymer having a styrene polymer block and an olefin polymer block. . Patent Document 2 discloses a hot melt adhesive containing an acid-modified thermoplastic block copolymer, a tackifying resin, a plasticizing oil and a wax. Furthermore, Patent Document 3 discloses a composition for an adhesive comprising an amorphous olefin polymer, an aromatic vinyl / conjugated diene block copolymer, or a hydrogenated product thereof.

JP-A-7-26210 JP-A JP 2005-104996 A JP 2005-325154 A

  The pressure-sensitive adhesive is required to exhibit a proper initial adhesive strength when attached to an adherend, and thereafter, can be easily peeled off and can be attached to the adherend again. However, the initial tack of the pressure sensitive adhesive may be insufficient depending on the type of adherend, and the use of the pressure sensitive adhesive may be limited. In addition, although the initial adhesive strength of the adhesive is high, the adhesive strength changes with time and rises at high temperature, and peeling of the adhesive from the adherend becomes difficult, or the adhesive on the surface of the adherend after peeling May survive.

  Therefore, the pressure-sensitive adhesive is required to have high initial adhesive strength to the adherend and to suppress temporal change in adhesive strength at high temperature.

  The present invention provides a composition having high initial tack and suppressed in change of tack with time under high temperature, and high initial tack and with time change of tack under high temperature An object of the present invention is to provide a suppressed pressure sensitive adhesive and a pressure sensitive adhesive film.

  The present invention relates to an amorphous olefin copolymer having units based on propylene and units based on at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms, An acid or amine modified product of a block copolymer comprising a segment based on an aromatic vinyl compound polymer and a segment based on a conjugated diene compound polymer or a hydrogenated product of the conjugated diene compound polymer, which is amorphous The present invention relates to a composition in which the content of the olefin copolymer is 60 to 99.5 parts by mass with respect to 100 parts by mass of the total of the non-crystalline olefin copolymer and the acid or amine modified product.

  The present invention also relates to a pressure-sensitive adhesive comprising the above composition. Furthermore, the present invention relates to a pressure-sensitive adhesive film comprising a base material layer and a pressure-sensitive adhesive layer containing the above-described composition formed on the base material layer.

  According to the present invention, a composition having high initial tackiness and in which temporal change in tackiness under high temperature is suppressed, and a pressure sensitive adhesive and pressure sensitive adhesive film in which temporal change in tackiness under high temperature is suppressed Can be provided.

  The present embodiment will be described in detail. The present invention is not limited to the following embodiments.

[Composition]
The composition of the present embodiment is an amorphous olefin-based copolymer comprising units based on propylene and units based on at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. Acid of block copolymer having combined (component (I)), segment based on aromatic vinyl compound polymer, and segment based on conjugated diene compound polymer or hydrogenated product of the conjugated diene compound polymer Or contains an amine-modified product (component (II)), and the content of the non-crystalline olefin copolymer is 60 parts per 100 parts by weight of the total of the non-crystalline olefin copolymer and the acid or amine modification. 99.5 parts by mass. The composition of the present embodiment is a tacky composition which has high initial tack and in which the change of tack with time under high temperature is suppressed.

(Component (I): Amorphous Olefin-Based Copolymer)
The non-crystalline olefin copolymer according to the present embodiment is at least one selected from the group consisting of a unit based on propylene (hereinafter simply referred to as "propylene unit"), ethylene and an α-olefin having 4 to 20 carbon atoms. And one olefin-based unit. Here, a "unit" is a structural unit when the polymeric compound (for example, propylene) just before that is superposed | polymerized.

  The content of propylene units in the non-crystalline olefin copolymer is preferably 60 to 99 mol%, more preferably 70 to 98.5 mol%, from the viewpoint of enhancing the adhesion of the composition. Preferably it is 77-98 mol%.

  The amorphous olefin copolymer has, in addition to propylene units, ethylene units and / or α-olefin units having 4 to 20 carbon atoms. The amorphous olefin-based copolymer is a copolymer of propylene and ethylene, a copolymer of propylene, ethylene and 4 to 20 α-olefins, or a copolymer of propylene and 4 to 20 α-olefins It may be.

  The ethylene unit in the amorphous olefin copolymer is a component that enhances the flexibility of the composition. When the amorphous olefin-based copolymer has an ethylene unit, the content of the ethylene unit is preferably 40 mol% or less, more preferably 30 from the viewpoint of imparting also the adhesive power while giving flexibility to the composition. It is at most mol%, more preferably at most 20 mol%. The content of the ethylene unit is preferably 0 mol% or more, more preferably 1 mol% or more, and still more preferably 2 mol% or more from the viewpoint of more effectively exhibiting the effect of imparting flexibility.

  The α-olefin unit in the amorphous olefin copolymer is a component that enhances the transparency of the composition. When the non-crystalline olefin copolymer has an α-olefin unit, the content of the α-olefin unit is preferably 40 mol% or less, more preferably 30 mol% or less, and further preferably from the viewpoint of transparency. It is 20 mol% or less. The content of the α-olefin unit is preferably 0 mol% or more, more preferably 1 mol% or more, and still more preferably 2 mol from the viewpoint of more effectively exerting the effect of increasing hardness and keeping appropriate transparency. % Or more.

  As the α-olefin to be an α-olefin unit, an α-olefin having 4 to 20 carbon atoms can be used, and in consideration of availability, cost, copolymerizability, etc., α having 4 to 10 carbon atoms can be used. -An olefin may be used. The α-olefins may be linear or branched.

  Examples of linear α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- There may be mentioned tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene and 1-eicosene. Examples of branched α-olefins include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene and 2,2,4-trimethyl- 1-pentene is mentioned. Among them, it is preferable to use 1-butene, 1-hexene, 1-octene or 1-decene as the α-olefin. The α-olefins may be used alone or in combination of two or more.

  As an amorphous olefin type copolymer, for example, propylene / ethylene copolymer, propylene / ethylene / 1-butene copolymer, propylene / ethylene / 1-hexene copolymer, propylene / 1-butene copolymer, Propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / 4-methyl-1-pentene copolymer and propylene / 1-butene / 1-hexene copolymer can be mentioned.

  The amorphous olefin copolymer according to the present embodiment can be produced using a Ziegler-Natta catalyst or a single site catalyst. A polymerization using a single site catalyst may be used because it has high molecular weight, narrow molecular weight distribution, and a copolymer having an intended composition is easily obtained.

  Single site catalysts include metallocene based catalysts or non-metallocene based complex catalysts. As a metallocene catalyst, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008. JP-A-61-130314, JP-A-3-163088, JP-A-4-268307, JP-A-9-12790, JP-A-9-87313, JP-A-11-80233 The metallocene-based catalysts described in JP-A-10-508055 and the like can be mentioned.

  Examples of nonmetallocene complex catalysts include: JP-A-10-316710, JP-A-11-100394, JP-A-11-80228, JP-A-11-80227, and JP-A-10-513489. Non-metallocene complex catalysts described in JP-A-10-338706, JP-A-11-71420 and the like can be mentioned.

  As a single site catalyst, preferably, it is a metallocene catalyst in view of easy availability. As an example of the manufacturing method of the amorphous olefin copolymer using a metallocene catalyst, the method as described in European Patent Application Publication 1211287 specification, etc. are mentioned.

  By using the non-crystalline olefin copolymer according to the present embodiment, the initial tack of the composition can be improved. The content of the amorphous olefin copolymer in the composition is a non-crystalline olefin copolymer and an amorphous olefin copolymer from the viewpoint of having a high initial tack and suppressing the change in tack with time at high temperature. It is 60 to 99.5 parts by mass, preferably 65 to 99 parts by mass, and more preferably 70 to 98 parts by mass with respect to 100 parts by mass of the total amount of the acid or amine modified product.

  The fact that the olefin copolymer is non-crystalline can be confirmed by having no peak of 1 J / g or more based on melting of crystals when the temperature is raised with a differential scanning calorimeter (DSC). In the present specification, an olefin copolymer having an endothermic peak with a heat quantity of 1 J / g or more due to melting of crystals is considered to be crystalline.

  Here, the presence or absence of an endothermic peak due to melting of the crystal of the olefin copolymer is immediately raised to -50 ° C after raising the temperature from room temperature (usually 20 to 30 ° C) to 200 ° C at a rate of 10 ° C / min. To confirm from the DSC thermogram obtained by measuring the differential scanning calorimetry, which includes 1st heating which is cooled at ° C / min and 2nd heating which is then heated from -50 ° C to 200 ° C at a rate of 10 ° C / min. Can. Specifically, if an endothermic peak of 1 J / g or more is not observed in the temperature raising process from -50 ° C to 200 ° C in the 2nd heating, the olefin copolymer is amorphous. The glass transition temperature of the olefin copolymer can also be confirmed from the DSC thermogram of the temperature rising process from -50 ° C to 200 ° C of 2nd heating in the above-mentioned differential scanning calorimetry.

  After sticking the composition to the adherend, the limiting viscosity measured in tetralin of 135 ° C. of the non-crystalline olefin copolymer from the viewpoint of preventing the composition from remaining on the adherend when peeling off the composition. [Η] is preferably 0.1 dL / g or more, more preferably 0.3 dL / g or more, still more preferably 0.5 dL / g or more, and particularly preferably 0.7 dL / g or more. is there. Further, from the viewpoint of enhancing the molding processability of the composition, the above-mentioned intrinsic viscosity is preferably 10 dL / g or less, more preferably 7 dL / g or less, still more preferably 5 dL / g or less, particularly preferably It is 4 dL / g or less. The measurement of the intrinsic viscosity [η] can be performed in tetralin at 135 ° C. using a Ubbelode viscometer.

  The molecular weight distribution of the non-crystalline olefin copolymer is preferably 3 or less from the viewpoint of preventing the composition from remaining on the adherend when the composition is adhered to the adherend and then peeled off. And 2.5 or less are more preferable. Molecular weight distribution is a ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Mw and Mn can be measured, for example, by 150 C / GPC apparatus made by Waters. As the column, for example, Shodex Packed Column A-80M manufactured by Showa Denko KK can be used. As a molecular weight standard substance, for example, standard polystyrene manufactured by Tosoh Corporation can be used.

(Component (II): acid or amine modified product of block copolymer)
The modified acid or amine according to the present embodiment is a block copolymer having a segment based on an aromatic vinyl compound polymer and a segment based on a conjugated diene compound polymer or a hydrogenated product of the conjugated diene compound polymer. , Acid or amine modified polymers.

  In this embodiment, the segment based on the aromatic vinyl compound polymer possessed by the block copolymer is “segment A”, the conjugated diene compound polymer or the segment based on the hydrogenated product of the conjugated diene compound polymer is “segment B” It is said. Component (II) may contain at least one selected from an A-B-A block copolymer and an A-B block copolymer.

  Examples of the aromatic vinyl compound include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, vinylethylbenzene, vinylxylene, vinylnaphthalene and diphenylethylene. You may use these individually or in combination of 2 or more types. Among these, styrene is preferred.

  Examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-heptadiene, and the like. 1,3-hexadiene is mentioned. These may be used alone or in combination of two or more. Among these, 1,3-butadiene and isoprene are preferable from the viewpoint of availability and economy.

  As a method of producing a block copolymer having a segment based on an aromatic vinyl compound polymer and a segment based on a conjugated diene compound polymer, for example, like the method described in Japanese Patent Publication No. 40-23798. A solution containing an aromatic vinyl compound, a conjugated diene compound and an anionic polymerization initiator is continuously supplied to a reactor to advance the polymerization reaction, and an aromatic vinyl compound / conjugated diene compound block copolymer having an active end A method of obtaining a solution may be used. Examples of methods for producing a block copolymer having a segment based on an aromatic vinyl compound polymer and a segment based on a hydrogenated product of a conjugated diene compound polymer include, for example, JP-B-42-8704 and JP-B-43. No. 6636, JP-A-59-133203 or JP-A-60-79005 to hydrogenate an aromatic vinyl compound / conjugated diene compound block copolymer to obtain a conjugated diene compound There is a method of hydrogenating segments based on coalescing.

  The acid- or amine-modified product according to the present embodiment is an acid-modified block copolymer obtained by adding a compound having an acidic functional group to the above-mentioned block copolymer, or an amine-modified block copolymer obtained by adding an amine compound. Examples of the compound having an acidic functional group include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid and methacrylic acid, and unsaturated carboxylic acid anhydrides such as maleic anhydride and itaconic anhydride. Be Examples of the amine compound include amine compounds such as alkylamines, alkenylamines, arylamines, arylalkylamines, cyclic alkylamines and heterocyclic amines. The compound having an acidic functional group and the amine compound may be used alone or in combination of two or more. From the viewpoint of obtaining high initial adhesion to the substrate, the acid-modified product preferably has a carboxy group or a carboxylic acid anhydride group, and the amine-modified product preferably has an amino group.

  The method for producing the acid or amine modified product is not particularly limited, and, for example, the acid or the acid or amine compound is subjected to a graft reaction under melt mixing conditions in an extruder or the like in an extruder or the like. An amine modified product may be obtained. Also, introducing a compound having an acidic functional group or an amine compound at the initiation end, termination or end of polymerization of the block copolymer obtained by living polymerization, at the initiation of polymerization, at any stage during or after polymerization. The acid or amine modification may also be obtained by

  4,000-120,000 are preferable and, as for the weight average molecular weight (Mw) of the segment A in the block copolymer which concerns on this embodiment, 8,000-60,000 are more preferable. The glass transition temperature (Tg) of the segment A is preferably 20 ° C. or more. 20,000-450,000 are preferable and, as for Mw of the segment B, 50,000-300,000 are more preferable. The Tg of the segment B is preferably -20 ° C or less.

  The mass ratio (A / B) of segment A to segment B is preferably 2/98 to 50/50, more preferably 5/95 to 30/70. The mass ratio (A-B-A / A-B) of the A-B-A type block copolymer and the A-B-type block copolymer is preferably 100/0 to 20/80, more preferably 100. / 0 to 50/50.

  By using the acid or amine modified substance, it is possible to suppress the change with time of the adhesive strength at high temperature of the composition. From the viewpoint of having a high initial tack and suppressing the change in tack over time at high temperature, the content of the acid or amine modification in the composition is a non-crystalline olefin copolymer and an acid or The amount is 0.5 to 40 parts by mass, preferably 1 to 35 parts by mass, and more preferably 2 to 30 parts by mass with respect to 100 parts by mass of the total amount of the amine-modified product.

(Other ingredients)
The composition of the present embodiment may further contain a crystalline propylene-based copolymer from the viewpoint of suppressing the change with time of the adhesive strength. The content of the crystalline propylene-based copolymer is 1 to 100 parts by mass, 1 to 70 parts by mass, or 1 to 50 parts by mass with respect to 100 parts by mass of the total of the amorphous olefin-based copolymer and the acid or amine modified product. It may be parts by mass.

  A tackifying resin, an olefin wax, a plasticizer, various additives, and the like may be added to the composition of the present embodiment without departing from the effects of the present invention.

  As the tackifying resin, for example, rosin-based resins such as rosin, polymerized rosin, rosin ester, etc .; A petroleum resin derived from a fraction, dicyclopentadiene or the like; a phenol resin such as a phenolxylene formaldehyde resin; a coumarone-indene resin; a styrene-diene copolymer; and hydrogenated products of these resins. You may use tackifying resin individually or in mixture of 2 or more types.

  As an olefin wax, the olefin resin obtained by the thermal decomposition method is mentioned, for example. Mn of the olefin resin may be 1,000 to 30,000. The olefin waxes may be used alone or in combination of two or more.

  Examples of the plasticizer include process oils such as paraffinic process oil, naphthene process oil and aromatic process oil; liquid resins such as liquid polybutene, liquid polybutadiene and liquid polyisoprene; hydrogenated products of these liquid resins; And low molecular weight polyisobutylene. The Mn of the liquid resin may be 300 to 6,000. You may use a plasticizer individually or in mixture of 2 or more types.

  Additives include, for example, antioxidants, ultraviolet light absorbers, light stabilizers, adsorbents, organic fillers, inorganic fillers, pigments, dyes and perfumes. The additives may be used alone or in combination of two or more.

  The method of preparing the composition is not particularly limited, and the composition may be prepared, for example, by kneading the non-crystalline olefin copolymer according to the present embodiment and the acid or amine modified product.

  The type or shape of the kneading apparatus is not particularly limited. As a kneading apparatus, for example, a laboplast mill, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a single screw extruder and a twin screw extruder can be mentioned. The kneader may be of either closed or open type, but a closed kneader which can be replaced by an inert gas such as nitrogen gas is preferred.

  The kneading temperature is usually 120 to 250 ° C., preferably 140 to 240 ° C. The kneading time may be appropriately determined depending on the type or amount of the component to be used, the type of the kneading apparatus, and the like. When a pressure kneader or Banbury mixer is used, the kneading time is usually about 3 to 10 minutes. As a kneading method, there may be used a method in which each component is collectively kneaded, or a multi-stage divided kneading method in which the remainder is added after kneading a part of each component and kneading is continued.

[Adhesive]
The pressure-sensitive adhesive of the present embodiment contains the above-described composition. The composition of the present embodiment can be used as a pressure-sensitive adhesive because it has a high initial tackiness and the change with time of the tackiness at high temperatures is suppressed.

[Adhesive film]
The pressure-sensitive adhesive film of the present embodiment includes a base material layer and a pressure-sensitive adhesive layer including the above-described composition formed on the base material layer. The adhesive layer according to the present embodiment has high initial adhesive strength and can suppress time-dependent change in adhesive strength under high temperature, so it can be easily peeled off after being attached to an adherend. , Can be used repeatedly.

  Although it does not specifically limit as a material which comprises a base material layer, For example, Polyester, such as polyolefin, such as polyethylene and a polypropylene, a polyethylene terephthalate, is mentioned.

  The pressure-sensitive adhesive film may be produced by coextruding the composition and the above-mentioned material by a multilayer T-die sheet forming method to simultaneously form the pressure-sensitive adhesive layer and the base material layer. In addition, a pressure-sensitive adhesive film is produced by forming a pressure-sensitive adhesive layer by extruding a composition on a film-like substrate, or by coating and drying a composition dissolved in an organic solvent. It is also good. The thickness of the base material layer is not particularly limited, and may be, for example, 10 to 1,000 μm. The thickness of the adhesive layer is not particularly limited, and may be 10 to 300 μm.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

The compositions of Examples and Comparative Examples were prepared using the following raw materials.
(Component (I))
As an amorphous olefin copolymer, a propylene-1-butene copolymer ("Tuffselenium X1102" manufactured by Sumitomo Chemical Co., Ltd., a constitutional unit of 1-butene: 4 mol%, MFR: 0.8 g / 10 min, a difference Scanning calorimetry: no peak of 1 J / g or more based on melting of crystals in the range of -50 ° C to 200 ° C), and a propylene-1-butene copolymer (constituent unit of 1-butene: 4 mol%, Differential scanning calorimetry: a mixture of 92 parts by mass of a crystalline propylene polymer (melting point: 164 ° C.) (without a peak of 1 J / g or more based on melting of crystals in the range of −50 ° C. to 200 ° C.) "Tough selenium H5002" manufactured by Sumitomo Chemical Co., Ltd., MFR: 10.0 g / 10 min) was prepared.

(Component (II))
As a modified block copolymer, maleic anhydride modified styrene-ethylene-butylene-styrene block copolymer (SEBS) ("Tuftec M1943" manufactured by Asahi Kasei Co., Ltd., MFR: 8.0 g / 10 minutes, styrene / ethylene / butylene ratio Amine-modified SEBS ("Tuftec MP10" manufactured by Asahi Kasei Corporation, MFR: 4.0 g / 10 min, styrene / ethylene / butylene ratio: 30/70) was prepared.

(Other ingredients)
As other components, unmodified SEBS ("Tough Tech H1041" manufactured by Asahi Kasei Co., Ltd., MFR: 5.0 g / 10 min, styrene / ethylene / butylene ratio: 30/70), maleic anhydride modified polypropylene resin (Mitsui Chemical Co., Ltd. "Admar QB510" manufactured by the company, has a peak of 1 J / g or more based on melting of crystals in the range of -50 ° C to 200 ° C, melting point: 160 ° C, MFR: 2.0 g / 10 min), polypropylene resin (Sumitomo Chemical Co., Ltd. "Nobren FLX80E4" manufactured by the company, with a peak of 1 J / g or more based on melting of crystals in the range of -50 ° C to 200 ° C, melting point: 164 ° C, MFR: 7.5 g / 10 min), alicyclic saturated hydrocarbon Resin (“Arcon P-125” manufactured by Arakawa Chemical Industries, Ltd.), paraffin oil (“PW-380” manufactured by Idemitsu Kosan Co., Ltd.), And polypropylene wax ("Ricosene PP1302" manufactured by Clariant) were prepared.

  The MFR is a value measured under the conditions of a temperature of 230 ° C. and a load of 2.16 kgf in accordance with JIS K 7210.

Example 1
A composition was prepared using 90 parts by weight of "Tough Selenium H5002" and 10 parts by weight of "Tuftec M 1943". The composition obtained is used as an adhesive layer, and a polypropylene resin "NOBRENE FLX80E4" is used as a substrate layer, and an adhesive layer and a substrate layer are provided by a multilayer T-die sheet forming method at a cylinder temperature of 230 ° C of an extruder. An adhesive film was produced. The thickness of the adhesive layer was 10 μm, and the thickness of the base layer was 50 μm.

(Example 2)
An adhesive film was obtained in the same manner as in Example 1, except that 70 parts by mass of "Tough Selenium H5002" and 30 parts by mass of "Tuftec M 1943" were used.

(Example 3)
A composition was prepared by kneading 91 parts by mass of "Tough Selenium X1102", 2 parts by mass of "Tough Tech M1943" and 7 parts by mass of "No-Blen FLX 80 E4" at 200 ° C for 5 minutes with a laboplast mill. Moreover, a polyester film ("Lumirror S10" manufactured by Toray Industries, Inc.) having a thickness of 75 μm was prepared as a base material layer. The obtained composition was used as a pressure-sensitive adhesive layer, and heat-fused to the base material layer by press molding at a temperature of 200 ° C. for 10 minutes to produce a pressure-sensitive adhesive film. The thickness of the adhesive layer was 100 μm.

(Example 4)
An adhesive film was obtained in the same manner as in Example 3, except that a composition was prepared using 90 parts by mass of "Tough Selenium X 1102" and 10 parts by mass of "Tuftec MP 10".

(Comparative example 1)
An adhesive film was obtained in the same manner as Example 1, except that 100 parts by mass of "Tough selenium H5002" was used to form an adhesive layer.

(Comparative example 2)
An adhesive film was obtained in the same manner as in Example 1 except that a composition was prepared using 50 parts by mass of "Tough Selenium H5002" and 50 parts by mass of "Tough Tech M1943".

(Comparative example 3)
An adhesive film was obtained in the same manner as in Example 1 except that a composition was prepared using 70 parts by mass of "Tough Selenium H5002" and 30 parts by mass of "Tuftec H1041".

(Comparative example 4)
An adhesive film was obtained in the same manner as in Example 3, except that a composition was prepared using 100 parts by mass of "Tough Tech M1943".

(Comparative example 5)
An adhesive film was obtained in the same manner as in Example 3, except that a composition was prepared using 100 parts by mass of "Tough Tech H1041".

(Comparative example 6)
An adhesive film was obtained in the same manner as in Example 3, except that a composition was prepared using 85 parts by mass of "Tough Selenium X 1102" and 15 parts by mass of "Admer QB 510".

(Comparative example 7)
An adhesive film was obtained in the same manner as in Example 3, except that a composition was prepared using 92 parts by mass of "Tough Selenium X 1102" and 8 parts by mass of "No Blen FLX 80 E 4".

(Comparative example 8)
The same as Example 3, except that the composition was prepared using 50 parts by mass of "Tough Tech M1943", 40 parts by mass of "Alcon P-125", 5 parts by mass of "PW-380" and 5 parts by mass of "Lycosene PP1302" To obtain an adhesive film.

(Tackiness)
The adhesive films prepared in Examples and Comparative Examples were cut into strips of 150 × 25 mm, and then the adhesive layer side was bonded to an acrylic plate using a 2 kgf load roll according to JIS Z 0237 to prepare a test piece . After leaving the test piece to stand at 23 ° C. for 30 minutes, a 180 ° peel test was performed in which the adhesive film was peeled from the acrylic plate at 23 ° C. and a peel rate of 300 mm / min to measure initial tack. Moreover, after leaving a test piece to stand for 24 hours at 50 degreeC, the same peeling test was done and the adhesive force after a heating was measured.

(Peelability)
After measuring the adhesive strength after heating, when there is no adhesive layer remaining on the acrylic plate, the case where the adhesive film is peeled is referred to as “layer peeling”, and the case where the adhesive layer remains on the acrylic plate as “cohesive failure”. It shows in 1 and Table 2.

  The adhesive layer formed using the composition of the example had a high initial adhesive strength, and the temporal change of the adhesive strength at high temperature was suppressed.

Claims (5)

An amorphous olefin copolymer having units based on propylene and units based on at least one olefin selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms,
An acid or amine modification of a block copolymer having a segment based on an aromatic vinyl compound polymer and a segment based on a conjugated diene compound polymer or a hydrogenated product of the conjugated diene compound polymer,
The composition wherein the content of the amorphous olefin copolymer is 60 to 99.5 parts by mass with respect to 100 parts by mass of the total of the amorphous olefin copolymer and the acid or amine modified product. object.   The composition according to claim 1, wherein the non-crystalline olefin copolymer has 60 to 99 mol% of units based on propylene.   The composition according to claim 1, further comprising a crystalline propylene-based copolymer.   The adhesive containing the composition as described in any one of Claims 1-3.   The adhesive film provided with the adhesion layer containing the base material layer and the composition as described in any one of Claims 1-3 formed on the said base material layer.