JP2018165374A - Method for producing adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an adhesive tape which allows production of the adhesive tape including an adhesive layer having excellent adhesion to a substrate (core) having a fine irregular surface, for example, a foam substrate, and excellent shear adhesion as well as adhesion retention in a high-temperature environment, even when an aqueous adhesive is used instead of a solvent type adhesive.SOLUTION: A method for producing an adhesive tape includes a step [1] of mixing an adhesive composition (a1) with a cross-linking agent (a2), a step [2] of keeping a mixture (a3) obtained by the step [1] at 0-80°C to obtain an aqueous adhesive (A) and a step [3] of forming an adhesive layer at both sides of a substrate (B) by using the aqueous adhesive (A), and a holding period in the step [2] is within one week.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer formed using a water-dispersed acrylic pressure-sensitive adhesive.

  The adhesive tape is used for the purpose of fixing components in the fields of OA equipment, home appliances, automobiles, and the like. Especially, the adhesive tape which has an adhesive layer on both surfaces of a foam base material is excellent in level | step difference followability and adhesiveness, Therefore For example, it is used suitably for the use etc. which fix components to a curved surface part.

  As the pressure-sensitive adhesive tape, for example, in a molded product adhesive fixing member having a foam as a core and a pressure-sensitive adhesive layer formed on both surfaces thereof, the long axis of the core is the length direction of the core. There is known a molded product adhesive fixing member characterized in that closed cells having an elliptical cross section extending in parallel are provided (for example, see Patent Document 1).

  On the other hand, in order to reduce the environmental burden, the industry has been demanding the development of an adhesive tape that suppresses the emission of volatile organic compounds (so-called VOC). Specifically, as a pressure-sensitive adhesive used for the production of the pressure-sensitive adhesive tape, replacement of a conventional solvent-type pressure-sensitive adhesive with a water-based pressure-sensitive adhesive is required.

  However, the pressure-sensitive adhesive layer formed using the water-based pressure-sensitive adhesive is often inferior in terms of adhesion as compared to the pressure-sensitive adhesive layer formed using the solvent-type pressure-sensitive adhesive, and thus constitutes a pressure-sensitive adhesive tape. In some cases, it is difficult to ensure sufficient adhesion to the core. In particular, the foam base material suitably used as the core is usually often provided with a surface having a fine uneven shape. For this reason, the pressure-sensitive adhesive layer formed using the water-based pressure-sensitive adhesive sometimes fails to exhibit practically sufficient adhesion to the foam substrate.

  In addition, the pressure-sensitive adhesive layer formed using the water-based pressure-sensitive adhesive is often inferior in terms of adhesion as compared with the pressure-sensitive adhesive layer formed using the solvent-type pressure-sensitive adhesive. In some cases, it has been difficult to develop a shear adhesive force and an adhesive retention force under a required high temperature environment.

Japanese Patent Application Laid-Open No. 7-090232

  The problem to be solved by the present invention is that even when a water-based pressure-sensitive adhesive is used instead of a solvent-type pressure-sensitive adhesive, for example, a substrate (core) having a fine uneven surface such as a foam substrate. Another object of the present invention is to provide a method for producing a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having excellent adhesiveness and having excellent shear adhesive strength and adhesive retention strength in a high-temperature environment.

  The present inventor has found that the above problem can be solved by controlling the time until the pressure-sensitive adhesive layer is provided on the substrate surface after mixing the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2). .

  That is, in the present invention, the step [1] of mixing the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2), and the mixture (a3) obtained in the step [1] are maintained at a temperature of 0 ° C. to 80 ° C. Pressure-sensitive adhesive tape which has process [2] which obtains water-based adhesive (A) by doing, and process [3] which provides an adhesive layer on both sides of a substrate (B) by using said water-based adhesive (A) The method for producing a pressure-sensitive adhesive tape is characterized in that the holding period in the step [2] is within one week.

  Since the pressure-sensitive adhesive tape obtained by the production method of the present invention uses an aqueous pressure-sensitive adhesive, adverse effects on the human body and the environment can be reduced. Moreover, the pressure-sensitive adhesive tape obtained by the production method of the present invention has excellent adhesion to a base material (core) having a fine uneven surface, and has excellent shear adhesive strength in a high temperature environment and Because it has adhesive holding power, for example, it is used to fix parts such as emblems to the body of automobiles, etc., and it is used to fix on-board devices such as electronic toll collection systems (electronic toll collection systems, so-called ETC) on-board devices and car navigation systems. Etc. can be suitably used.

  In the production method of the present invention, the step [1] of mixing the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2), and the mixture (a3) obtained in the step [1] at a temperature of 0 ° C. to 80 ° C. Adhesion having step [2] of obtaining aqueous adhesive (A) by holding, and step [3] of providing an adhesive layer on both surfaces of substrate (B) by using said aqueous adhesive (A) Among the tape manufacturing methods, the holding period in the step [2] is within one week.

  First, the step [1] will be described.

  The step [1] is a step of mixing the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2).

  The pressure-sensitive adhesive composition (a1) and the cross-linking agent (a2) are mixed, for example, after supplying one of the pressure-sensitive adhesive composition (a1) and the cross-linking agent (a2) to the other and stirring as necessary. Or by supplying them to other containers and stirring them as necessary.

  The stirring is preferably performed for 10 minutes or more, more preferably 15 minutes or more, and more preferably 20 minutes to 60 minutes, for example, after supplying the crosslinking agent (a2) to the pressure-sensitive adhesive composition (a1). The pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2) are preferable because they can be mixed without variation.

  The step [1] is preferably performed in a temperature environment of 0 ° C. to 60 ° C., and performed in a temperature environment of 10 ° C. to 40 ° C., and a base material (B) such as a foam base material and an adhesive layer It is more preferable to further improve the adhesiveness to and the shear adhesive force and holding force in a high temperature environment.

  Next, the step [2] will be described.

  In the step [2], the mixture (a3) of the pressure-sensitive adhesive composition (a1) and the cross-linking agent (a2) obtained in the step [1] is maintained for a predetermined time under a predetermined temperature condition to thereby form an aqueous pressure-sensitive adhesive. This is a process for manufacturing (A).

  The temperature for holding the mixture (a3) is in the range of 0 ° C to 80 ° C, preferably in the range of 5 ° C to 60 ° C, more preferably in the range of 10 ° C to 50 ° C, and more preferably 15 ° C. A pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer having excellent adhesiveness to the base material (B) and having excellent shear adhesive strength and adhesive retention strength in a high-temperature environment to be in the range of ˜40 ° C. It is further preferable when manufacturing a tape.

  Further, the present invention is characterized in that the holding period in the step [2] is set within one week.

  Even if the holding period is a case where an aqueous pressure-sensitive adhesive is used instead of a solvent-type pressure-sensitive adhesive, for example, excellent adhesion to a substrate (core) having a fine uneven surface such as a foam substrate In order to produce a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer having excellent shearing adhesive strength and adhesive retention in a high-temperature environment, it is set within one week, preferably 10 minutes to 7 days More preferably 15 minutes to 4 days, and even more preferably 30 minutes to 3 days.

  The aqueous pressure-sensitive adhesive (A) obtained by passing through the step [2] may be a non-volatile component in the range of 40% by mass to 70% by mass using a substrate (such as a foam substrate) ( It is preferable for maintaining good workability when coating the surface of B) to form an adhesive layer.

  Next, the step [3] will be described.

  The step [3] is a step of providing a pressure-sensitive adhesive layer on both sides of the substrate (B) using the aqueous pressure-sensitive adhesive (A) obtained in the step [2]. Specifically, as the step [3], the water-based pressure-sensitive adhesive (A) is applied to both surfaces of the base material (B) and dried, so that the pressure-sensitive adhesive layer is formed on both surfaces of the base material (B). Or a pressure-sensitive adhesive layer formed by applying an aqueous pressure-sensitive adhesive (A) on the surface of the release liner and drying, etc., is transferred to both surfaces of the base material (B), and the base material (B ), And a pressure-sensitive adhesive layer is provided on both sides, and the latter step is preferably employed because it is easy to adjust the thickness of the pressure-sensitive adhesive layer and the pressure-sensitive adhesive tape.

Examples of the method of applying the aqueous pressure-sensitive adhesive (A) to the base material (B) or the release liner include a method using a roll coater, a die coater, a lip coater and the like. Moreover, as a method of drying the layer which apply | coated the said water-based adhesive (A), the method of drying in the temperature environment of 20 to 80 degreeC is mentioned. As the method of the said process [3], the dry lamination method is mentioned. And the like. In the step of transferring the formed pressure-sensitive adhesive layer to the substrate (B), it is preferable to use a heating roll. It is preferable to set the temperature of the heating roll to 20 ° C. to 100 ° C., and being carried out in a temperature environment of 40 ° C. to 80 ° C. further improves the adhesion between the pressure-sensitive adhesive layer and the base material (B). In order to further improve the shearing adhesive strength and holding strength in a high temperature environment, it is more preferable.

  As a manufacturing method of the said adhesive tape, you may have the process [4] of curing an adhesive tape as needed other than the said process [1]-[3].

  The step [4] is a step for curing the pressure-sensitive adhesive tape obtained in the step [3].

The curing is preferably performed in a temperature environment of, for example, 20 ° C. to 50 ° C., in order to facilitate the crosslinking reaction of the pressure-sensitive adhesive (A) and to form a pressure-sensitive adhesive layer having a suitable cohesive force.
The curing period is preferably 12 hours or more, more preferably 24 hours or more, and even more preferably 24 hours to 72 hours.

  The curing in the step [4] may be performed in a state where a release liner is laminated on the surface of the pressure-sensitive adhesive layer.

  The pressure-sensitive adhesive tape obtained through the steps [1], [2], [3] and, if necessary, the step [4] is used after obtaining the step [3] or [4]. In order to maintain excellent adhesive force, holding force, etc., it is preferable to store in a temperature environment of 40 ° C. or lower (until it is attached to the adherend).

  In the manufacturing method of the adhesive tape of this invention, a base material (B) is used as a center.

  As said base material (B), a resin film base material, a foam base material, etc. can be used, for example. Especially, it is more preferable when using a foam base material as said base material (B), when providing favorable base material followability and adhesiveness.

  Examples of the foam base material include a foam base material obtained by using an olefin resin such as polyethylene, polypropylene, an ethylene-propylene copolymer, an ethylene-vinyl acetate copolymer, and a foam obtained by using polystyrene. It is obtained by using a body base material, a foam base material obtained using polyurethane, a foam base material obtained using polyvinyl chloride, a foam base material obtained using acrylic rubber, and other elastomers. A foam substrate or the like can be used. Among them, as the foam base material, a foam base material obtained using a polyolefin-based resin is used in order to obtain a pressure-sensitive adhesive tape having even better adhesion to the curved surface portion of the adherend. It is preferable to use a foam base material obtained by using polyethylene, and it is more preferable to use a polyethylene resin obtained by using a metallocene compound containing a tetravalent transition metal. It is more preferable to use a foam base material containing 40% by mass or more based on the mass.

  Polyolefin foams can be preferably used because it is easy to produce a foam base material excellent in step following ability and adhesion to an adherend formed on a tertiary curved surface. In particular, a polyethylene foam can be more preferably used in terms of excellent step following ability.

  As the foam base material, it is possible to use a structure that is elongated in the length direction of the foam base material, and has excellent followability and adhesion to the three-dimensional curved surface of the adherend. It is more preferable in obtaining a pressure-sensitive adhesive tape.

  The average cell diameter in the flow direction of the foam substrate is preferably 1.2 μm to 840 μm, more preferably 12 μm to 600 μm, and further preferably 60 μm to 360 μm. On the other hand, the average cell diameter in the width direction of the foam substrate is preferably 1 μm to 700 μm, more preferably 10 μm to 500 μm, and further preferably 50 μm to 300 μm.

  As the foam base material, it is preferable to use a material having a ratio of an average length in the flow direction and an average length in the width direction of 1.2 to 15, and that having a ratio of 3 to 8 is used. It is more preferable because the flexibility and the tensile strength in the flow direction and the width direction of the foam base material hardly occur.

  In addition, the average bubble diameter of the flow direction of the said foam base material and the width direction points out the value measured in the following way.

  First, a foam base material is cut | disconnected to the magnitude | size of the width method 1cm and the flow direction 1cm.

  Next, a digital microscope (trade name “KH-7700”, manufactured by HiROX) is set to a magnification of 200 times, and a cut surface in the width direction or the flow direction of the foam substrate is observed. In that case, the full length of the thickness direction of the cut surface of the said foam base material is observed. In the observation, all the bubble diameters of the bubbles existing in the range of 2 mm in the flow direction or the width direction of the cut surface are measured. Next, the range of 2 mm is changed, and all the bubble diameters of bubbles existing in arbitrary 10 ranges are measured.

  The value obtained by calculating the average value of the bubble diameters measured above was defined as the average bubble diameter.

  As said foam base material, what has a structure of any one or both of a closed-cell structure and an open-cell structure can be used.

  As said foam base material, it is preferable to use what has a foaming magnification of 1.5 times-20 times, It is more preferable to use what has a foaming magnification of 2 times-10 times, 2.5. In order to further improve the adhesion between the foam base material and the pressure-sensitive adhesive layer, it is more preferable to use a material having a foaming ratio of 2 to 8 times.

  In addition, as the foam base material, it is possible to use one having a foaming ratio of 3 to 6 times, which provides excellent adhesion between the foam base material and the pressure-sensitive adhesive layer, and good flexibility and tension. It is preferable when obtaining an adhesive tape having strength.

As the foam ^substrate, it is preferable to use those having an apparent density of ^{0.1g / cm 3 ~0.7g / cm 3} , 0.2g / cm 3 apparent density of ~0.6g / cm ³ more preferable to use those ^having, it is more preferable to use one having an apparent density of ^{0.25g / cm 3 ~0.5g / cm 3} . The apparent density is a value obtained according to JIS K 6767, and a foam substrate cut into a square of 4 cm in length and 4 cm in width is prepared in an amount corresponding to about 15 cm ³ , and its mass is measured. The apparent density was obtained.

The foam base material is, for example, irradiated with an electron beam or the like, if necessary, by supplying the polyolefin resin and a pyrolytic foaming agent to an extruder, melt-kneading, and forming into a sheet shape, etc. Then, after being crosslinked, it can be produced by foaming and stretching and thinning as necessary.
In addition, after foaming the foam, the foamed sheet may be sliced in the thickness direction and then stretched and peeled with a hot roll.

  Moreover, as a resin film base material which can be used for the said base material (B), polyester base materials, such as a polyethylene terephthalate base material, etc. can be used, for example.

As said base material (B), it is preferable to use what has a thickness of 6 micrometers-25 micrometers. When using the said foam base material as said base material (B), it is preferable to use what has a thickness of 25 micrometers-1200 micrometers as said foam base material, What has a thickness of 50 micrometers-500 micrometers It is more preferable to use, it is more preferable to use a material having a thickness of 100 μm to 300 μm, and a material having a thickness of 150 μm to 250 μm is excellent for the three-dimensional curved surface of the adherend. It is preferable because the repulsive force derived from the base material (B) generated when the adhesive tape is curved is suppressed.
Is particularly preferable.

  As the base material (B), a corona treatment, a flame treatment, a plasma treatment, a hot air treatment, an ozone treatment, an ultraviolet ray treatment, an easy adhesion treatment agent for the purpose of further improving the adhesiveness with the pressure-sensitive adhesive layer and other layers. Those having been subjected to a surface treatment such as coating can be used.

  As the base material (B), if necessary, a filler (inorganic filler, organic filler, etc.), an antioxidant, an antioxidant, an ultraviolet absorber, a colorant (pigment, dye, etc.), a slip agent A material containing a plasticizer or the like can be used.

  Next, the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2) used in the production method of the present invention will be described.

  As said adhesive composition (a1), what contains other components, such as an acrylic polymer (a1-1) and a tackifier resin and a solvent as needed, can be used, for example.

  Examples of the acrylic polymer (a1-1) include those obtained by polymerizing monomer components.

  Examples of the monomer component include alkyl (meth) acrylate.

  Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. , T-butyl (meth) acrylate, n-pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate Undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, it is preferable to use a tetradecyl (meth) having an alkyl group of carbon number 1 to 14 such as acrylates (meth) acrylate.

  Among the above-mentioned alkyl (meth) acrylates, among those described above, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl acrylate, isooctyl (meth) acrylate, n-octyl It is preferable to use (meth) acrylate, and it is more preferable to use n-butyl acrylate and 2-ethylhexyl acrylate in order to impart even more excellent adhesion, and n-butyl acrylate and 2-ethylhexyl acrylate It is more preferable to use in combination in order to achieve both excellent adhesion to the adherend and high heat resistance.

  The alkyl (meth) acrylate is preferably used in an amount of 50% by mass or more, more preferably 70% by mass or more based on the total amount of monomer components used in the production of the acrylic polymer (a1-1). More preferably, it is more preferable to use 80 mass% or more, and it is especially preferable to use 90 mass% or more.

  Moreover, as a monomer component used for manufacture of the said acrylic polymer (a1-1), the vinyl monomer which has a carboxyl group can be used.

  Examples of the vinyl monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, acrylic acid dimer, ethylene oxide-modified succinic acid acrylate, and the like.

  Among these, as the vinyl monomer having a carboxyl group, it is preferable to use acrylic acid or methacrylic acid in order to impart even better adhesion, and it is possible to use acrylic acid and methacrylic acid in combination. In order to achieve both better adhesion to the adherend and high heat resistance

  The vinyl monomer having a carboxyl group is preferably used in an amount of 0.1% by mass to 10% by mass with respect to the total amount of monomer components used in the production of the acrylic polymer (a1-1). 0.5% to 5% by weight is more preferable, 1.5% to 4.5% by weight is more preferable, 2% to 4% by weight is particularly preferable, and 2% to 4% by weight is particularly preferable. It is particularly preferable to use 5 mass% to 3.5 mass%.

  As said monomer component, the vinyl monomer which has a functional group which reacts with the crosslinking agent (a2) mentioned later can be used. For example, in the case of using an epoxy crosslinking agent, a silane crosslinking agent, a carbodiimide crosslinking agent, or an oxazoline crosslinking agent as the crosslinking agent (a2), the vinyl monomer having a functional group that reacts with the crosslinking agent is used. The vinyl monomer having a carboxyl group, the vinyl monomer having a hydroxyl group, and the like can be used.

  The vinyl monomer having a functional group that reacts with the crosslinking agent (a2) is 0.1% by mass to the total amount of monomer components used in the production of the acrylic polymer (a1-1). It is preferable to use 10% by mass, more preferably 0.5% to 5% by mass, more preferably 1.5% to 4.5% by mass, and more preferably 2% to 4% by mass. It is particularly preferable to use 2.5% by mass to 3.5% by mass.

  Moreover, as a monomer component used for manufacture of the said acrylic polymer (a1-1), the vinyl monomer which has a nitrogen atom can be used.

  Examples of the vinyl monomer having a nitrogen atom include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N, N-diethylmethacrylamide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropylacrylamide, N, N-dimethylaminopropylmethacrylamide, diacetoneacrylamide, etc. can be used. It is preferable to use it because it is easy to realize an excellent cohesive force and the shear adhesive strength and the peel adhesive strength can be improved in a high temperature environment.

  The vinyl monomer having a nitrogen atom is preferably used in an amount of 0% by mass to 5% by mass based on the total amount of monomer components used in the production of the acrylic polymer (a1-1). It is more preferable to use 1% by mass to 4% by mass, more preferable to use 0.5% by mass to 3% by mass, and more preferable to use 1% by mass to 2% by mass to achieve excellent cohesive force. It is particularly preferable because it can easily improve the shear adhesive strength and peel adhesive strength in a high temperature environment.

  Moreover, as a monomer component used for manufacture of the said acryl-type polymer (a1-1), in addition to the above-mentioned thing, the vinyl monomer which has a sulfonic acid group, glycol-type acrylic ester single quantity as needed Body, olefinic monomer, vinyl monomer having alkoxysilyl group, vinyl monomer having phosphoric acid group, and the like may be used.

  The acrylic polymer (a1-1) can be produced, for example, by polymerizing the monomer component described above by an emulsion polymerization method.

  The aqueous medium that can be used in the emulsion polymerization may be water alone or a mixed solvent of water and a water-soluble solvent. The above-mentioned “mixed solvent of water and water-soluble solvent” usable in the present invention is a mixed solvent of a water-soluble solvent mainly composed of water, and the water-soluble solvent with respect to the total amount of the mixed solvent. The content of is preferably 10% by mass or less, and more preferably 5% by mass. Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, or polar solvents such as N-methylpyrrolidone, which are used alone. Two or more types may be used in combination.

  Examples of the polymerization initiator that can be used in the emulsion polymerization include 2,2 ′,-azobis (2-methylpropionamidine) dihydrochloride and 2,2′-azobis (2-methylpropionamidine) disulfate. 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-alkoxyethyl) -2-methylpropionamidine] hydrate, 2,2′-azobis Azo initiators such as (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, potassium persulfate, Persulfate initiators such as ammonium sulfate and sodium persulfate, peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, hydrogen peroxide, aromatic carbonyl compounds, etc. Carbonyl-based initiators, combinations of a persulfate and sodium hydrogen sulfite, and the like redox initiators such as a combination of a peroxide and sodium ascorbate.

  Examples of emulsifiers that can be used in the emulsion polymerization include anionic emulsifiers such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, Nonionic emulsifiers such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether can be used.

  As the emulsifier, an emulsifier having a polymerizable unsaturated group generally called “reactive emulsifier” in the molecule is preferably used. For example, LATEMUL S-180 (manufactured by Kao Corporation), LATEMUL PD-104 [Kao Co., Ltd.], Aqualon HS-10 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon HS-20 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon KH-10 [Daiichi Kogyo Seiyaku Co., Ltd.] , Aqualon KH-1025 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon KH-05 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon RN-10 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon RN -20 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon ER-10 [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon ER-20 [Daiichi Kogyo Seiyaku Co., Ltd.], New Frontier A-229E [No. Ichi Kogyo Seiyaku Co., Ltd.] ADEKA rear soap SE-10 [manufactured by ADEKA Corp.], ADEKA rear soap SE-20 [manufactured by ADEKA Corp.], ADEKA rear soap SR-10N [manufactured by ADEKA Corp.], ADEKA rear soap SR-20N [( ADEKA Co., Ltd.] and the like.

  The acrylic polymer (a1-1) preferably has a weight average molecular weight of 500,000 to 1,200,000, more preferably 600,000 to 1,000,000, still more preferably 650,000 to 750,000. By doing so, a high cohesive force can be maintained without impairing the adhesion to the foam substrate, so that a pressure-sensitive adhesive layer excellent in shearing adhesive force, holding force and the like in a high temperature environment can be formed. The said weight average molecular weight is standard polystyrene conversion by a gel permeation chromatography (GPC). As measurement conditions, TSKgel GMHXL [manufactured by Tosoh] is used as the column, the column temperature is 40 ° C., the eluent is tetrahydrofuran, the flow rate is 1.0 mL / min, and the standard polystyrene indicates a value measured using TSK standard polystyrene.

  As said adhesive composition (a1), it is preferable to use what contains tackifying resin other than the said acrylic polymer (a1-1) as needed.

  As the tackifying resin, an emulsion type tackifying resin is preferably used.

  Examples of the emulsion-type tackifying resin include rosin-based tackifying resins, rosin ester-based tackifying resins, modified rosin ester-based tackifying resins, polymerized rosin-based tackifying resins, polymerized rosin ester-based tackifying resins, and rosin phenol-based resins. Examples include tackifier resins, stabilized rosin ester tackifier resins, disproportionated rosin ester tackifier resins, terpene tackifier resins, terpene phenol tackifier resins, petroleum resin tackifier resins, and the like.

  Among these, as the emulsion-type tackifying resin, the adhesiveness between the pressure-sensitive adhesive layer and the base material (B) can be further improved, and the shear adhesive force and holding force under a high temperature environment are further improved. In addition, it is preferable to use a polymerized rosin ester-based tackifier resin.

  Specific examples of the polymerized rosin ester-based tackifier resin include Superester E-625NT [Arakawa Chemical Industries, Ltd.], Superester E-650 [Arakawa Chemical Industries, Ltd.], Superester E- 786-60 [Arakawa Chemical Industries, Ltd.], Superester E-788 [Arakawa Chemical Industries, Ltd.], Superester E-865 [Arakawa Chemical Industries, Ltd.], Superester E-865-NT [Arakawa Chemical Industry Co., Ltd.], Harrier Star SK-508 [Harima Kasei Co., Ltd.], Harrier Star SK-508H [Harima Kasei Co., Ltd.], Harrier Star SK-816E [Harima Kasei Co., Ltd.] ], Harrier Star SK-822E [manufactured by Harima Kasei Co., Ltd.], Harrier Star SK-218NS [manufactured by Harima Kasei Co., Ltd.], Harrier Star SK-218MT [ Lima Kasei Co., Ltd.], HARIESTER SK-323NS [Harima Chemicals Co., Ltd.], and the like can be exemplified.

  The tackifier resin is preferably used in a range of 50 parts by mass or less, and in a range of 5 parts by mass to 40 parts by mass with respect to 100 parts by mass of the acrylic polymer (a1-1). More preferably, it is more preferably used in the range of 10 to 35 parts by mass, and more preferably in the range of 15 to 30 parts by mass in terms of shearing adhesive force and holding force in a high temperature environment. It is particularly preferable for improvement.

  As said adhesive composition (a1), what contains an additive as needed can be used.

  Examples of the additives include plasticizers, softeners, antioxidants, fillers such as glass and plastic fibers, balloons, beads, and metal powders, colorants such as pigments and dyes, pH adjusters, and film formation aids. Agents, leveling agents, thickeners, water repellents, antifoaming agents and the like can be used.

  In the step [1], as the crosslinking agent (a2) used by mixing with the pressure-sensitive adhesive composition (a1), an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a keto-hydrazide crosslinking agent, Oxazoline crosslinking agents, silane coupling agents (silane crosslinking agents), polyvalent metal salts, metal chelates and the like can be used. Especially, as said crosslinking agent (a2), it is preferable to use the crosslinking agent which has 1 or more types of functional groups chosen from the group which consists of an epoxy group, a silanol group, and a hydrolysable silyl group, and an epoxy-type crosslinking agent It is more preferable to use a silane coupling agent in order to achieve the effect of improving the shearing adhesive force and holding force in a high temperature environment.

  Examples of the epoxy-based crosslinking agent include Denacol EX-832 [manufactured by Nagase Kasei Kogyo Co., Ltd.], Denacol EX-841 [manufactured by Nagase Kasei Kogyo Co., Ltd.], Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], Tetrad X [Mitsubishi Gas Chemical Co., Ltd.] etc. can be used.

  Examples of the silane coupling agent include 2- (3,4-epoxycyclohexylethyltrimethoxysilane [KBM-303; manufactured by Shin-Etsu Silicone Co., Ltd.], γ-glycidoxypropyltrimethoxysilane [KBM-403; Shin-Etsu Silicone]. Co., Ltd.], γ-glycidoxypropylmethyldiethoxysilane [KBE-402; Shin-Etsu Silicone Co., Ltd.], γ-glycidoxypropyltriethoxysilane [KBE-403; Shin-Etsu Silicone Co., Ltd.] Etc. can be used.

  The said crosslinking agent (a2) can be suitably adjusted and used in the range which does not impair the effect of this invention. As an index of the degree of cross-linking, there is a gel fraction for measuring the insoluble content after the cured adhesive layer is immersed in toluene for 24 hours. The gel fraction after the curing is preferably 15% by mass to 75% by mass, more preferably 20% by mass to 60% by mass, and further preferably 25% by mass to 55% by mass, It is particularly preferable that the content is 50% by mass to 50% by mass because a further excellent shear adhesive force and holding force can be secured in a high temperature environment.

  On the other hand, the gel fraction obtained by measuring the insoluble content after immersing the adhesive layer before curing in toluene for 24 hours is preferably 0% by mass to 30% by mass, and 0% by mass to 20% by mass. %, More preferably 0% by mass to 15% by mass, particularly preferably 0% by mass to 10% by mass, and 0% by mass to 5% by mass on the surface. This is preferable because the adhesion to a foam substrate having fine irregularities can be further improved.

  The pressure-sensitive adhesive tape obtained by the above method is preferably one having a thickness of 35 μm to 1,600 μm, more preferably one having a thickness of 80 μm to 860 μm, and a thickness of 150 μm to 600 μm. It is more preferable to use a tape having a thickness of 220 μm to 450 μm, and a pressure-sensitive adhesive tape having excellent followability and adhesion to a three-dimensional curved surface of an adherend is used. It is particularly preferable for obtaining.

  The total thickness of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape is preferably 10 μm or more in order to ensure sufficient adhesion to the surface having a fine uneven shape on the surface of the substrate (B). 20 μm to 400 μm is more preferable, 60 μm to 360 μm is further preferable, 100 μm to 300 μm is particularly preferable, and 140 μm to 200 μm is particularly preferable.

  The pressure-sensitive adhesive tape of the present invention obtained by the above method has excellent shear adhesive force and holding force in a high-temperature environment.For example, in the automotive industry field, an emblem, a protective molding, etc. Applications for bonding and fixing resin moldings, applications for mounting electronic fare collection systems (electronic toll collection systems, so-called ETC) on-board devices and car navigation systems (so-called car navigation) on-board devices, etc. on dashboards in automobiles, etc. Can be used for

  Next, the present invention will be described in detail with reference to examples and comparative examples. The evaluation method of each characteristic of the double-sided adhesive tape obtained by the Example and the comparative example is as follows.

(Measurement of average particle size)
The value of the average particle diameter (50% median diameter on a volume basis) measured using a Nikkiso Co., Ltd. Microtrac UPA type particle size distribution measuring device was determined.

(Measurement of molecular weight)
Using a GPC measuring device HLC-8320 manufactured by Tosoh Corporation, using a column TSKgel GMHXL manufactured by Tosoh Corp., column temperature is 40 ° C., eluent is tetrahydrofuran, and flow rate is 1.0 mL / min. The weight average molecular weight was determined. In addition, a weight average molecular weight is standard polystyrene conversion, and TSK standard polystyrene was used for standard polystyrene.

(Measurement of gel fraction)
First, the mass (G0) of what cut the base material which comprises an adhesive tape into a 50 mm square was measured.

  Next, the pre-curing and post-curing pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples were each cut into 50 mm squares and used as samples.

  Next, the mass (G1) of the sample was measured.

  Next, after the sample was immersed in toluene at room temperature for 24 hours, the residue in toluene (insoluble component in toluene) was filtered through a 300 mesh wire mesh and dried at 110 ° C. for 1 hour (G2) Was measured.

  The gel fraction of the pressure-sensitive adhesive layer was calculated based on the masses (G0), (G1) and (G2) and the following formula.

    Gel fraction (mass%) = [(G2-G0) / (G1-G0)] × 100

(Measurement of 180 degree peeling adhesion in 23 ° C environment)
One release liner of the adhesive tape is peeled off, the adhesive layer is lined with 25 μm thick polyethylene terephthalate (PET film), cut into a rectangle with a length of 300 mm and a width of 20 mm, and then the other release liner is peeled off The agent layer was affixed to a stainless steel plate (SUS304 steel plate), subjected to one-time reciprocating pressure bonding with a 2 kg roller, and then allowed to stand in a 23 ° C. environment for 1 hour, which was used as a test piece. Adhesive strength when peeling double-sided adhesive tape from stainless steel plate at a speed of 300 mm / min in a 180 degree direction with a tensile tester (manufactured by A & D Co., Ltd., model: RTM-100) in an environment of 23 ° C. Was measured.

(Measurement of 180 degree peeling adhesion in 70 ° C environment)
One release liner of the adhesive tape is peeled off, the adhesive layer is lined with 25 μm thick polyethylene terephthalate (PET film), cut into a rectangle with a length of 300 mm and a width of 20 mm, and then the other release liner is peeled off The layer was affixed to a stainless steel plate (SUS304 steel plate), subjected to one-time reciprocating pressure bonding with a 2 kg roller, and then allowed to stand in a 23 ° C. environment for 1 hour, which was used as a test piece. The double-sided adhesive tape was peeled off from the stainless steel plate at a speed of 300 mm / min in the direction of 180 ° under a 70 ° C. environment using a tensile testing machine with a thermostatic chamber (manufactured by A & D Co., Ltd., model: RTG-1210). The adhesive strength was measured.

(Measurement of shear adhesive strength at 23 ° C)
After the adhesive tape is cut into squares with a length of 20 mm and a width of 20 mm, the release liners on both sides are peeled off, the adhesive layers on both sides are affixed to a stainless steel plate (SUS304 steel plate), and one-time reciprocating pressure bonding with a 2 kg roller After performing, it left still in 23 degreeC environment for 1 hour, and this was made into the test piece. Under a 23 ° C. environment, the adhesive strength when both stainless steel plates were pulled in the shearing direction at a speed of 300 mm / min was measured with a tensile tester (manufactured by A & D, model: RTM-100).

(Measurement of shear adhesive strength at 70 ° C)
After the adhesive tape is cut into squares with a length of 20 mm and a width of 20 mm, the release liners on both sides are peeled off, the adhesive layers on both sides are affixed to a stainless steel plate (SUS304 steel plate), and one-time reciprocating pressure bonding with a 2 kg roller After performing, it left still in 23 degreeC environment for 1 hour, and this was made into the test piece. Using a tensile tester with a thermostatic chamber (manufactured by A & D Co., Ltd., model: RTG-1210), the adhesive strength when both stainless steel plates were pulled in the shear direction at a speed of 300 mm / min in a 70 ° C environment. It was measured.

(Measurement of adhesion holding force in 23 ° C environment)
One release liner of the adhesive tape is peeled off, the adhesive layer is lined with a 50 μm thick aluminum foil, cut into a rectangle with a length of 60 mm and a width of 20 mm, the other release liner is then peeled off, and the adhesive layer is made of a stainless steel plate (SUS304 steel plate) is pasted so that the pasting area is 400 mm ² (vertical 20 mm, lateral 20 mm), and after one-way pressure bonding with a 2 kg roller, it is allowed to stand in a 23 ° C. environment for 1 hour. This was used as a test piece. Using a holding force tester manufactured by Tester Sangyo Co., Ltd., a load was applied in the shearing direction in a 23 ° C. environment, and the time until dropping was measured. The load conditions were 500 g and 1 kg.

  Evaluation was made according to the following criteria. The evaluation results of ◎ or ○ were evaluated as having practically excellent holding power.

◎: Hold for 24 hours or more ○: Hold for 18 hours or more and dropped in less than 24 hours Δ: Hold for 12 hours or more and dropped in less than 18 hours ×: Dropped in less than 12 hours

(Measurement of adhesive retention in 70 ° C environment)
One release liner of the adhesive tape is peeled off, the adhesive layer is lined with a 50 μm thick aluminum foil, cut into a rectangle with a length of 60 mm and a width of 20 mm, the other release liner is then peeled off, and the adhesive layer is made of a stainless steel plate (SUS304 steel plate) is pasted so that the pasting area is 400 mm ² (vertical 20 mm, lateral 20 mm), and after one-way pressure bonding with a 2 kg roller, it is allowed to stand in a 23 ° C. environment for 1 hour. This was used as a test piece. Using a holding force tester manufactured by Tester Sangyo Co., Ltd., a load was applied in the shearing direction in an environment of 70 ° C., and the time until dropping was measured. The load condition was 500 g.

  Evaluation was made according to the following criteria. The evaluation results of ◎ or ○ were evaluated as having practically excellent holding power.

◎: Hold for 24 hours or more ○: Hold for 18 hours or more and dropped in less than 24 hours Δ: Hold for 12 hours or more and dropped in less than 18 hours ×: Dropped in less than 12 hours

(Preparation Example 1)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (1)>
In a container, 75 g of deionized water and Aqualon KH-1025 as a surfactant (Daiichi Kogyo Seiyaku Co., Ltd .; active ingredient 25% by mass) and Latem PD-104 as a surfactant (Kao Corporation); Active ingredient 20% by mass] 37.5 g was added and dissolved uniformly. Emulsified by adding 227.5 g of n-butyl acrylate, 227.5 g of 2-ethylhexyl acrylate, 25 g of methyl methacrylate, 6 g of N-vinylpyrrolidone, 4 g of acrylic acid, 10 g of methacrylic acid, and 0.2 g of lauryl mercaptan as a chain transfer agent. As a result, 632.7 g of emulsion (1) was obtained.

  A reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel was charged with 333.35 g of deionized water, and the temperature was raised to 60 ° C. while blowing nitrogen. While stirring, a part of emulsion (1) 7.59 g, ammonium persulfate aqueous solution 2.5 g [active ingredient 6% by mass], sodium hydrogen sulfite aqueous solution 2.5 g [active ingredient 2% by mass] were added, While maintaining, polymerization was carried out in 1 hour.

  Next, 625.11 g of the remaining emulsion (1) and 50 g of an aqueous solution of a water-soluble azo initiator 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride [active ingredient] 0.5% by mass] was dropped and polymerized over 8 hours using a separate funnel while keeping the reaction vessel at 60 ° C.

  Next, 2.5 g of an aqueous solution of ammonium persulfate [active ingredient 6% by mass] and an aqueous solution of sodium bisulfite 2.5 g [active ingredient 2% by mass] were used for 1 hour while maintaining the reaction vessel at 60 ° C. using separate funnels. It was dripped over.

  After completion of dropping, the reaction vessel was stirred for 1 hour while maintaining the temperature at 60 ° C., and then the contents were cooled and adjusted with ammonia water [10% by mass of active ingredient] so that the pH was 8.0. This was filtered with a 200 mesh wire net to obtain an aqueous dispersion (1) of an aqueous dispersion type acrylic polymer. Here, the solid content concentration of the aqueous dispersion (1) of the obtained water-dispersed acrylic polymer was 50% by mass, the average particle size was 330 nm, and the weight average molecular weight was 700,000.

  Superester E-865NT (made by Arakawa Chemical Industries, Ltd .; softening point 160), which is an emulsion-type polymerized rosin ester-based tackifier resin, is used as a tackifier resin in 1000 g of the water-dispersed acrylic polymer (1). 200g, Surfynol PSA-336 [made by Air Products Japan Co., Ltd.] 2.5g as a leveling agent, Surfynol DF-110D [Air Products Japan (as an antifoaming agent) 2.5 g) was added. After uniformly stirring, the mixture was filtered through a 200 mesh wire net to obtain a water-dispersed acrylic pressure-sensitive adhesive composition (1).

(Preparation Example 2)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (2)>
The amount of n-butyl acrylate was changed from 227.5 g to 227 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 227 g, the amount of acrylic acid was changed from 4 g to 15 g, An emulsion (2) was prepared in the same manner as described in Preparation Example 1 except that the amount used was changed from 10 g to 0 g.

  An aqueous dispersion (2) of a water-dispersed acrylic polymer was obtained in the same manner as described in Preparation Example 1, except that the above-mentioned emulsion (2) was used instead of the emulsion (1). The resulting aqueous dispersion (2) of the water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 323 nm, and a weight average molecular weight of 680,000.

  Similar to the method described in Preparation Example 1, except that the water dispersion (2) of the water-dispersed acrylic polymer was used instead of the water dispersion (1) of the water-dispersed acrylic polymer. Thus, a water-dispersed acrylic pressure-sensitive adhesive composition (2) was obtained.

(Preparation Example 3)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (3)>
The amount of n-butyl acrylate was changed from 227.5 g to 227 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 227 g, the amount of acrylic acid was changed from 4 g to 0 g, An emulsion (3) was prepared by the same method as described in Preparation Example 1 except that the amount used was changed from 10 g to 15 g.

  An aqueous dispersion (3) of a water-dispersed acrylic polymer is obtained in the same manner as in Preparation Example 1 except that the above-mentioned emulsion (3) is used instead of the emulsion (1). It was. The aqueous dispersion (3) of the obtained water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 344 nm, and a weight average molecular weight of 720,000.

  Similar to the method described in Preparation Example 1, except that the water dispersion (3) of the water-dispersed acrylic polymer was used instead of the water dispersion (1) of the water-dispersed acrylic polymer. Thus, a water-dispersed acrylic pressure-sensitive adhesive composition (3) was obtained.

(Preparation Example 4)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (4)>
The amount of n-butyl acrylate was changed from 227.5 g to 230.5 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 230.5 g, and the amount of N-vinyl pyrrolidone was changed from 6 g to 0 g. Except having changed, the emulsion (4) was prepared by the method similar to the preparation example 1.

  An aqueous dispersion (4) of a water-dispersed acrylic polymer is obtained in the same manner as in Preparation Example 1 except that the above-mentioned emulsion (4) is used instead of the emulsion (1). It was. The aqueous dispersion (4) of the obtained water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 341 nm, and a weight average molecular weight of 750,000.

  Similar to the method described in Preparation Example 1 except that the water dispersion (4) of the water-dispersed acrylic polymer was used instead of the water dispersion (1) of the water-dispersed acrylic polymer. Thus, a water-dispersed acrylic pressure-sensitive adhesive composition (4) was obtained.

(Preparation Example 5)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (5)>
The amount of n-butyl acrylate was changed from 227.5 g to 230 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 230 g, the amount of N-vinylpyrrolidone was changed from 6 g to 0 g, and acrylic An emulsion (5) was prepared in the same manner as described in Preparation Example 1 except that the amount of acid used was changed from 4 g to 15 g and the amount of methacrylic acid was changed from 10 g to 0 g.

  An aqueous dispersion (5) of a water-dispersed acrylic polymer was obtained in the same manner as in Preparation Example 1 except that the above-mentioned emulsion (5) was used instead of the emulsion (1). . The aqueous dispersion (5) of the obtained water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 318 nm, and a weight average molecular weight of 710,000.

  The same method as described in Preparation Example 1 except that the water dispersion type acrylic polymer aqueous dispersion (5) was used instead of the water dispersion type acrylic polymer aqueous dispersion (1). A water-dispersed acrylic pressure-sensitive adhesive composition (5) was obtained by the method.

(Preparation Example 6)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (6)>
The amount of n-butyl acrylate was changed from 227.5 g to 460 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 0 g, the amount of N-vinylpyrrolidone was changed from 6 g to 0 g, and acrylic An emulsion (6) was prepared in the same manner as described in Preparation Example 1 except that the amount of acid used was changed from 4 g to 15 g and the amount of methacrylic acid was changed from 10 g to 0 g.

  An aqueous dispersion (6) of a water-dispersed acrylic polymer was obtained in the same manner as in Preparation Example 1 except that the above-mentioned emulsion (6) was used instead of the emulsion (1). The aqueous dispersion (6) of the obtained water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 319 nm, and a weight average molecular weight of 740,000.

  Similar to the method described in Preparation Example 1, except that the water dispersion type acrylic polymer aqueous dispersion (6) was used instead of the water dispersion type acrylic polymer aqueous dispersion (1). A water-dispersed acrylic pressure-sensitive adhesive composition (6) was obtained by the method.

(Preparation Example 7)
<Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (7)>
The amount of n-butyl acrylate was changed from 227.5 g to 0 g, the amount of 2-ethylhexyl acrylate was changed from 227.5 g to 460 g, the amount of N-vinylpyrrolidone was changed from 6 g to 0 g, and acrylic An emulsion (7) was prepared in the same manner as described in Preparation Example 1, except that the amount of acid used was changed from 4 g to 15 g and the amount of methacrylic acid was changed from 10 g to 0 g.

  An aqueous dispersion (7) of a water-dispersed acrylic polymer was obtained in the same manner as described in Preparation Example 1 except that the above-mentioned emulsion (7) was used instead of the emulsion (1). . The aqueous dispersion (7) of the obtained water-dispersed acrylic polymer had a solid content concentration of 50% by mass, an average particle size of 340 nm, and a weight average molecular weight of 800,000.

  Similar to the method described in Preparation Example 1, except that the water dispersion type acrylic polymer aqueous dispersion (7) was used instead of the water dispersion type acrylic polymer aqueous dispersion (1). A water-dispersed acrylic pressure-sensitive adhesive composition (7) was obtained by the method.

  The composition of the above preparation examples is shown in the table below. “Mass%” of the monomer composition in the table represents the content of each monomer in the monomer component constituting the acrylic polymer, and “mass part” of the tackifier resin represents the adhesion to 100 parts by mass of the acrylic polymer. It represents the mass part of the imparted resin.

Example 1
Under a 23 ° C. environment, the total amount of the water-dispersed acrylic pressure-sensitive adhesive composition (1) and 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.] as an epoxy-based crosslinking agent are mixed. A water-dispersed acrylic pressure-sensitive adhesive (1) was obtained by stirring for 15 minutes.

  Next, the water-dispersed acrylic pressure-sensitive adhesive (1) is allowed to stand for 30 minutes in a 23 ° C. environment, then filtered through a 200 mesh wire mesh, and dried on a release liner using a knife coater. The film was coated to have a thickness of 80 μm and dried at 100 ° C. for 5 minutes to form two laminated sheets each having an adhesive layer formed on the release liner.

  Next, the laminated sheet is placed on both sides of Bora La XL-H # 05002 (black) [Sekisui Chemical Co., Ltd., thickness 200 μm, expansion ratio 5 times, polyethylene foam] as a foam base material at 60 ° C. The laminated body in which the said adhesive layer was provided on both surfaces of the foam base material was obtained by bonding together using the laminating roll warmed to. In addition, the holding period in the said process [2] was 30 minutes.

  Next, a pressure-sensitive adhesive tape was produced by curing the laminate of the foam base material and the pressure-sensitive adhesive layer in a 40 ° C. environment for 72 hours. In addition, the gel fraction of the adhesive layer before curing was 0.3% by mass, and the gel fraction of the adhesive layer after curing was 44.2% by mass.

(Example 2)
A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that the holding period in Step [2] was changed from 30 minutes to 1 day (24 hours).

(Example 3)
An adhesive tape was produced in the same manner as in Example 1 except that the holding period in the step [2] was changed from 30 minutes to 3 days (72 hours).

Example 4
Example 1 except that the holding period in the step [2] was changed from 30 minutes to 3 days (72 hours), and the holding temperature in the step [2] was changed from 23 ° C. to 40 ° C. The adhesive tape was manufactured by the method.

(Example 5)
Example 1 except that the holding period in the step [2] was changed from 30 minutes to 3 days (72 hours), and the holding temperature in the step [2] was changed from 23 ° C. to 60 ° C. The adhesive tape was manufactured by the method.

(Example 6)
A pressure-sensitive adhesive tape was produced in the same manner as in Example 1 except that the holding period in Step [2] was changed from 30 minutes to 7 days (168 hours).

(Example 7)
Instead of 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100% by mass] as a silane crosslinking agent is dispersed in the water. A pressure-sensitive adhesive tape was produced in the same manner as in Example 1, except that 1 g was used for the total amount of the acrylic acrylic pressure-sensitive adhesive composition (1).

(Example 8)
An adhesive tape was produced in the same manner as in Example 7, except that the holding period in the step [2] was changed from 30 minutes to 1 day (24 hours).

Example 9
An adhesive tape was produced in the same manner as in Example 7, except that the holding period in the step [2] was changed from 30 minutes to 3 days (72 hours).

(Example 10)
A pressure-sensitive adhesive tape is produced in the same manner as in Example 7, except that the holding period in Step [2] is changed from 30 minutes to 3 days (72 hours) and the environmental temperature is changed from 23 ° C. to 40 ° C. did.

(Example 11)
A pressure-sensitive adhesive tape is produced in the same manner as in Example 7 except that the holding period in Step [2] is changed from 30 minutes to 3 days (72 hours) and the environmental temperature is changed from 23 ° C. to 60 ° C. did.

(Example 12)
An adhesive tape was produced in the same manner as in Example 7, except that the holding period in the step [2] was changed from 30 minutes to 7 days (168 hours).

(Example 13)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (2) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 14)
An adhesive tape was produced in the same manner as in Example 13 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 15)
The adhesive tape was removed in the same manner as in Example 13 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C. Manufactured.

(Example 16)
Instead of 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100% by mass] as a silane crosslinking agent is dispersed in the water. A pressure-sensitive adhesive tape was produced in the same manner as in Example 13 except that 1 g was used with respect to the total amount of the type acrylic pressure-sensitive adhesive composition (2).

(Example 17)
An adhesive tape was produced in the same manner as in Example 16 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 18)
The adhesive tape was removed in the same manner as in Example 16 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C. Manufactured.

(Example 19)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (3) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 20)
An adhesive tape was produced in the same manner as in Example 21, except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 21)
The adhesive tape was removed in the same manner as in Example 19 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C. Manufactured.

(Example 22)
Instead of 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100% by mass] as a silane crosslinking agent is dispersed in the water. A pressure-sensitive adhesive tape was produced in the same manner as in Example 19 except that 1 g was used with respect to the total amount of the type acrylic pressure-sensitive adhesive composition (2).

(Example 23)
An adhesive tape was produced in the same manner as in Example 22 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 24)
Except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C., the adhesive tape was prepared in the same manner as in Example 22. Manufactured.

(Example 25)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (4) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 26)
An adhesive tape was produced in the same manner as in Example 25 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 27)
Except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C., the adhesive tape was prepared in the same manner as in Example 25. Manufactured.

(Example 28)
Instead of 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100% by mass] as a silane crosslinking agent is dispersed in the water. A pressure-sensitive adhesive tape was produced in the same manner as in Example 25 except that 1 g was used with respect to the total amount of the acrylic acrylic pressure-sensitive adhesive composition (2).

(Example 29)
An adhesive tape was produced in the same manner as in Example 28, except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 30)
The adhesive tape was removed in the same manner as in Example 29 except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C. Manufactured.

(Example 31)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (5) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 32)
An adhesive tape was produced in the same manner as in Example 31, except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 33)
Except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C., the adhesive tape was prepared in the same manner as in Example 31. Manufactured.

(Example 34)
Instead of 1.5 g of a 10% by mass ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd.], KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient 100% by mass] as a silane crosslinking agent is dispersed in the water. A pressure-sensitive adhesive tape was produced in the same manner as in Example 31 except that 1 g was used for the total amount of the acrylic acrylic pressure-sensitive adhesive composition (2).

(Example 35)
An adhesive tape was produced in the same manner as in Example 34, except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 36)
The adhesive tape was removed in the same manner as in Example 34, except that the holding period in Step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C to 40 ° C. Manufactured.

(Example 37)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (6) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 38)
An adhesive tape was produced in the same manner as in Example 39, except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours).

(Example 39)
Except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C., the adhesive tape was prepared in the same manner as in Example 37. Manufactured.

(Example 40)
Instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), the water-dispersed acrylic pressure-sensitive adhesive composition (7) is used, and the retention period in the step [2] is 30 minutes to 1 day ( The adhesive tape was manufactured by the same method as Example 1 except having changed to 24 hours.

(Example 41)
A pressure-sensitive adhesive tape was produced in the same manner as in Example 40 except that the holding period in Step [2] was changed from 1 day to 3 days (72 hours).

(Example 42)
Except that the holding period in the step [2] was changed from 1 day to 3 days (72 hours) and the environmental temperature was changed from 23 ° C. to 40 ° C., the adhesive tape was prepared in the same manner as in Example 40. Manufactured.

(Example 43)
An adhesive tape was produced in the same manner as in Example 1 except that the curing time was changed from 72 hours to 24 hours.

(Example 44)
An adhesive tape was produced in the same manner as in Example 1 except that the curing time was changed from 72 hours to 36 hours.

(Example 45)
An adhesive tape was produced in the same manner as in Example 1 except that the curing time was changed from 72 hours to 48 hours.

(Comparative Example 1)
An adhesive tape was produced in the same manner as in Example 1 except that the holding period in the step [2] was changed from 1 day to 30 days.

(Comparative Example 2)
An adhesive tape was produced in the same manner as in Example 7 except that the holding period in the step [2] was changed from 1 day to 30 days.

Claims (6)

Step [1] for mixing the pressure-sensitive adhesive composition (a1) and the crosslinking agent (a2), and maintaining the mixture (a3) obtained in the step [1] at a temperature of 15 ° C. to 40 ° C. After the step [2] of obtaining (A), the step [3] of providing an adhesive layer on both surfaces of the substrate (B) using the aqueous adhesive (A), and the step [3], curing the adhesive tape A method for producing a pressure-sensitive adhesive tape comprising the step [4], wherein the holding period in the step [2] is 30 minutes to 3 days, the temperature environment in the step [4] is 20 ° C. to 50 ° C., and curing A method for producing an adhesive tape, wherein the period is 24 hours to 72 hours. The process [3] is a process of transferring the pressure-sensitive adhesive layer formed by applying the aqueous pressure-sensitive adhesive (A) to a release liner and drying it on both surfaces of the base material (B). The manufacturing method of the adhesive tape of description. The pressure-sensitive adhesive tape according to claim 1 or 2, wherein the pressure-sensitive adhesive composition (a1) contains an aqueous dispersion of an acrylic polymer (a1-1) and a tackifier resin (a1-2). Manufacturing method. The said crosslinking agent (a2) is a crosslinking agent which has a 1 or more types of functional group chosen from the group which consists of an epoxy group, a silanol group, and a hydrolyzable silyl group. Manufacturing method of adhesive tape. The said base material (B) is a foam base material, The manufacturing method of the adhesive tape of any one of Claims 1-4. The method for producing an adhesive tape according to claim 5, wherein the foam base material has a foaming ratio of 3 to 6 times and a thickness of 100 to 300 µm.