JP2015221846A - Adhesive tape - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an emulsion-type adhesive tape which satisfy both of: heat resistant adhesivity which does not cause temporal peeling even when used for a long period under an environment of large temperature variation; and resistance to resilience of such a level that does not cause peeling and the like due to repulsion and the like of a foam material.SOLUTION: Provided is an adhesive tape used for fixing an air-conditioner unit mounted on an automobile and a foam material. The adhesive tape comprises an adhesive layer formed by using an emulsion-type adhesive comprising an acrylic polymer having either one or both of an alkoxysilyl group and a silanol group.

Description

  The present invention relates to an adhesive tape used exclusively for fixing an air conditioner unit mounted on an automobile and a foam material.

  Adhesive tapes generally have high adhesion reliability and excellent workability when adhering two or more adherends. For example, adhesive tapes can be used for fixing parts in various fields including the electronic equipment field and the automobile field. It is used for attaching labels and labels.

  As the pressure-sensitive adhesive tape, conventionally, pressure-sensitive adhesive tapes obtained using so-called solvent-based pressure-sensitive adhesives are known as having excellent adhesiveness and holding power.

  However, the pressure-sensitive adhesive tape obtained by using an emulsion-type pressure-sensitive adhesive in place of the solvent-based pressure-sensitive adhesive while the suppression of the organic solvent discharge is required from the fields of automobiles, building materials, OA, home appliances, etc. Development is demanded.

  The pressure-sensitive adhesive tape obtained using the emulsion-type pressure-sensitive adhesive includes, for example, a pressure-sensitive adhesive layer formed using a water-dispersed pressure-sensitive adhesive composition, and a support that supports the pressure-sensitive adhesive layer. There is known a double-sided pressure-sensitive adhesive tape comprising a nonwoven fabric substrate (see, for example, Patent Document 1).

  However, the pressure-sensitive adhesive tape obtained using the emulsion-type pressure-sensitive adhesive is generally used for a difficult-to-adhere adherend such as a foam material having a large surface uneven shape as compared with a pressure-sensitive adhesive tape obtained using a solvent-based pressure-sensitive adhesive. On the other hand, there are cases where it is difficult to develop a practically sufficient adhesive force. Further, in the pressure-sensitive adhesive tape obtained using the emulsion-type pressure-sensitive adhesive, the foam material is caused by the repulsive force of the foam material when the foam material is attached to a corner portion or a curved surface portion constituting another adherend. In some cases, it is easy to cause peeling over time.

  In addition, air conditioner units and their peripheral equipment mounted on automobiles, for example, in Japan, can be used continuously for a long period of time in an environment with a large temperature change from about 40 ° C in summer to about -10 ° C in winter. Often done.

  Development of pressure-sensitive adhesive tapes obtained using emulsion-type pressure-sensitive adhesives that do not cause peeling of the foam material even when used for a long time in such a harsh environment is required in the automotive field. It was.

Japanese Patent Laid-Open No. 2007-23068

  The problem to be solved by the present invention is due to the heat-resistant adhesive strength at a level that does not cause peeling over time even when used for a long time in an environment with a large temperature change, and the repulsive force of the foam material, etc. Another object of the present invention is to provide an emulsion-type pressure-sensitive adhesive tape that is compatible with a level of resilience that does not cause peeling.

  The present invention relates to an adhesive tape used for fixing an air conditioner unit mounted on an automobile and a foam material, wherein the adhesive tape has one or both of an alkoxysilyl group and a silanol group. The above-mentioned problems are solved by an adhesive tape characterized by having an adhesive layer formed using an emulsion-type adhesive that contains.

  The pressure-sensitive adhesive tape of the present invention has a heat-resistant adhesive strength at a level that does not cause peeling over time even when used for a long time in an environment with a large temperature change, and peeling due to the resilience of the foam material, etc. Therefore, it can be suitably used when an air conditioner unit mounted on an automobile and a foam material are bonded together.

  In addition, the pressure-sensitive adhesive tape of the present invention is obtained by using an emulsion-type pressure-sensitive adhesive, and realizes a reduction in environmental burden. Therefore, the odor caused by the organic solvent contained in the solvent-based pressure-sensitive adhesive is greatly reduced. Can be reduced. Therefore, the odor caused by the organic solvent in the air sent from the air conditioner unit into the automobile can be remarkably reduced.

It is a conceptual diagram which shows the resilience test method at the time of 180 degree | times bending. It is a top view of the test piece (Y) obtained by stamping the test piece obtained by sticking the foam material on one side of the adhesive tape.

  The pressure-sensitive adhesive tape of the present invention has a pressure-sensitive adhesive layer formed using an emulsion-type pressure-sensitive adhesive containing an acrylic polymer having either one or both of an alkoxysilyl group and a silanol group. It is used exclusively for fixing an air conditioner unit mounted on a car and a foam material.

  As the pressure-sensitive adhesive tape of the present invention, for example, a pressure-sensitive adhesive tape provided with the pressure-sensitive adhesive layer on one side or both sides of a base material such as a nonwoven fabric base material or a resin film base material, or a so-called base composed of only the pressure-sensitive adhesive layer. A materialless adhesive tape can be mentioned.

  As the pressure-sensitive adhesive tape of the present invention, it is preferable to use one having a total thickness of the pressure-sensitive adhesive layer and the base material in a range of 80 μm to 200 μm, and using a tape having a range of 100 μm to 160 μm, When used to fix an air conditioner unit mounted on an automobile and a foam material, it is more preferable to achieve both excellent adhesion and repulsion resistance.

  The pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape of the present invention is formed using an emulsion-type pressure-sensitive adhesive containing an acrylic polymer having either one or both of an alkoxysilyl group and a silanol group.

  The pressure-sensitive adhesive layer has a thickness of 40 μm to 180 μm in order to achieve both excellent adhesion and repulsion resistance when used for fixing an air conditioner unit mounted on an automobile and a foam material. It is preferable that the thickness is 60 μm to 150 μm.

The pressure-sensitive adhesive layer has a siloxane bond formed by a dehydration condensation reaction between one or both functional groups of the alkoxysilyl group and silanol group of the acrylic polymer. As a result, it is preferable to use a pressure-sensitive adhesive layer having a gel fraction in the range of 20% by mass to 60% by mass, and a gel fraction in the range of 25% by mass to 50% by mass. It is more preferable to use a thing, and it is still more preferable to use what has a gel fraction of the range of 30 mass%-40 mass%. The gel fraction is determined by immersing the adhesive tape in toluene for 24 hours under the environment of 25 ° C and the mass of the base material (G ₀ ), the adhesive tape (G ₁ ), and then under the environment of 105 ° C. The value calculated based on the mass (G ₂ ) of the dried product. Gel fraction (% by mass) = [(G ₂ −G ₀ ) / (G ₁ −G ₀ )] × 100

  As said emulsion type adhesive used for formation of the said adhesive layer, what contains the acrylic polymer etc. which have any one or both of an alkoxy silyl group or a silanol group, and an aqueous medium can be used.

  As said acrylic polymer, it is preferable to use what has the said alkoxysilyl group and silanol group 0.001 mass%-1 mass% in total with respect to the whole quantity of the said acrylic polymer, 0.01 mass% It is possible to form a pressure-sensitive adhesive layer having a gel fraction in the above-mentioned preferable range by using a material having ~ 0.1% by mass, and it is used for fixing an air conditioner unit mounted on an automobile and a foam material. Even in the case of being subjected to an environment with a large temperature change over a long period of time, it is more preferable because it is possible to achieve both excellent adhesion and rebound resistance.

  Moreover, as said acrylic polymer, containing the functional group shown by following General formula (1) can make compatible both favorable softness | flexibility and the outstanding cohesion force, and the repulsive force of foam materials, such as a polyurethane foam, It is preferable because it is possible to further prevent peeling due to the above.

  [R in Formula (1) represents an alkyl group having 1 or 2 carbon atoms. ]

  As said acrylic polymer, it is preferable to use what has 1 mass%-20 mass% of functional groups shown by General formula (1) with respect to the whole quantity of the said acrylic polymer. It is more preferable to use a material having 2% by mass to 8% by mass, even more preferable to use a material having 3% by mass to 5% by mass in an environment with a large temperature change. Even when it is used, it is preferable because peeling of the foam material and peeling due to the repulsive force of the foam material can be further prevented.

  Examples of the acrylic polymer include one or both of a monomer having an alkoxysilyl group and a monomer having a silanol group, and a monomer having a structure represented by the general formula (1) as necessary. What is obtained by polymerizing the monomer mixture containing etc. can be used.

  Examples of the monomer having an alkoxysilyl group include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc. may be used alone or in combination of two or more. Kill.

  Moreover, what uses the thing obtained by hydrolyzing the monomer which has the said alkoxysilyl group can be used as a monomer which has the said silanol group. The acrylic polymer having a silanol group may be obtained by hydrolyzing a part or all of the alkoxysilyl group after the acrylic polymer is produced, and obtained by hydrolysis in advance. Further, it may be obtained by polymerizing a mixture containing a monomer having a silanol group.

  The monomer having an alkoxysilyl group and the monomer having a silanol group are in the range of 0.001% by mass to 1% by mass with respect to the total amount of the monomer mixture used for the production of the acrylic polymer. It is preferable to use it, and it is more preferable to use it in the range of 0.01% by mass to 0.1% by mass.

  As a monomer that can be used in the production of the acrylic polymer, other monomers can be used as necessary in addition to the above-described monomers.

  As said other monomer, the (meth) acrylate which has an alkyl group can be used, for example, It is preferable to use the (meth) acrylate which has a C4-C10 alkyl group.

  Examples of the (meth) acrylate having an alkyl group having 4 to 10 carbon atoms include n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, and isopentyl. (Meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate , Isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, cyclohexyl (meth) acrylate and the like can be used alone or in combination of two or more. Especially, as said (meth) acrylate which has a C4-C10 alkyl group, it is preferable to use n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, and 2-ethylhexyl (meth). The use of acrylate is used to fix the air conditioner unit mounted on the automobile and the foam material, and even better adhesion even when placed in an environment where the temperature changes greatly over a long period of time. It is more preferable because both strength and resilience resistance can be achieved.

As the (meth) acrylate having an alkyl group having 4 to 10 carbon atoms, 2-ethylhexyl (meth) acrylate is used alone, or 2-ethylhexyl (meth) acrylate and n-butyl (meth) acrylate are used. And the ratio [M _BA / M _EHA ] of the mass [M _EHA ] of the mass [M _BA ] of n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is _0/10 . Is more preferably within the range of ˜9 / 1, even more preferably within the range of 0/10 to 7/3, even more preferably within the range of 0/10 to 5/5, A range of / 10 to 7/3 is particularly preferable.

  The (meth) acrylate having an alkyl group having 4 to 10 carbon atoms is preferably used in an amount of 50% by mass or more, and 75% by mass or more, based on the total amount of monomers used in the production of the acrylic polymer. More preferably, it is 85% by mass or more, more preferably 90% by mass or more, and the use in the range of 90 to 98 parts by mass is mounted on an automobile. Used to fix the air conditioner unit and foam material, and is particularly preferable because it can achieve both better adhesion and rebound resistance even when placed in an environment with a large temperature change over a long period of time. .

  Moreover, as a monomer which can be used when introducing the acrylic polymer into the structure represented by the general formula (1), for example, a (meth) acrylate having an alkyl group having 1 to 2 carbon atoms is used. Is preferred. As said (meth) acrylate which has a C1-C2 alkyl group, methyl (meth) acrylate and ethyl (meth) acrylate can be used individually or in combination of 2 or more, for example.

  The (meth) acrylate having an alkyl group having 1 to 2 carbon atoms may be used in the range of 1% by mass to 20% by mass with respect to the total amount of monomers used for the production of the acrylic polymer. Preferably, it is used in the range of 1% by mass to 10% by mass, more preferably in the range of 2% by mass to 8% by mass, and in the range of 3% by mass to 5% by mass. It is used for fixing the air conditioner unit mounted on automobiles and foam material, and even when it is placed in an environment where the temperature changes greatly over a long period of time, it has even better adhesion and repulsion resistance. It is particularly preferable because it can be compatible with the properties.

  As another monomer that can be used in the production of the acrylic polymer, a monomer having a carboxyl group can be used in order to develop a more excellent cohesive force.

  As the monomer having a carboxyl group, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, phthalic acid, phthalic anhydride, crotonic acid and the like can be used alone or in combination of two or more. . Among them, as the monomer having a carboxyl group, at least one selected from the group consisting of acrylic acid and methacrylic acid is used for fixing an air conditioner unit mounted on an automobile and a foam material. Even in the case of being subjected to an environment with a large temperature change over a long period of time, it is particularly preferable because it can achieve both excellent adhesion and repulsion resistance.

  The monomer having a carboxyl group is preferably used in the range of 1% by mass to 10% by mass with respect to the total amount of monomers used for the production of the acrylic polymer. %, More preferably 2% to 4% by weight is used to fix the air conditioner unit mounted on the automobile and the foam material, and the temperature changes over a long period of time. Even when placed in a large environment, it is particularly preferable because it can achieve both better adhesion and repulsion resistance.

  As said other monomer, the monomer which has a nitrogen atom can be used when expressing the further outstanding cohesion force.

  Examples of the monomer having a nitrogen atom include N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth). Acrylamide, N-methylol (meth) acrylamide, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidone, N- (meth) acryloylpiperidine, N- (meth) acryloylpyrrolidine, N- (meth) acryloyl-4 -Piperidone, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylmorpholinone, N-vinylcaprolactam, N-cyclohexylmaleimide, N-butylmaleimide and the like can be used alone or in combination of two or more.

  As the monomer having a nitrogen atom, N-isopropyl (meth) acrylamide or N-vinylpyrrolidone is used for fixing an air conditioner unit mounted on an automobile and a foam material for a long time. Even in the case of being placed in an environment where the temperature change is large over time, it is particularly preferable because it is possible to achieve both excellent adhesive strength and resilience resistance.

  The monomer having a nitrogen atom is preferably used in the range of 0.1% by mass to 5% by mass with respect to the total amount of monomers used for the production of the acrylic polymer, and 0.1% by mass. It is more preferable to use in the range of 3% to 3% by weight, and it is preferable to use in the range of 0.5% to 1.5% by weight to fix the air conditioner unit mounted on the automobile and the foam material. Even when it is used and placed in an environment with a large temperature change over a long period of time, it is particularly preferable because it can achieve both better adhesion and rebound resistance.

  The monomer having a nitrogen atom may be used in combination with the monomer having a carboxyl group for fixing an air conditioner unit mounted on an automobile and a foam material. Even when placed in a large environment, it is particularly preferable because it can achieve both better adhesion and repulsion resistance.

  As said other monomer, the monomer etc. which have functional groups, such as a hydroxyl group, a sulfonic acid, and a phosphoric acid group, can be used as needed other than the above-mentioned thing.

  The acrylic polymer or the acrylic polymer emulsion in which the acrylic polymer is dispersed in an aqueous medium can be produced, for example, by an emulsion polymerization method. Examples of the emulsion polymerization method include a method of emulsion polymerization by supplying the monomer in the presence of a polymerization initiator, an aqueous medium, an emulsifier, or the like.

  As the emulsifier, an anionic emulsifier, a nonionic emulsifier, and other dispersion stabilizers can be used in appropriate amounts to ensure the stability of the emulsion polymerization.

  Examples of the anionic emulsifier include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate and the like. Oxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and the like can be used.

  Further, as the emulsifier, it is preferable to use an emulsifier having a polymerizable unsaturated group in the molecule, generally called “reactive emulsifier”. Specifically, Latemul S-180 [manufactured by Kao Corporation], Latemu PD-104 [manufactured by Kao Corporation], Aqualon HS-10 [manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon HS-20 [No. Ichi 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 [Daiichi Kogyo Seiyaku Co., Ltd.], Adekaria Soap SE-10 [Adeka Co., Ltd.], Adekaria Soap SE-20 [Adeka Co., Ltd.], ADEKA Asopu SR-10 N [(Ltd.) ADEKA Ltd.], ADEKAREASOAP SR-20 N [(Ltd.) ADEKA Ltd.] and the like. It is preferable to use the reactive emulsifier because it can improve the polymerization stability when the acrylic polymer is produced and can improve the water resistance and moisture resistance of the pressure-sensitive adhesive layer.

  Examples of the polymerization initiator include 4,4-azobis (4-cyanopentanoic acid), 2,2 ′,-azobis (2-methylpropionamidine) dihydrochloride, and 2,2′-azobis (2-methylpropion). Amidine) sulfate, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [N- (2-alkoxyethyl) -2-methylpropionamidine] hydrate, 2, 2′-azobis (N, N′-dimethyleneisobutylamidine) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [ 2- (2-imidazolin-2-yl) propane] sulfate, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (5-Me Ru-2-imidazolin-2-yl) propane] sulfate, 2-2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2 ′ Azo initiators such as azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis (2-methylpropanamidooxime), Persulfate initiators such as potassium persulfate, ammonium persulfate and sodium persulfate, peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, hydrogen peroxide, and carbonyls such as aromatic carbonyl compounds Redox initiators such as initiators, combinations of persulfate and sodium bisulfite, and peroxides and sodium ascorbate can be used. .

  Among these, it is preferable to use an azo initiator because it is excellent in polymerization stability and easily obtains desired adhesive performance.

  In the emulsion polymerization, a chain transfer agent can be used for the purpose of adjusting the molecular weight of the acrylic polymer.

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimethylcapto-1-propanol.

  On the other hand, the chain transfer agent generally tends to remain in the pressure-sensitive adhesive layer, and may generate odor during decomposition. In the present invention, it is preferable not to use the chain transfer agent excessively in order to prevent odorous air from being sent into the automobile, with respect to the total amount of monomers used in the production of the acrylic polymer. It is preferably 1% by mass or less, more preferably in the range of 0.01% by mass to 0.5% by mass, still more preferably 0.01% by mass to 0.1% by mass, The range of 0.02% by mass to 0.05% by mass is particularly preferable.

  As the acrylic polymer, those having a weight average molecular weight in the range of 300,000 to 1,200,000 are preferably used, and those having a weight average molecular weight in the range of 400,000 to 1,000,000 are more preferably used. It is preferable to use those having a weight average molecular weight in the range of 600,000 to 800,000. By using an acrylic polymer having a weight average molecular weight within the above range, a pressure-sensitive adhesive layer having even more excellent adhesion and rebound resistance can be formed on a foam material such as polyurethane foam. In addition, the said weight average molecular weight is standard polystyrene conversion by a gel permeation chromatography (GPC). As measurement conditions, TSKgel GMHXL [manufactured by Tosoh] was used as the column, the column temperature was 40 ° C., the eluent was tetrahydrofuran, the flow rate was 1.0 mL / min, and the standard polystyrene was TSK standard polystyrene.

  The acrylic polymer obtained by the emulsion polymerization method is preferably one that can be dissolved or dispersed in an aqueous medium.

  The average particle diameter of the acrylic polymer particles is not particularly limited, but is preferably 100 nm to 1000 nm, and 150 nm to 500 nm causes aggregation and sedimentation even when stored for a long time. It is preferable because it is difficult to disperse and has excellent dispersion stability. The average particle diameter refers to a 50% median diameter based on the volume of the emulsion particles, and the numerical values are based on values obtained by measurement by a dynamic light scattering method.

  As the aqueous medium, water alone or a mixed solvent of water and a water-soluble solvent can be used. The “mixed solvent of water and a water-soluble solvent” is a mixed solvent of a water-soluble solvent mainly composed of water, and the content of the water-soluble solvent is preferably 10 with respect to the total amount of the mixed solvent. It is preferable to use those that are not more than wt%, more preferably not more than 5 wt%.

  Examples of the water-soluble solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, ethyl carbitol, ethyl cellosolve, and butyl cellosolve, and polar solvents such as N-methylpyrrolidone alone or in combination of two or more. it can.

  The acrylic polymer emulsion containing the acrylic polymer obtained by the above method and an aqueous medium reduces the cost when producing the emulsion-type pressure-sensitive adhesive and the pressure-sensitive adhesive tape, and also produces when the pressure-sensitive adhesive tape is produced. In order to improve efficiency, it is preferable that it is a solid content concentration of the range of 40 mass%-70 mass%.

  As the emulsion-type pressure-sensitive adhesive, in addition to the acrylic polymer emulsion, if necessary, a tackifier resin is contained in forming a pressure-sensitive adhesive layer having a more excellent constant load holding force and pressure-sensitive adhesive force. You can use what you want.

  As the tackifying resin, an emulsion type tackifying resin is preferably used when used for an emulsion type pressure sensitive adhesive.

  Examples of the emulsion-type tackifying resins include rosin-based tackifying resins, polymerized rosin-based tackifying resins, polymerized rosin ester-based tackifying resins, rosin phenol-based tackifying resins, stabilized rosin ester-based tackifying resins, disproportionately. A rosin ester tackifier resin, a terpene tackifier resin, a terpene phenol tackifier resin, a petroleum resin tackifier resin, or the like can be used. Among these, as the emulsion-type tackifying resin, a polymerized rosin ester-based tackifying resin or a rosin phenol-based tackifying resin is used, even when used for a long period of time in an environment with a large temperature change. This is preferable in order to achieve both a more excellent heat-resistant adhesive strength at a level that does not cause general peeling and a more excellent repulsion resistance at a level that does not cause peeling due to the resilience of the foam material.

  Examples of the polymerized rosin ester-based tackifying resin include super ester E-650 [manufactured by Arakawa Chemical Co., Ltd.], super ester E-788 [manufactured by Arakawa Chemical Industry Co., Ltd.], and super ester E-786-60 [Arakawa]. Chemical Industry Co., Ltd.], Super Ester E-865 [Arakawa Chemical Industries, Ltd.], Super Ester E-865NT [Arakawa Chemical Industries, Ltd.], Harrier Star SK-508 [Harima Kasei Co., Ltd.] ] Harrier Star SK-508H [manufactured by Harima Kasei Co., Ltd.], Harrier Star SK-816E [manufactured by Harima Kasei Co., Ltd.], Harrier Star SK-822E [manufactured by Harima Kasei Co., Ltd.], Harrier Star SK-323NS [Harima Kasei Co., Ltd.] can be used.

  Examples of the rosin phenol-based tackifier resin include Tamanol E-100 [manufactured by Arakawa Chemical Co., Ltd.], Tamanol E-200 [manufactured by Arakawa Chemical Industry Co., Ltd.], and Tamanol E-200NT [manufactured by Arakawa Chemical Industries, Ltd.] ] Can be used.

  As the tackifier resin, those having a softening point in the range of 120 ° C. to 180 ° C. are preferably used, and those having a softening point in the range of 140 ° C. to 180 ° C. have a large temperature change. Even when it is used for a long time in the environment, it has even better heat-resistant adhesive strength at a level that does not cause peeling over time, and at a level that does not cause peeling due to the repulsive force of the foam material, etc. It is preferable for achieving both excellent repulsion resistance.

  The tackifying resin is preferably used in the range of 5 to 50 parts by mass, more preferably in the range of 10 to 40 parts by mass, with respect to 100 parts by mass of the acrylic polymer. Use in the range of 15 parts by weight to 35 parts by weight is even more excellent in heat-resistant adhesive strength at a level that does not cause peeling over time even when used for a long time in an environment with a large temperature change. It is preferable for achieving both excellent rebound resistance at a level that does not cause peeling due to the repulsive force of the foam material.

  As said emulsion type adhesive, what contains a crosslinking agent as needed can be used.

  As the crosslinking agent, for example, an epoxy compound, a compound having an oxazoline group, a compound having a carbodiimide group, a compound having an isocyanate group, or the like can be used, and an epoxy compound is preferably used.

  Examples of the epoxy compound include Tetrad C [Mitsubishi Gas Chemical Co., Ltd.], Denacol EX-832 [Nagase Kasei Kogyo Co., Ltd.], and the like.

  By using the emulsion-type pressure-sensitive adhesive containing the cross-linking agent, even better heat-resistant adhesive strength that does not cause peeling over time even when used for a long time in an environment with a large temperature change In addition, a pressure-sensitive adhesive tape that achieves both excellent rebound resistance at a level that does not cause peeling due to the repulsive force and the like of the foam material can be obtained.

  The cross-linking agent is preferably used in the range of 0 to 1 part by mass and used in the range of 0.001 to 0.1 part by mass with respect to 100 parts by mass of the acrylic polymer. More preferably, it is used in the range of 0.01 parts by mass to 0.05 parts by mass at a level that does not cause peeling over time even when used for a long time in an environment with a large temperature change. It is possible to obtain a pressure-sensitive adhesive tape that achieves both excellent heat-resistant adhesive strength and even more excellent repulsion resistance at a level that does not cause peeling due to the resilience of the foam material.

  As said emulsion type adhesive, what contains various additives as needed can be used.

  Examples of the additive include a base for adjusting pH (such as aqueous ammonia), an acid, a plasticizer, a softening agent, an antioxidant, a filler such as glass or plastic fibers, balloons, beads, metal powder, Colorants such as pigments and dyes, pH adjusters, film forming aids, leveling agents, thickeners, water generating agents, antifoaming agents, and the like can be used.

  Moreover, as a base material which can be used when manufacturing the adhesive tape of this invention, a nonwoven fabric, a polyester film, a polystyrene film, a polyethylene film etc. can be used, for example. Among them, as the base material, the use of a non-woven fabric has a further excellent heat-resistant adhesive strength that does not cause peeling over time even when used for a long time in an environment with a large temperature change. And a pressure-sensitive adhesive tape that achieves both excellent rebound resistance at a level that does not cause peeling due to the repulsive force of the foam material.

  Examples of the non-woven fabric include non-woven fabrics obtained using manila hemp, wood pulp, rayon, acetate fiber, polyester fiber, vinylon fiber (polyvinyl alcohol fiber), chemical fiber such as polyamide fiber, and mixtures thereof.

  As the nonwoven fabric, the tensile strength in the MD direction (longitudinal direction; flow direction) is preferably 10 N / 20 mm to 20 N / 20 mm, and more preferably 14 N / 20 mm to 18 N / 20 mm. By using a non-woven fabric having a tensile strength in the above range, when a foam material such as polyurethane foam is affixed to an air conditioner unit, an adhesive tape that is difficult to tear and excellent in affixing workability can be obtained. The tensile strength is the maximum strength when a nonwoven fabric having a width of 20 mm and a marked line length of 100 mm is pulled at a speed of 300 mm / min in a 23 ° C./50% RH environment using a Tensilon tensile tester. I mean.

As the nonwoven fabric, it is preferred to use those which are basis weight ^{10g / m 2 ~30g / m 2} , it is more preferable to use those which are ^{13g / m 2 ~25g / m 2} , 14g / m 2 It is more preferable to use one that is ˜20 g / m ² .

As the nonwoven fabric, it is preferable to use those which are the density ^{0.1g / cm 3 ~0.8g / cm 3} , is the use of what is 0.2g / cm ³ ~0.4g / cm 3 More preferred.

  By using a non-woven fabric having a basis weight and density in the above ranges, an adhesive tape that is difficult to break when pasting a foam material such as polyurethane foam to an air conditioner unit and excellent in workability can be obtained.

  As said nonwoven fabric, it is preferable to use what is 100 micrometers or less in thickness, It is more preferable to use what is 10 micrometers-100 micrometers, It is further more preferable to use what is 40 micrometers-70 micrometers.

    By using a non-woven fabric having a thickness in the above range, when a foam material such as polyurethane foam is affixed to an air conditioner unit, an adhesive tape that is difficult to tear and excellent in affixing workability can be obtained.

  The nonwoven fabric can be produced, for example, by a known wet method. Examples of the paper machine that can be used when producing the nonwoven fabric include a circular paper machine, a short paper machine, a long paper machine, and an inclined short paper machine. It is preferable to use it.

  When manufacturing the said nonwoven fabric, a reinforcing agent can be used as needed.

  As the reinforcing agent, for example, an internal additive reinforcing agent or an external additive reinforcing agent can be used alone or in combination of two or more.

  As the internally added reinforcing agent, polyacrylamide resins, urea-formaldehyde resins, melamine-formaldehyde resins, epoxy-polyamide resins and the like can be used.

  As the external additive reinforcing agent, it is possible to use a thermoplastic resin such as starch, viscose, carboxymethyl cellulose, polyvinyl alcohol, polyacrylamide or the like.

  The pressure-sensitive adhesive tape of the present invention can be produced, for example, by applying the emulsion-type pressure-sensitive adhesive on one side or both sides of the base material using a knife coater or a die coater and drying it (so-called direct coating method). ). A release liner may be laminated on the surface of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape obtained by the above method.

  In addition, the pressure-sensitive adhesive tape of the present invention previously forms a pressure-sensitive adhesive layer by applying the emulsion-type pressure-sensitive adhesive on the surface of the release liner, using a knife coater or a die coater, and drying. The pressure-sensitive adhesive layer can also be produced by a method of transferring to one side or both sides of the substrate (so-called transfer method).

  The pressure-sensitive adhesive tape of the present invention has an excellent adhesion to a material having an uneven surface such as a foam material such as polyurethane foam. For example, the pressure-sensitive adhesive tape and the foam material are pasted. Even when the state is punched into a desired shape, it is difficult to cause peeling. In addition, the adhesive tape causes the foam material to peel off due to the repulsive force even when the foam material or the like having a large repulsive force is attached to the curved surface portion or corner portion of another adherend. Hateful.

  The pressure-sensitive adhesive tape of the present invention can maintain the excellent adhesive force and repulsion resistance even when placed in an environment with a large temperature change for a long period of time.

  Therefore, the pressure-sensitive adhesive tape of the present invention can be suitably used exclusively as a pressure-sensitive adhesive tape for manufacturing an automobile, and in particular, it can be used for fixing an air conditioner unit mounted on an automobile and a foam material. it can.

  Specifically, the adhesive tape is suitable for fixing to the foam material installed between the air conditioner unit and a duct for sending air whose temperature or humidity is adjusted by the air conditioner unit into an automobile. Can be used. The adhesive tape of the present invention has excellent adhesive strength over a long period of time regardless of the temperature and humidity of the air sent from the air conditioner unit, and regardless of the outside air temperature and humidity, even when used in the above applications. And has repulsion resistance.

  As said adhesive tape, the said foam material may be affixed previously to one adhesive layer.

  As the foam material, it is possible to use a porous body containing closed cells or bubbles in which some of them communicate. Specifically, as the foam material, for example, an ether polyurethane foam, an ester polyurethane foam, an ethylene propylene diene rubber (EPDM) opsealer, or the like can be used.

  Among the foam materials, urethane foam materials, particularly ether-based polyurethane foam materials, generally tend to have a large repulsive force when folded, but if the adhesive tape of the present invention, the foam material can be fixed, It can be preferably used.

  In addition, the pressure-sensitive adhesive tape of the present invention may be in a state where a release liner is stuck on the surface of the pressure-sensitive adhesive layer before being stuck to the air conditioner unit and the foam material.

  As the release liner, a conventional one can be used. For example, in the case where a foam material is previously affixed to one surface of the adhesive tape and the other adhesive layer surface is bonded to a predetermined position of the air conditioner unit, the other adhesive layer When the release liner attached to the surface is peeled off, the release liner may be broken. The tearing is not preferable because it causes a decrease in the workability of the sticking.

  Therefore, as the release liner, the tensile strength when the release liner is pulled at a speed of 20 m / min along the flow direction is 35 N / 5 mm or more, and the release liner is arranged in the width direction. It is preferable to use the one having a tensile strength of 35 N / 5 mm or more when pulled at a speed of 20 m / min. By using a release liner having such a tensile strength, it is possible to prevent the release liner from being torn when the release liner is peeled off. As a result, when foam material such as polyurethane foam is bonded and fixed to the air conditioner unit. A reduction in work efficiency can be prevented.

  The release liner has a tensile strength in the flow direction of 45 N / 5 mm or more, more preferably a tensile strength in the width direction of 35 N / 5 mm or more, and a tensile strength in the flow direction of 45 N / 5 mm or more. Further, it is more preferable that the tensile strength in the width direction is 40 N / 5 mm or more, the tensile strength in the flow direction is 55 N / 5 mm or more, and the tensile strength in the width direction is 45 N / 5 mm or more. preferable. Moreover, it is preferable that the upper limits of the tensile strength in the flow direction and the width direction of the release liner are both 125 N / 5 mm.

  Further, as the release liner used in the present invention, the release liner conforms to the JIS L 1085 standard along the flow direction, and the bending resistance measured with a Gurley type tester is 1,000 mg or more. In addition, it is preferable to use a release liner having a bending resistance measured in the width direction of 1,000 mg or more. By using such a release liner, it is possible to prevent the release liner from being torn when the release liner is peeled off. As a result, the work efficiency when the foam material such as polyurethane foam is bonded and fixed to the air conditioner unit is reduced. Can be prevented.

  The release liner has a flow direction bending resistance of 2,000 mg or more, a width direction bending resistance of preferably 1,000 mg or more, and a flow direction bending resistance of 2,000 mg. More preferably, the bending resistance in the width direction is 1,200 mg or more, the bending resistance in the flow direction is 2,000 mg or more, and the bending resistance in the width direction is 1,300 mg or more. It is even more preferable that the bending resistance in the flow direction is 2,000 mg or more, and it is particularly preferable that the bending resistance in the width direction is 2,000 mg or more.

  Moreover, as a release liner used by this invention, it is preferable to use what the tear strength of the flow direction of the said release liner is the range of 0.1N-4N. By using such a release liner, it is possible to prevent the release liner from being torn when the release liner is peeled off. As a result, the work efficiency when the foam material such as polyurethane foam is bonded and fixed to the air conditioner unit is reduced. Can be prevented.

  The tear strength here is based on the strength at the time of tearing at 0.2 m / min after making a cut with scissors or the like at the center of the end of the release liner.

  More preferably, the release liner has a tear strength in the flow direction of the release liner in the range of 0.5N to 2N.

  The tensile strength, bending resistance, and tear strength of the release liner can be adjusted within the predetermined range by appropriately setting the material constituting the release liner, the laminated structure, and the like. Specifically, the tensile strength, bending resistance, and tear strength of the release liner include the type and basis weight of the base paper constituting it, the presence or absence of a resin layer such as a polyolefin layer, the thickness of the resin layer, the release liner. Can be adjusted as appropriate by adjusting the total thickness, basis weight, and the like. In order to adjust the release load of the release liner within a desired range, it is preferable to adjust the type and application amount of the silicone layer constituting the release liner.

  The total thickness of the release liner is preferably 100 μm to 200 μm, more preferably 120 μm to 150 μm, and 130 μm to 140 μm. This is particularly preferable since the handling workability in the production process of the pressure-sensitive adhesive tape is good, and the release liner is not easily broken when peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape.

As the release liner, on one or both sides of the paper basis weight 75g / m ² ~110g / m ² obtained by using chemical pulp, having a polyolefin layer on one or both surfaces of the polyolefin layer, It is preferable to use one having a layer containing silicone.

  As the paper, it is preferable to use paper obtained using chemical pulp.

  As the chemical pulp, for example, kraft pulp, sulfide pulp, alkaline pulp, and the like can be used. Kraft pulp and sulfide pulp are preferably used, and sulfide pulp is more preferably used.

  Among the papers, so-called high-quality paper having a blending ratio of 100% by mass of sulfide pulp can be preferably used, and among the sulfide pulps, softwood bleached sulfate pulp (N material) and hardwood bleached sulfate pulp (L material). It is preferable to use a high-quality paper obtained by mixing with a) because the release liner is difficult to break in the step of peeling the release liner. In addition, the ratio of the above-mentioned softwood bleached sulfate pulp (N material) and hardwood bleached sulfate pulp (L material) is not particularly limited, and according to the handling workability in the production process and use process of the adhesive tape. The ratio of the N material and the L material can be adjusted as appropriate.

  The paper constituting the release liner may contain an internally added wet paper strength enhancer, a dry paper strength enhancer, and a surface paper strength enhancer. An internal addition type dry paper strength enhancer and a surface type paper strength enhancer are more preferable, and it is more preferable to use both paper strength enhancers in combination. Examples of the internally added dry paper strength enhancer include cationized starch and polyacrylamide polymers. Examples of the surface type paper strength enhancer include modified starch and polyvinyl alcohol.

  As the paper, those containing a sizing agent, a yield improver, a drainage improver, an antifoaming agent, a dispersant, a bleaching agent, a dye, and the like can be used.

  In addition, the method for making the paper is not particularly limited, and examples thereof include a method using a circular paper machine, a short paper machine, a long paper machine, and the like.

  As the release liner, it is preferable to form a polyolefin layer on one side or both sides of the paper. Examples of the polyolefin layer include a layer formed using polyethylene, polypropylene, and the like, and a resin layer formed using polyethylene or the like has high adhesion to paper, and when the release liner is peeled off. It is more preferable in making it difficult to break.

  Further, the thickness of the polyolefin layer is preferably one having a resin layer in the range of 10 μm to 40 μm, more preferably one having a resin layer in the range of 20 μm to 30 μm, Use of a resin layer having a resin layer in the range of 27 μm is particularly preferable in terms of high adhesion to the paper and making it difficult to break when the release liner is peeled off.

  The polyolefin layer can be formed, for example, by applying polyethylene to one or both sides (one side or both sides) of the base paper with a T-die extruder and laminating.

  As the release liner, it is preferable to use a release liner having a polyolefin layer on one or both sides of the paper and a layer containing silicone on the outer surface of the polyolefin layer. The silicone-containing layer can be formed by applying a silicone release agent, drying and curing.

  The silicone-based release agent is preferably an addition reaction type, a condensation reaction type, or a UV curing reaction type in order to give the predetermined release load, and among them, an addition reaction type silicone release agent is used. Even when the release liner is peeled from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape at a high speed, it is particularly preferable because the release liner is not easily broken and easily peeled off.

  The layer containing the silicone preferably contains a catalyst together with the silicone release agent, and among them, the one containing a platinum catalyst together with the silicone release agent peels the release liner from the adhesive layer. This is particularly preferable because the amount of the silicone release agent transferred to the pressure-sensitive adhesive layer can be reduced.

  The layer containing silicone may contain a heavy release additive as necessary in appropriately adjusting the peeling load.

  Examples of the addition reaction type silicone release agent include KS-847T (manufactured by Shin-Etsu Chemical Co., Ltd.), KS-774 (manufactured by Shin-Etsu Chemical Co., Ltd.), and KS-776A (manufactured by Shin-Etsu Chemical Co., Ltd.). KS-778 [manufactured by Shin-Etsu Chemical Co., Ltd.], KS-779H [manufactured by Shin-Etsu Chemical Co., Ltd.], KS-830 [manufactured by Shin-Etsu Chemical Co., Ltd.], KS-837 [Shin-Etsu Chemical Co., Ltd.] KS-839L [Shin-Etsu Chemical Co., Ltd.], KS-3502 [Shin-Etsu Chemical Co., Ltd.], KS-3703 [Shin-Etsu Chemical Co., Ltd.], SRX357 [Toray Dow Corning Co., Ltd.] )], BY23-749 [Toray Dow Corning Co., Ltd.], SD7333 [Toray Dow Corning Co., Ltd.], BY24-179 [Toray Dow Corning Co., Ltd.], SRX211 [Toray Dow Corning] Co., Ltd.], BY23-746 [Toray Dow Corning Co., Ltd.], SRX345 [Toray Dow Corning Co., Ltd.], BY24-4103 [Toray Dow Corning Co., Ltd.], SD7320 [Toray Dow Corning] Corning Co., Ltd.], SD7236 [Toray Dow Corning Co., Ltd.] and the like.

  Examples of the heavy release additive include KS-3800 [manufactured by Shin-Etsu Chemical Co., Ltd.], SD7292 [manufactured by Toray Dow Corning Co., Ltd.], BY24-843 [manufactured by Toray Dow Corning Co., Ltd.], BY24-4980. [Toray Dow Corning Co., Ltd.] and the like.

  As the catalyst, a platinum-based catalyst can be suitably used. SRX212 [manufactured by Toray Dow Corning Co., Ltd.], NC-25 [manufactured by Toray Dow Corning Co., Ltd.], CAT-PL-50T [Shin-Etsu Chemical Co., Ltd. ( Etc.].

  Among the addition reaction type silicone release agents, KS-847T [manufactured by Shin-Etsu Chemical Co., Ltd.], SD7333 [manufactured by Toray Dow Corning Co., Ltd.], SRX345 [manufactured by Toray Dow Corning Co., Ltd.] It is particularly preferable to use it even if the release liner is peeled off at a speed of 20 m / min since it is easy to peel off with a light force and the release liner is not easily broken.

The coating amount of the layer containing the silicone, in order to adjust the peeling load in a predetermined ^range, preferably in the range of ^{0.5g / m 2 ~1.0g / m 2} . In adjusting the coating amount as appropriate, the silicone release agent may be diluted with an organic solvent such as toluene. When preparing a diluted solution, it is preferable that it is in the range of 1% by mass to 10% by mass in order to adjust the coating amount to a predetermined range.

  As a method for forming the silicone-containing layer, the silicone release agent diluted with an organic solvent such as toluene, the direct gravure coater, the offset gravure coater, the Mayer bar coater, the 5-roll coater, etc. Examples of the method include coating on the surface of the resin layer and drying. The silicone-containing layer is preferably dried at 90 to 110 ° C. for 3 to 40 seconds and cured. The silicone-containing layer is preferably formed by curing at 30 ° C. to 60 ° C. over 48 hours after the curing.

  As the release liner, use may be made of a release load of 1 N / 20 mm or less when the release liner is peeled from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape at a rate of 5 m / min in the 180 degree direction. preferable. By using such a release liner, even when the release liner is peeled off at a slow speed, it is possible to prevent the release liner from being torn, and as a result, when foam material such as polyurethane foam is bonded and fixed to the air conditioner unit. A reduction in work efficiency can be prevented.

  The release liner has a peeling load of 0.5 N / 20 mm or less with respect to a 90 μm-thick adhesive layer formed using “SK Dyne 801B” (manufactured by Soken Chemical Co., Ltd., solvent-based adhesive). The release liner is preferably 0.3N / 20 mm or less, more preferably 0.25 N / 20 mm or less, and 0.16 N / 20 mm or less. It is particularly preferable because it is easy to peel off and improves work efficiency.

  The release load was applied on a release liner by applying “SK Dyne 801B” (Soken Chemical Co., Ltd., solvent-based adhesive) to a thickness of 90 μm after drying, Based on the strength when a PET film with a thickness of 75 μm is stuck on the surface, cured for 20 hours in a 40 ° C. environment, gripped on the release liner side of the test piece cut to a width of 20 mm, and peeled off in the 180 ° direction. is there.

  More preferably, the release liner has a peeling load in the range of 0.01 N / 20 mm to 0.5 N / 20 mm when peeled off at 5 m / min in the 180 degree direction, and 0.01 N / 20 mm to 0 More preferably, it is in the range of 4 N / 20 mm, more preferably in the range of 0.1 N / 20 mm to 0.3 N / 20 mm, and particularly preferably in the range of 0.12 N / 20 mm to 0.22 N / 20 mm. preferable.

  Further, as the release liner, a release liner having a peeling load of 1 N / 20 mm or less when the release liner is peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape at a rate of 20 m / min in the 180 degree direction is used. It is preferable. By using such a release liner, even when the release liner is peeled off at a high speed, it is possible to prevent the release liner from being broken, and as a result, when foam material such as polyurethane foam is bonded and fixed to the air conditioner unit. A reduction in work efficiency can be prevented.

  The release liner has a peeling load in the range of 0.01 N / 20 mm to 0.7 N / 20 mm when the release liner is peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape at 180 m in a direction of 20 m / min. More preferably, it is more preferably in the range of 0.01 N / 20 mm to 0.5 N / 20 mm, still more preferably 0.1 N / 20 mm to 0.4 N / 20 mm, and 0.1 N / 20 mm. It is especially preferable that it is -0.2N / 20mm.

In addition, as the release liner, it is preferable to use a release liner that does not become heavy even when the peeling speed is increased, that is, a so-called speed-dependent liner. It is preferable to prevent tearing, and as a result, it is possible to prevent a reduction in work efficiency when a foam material such as polyurethane foam is applied to an air conditioner unit, and is preferably separated from the adhesive layer of the adhesive tape. When the release liner is peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape at 20 m / min with respect to the peeling load [R _5m ] when the mold liner is peeled off in the 180-degree direction at 5 m / min. the ratio of peel load _{[R 20m] [R 20m /} R 5m] is preferably in the range of 1 to 3, more in the range of 1 to 2.5 Preferred, even more preferably in the range of 1 to 2, particularly preferably in the range of 1.1 to 1.5.

  Next, the present invention will be described in detail with reference to examples and comparative examples.

[Evaluation method]
(Measurement of the gel fraction of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape)
The mass (G ₀ ) of the base material used in the production of the adhesive tapes of Examples and Comparative Examples was measured.

Next, the pressure-sensitive adhesive tape was cut into a size of 50 mm in length and 40 mm in width, and the mass (G ₁ ) of a sample obtained by removing the release liners on both sides thereof was measured.

  Next, the sample immersed in toluene was allowed to stand at 25 ° C. (normal temperature) for 24 hours.

After 24 hours, the sample that was not dissolved in toluene was separated by filtration using a 300 mesh wire net, and the mass (G ₂ ) of the sample dried at 105 ° C. for 1 hour was measured.

The gel fraction was calculated according to the following formula. Gel fraction (% by mass) = [(G ₂ −G ₀ ) / (G ₁ −G ₀ )] × 100

(Repulsion resistance when bent 180 degrees in a 23 ° C environment)
The release liner on one side constituting the pressure-sensitive adhesive tapes of Examples and Comparative Examples is peeled off, and an ether-based polyurethane foam (trade name: ECS, manufactured by Inoac Corporation) is pasted on the surface of the pressure-sensitive adhesive layer. Combined. At that time, they were pressure-bonded by applying a compressive load such that the thickness of the ether polyurethane foam was 5 mm.

  A test piece (X) was obtained by cutting the paste of the ether-based polyurethane foam and the adhesive tape obtained by the above method into a size having a width of 20 mm and a length of 100 mm and leaving it in a 23 ° C. and 50% RH environment for 24 hours. ).

  Next, the other release liner constituting the test piece (X) is peeled off, and this is pasted on one surface of a polypropylene plate 1 having a thickness of 4 mm so that the pasting area is 20 mm wide and 20 mm long. did.

  Next, the test piece (X) not attached to the polypropylene plate 1 is attached to the other side of the polypropylene plate 1 by bending it 180 degrees, and the end is attached to the one surface side. Affixed to. Specifically, as shown in FIG. 1, the test piece (X) was attached to the polypropylene plate 1. The affixed material was allowed to stand at 23 ° C. and 50% RH for 24 hours.

  After the standing, the distance that the ether polyurethane foam was peeled off from the surface of the pressure-sensitive adhesive tape (floating distance) was measured (FIG. 1).

A: The lift-off distance was less than 5 mm.
○: The lift-off distance was 5 mm or more and less than 10 mm.
Δ: The lift-off distance was 10 mm or more and less than 20 mm.
X: The lift-off distance was 20 mm or more.

(Repulsion resistance at the time of 180 degree bending under a cold cycle condition)
The release liner on one side constituting the pressure-sensitive adhesive tapes of Examples and Comparative Examples is peeled off, and an ether-based polyurethane foam (trade name: ECS, manufactured by Inoac Corporation) is pasted on the surface of the pressure-sensitive adhesive layer. Combined. At that time, they were pressure-bonded by applying a compressive load such that the thickness of the ether polyurethane foam was 5 mm.

  A test piece was prepared by cutting the paste of the ether-based polyurethane foam and the adhesive tape obtained by the above method into a size of 20 mm in width and 100 mm in length and leaving it in an environment of 23 ° C. and 50% RH for 24 hours. .

  Next, the other release liner constituting the test piece was peeled off, and it was pasted on one surface of a 4 mm thick polypropylene plate so that the pasting area was 20 mm wide and 20 mm long.

  Next, the test piece (X) not attached to the polypropylene plate 1 is attached to the other side of the polypropylene plate 1 by bending it 180 degrees, and the end is attached to the one surface side. Affixed to. Specifically, as shown in FIG. 1, the test piece (X) was attached to the polypropylene plate 1. The affixed material was allowed to stand at 23 ° C. and 50% RH for 24 hours.

  Next, using a small environmental tester [manufactured by ESPEC Co., Ltd., model number: SH-241], cooled to 85 ° C. to −35 ° C. over 2 hours after being left for 2 hours at 85 ° C. , After leaving at -35 ° C. for 2 hours and then standing for 125 cycles under the condition of heating from -35 ° C. to 85 ° C. over 2 hours), the ether polyurethane foam The distance peeled off from the surface (the lift-off distance) was measured.

A: The lift-off distance was less than 5 mm.
○: The lift-off distance was 5 mm or more and less than 10 mm.
Δ: The lift-off distance was 10 mm or more and less than 20 mm.
X: The lift-off distance was 20 mm or more.

(180 degree peel adhesive strength after standing in 23 ° C environment)
A single-sided release liner constituting the pressure-sensitive adhesive tapes of Examples and Comparative Examples was peeled off, and a 25 μm-thick polyethylene terephthalate film was pasted on the surface of the pressure-sensitive adhesive layer to be used as a test piece.

  Next, the other release liner constituting the test piece is peeled off, and adherends (1) to (3) described later are bonded to the surface of the pressure-sensitive adhesive layer, and the pressure is reciprocated once using a 2 kg roller. To make them adhere.

The material bonded by the above method is allowed to stand in an environment of 23 ° C. and 50% RH for 24 hours, and then in the same environment, using the Tensilon tensile tester [manufactured by A & D Co., Ltd., model: RTM-100], the test The adherend (1) whose adhesion was measured by peeling the piece at a speed of 300 mm / min in the direction of 180 ° with respect to the horizontal direction of the adherend; the stainless plate adherend (2) having a thickness of 4 mm A 4 mm thick polypropylene plate adherend (3); a 10 mm thick ether polyurethane foam (trade name; ECS, manufactured by Inoac Corporation)

  Adhesive strength of 14 N / 20 mm or more to the stainless steel plate, adhesive strength of 12 N / 20 mm or more to the polypropylene plate, and adhesive strength of 4 N / 20 mm or more to the ether polyurethane foam. What was shown was rated as excellent. In addition, what showed the adhesive force with respect to ether type polyurethane foam more than 7N / 20mm was described as 7 <.

(180 degree peeling adhesive strength after standing under cold cycle conditions)
A single-sided release liner constituting the pressure-sensitive adhesive tapes of Examples and Comparative Examples was peeled off, and a 25 μm-thick polyethylene terephthalate film was pasted on the surface of the pressure-sensitive adhesive layer to be used as a test piece.

  Next, the other release liner constituting the test piece is peeled off, and adherends (1) to (3) described later are bonded to the surface of the pressure-sensitive adhesive layer, and the pressure is reciprocated once using a 2 kg roller. To bond them and leave them in a 23 ° C. and 50% RH environment for 24 hours to obtain an adhesive.

Next, using a small environmental tester [manufactured by ESPEC Co., Ltd., model number: SH-241], cooled to 85 ° C. to −35 ° C. over 2 hours after being left for 2 hours at 85 ° C. , After standing at −35 ° C. for 2 hours and then standing for 125 cycles under the condition of heating from −35 ° C. to 85 ° C. over 2 hours), in an environment of 23 ° C. and 50% RH, Using a Tensilon tensile tester [manufactured by A & D Co., Ltd., model: RTM-100], the test piece constituting the adhesive is pulled at a speed of 300 mm / min in the direction of 180 degrees with respect to the horizontal direction of the adherend. Adhesive (1) whose adhesion was measured by peeling off; stainless steel plate adherend (2) having a thickness of 4 mm; polypropylene plate adherend (3) having a thickness of 4 mm; ether-based polyurethane foam having a thickness of 10 mm ( Lee Co., Ltd. ACK Corporation, trade name; ECS)
Adhesive strength of 14 N / 20 mm or more to the stainless steel plate, adhesive strength of 12 N / 20 mm or more to the polypropylene plate, and adhesive strength of 4 N / 20 mm or more to the ether polyurethane foam. What was shown was rated as excellent. In addition, what showed the adhesive force with respect to ether type polyurethane foam more than 7N / 20mm was described as 7 <.

(Evaluation of peelability of release liner)
The release liner on one side constituting the pressure-sensitive adhesive tapes of Examples and Comparative Examples is peeled off, and an ether-based polyurethane foam (trade name: ECS, manufactured by Inoac Corporation) is pasted on the surface of the pressure-sensitive adhesive layer. Three pieces were prepared. At that time, they were pressure-bonded by applying a compressive load such that the thickness of the ether polyurethane foam was 5 mm.

  Next, a test piece (Y) was punched into the shape shown in FIG.

  From one corner (point A in FIG. 2) of the test piece (Y) to the diagonal direction (point B direction in FIG. 2), the other release liner constituting the test piece (Y) is 20 m / second. The ease of peeling when peeling at a speed of minutes was evaluated. Five testers carried out three times for each test piece, and the most frequent evaluation was adopted.

A: The release liner did not break and could be peeled off with a light force.
○: The release liner was not torn and it was able to be peeled off although it was somewhat heavy.
Δ: The release liner was torn once or twice.
X: The release liner was broken 3 times.

(Adhesive tape peeling load)
What cut | disconnected the adhesive tape of the Example and the comparative example in width 20mm was used as the test piece. Under a 23 ° C. and 50% RH environment, the release liner of the test piece was grasped, and using a high-speed peel tester [manufactured by Tester Sangyo Co., Ltd.], 5 m / min and 180 m from the adhesive layer in the direction of 180 degrees. The peel load when peeled at a rate of minutes was measured.

(Release load of release liner)
SK Dyne 801B (manufactured by Soken Chemical Co., Ltd., solvent-based adhesive) was applied to the release liner so that the thickness after drying was 90 μm, and after drying, it was bonded to a 75 μm thick polyethylene terephthalate film The test piece was cured for 20 hours in a 40 ° C. environment and cut to a width of 20 mm. The release liner of the test piece was gripped, and the peel load when peeled at a speed of 5 m / min in the 180 ° direction was measured using a high-speed peel tester [manufactured by Tester Sangyo Co., Ltd.].

(Tensile strength of release liner)
Five test pieces were prepared by cutting the release liner into a dimension of 5 mm in the flow direction and 180 mm in the width direction. The tensile strength in the width direction of the test piece was measured and averaged using a high-speed tensile tester [manufactured by Tester Sangyo Co., Ltd.] under conditions of a marked line interval of 150 mm and a tensile speed of 20 m / min. Also, five test pieces were prepared by cutting the release liner into a dimension of 180 mm in the flow direction and 5 mm in the width direction. The tensile strength in the width direction of the test piece was measured and averaged using a high-speed tensile tester [manufactured by Tester Sangyo Co., Ltd.] under conditions of a marked line interval of 150 mm and a tensile speed of 20 m / min.

(Flexibility of release liner)
The bending resistance of the release liner was measured according to JIS L 1085 standard. Five test pieces were prepared by cutting the release liner into a dimension of 20 mm in the flow direction and 340 mm in the width direction.

  Next, using the Gurley-type bending resistance tester [Tester Sangyo Co., Ltd., model; ST-401], the test piece was fixed with a five-layer chuck.

  Next, a load of 25 g was applied 10 cm away from the fulcrum to rotate the arm at a constant speed, and the scale (RG) when the test piece was separated from the pendulum was read. The measurement was performed 5 times for each of the front and back sides, and the average value was calculated. Based on the measured value, the bending resistance was calculated from the following equation.

  Formula: Bending softness (mg) = (RG) × 10 × 25 × (3.4 × 3.4 ÷ 2) × 0.306

  Five test pieces were prepared by cutting the release liner into a dimension of 340 mm in the flow direction and 20 mm in the width direction.

  Next, using the Gurley-type bending resistance tester [manufactured by Tester Sangyo Co., Ltd., model; ST-401], the test piece was fixed with a five-layer chuck.

  Next, a load of 25 g was applied 10 cm away from the fulcrum to rotate the arm at a constant speed, and the scale (RG) when the test piece was separated from the pendulum was read. The measurement was performed 5 times for each of the front and back sides, and the average value was calculated. Based on the measured value, the bending resistance was calculated from the following equation.

  Formula: Bending softness (mg) = (RG) × 10 × 25 × (3.4 × 3.4 ÷ 2) × 0.306

(Tear strength of release liner)
The release liner was cut into a width of 50 mm and a length of 100 mm to obtain a test piece.

  Next, a 25 mm long cut is made in the center of the end in the width direction, and then teared at a speed of 0.2 m / min using a Tensilon tensile tester [manufactured by A & D Corporation, model: RTM-100]. The strength was measured.

(Tensile strength of nonwoven substrate)
The non-woven fabric substrate was cut to a width of 20 mm and a length of 120 mm to obtain a test piece, and the marked line length was set to 100 mm. Subsequently, in an environment of 23 ° C. and 50% RH, using a Tensilon tensile tester [manufactured by A & D Co., Ltd., Model: RTM-100], both ends were gripped so that the marked line length was 100 mm, and 300 mm / The maximum strength was measured by pulling at a speed of minutes.

(Preparation Example 1) Preparation of water-dispersed acrylic pressure-sensitive adhesive composition (1) In a container, 75 g of ion exchange water and Aqualon KH-1025 as a surfactant [Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 25% by mass ] 20 g and 37.5 g of Latemul PD-104 [manufactured by Kao Corporation, active ingredient 20% by mass] as a surfactant were added and dissolved uniformly. There, 470 g of 2-ethylhexyl acrylate, 15 g of methyl methacrylate, 15 g of acrylic acid, KBM-503 [manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltrimethoxysilane] 0.1 g, lauryl mercaptan 0. 2g was added and emulsified and the emulsion (1) 632.8g was obtained.

  In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel, 331.5 g of ion-exchanged water was added, and the temperature was raised to 60 ° C. while blowing nitrogen. Under stirring, a part of the emulsion (1) [7.59 g], VA-044 [Wako Pure Chemical Industries, Ltd., azo polymerization initiator, 2,2′-azobis [2- (2-imidazoline] 2-yl) propane] dihydrochloride, 10 hours half-life temperature 44 ° C.] 2.5 g [active ingredient 10% by mass] was added, and polymerization was carried out in 1 hour while maintaining 60 ° C.

  Subsequently, 625.21 g of the remaining emulsion (1) and VA-057 [Wako Pure Chemical Industries, Ltd., 2,2′-azobis [N- (2-carboxyethyl)-] which is an azo polymerization initiator 2-methylpropionamidine] hydrate, 10-hour half-life temperature 57 ° C.] 50 g [active ingredient 1%] was dropped and polymerized over 8 hours using a separate funnel while keeping the reaction vessel at 60 ° C. .

  Subsequently, 1 hour after the completion of dropping of the emulsion and the polymerization initiator, 5 g of an aqueous ammonium persulfate solution (5% by mass of active ingredient) and 5.0 g of an aqueous solution of sodium bisulfite (2% by mass of active ingredient) were separately added. Using a funnel, dropwise polymerization was carried out over 1 hour while keeping the reaction vessel at 60 ° C.

  Subsequently, one hour after the dropping of the ammonium persulfate aqueous solution and the sodium hydrogen sulfite aqueous solution was completed, the contents were cooled and adjusted with ammonia water [active ingredient 10 mass%] so that the pH was 7.5. This was filtered through a 200-mesh wire mesh to obtain 1027.9 g of an acrylic polymer emulsion (1). The acrylic polymer emulsion (1) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 303 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (1) was 800,000.

  1000 g of the acrylic polymer emulsion (1), 7.5 g of B-500 [manufactured by Toagosei Co., Ltd., solid content 36 mass%, carboxylic acid copolymer] as a viscosity modifier, Surfynol PSA as a leveling agent -336 [Air Products Japan Co., Ltd., active ingredient 100% by mass] 2.5 g, Surfynol DF-110D [Air Products Japan Co., Ltd., active ingredient 100% by mass] as an antifoaming agent 2 .5 g, Superester E-865NT [made by Arakawa Chemical Industries, Ltd .; softening point 160 ° C., solid content concentration 50 mass%, emulsion-type polymerized rosin ester-based tackifier resin] as a tackifier resin was added and stirred for 2 hours. did. Then, the water dispersion type acrylic adhesive composition (1) was obtained by filtering with a 200 mesh metal-mesh.

(Preparation Example 2)
An emulsion (2) was prepared in the same manner as in Preparation Example 1, except that 2-ethylhexyl acrylate was changed from 470 g to 460 g and methyl methacrylate was changed from 15 g to 25 g.

  Next, an acrylic polymer emulsion (2) was prepared in the same manner as in Preparation Example 1, except that the emulsion (2) was used instead of the emulsion (1). The acrylic polymer emulsion (2) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 311 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (2) was 850,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (2) was prepared in the same manner as in Preparation Example 1, except that the acrylic polymer emulsion (2) was used instead of the acrylic polymer emulsion (1). Obtained.

(Preparation Example 3)
An emulsion (3) was prepared in the same manner as in Preparation Example 1, except that 2-ethylhexyl acrylate was changed from 470 g to 435 g and methyl methacrylate was changed from 15 g to 50 g.

  Next, an acrylic polymer emulsion (3) was prepared in the same manner as in Preparation Example 1, except that the emulsion (3) was used instead of the emulsion (1). The acrylic polymer emulsion (3) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 300 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (3) was 780,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (3) was obtained in the same manner as in Preparation Example 1, except that the acrylic polymer emulsion (3) was used instead of the acrylic polymer emulsion (1). It was.

(Preparation Example 4)
An emulsion (4) was prepared in the same manner as in Preparation Example 2, except that the methyl methacrylate was changed from 25 g to 25 g of ethyl acrylate.

  Next, an acrylic polymer emulsion (4) was prepared in the same manner as in Preparation Example 2, except that the emulsion (4) was used instead of the emulsion (2). The acrylic polymer emulsion (4) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 318 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (4) was 770,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (4) was prepared in the same manner as in Preparation Example 2, except that the acrylic polymer emulsion (4) was used instead of the acrylic polymer emulsion (2). Obtained.

(Preparation Example 5)
An emulsion (5) was prepared in the same manner as in Preparation Example 1, except that 2-ethylhexyl acrylate was changed from 470 g to 485 g and methyl methacrylate was changed from 15 g to 0 g.

  Next, an acrylic polymer emulsion (5) was prepared in the same manner as in Preparation Example 1, except that the emulsion (5) was used instead of the emulsion (1). The acrylic polymer emulsion (5) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 322 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (5) was 700,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (5) was prepared in the same manner as in Preparation Example 1, except that the acrylic polymer emulsion (5) was used instead of the acrylic polymer emulsion (1). Obtained.

(Preparation Example 6)
An emulsion (6) was prepared in the same manner as in Preparation Example 2, except that 2-ethylhexyl acrylate was changed from 460 g to 322 g and n-butyl acrylate 138 g was added.

  Next, an acrylic polymer emulsion (6) was prepared in the same manner as in Preparation Example 2, except that the emulsion (6) was used instead of the emulsion (2). The acrylic polymer emulsion (6) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 332 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (6) was 840,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (6) was prepared in the same manner as in Preparation Example 1, except that the acrylic polymer emulsion (6) was used instead of the acrylic polymer emulsion (2). Obtained.

(Preparation Example 7)
An emulsion (7) was prepared in the same manner as in Preparation Example 6 except that 2-ethylhexyl acrylate was changed from 322 g to 230 g and n-butyl acrylate was changed from 138 g to 230 g.

  Next, an acrylic polymer emulsion (7) was prepared in the same manner as in Preparation Example 6, except that the emulsion (7) was used instead of the emulsion (6). The resulting acrylic polymer emulsion (7) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 341 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (7) was 890,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (7) was prepared in the same manner as in Preparation Example 6 except that the acrylic polymer emulsion (7) was used instead of the acrylic polymer emulsion (6). Obtained.

(Preparation Example 8)
An emulsion (7) was prepared in the same manner as in Preparation Example 6 except that 2-ethylhexyl acrylate was changed from 322 g to 138 g and n-butyl acrylate was changed from 138 g to 322 g.

  Next, an acrylic polymer emulsion (8) was prepared in the same manner as in Preparation Example 6, except that the emulsion (8) was used instead of the emulsion (6). The acrylic polymer emulsion (8) thus obtained had a solid content concentration of 50% by mass, and the average particle size of the acrylic polymer was 300 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (8) was 780,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (8) was prepared in the same manner as in Preparation Example 5, except that the acrylic polymer emulsion (8) was used instead of the acrylic polymer emulsion (6). Obtained.

(Preparation Example 9)
An emulsion (9) was prepared in the same manner as in Preparation Example 6 except that 2-ethylhexyl acrylate was changed from 322 g to 0 g and n-butyl acrylate was changed from 138 g to 460 g.

  Next, an acrylic polymer emulsion (9) was prepared in the same manner as in Preparation Example 6 except that the emulsion (9) was used instead of the emulsion (6). The resulting acrylic polymer emulsion (9) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 341 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (9) was 880,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (9) was prepared in the same manner as in Preparation Example 5, except that the acrylic polymer emulsion (9) was used instead of the acrylic polymer emulsion (6). Obtained.

(Preparation Example 10)
An emulsion (10) was prepared in the same manner as in Preparation Example 2, except that 2-ethylhexyl acrylate was changed from 460 g to 455 g and 5 g of N-vinylpyrrolidone was added.

  Next, an acrylic polymer emulsion (10) was prepared in the same manner as in Preparation Example 2, except that the emulsion (10) was used instead of the emulsion (2). The acrylic polymer emulsion (10) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 380 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (10) was 830,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (10) was prepared in the same manner as in Preparation Example 2, except that the acrylic polymer emulsion (10) was used instead of the acrylic polymer emulsion (2). Obtained.

(Preparation Example 11)
An emulsion (11) was prepared in the same manner as in Preparation Example 2, except that 2-ethylhexyl acrylate was changed from 460 g to 455 g and N-isopropylacrylamide 5 g was added.

  An acrylic polymer emulsion (11) was prepared in the same manner as in Preparation Example 2, except that the emulsion (11) was used instead of the emulsion (2). The resulting acrylic polymer emulsion (11) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 360 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (11) was 800,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (11) was prepared in the same manner as in Preparation Example 2, except that the acrylic polymer emulsion (11) was used instead of the acrylic polymer emulsion (2). Obtained.

(Preparation Example 12)
An emulsion (12) was prepared in the same manner as in Preparation Example 2, except that acrylic acid was changed from 15 g to 5 g and methacrylic acid 10 g was added.

  An acrylic polymer emulsion (12) was prepared in the same manner as in Preparation Example 2, except that the emulsion (12) was used instead of the emulsion (2). The resulting acrylic polymer emulsion (12) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 355 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (12) was 690,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (12) was prepared in the same manner as in Preparation Example 2, except that the acrylic polymer emulsion (12) was used instead of the acrylic polymer emulsion (2). Obtained.

(Preparation Example 13)
An emulsion (13) was prepared in the same manner as in Preparation Example 12 except that 2-ethylhexyl acrylate was changed from 460 g to 455 g and 5 g of N-vinylpyrrolidone was added.

  An acrylic polymer emulsion (13) was prepared in the same manner as in Preparation Example 12 except that the emulsion (13) was used instead of the emulsion (12). The resulting acrylic polymer emulsion (13) had a solid content concentration of 50 mass%, and the acrylic polymer had an average particle size of 360 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (13) was 830,000.

  Next, the water-dispersed acrylic pressure-sensitive adhesive composition (13) was prepared in the same manner as in Preparation Example 12, except that the acrylic polymer emulsion (13) was used instead of the acrylic polymer emulsion (12). Obtained.

(Preparation Example 14)
An emulsion (14) was prepared in the same manner as in Preparation Example 13 except that 5 g of N-vinylpyrrolidone was changed to 5 g of N-isopropylacrylamide.

  An acrylic polymer emulsion (14) was prepared in the same manner as in Preparation Example 13 except that the emulsion (14) was used instead of the emulsion (13). The resulting acrylic polymer emulsion (14) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle diameter of 377 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (14) was 810,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (14) was prepared in the same manner as in Preparation Example 13, except that the acrylic polymer emulsion (14) was used instead of the acrylic polymer emulsion (13). Obtained.

(Preparation Example 15)
The aqueous solution of VA-044 was changed to 1.25 g of ammonium persulfate aqueous solution [active ingredient 20% by mass] and 1.25 g of sodium hydrogensulfite aqueous solution [8% by mass of active ingredient], and the aqueous solution of VA-057 was changed to ammonium persulfate. An acrylic polymer emulsion (15) was prepared in the same manner as in Preparation Example 2, except that the aqueous solution was changed to 50 g [active ingredient 1 mass%]. The acrylic polymer emulsion (15) thus obtained had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 340 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (15) was 830,000.

  Next, a water-dispersed acrylic pressure-sensitive adhesive composition (15) was prepared in the same manner as in Preparation Example 2, except that the acrylic polymer emulsion (15) was used instead of the acrylic polymer emulsion (2). Got.

(Preparation Example 16)
Instead of using Superester E-865NT, Harrier Star SK-822E (Harima Kasei Group Co., Ltd., softening point 170 ° C., solid content concentration 50 mass%, emulsion-type polymerized rosin ester tackifying resin) 200 g was used. Obtained a water-dispersed acrylic pressure-sensitive adhesive composition (16) in the same manner as in Preparation Example 2.

(Preparation Example 17)
Instead of Superester E-865NT, Tamanol E-200NT [Arakawa Chemical Industries, softening point 150 ° C., solid content concentration 53 mass%, emulsion type rosin phenolic tackifying resin] 188.68 g was used. Obtained a water-dispersed acrylic pressure-sensitive adhesive composition (17) in the same manner as in Preparation Example 2.

(Preparation Example 18)
A water-dispersed acrylic pressure-sensitive adhesive composition (18) was obtained in the same manner as in Preparation Example 2, except that Superester E-865NT was changed from 200 g to 100 g.

(Preparation Example 19)
A water-dispersed acrylic pressure-sensitive adhesive composition (19) was obtained in the same manner as in Preparation Example 2, except that Superester E-865NT was changed from 200 g to 300 g.

(Comparative Preparation Example 1)
An emulsion (H1) was prepared in the same manner as in Preparation Example 2, except that KBM-503 was not used. Next, an acrylic polymer emulsion (H1) was prepared in the same manner as in Preparation Example 2, except that the emulsion (H1) was used instead of the emulsion (2). The resulting acrylic polymer emulsion (H1) had a solid content concentration of 50 mass%, and the acrylic polymer had an average particle size of 336 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (H1) was 800,000.

  Next, instead of the acrylic polymer emulsion (2), the acrylic polymer emulsion (H1) was used, and 1.25 g of a 10 mass% ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy compound] was used. A water-dispersed acrylic pressure-sensitive adhesive composition (H1) was obtained in the same manner as in Preparation Example 2 except that was used.

(Comparative Preparation Example 2)
An emulsion (H2) was prepared in the same manner as in Preparation Example 7, except that KBM-503 was not used. Next, an acrylic polymer emulsion (H2) was prepared in the same manner as in Preparation Example 7, except that the emulsion (H2) was used instead of the emulsion (7). The resulting acrylic polymer emulsion (H2) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 300 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (H2) was 790,000.

  Next, instead of the acrylic polymer emulsion (7), the acrylic polymer emulsion (H2) was used, and 1.25 g of a 10 mass% ethanol solution of Tetrad C [Mitsubishi Gas Chemical Co., Ltd., epoxy compound] was used. A water-dispersed acrylic pressure-sensitive adhesive composition (H2) was obtained in the same manner as in Preparation Example 7 except that was used.

(Comparative Preparation Example 3)
An emulsion (H3) was prepared in the same manner as in Preparation Example 9 except that KBM-503 was not used. Next, an acrylic polymer emulsion (H3) was prepared in the same manner as in Preparation Example 9 except that the emulsion (H3) was used instead of the emulsion (9). The resulting acrylic polymer emulsion (H3) had a solid content concentration of 50 mass%, and the average particle size of the acrylic polymer was 311 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (H3) was 880,000.

  Next, instead of the acrylic polymer emulsion (9), the acrylic polymer emulsion (H3) was used, and 1.25 g of a 10 mass% ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy compound] was used. A water-dispersed acrylic pressure-sensitive adhesive composition (H3) was obtained in the same manner as in Preparation Example 9 except that was used.

(Comparative Preparation Example 4)
An emulsion (H4) was prepared in the same manner as in Preparation Example 5, except that KBM-503 was not used. Next, an acrylic polymer emulsion (H4) was prepared in the same manner as in Preparation Example 5, except that the emulsion (H4) was used instead of the emulsion (5). The resulting acrylic polymer emulsion (H4) had a solid content concentration of 50% by mass, and the acrylic polymer had an average particle size of 354 nm. The weight average molecular weight of the acrylic polymer contained in the acrylic polymer emulsion (H4) was 870,000.

  Next, instead of the acrylic polymer emulsion (5), the acrylic polymer emulsion (H4) was used, and 1.25 g of a 10 mass% ethanol solution of Tetrad C [manufactured by Mitsubishi Gas Chemical Co., Ltd., epoxy compound] was used. A water-dispersed acrylic pressure-sensitive adhesive composition (H4) was obtained in the same manner as in Preparation Example 5 except that was used.

(Comparative Preparation Example 5)
The same as Comparative Preparation Example 1 except that 40 g of Epocross WS-700 [manufactured by Nippon Shokubai Co., Ltd., compound having an oxazoline group, non-volatile content: 25 mass%] was used instead of the 10 mass% ethanol solution of tetrad C. By the method, a water-dispersed acrylic pressure-sensitive adhesive composition (H5) was obtained.

<Preparation of release liner (1)>
Thickness is obtained by extruding polyethylene at 310 ° C. with a T-die extruder on both sides of high-quality paper [Nippon Paper Co., Ltd., N / L mixed, basis weight 78 g / m ² ], and then cooling and laminating. A 25 μm polyolefin layer was formed. Addition-type silicone release agent [Toray Dow Corning Co., Ltd., trade name: SD7333] 100 parts by mass of platinum catalyst [Toray Dow Corning Co., Ltd., trade name: SRX212] 1 part by mass is added to toluene. And a coating solution having a solid content concentration of 5% by mass was prepared. This coating solution is applied to the upper surface of the polyethylene layer so that the coating amount is 0.6 g / m 2 (solid content), dried at 100 ° C. for 10 seconds and cured to form a silicone layer. Cured for 72 hours in a 40 ° C. environment to obtain a release liner (1). The obtained release liner (1) has a total basis weight of 127 g / m ² , a total thickness of 135 μm, a tensile strength in the flow direction of 60 N / 5 mm, and a tensile strength in the width direction of 50 N / 5 mm. The bending resistance in the direction was 2130 mg, the bending resistance in the width direction was 1410 mg, and the tear strength in the flow direction was 0.6N. Moreover, the peeling load of the release liner (1) measured using SK Dyne 801B was 0.12 N / 20 mm.

<Preparation of release liner (2)>
100 mass of addition type silicone release agent [manufactured by Toray Dow Corning Co., Ltd., trade name: SRX345] instead of a coating liquid in which addition type silicone release agent (SD7333) and platinum catalyst (SRX212) are mixed. 1 part by weight of platinum catalyst [manufactured by Toray Dow Corning Co., Ltd., trade name: SRX212] was added to the part and dissolved in toluene to obtain a solid content concentration of 5% by weight. A release liner (2) was prepared in the same manner as in the preparation example of the mold liner (1). The obtained release liner (2) has a total basis weight of 100 g / m ² , a total thickness of 100 μm, a tensile strength in the flow direction of 17 N / 5 mm, and a tensile strength in the width direction of 9 N / 5 mm. The bending resistance in the direction was 980 mg, the bending resistance in the width direction was 620 mg, and the tear strength in the flow direction was 0.5 N. Moreover, the peeling load of the release liner (2) measured using SK Dyne 801B was 0.41 N / 20 mm.

Example 1
The release liner (1) is coated with the water-dispersed acrylic pressure-sensitive adhesive composition (1) prepared in Preparation Example 1 so that the thickness after drying is 65 μm and dried, thereby releasing the mold. Two sheets with the pressure-sensitive adhesive layer provided on the liner (1) were prepared.

Next, the adhesive that the sheet has on both surfaces of a non-woven fabric base material [manufactured by Isagawa Paper Co., Ltd., trade name: DI-Tex LC-N, pulp / rayon mixture, basis weight 14 g / m ² , thickness 38 μm] The adhesive layer (1) was obtained by transferring the agent layer and curing for 48 hours in a 40 ° C. environment. The gel fraction of the pressure-sensitive adhesive layer constituting the pressure-sensitive adhesive tape (1) was 33.5% by mass.

(Example 2)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (2) prepared in Preparation Example 2 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (2) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (2) was 34.4% by mass.

(Example 3)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (3) prepared in Preparation Example 3 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (3) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (3) was 36.5% by mass.

Example 4
In the same manner as in Example 1 except that the water-dispersed acrylic pressure-sensitive adhesive composition (4) prepared in Preparation Example 4 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (4) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (4) was 32.4 mass%.

(Example 5)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (5) prepared in Preparation Example 5 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (5) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (5) was 31.1 mass%.

(Example 6)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (6) prepared in Preparation Example 6 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (6) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (6) was 32.1 mass%.

(Example 7)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (7) prepared in Preparation Example 7 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (7) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (7) was 30.6% by mass.

(Example 8)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (8) prepared in Preparation Example 8 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (8) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (8) was 34.4% by mass.

Example 9
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (9) prepared in Preparation Example 9 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (9) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (9) was 32.6 mass%.

(Example 10)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (10) prepared in Preparation Example 10 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (10) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (10) was 34.3 mass%.

(Example 11)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (11) prepared in Preparation Example 11 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (11) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (11) was 35.1 mass%.

(Example 12)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (12) prepared in Preparation Example 12 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (12) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (12) was 36.2 mass%.

(Example 13)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (13) prepared in Preparation Example 13 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (13) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (13) was 33.0 mass%.

(Example 14)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (14) prepared in Preparation Example 14 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (14) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (14) was 34.2 mass%.

(Example 15)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (15) prepared in Preparation Example 15 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (15) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (15) was 37.7% by mass.

(Example 16)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (16) prepared in Preparation Example 16 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (16) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (16) was 35.5 mass%.

(Example 17)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (17) prepared in Preparation Example 17 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (17) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (17) was 34.8% by mass.

(Example 18)
In the same manner as in Example 1 except that the water-dispersed acrylic pressure-sensitive adhesive composition (18) prepared in Preparation Example 18 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (18) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (18) was 34.9% by mass.

(Example 19)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (19) prepared in Preparation Example 19 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1), An adhesive tape (19) was obtained. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (19) was 34.2 mass%.

(Example 20)
Instead of the non-woven fabric substrate (1), the non-woven fabric substrate (2) [manufactured by Nippon Paper Papillia Co., Ltd., trade name: D-02, Manila hemp, basis weight 20 g / m ² , thickness 60 μm] An adhesive tape (20) was obtained in the same manner as in Example 2 except that it was used. The gel fraction of the adhesive layer which comprises the obtained adhesive tape (20) was 34.4 mass%.

(Comparative Example 1)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (H1) prepared in Comparative Preparation Example 1 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1). An adhesive tape (H1) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H1) was 34.8% by mass.

(Comparative Example 2)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (H2) prepared in Comparative Preparation Example 2 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1). An adhesive tape (H2) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H2) was 33.5% by mass.

(Comparative Example 3)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (H3) prepared in Comparative Preparation Example 3 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1). An adhesive tape (H3) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H3) was 34.0% by mass.

(Comparative Example 4)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (H4) prepared in Comparative Preparation Example 4 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1). An adhesive tape (H4) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H4) was 32.2% by mass.

(Comparative Example 5)
In the same manner as in Example 1, except that the water-dispersed acrylic pressure-sensitive adhesive composition (H5) prepared in Comparative Preparation Example 5 was used instead of the water-dispersed acrylic pressure-sensitive adhesive composition (1). An adhesive tape (H5) was obtained. The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H5) was 39.5% by mass.

(Comparative Example 6)
An adhesive tape (H6) was obtained in the same manner as in Comparative Example 1 except that the release liner (2) was used instead of the release liner (1). The gel fraction of the pressure-sensitive adhesive layer constituting the obtained pressure-sensitive adhesive tape (H6) was 34.8% by mass.

1 Polypropylene plate 1
2 Test piece (X)
3 Lifting distance 4 Test piece (Y)

Claims (6)

An adhesive tape used for fixing an air conditioner unit mounted on an automobile and a foam material, wherein the adhesive tape contains an acrylic polymer having one or both of an alkoxysilyl group and a silanol group A pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer formed using a mold-type pressure-sensitive adhesive. The pressure-sensitive adhesive tape according to claim 1, wherein the pressure-sensitive adhesive layer is provided on both surfaces of the nonwoven fabric substrate. The pressure-sensitive adhesive tape according to claim 1 or 2, wherein the acrylic polymer has an alkoxysilyl group or a silanol group in a total range of 0.01% by mass to 0.1% by mass. The pressure-sensitive adhesive tape according to any one of claims 1 to 3, wherein the acrylic polymer has a functional group represented by the following general formula (1).

[R in Formula (1) represents an alkyl group having 1 or 2 carbon atoms. ] The pressure-sensitive adhesive tape according to any one of claims 1 to 4, wherein the acrylic polymer has a carboxyl group, and the carboxyl group is derived from acrylic acid and methacrylic acid. The said foam material is a foam material installed between the said air conditioner unit and the duct which sends the air of which temperature or humidity was adjusted with the said air conditioner unit in a motor vehicle. The adhesive tape as described in.

Images