JP2014189672A - Electrically peelable adhesive composition, electrically peelable adhesive sheet and method for using electrically peelable adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrically peelable adhesive composition which has high adhesive force before voltage application and can effectively reduce adhesive force by voltage application for a short time, and to provide an electrically peelable adhesive sheet having an adhesive layer formed of a material containing the adhesive composition and a method for using the electrically peelable adhesive sheet.SOLUTION: There is provided an electrically peelable adhesive composition which is composed of an emulsion type acrylic adhesive containing an emulsion type acrylic polymer (A1) obtained by emulsion polymerization of a monomer mixture containing a (meth)acrylic acid alkyl ester in the presence of a surfactant and a (poly)alkylene polyol (B) having a hydroxyl value of 70 to 1500 mgKOH/g, where the content of the (B) component is 3.5 pts.mass or more based on 100 pts.mass of an active ingredient of the (A) component.

Description

  The present invention relates to an electrically peelable pressure-sensitive adhesive composition whose adhesive strength is reduced by applying a voltage, an electrically peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a material containing the pressure-sensitive adhesive composition, and the electricity It is related with the usage method of a peelable adhesive sheet.

As one of the characteristics of the pressure-sensitive adhesive sheet, removability may be required in applications such as a surface protective film, a masking tape for painting or decoration, and a removable memo.
When the peelable adhesive sheet is affixed to the adherend, it is required to have an adhesive strength that does not peel from the adherend during transportation, storage, processing, etc. Therefore, re-peelability that can be easily removed is required.

By the way, as an adhesive used for such a releasable adhesive sheet, an adhesive whose adhesive strength is reduced by applying a voltage is known.
For example, Patent Document 1 discloses an electrochemically debondable adhesive containing an electrolyte and a high load-resistant binding polymer having high mechanical strength.
Further, Patent Document 2 discloses a composition for energization peeling containing an ionic liquid as an adhesive that can be peeled off when a voltage is applied. According to Patent Document 2, an ionic liquid is a molten salt that is liquid at room temperature, has no vapor pressure, and has properties such as high heat resistance, nonflammability, and high chemical stability.

JP 2003-129030 A WO2007 / 018239

However, when an adhesive sheet disclosed in Patent Document 1 is used to form an adhesive sheet, workability is inferior because it takes about 10 to 15 minutes to peel the adhesive sheet from the adherend.
Moreover, since the ionic liquid contained in the composition disclosed in Patent Document 2 is a compound having a special structure as described in the document, it is expensive and provides an inexpensive adhesive tape using them. It is difficult to do. Furthermore, the composition disclosed in Patent Document 2 still has room for improvement in the rate of decrease in adhesive strength before and after voltage application.

  The present invention is formed from an electro-peelable pressure-sensitive adhesive composition that has high adhesive strength before voltage application but can effectively reduce the adhesive strength by applying a voltage for a short time, and a material containing the pressure-sensitive adhesive composition. Another object of the present invention is to provide an electric peelable pressure-sensitive adhesive sheet having an adhesive layer, and a method of using the electric peelable pressure-sensitive adhesive sheet.

  The inventors of the present invention have an electricity containing a specific amount of a (poly) alkylene polyol having a specific hydroxyl value together with an emulsion-type acrylic pressure-sensitive adhesive containing an emulsion-type acrylic polymer obtained by emulsion polymerization in the presence of a surfactant. It has been found that a peelable pressure-sensitive adhesive composition can solve the above problems, and has completed the present invention.

That is, the present invention provides the following [1] to [11].
[1] An emulsion-type acrylic pressure-sensitive adhesive containing an emulsion-type acrylic polymer (A1) obtained by emulsion polymerization in the presence of a surfactant using a monomer mixture containing a (meth) acrylic acid alkyl ester (A) and an electro-releasable pressure-sensitive adhesive composition comprising a (poly) alkylene polyol (B) having a hydroxyl value of 70 to 1500 mgKOH / g, wherein (B) relative to 100 parts by mass of the active ingredient of component (A) An electrodetachable pressure-sensitive adhesive composition, wherein the component content is 3.5 parts by mass or more.
[2] The electroreleasable pressure-sensitive adhesive composition according to the above [1], wherein the content of the component (B) is 3.5 to 50 parts by mass with respect to 100 parts by mass of the active ingredient of the component (A).
[3] The electrodetachable pressure-sensitive adhesive composition according to [1] or [2] above, wherein the component (B) contains (poly) alkylene glycol.
[4] The electropeelable pressure-sensitive adhesive composition according to [3], wherein the (poly) alkylene glycol is a compound represented by the following general formula (b-1).
[In the formula (b-1), EO represents ethylene oxide, PO represents propylene oxide, and p and q are real numbers that satisfy p ≧ 0, q ≧ 0, and p + q ≧ 1. In addition, as for the compound represented by general formula (b-1), EO and PO may be a compound formed by block copolymerization, and may be a compound formed by random copolymerization. ]
[5] The electrodetachable pressure-sensitive adhesive composition according to any one of the above [1] to [4], wherein the number average molecular weight of the component (B) is 2000 or less.
[6] The emulsion type acrylic polymer (A1) is 60 to 99.9% by mass of the structural unit (a1) derived from (meth) acrylic acid alkyl ester, and the structural unit derived from the functional group-containing unsaturated monomer. The electrodetachable pressure-sensitive adhesive composition according to any one of the above [1] to [5], which is a copolymer containing 0.1 to 40% by mass of (a2).
[7] The electrodetachable pressure-sensitive adhesive composition according to any one of [1] to [6], wherein the surfactant is an anionic reactive emulsifier.
[8] The electropeelable pressure-sensitive adhesive composition according to [7], wherein the anionic reactive emulsifier is an ammonium salt.
[9] An electro-peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a material containing the electro-peelable pressure-sensitive adhesive composition according to any one of [1] to [8].
[10] The electroreleasable pressure-sensitive adhesive sheet according to [9] above, wherein the water content calculated by the Karl Fischer method of the pressure-sensitive adhesive layer is 0.53 to 15.0%.
[11] The electroreleasable pressure-sensitive adhesive sheet according to [9] or [10], wherein the pressure-sensitive adhesive layer is provided on at least one surface of a conductive substrate.
[12] The electroreleasable pressure-sensitive adhesive sheet according to [9] or [10], wherein the pressure-sensitive adhesive layer has a configuration sandwiched between two release sheets.
[13] The surface of the pressure-sensitive adhesive layer connected to the cathode side when a voltage is applied between two surfaces of the adherend, or both surfaces of the pressure-sensitive adhesive layer sandwiched between the adherend and the substrate, The electroreleasable pressure-sensitive adhesive sheet according to any one of the above [9] to [12], which is peeled between the surface of the pressure-sensitive adhesive layer and the adherend or the substrate attached.
[14] A method for using an electro-releasable pressure-sensitive adhesive sheet, wherein the electro-releasable pressure-sensitive adhesive sheet according to any one of [9] to [13] is attached to an adherend having conductivity.

  The electro-releasable pressure-sensitive adhesive composition of the present invention has high adhesive force before voltage application, but can effectively reduce the adhesive force by applying voltage for a short time. Therefore, the electrically peelable pressure-sensitive adhesive sheet of the present invention having a pressure-sensitive adhesive layer formed from a material containing the pressure-sensitive adhesive composition can achieve both excellent adhesive strength and removability.

It is sectional drawing of this adhesive sheet which shows an example of a structure of the electrically peelable adhesive sheet of this invention. It is a figure which shows the difference of (a) the said adhesive sheet before voltage application, (b) the said adhesive sheet after voltage application regarding the electrically peelable adhesive sheet of this invention. It is a figure which shows the difference of (a) the said adhesive sheet before voltage application, (b) the said adhesive sheet after voltage application regarding the electrically peelable adhesive sheet of this invention.

  In the present invention, for example, “(meth) acrylic acid” refers to both “acrylic acid” and “methacrylic acid”, and “(poly) alkylene glycol” refers to “polyalkylene glycol” and It is used as a term indicating both “alkylene glycol”. The same applies to other similar terms.

(Electrically peelable adhesive composition)
The electroreleasable pressure-sensitive adhesive composition of the present invention (hereinafter, also simply referred to as “pressure-sensitive adhesive composition”) is obtained by emulsion polymerization using a monomer mixture containing (meth) acrylic acid ester in the presence of a surfactant. Emulsion-type acrylic pressure-sensitive adhesive (A) (hereinafter simply referred to as “pressure-sensitive adhesive (A)”) or emulsion-type acrylic polymer (A1) (hereinafter also simply referred to as “polymer (A1)”) And (poly) alkylene polyol (B) having a hydroxyl value of 70 to 1500 mg KOH / g (hereinafter also referred to as “component (B)”).
Hereinafter, each component contained in the pressure-sensitive adhesive composition of the present invention will be described.

<(A) component: Emulsion type acrylic adhesive (A)>
The emulsion-type acrylic pressure-sensitive adhesive (A) contained in the pressure-sensitive adhesive composition of the present invention is obtained by emulsion polymerization using a monomer mixture containing (meth) acrylic acid ester in the presence of a surfactant. It contains an emulsion type acrylic polymer (A1).

In addition to the polymer (A1), the pressure-sensitive adhesive (A) includes a surfactant, a polymerization initiator, a chain transfer agent, a pH buffer, etc. used in the synthesis of the polymer (A1), a crosslinking agent, and tackifying. Other additives such as resin and wetting agent may be contained.
Content of the polymer (A1) in an adhesive (A) becomes like this. Preferably it is 70-99 mass%, More preferably, it is 80-97 mass%, More preferably, it is 85-95 mass%.

[(A1) component: emulsion-type acrylic polymer (A1)]
The polymer (A1) is obtained by emulsion polymerization in the presence of a surfactant using a monomer mixture containing (meth) acrylic acid alkyl ester (hereinafter also referred to as “monomer (a1)”). Therefore, the structural unit (a1) derived from at least (meth) acrylic acid alkyl ester is included.
The polymer (A1) may be a polymer composed only of the structural unit (a1), but has a functional group in the molecule and at least one double bond together with the structural unit (a1). A copolymer containing a structural unit (a2) derived from a compound (hereinafter also referred to as monomer (a2)) is preferable.
The acrylic polymer (A) is a copolymer containing a structural unit (a3) derived from another monomer other than the monomers (a1) and (a2) (hereinafter also referred to as “monomer (a3)”). May be.
When the component (A1) is a copolymer, the form of copolymerization is not particularly limited, and may be any of a random copolymer, a block copolymer, and a graft copolymer.
In the present invention, the component (A1) may be used alone or in combination of two or more.

(Monomer (a1), Structural unit (a1))
Examples of the monomer (a1) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. , Heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, and the like.
These monomers (a1) may be used alone or in combination of two or more.
Among these, from the viewpoint of improving the adhesive strength before voltage application, an alkyl (meth) acrylate having an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl (meth) acrylate having an alkyl group having 4 to 8 carbon atoms is preferable. More preferred.
Specifically preferred as the monomer (a1) is butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate, and butyl (meth) ) Acrylate or 2-ethylhexyl (meth) acrylate is more preferable, and 2-ethylhexyl (meth) acrylate is still more preferable.

The content of the structural unit (a1) in the polymer (A1) is preferably 60 to 99.9% by mass, more preferably 75 to 99.6% by mass, based on all the structural units of the polymer (A1). More preferably, it is 85 to 99.3 mass%, and still more preferably 95 to 99.0 mass%.
If content of a structural unit (a1) is 60 mass% or more, the adhesive force before a voltage application can be made favorable. Moreover, if the said content is 99.9 mass% or less, content of the structural unit (a2) derived from the above-mentioned monomer (a2) can be ensured, cohesion force is improved, and the pressure-sensitive adhesive sheet obtained is obtained. The removability can be improved.

  In addition, content of the structural unit derived from the alkyl (meth) acrylate which has a C4-C12 alkyl group in a polymer (A1) is a polymer (A1) from a viewpoint of the adhesive force improvement before voltage application. Preferably, it is 50-99.9 mass%, More preferably, it is 60-99.6 mass%, More preferably, it is 70-99.0 mass% with respect to all the structural units.

(Monomer (a2), Structural unit (a2))
The monomer (a2) is a compound having a functional group in the molecule and one or more double bonds. The functional group of the monomer (a2) serves as a cross-linking point for the cross-linking reaction, can improve the cohesive force, and can improve the removability.
Examples of the monomer (a2) include a carboxy group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, and an epoxy group-containing unsaturated monomer.

  Examples of the carboxy group-containing unsaturated monomer include ethylenically unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid; ethylenically unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, maleic acid and citraconic acid; 2 -Carboxyethyl (meth) acrylate etc. are mentioned.

  Examples of the hydroxyl group-containing unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxy. Examples thereof include hydroxyalkyl (meth) acrylates such as butyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and glycerin di (meth) acrylate.

  Examples of the epoxy group-containing unsaturated monomer include glycidyl (meth) acrylate.

These monomers (a2) may be used alone or in combination of two or more.
Among these, from the viewpoint of versatility, a carboxy group-containing unsaturated monomer is preferable, an ethylenically unsaturated monocarboxylic acid is more preferable, (meth) acrylic acid is more preferable, and the carboxyl group plays a role as a crosslinking point. In view of the above, acrylic acid is still more preferable from the viewpoint that the carboxy group serving as the crosslinking point is easily oriented on the emulsion particle surface layer.

The content of the structural unit (a2) in the polymer (A1) is preferably 0.1 with respect to all the structural units of the polymer (A1) from the viewpoint of improving the adhesive strength and removability of the pressure-sensitive adhesive sheet. It is -40 mass%, More preferably, it is 0.4-25 mass%, More preferably, it is 0.7-10 mass%, More preferably, it is 1.0-5 mass%.
When the content of the structural unit (a2) is 0.1% by mass or more, a crosslinking bond can be sufficiently formed with the crosslinking agent, the cohesive force can be improved, and the releasability of the pressure-sensitive adhesive sheet can be improved. it can. On the other hand, if content of a structural unit (a2) is 40 mass% or less, since content of the structural unit (a1) derived from a monomer (a1) can be ensured, adhesive force can be made favorable. .

The polymer (A1) may further be a copolymer having a structural unit (a3) derived from another monomer (a3) other than the monomers (a1) and (a2).
Examples of other monomers include olefins such as ethylene, propylene and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, diene monomers such as butadiene, isoprene and chloroprene, styrene, α-methylstyrene and vinyl. Examples include toluene, vinyl formate, vinyl acetate, acrylonitrile, (meth) acrylamide, (meth) acrylonitrile, (meth) acryloylmorpholine, N-vinylpyrrolidone and the like.

(Method for synthesizing emulsion type acrylic polymer (A1))
In the present invention, the polymer (A) can be obtained by emulsion polymerization using a monomer mixture containing the above-mentioned monomers as a raw material in the presence of a surfactant.
As the surfactant to be used, an anionic reactive emulsifier is preferable, and an anionic reactive emulsifier which is an ammonium salt is more preferable from the viewpoint of obtaining a pressure-sensitive adhesive composition capable of effectively reducing the adhesive strength after voltage application. In the present invention, the ammonium salt refers to a salt having a cation represented by NH ₄ ⁺ and does not include a quaternary ammonium salt.
An anionic reactive emulsifier is an anionic emulsifier having a functional group-containing reactivity containing an ethylenically unsaturated double bond, such as compounds represented by the following general formulas (1) to (11). Can be mentioned.

In the general formulas (1) to (11), R ¹ is an alkyl group, R ² is hydrogen or a methyl group, R ³ is an alkylene group, n is an integer of 1 or more, m and l are integers of 1 or more, The sum of m and l is 3.
Further, X is a -SO ₃ NH ₄ or -SO ₃ Na independently, from the viewpoint of obtaining a pressure-sensitive adhesive composition which can effectively reduce the adhesive force after the voltage application, in -SO ₃ NH ₄ Preferably there is.

  Among the anionic reactive emulsifiers represented by the above formulas (1) to (11), an anionic reactive emulsifier having no alkylphenol structure is preferable from the viewpoint of environmental safety. The compounds represented by (3), (4), (5), (8), (9) and (10) are more preferred.

Examples of commercially available anionic reactive emulsifiers represented by the general formulas (1) to (11) include, for example, Adeka Soap SE-20N, Adekalia Soap SE-10N, Adekalia Soap PP-70, and Adekalia. Soap PP-710, Adekaria Soap SR-10, and Adekaria Soap SR-20 (above, product name, manufactured by ADEKA Corporation), Eleminol JS-2, and Eleminol RS-30 (above, product name, Sanyo Chemical Industries) Latemu S-180A, Latemu S-180, and Latemu PD-104 (product name, manufactured by Kao Corporation), Aqualon BC-05, Aqualon BC-10, Aqualon BC-20, Aqualon HS-05 , Aqualon HS-10, Aqualon HS-20, New Frontier S-510, Aqualon KH-05 And Aqualon KH-10 (or more, trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), phosphino - Le TX (Toho Chemical Industry Co., Ltd.).
These anionic reactive emulsifiers may be used alone or in combination of two or more.

The amount of the surfactant used is preferably 0.5 to 10 parts by mass, more preferably 0.8 to 7 parts by mass, and further preferably 1 to 4 parts by mass with respect to 100 parts by mass of the monomer mixture. .
If the usage-amount of surfactant is 0.5 mass part or more, emulsion polymerization can be advanced stably. On the other hand, if the amount of the surfactant used is 10 parts by mass or less, it is possible to prevent adverse effects such as deterioration of substrate adhesion, water whitening resistance, adhesive strength and removability due to remaining unreacted surfactant. Can do.
The surfactant may be added to the emulsion composed of the monomer mixture, may be added in advance to the polymerization vessel, may be added after the polymerization, or they may be used in combination. .

The polymerization initiator added at the time of emulsion polymerization is not particularly limited, and may be either water-soluble or oil-soluble.
Examples of such polymerization initiators include alkyl peroxides, t-butyl hydroperoxide, cumene hydroperoxide, p-methane hydroperoxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, Octanoyl peroxide, t-butylcumyl peroxide, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 1,1-bis (t-butylperoxy) -3, 3,5-trimethylcyclohexane, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, di-isobutyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, t-butyl Organic peroxides such as ruperoxyisobutyrate, 2,2′-azobisisobutyronitrile, dimethyl-2,2′-azobisisobutyrate, 2,2′-azobis (2,4-dimethylvalero) Nitrile), 2,2′-azobis (2-methylbutyronitrile), potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, ammonium 4,4′-azobis-4-cyanovaleric acid (amine) ) Salt, 2,2′-azobis (2-methylamidooxime) dihydrochloride, 2,2′-azobis (2-methylbutanamidoxime) dihydrochloride tetrahydrate, 2,2′-azobis {2-methyl- N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] -propionamide}, 2,2′-azobis [2-methyl-N— 2-hydroxyethyl) -propionamide], various redox catalysts (in this case, as the oxidizing agent, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene Hydroperoxide, p-methane hydroperoxide, etc., and sodium sulfite, acidic sodium sulfite, Rongalite, ascorbic acid, etc. are used as the reducing agent.
These polymerization initiators may be used alone or in combination of two or more.

  Among these, from the viewpoint of excellent polymerization stability, ammonium persulfate, potassium persulfate, sodium persulfate, redox catalyst (as the oxidizing agent to be used, ammonium persulfate, potassium persulfate, sodium persulfate, etc. can be mentioned and used. Preferred examples of the reducing agent include sodium sulfite and acidic sodium sulfite.

  The addition amount of the polymerization initiator is preferably 0.01 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, and still more preferably from 100 parts by mass of the monomer mixture from the viewpoint of increasing the polymerization rate. 0.1 to 2 parts by mass.

These polymerization initiators may be added in advance to the polymerization vessel, may be added immediately before the start of polymerization, or may be added in a plurality of times after the start of polymerization. Moreover, you may add to a monomer mixture previously, and may add to the said emulsion after adjusting the emulsion which consists of this mixture.
In the addition, the polymerization initiator may be separately dissolved in a solvent or a monomer mixture and added, or the dissolved polymerization initiator may be further emulsified and added.

Further, a chain transfer agent may be further added during the polymerization.
Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol.
These chain transfer agents may be used alone or in combination of two or more.
The addition amount of the chain transfer agent is preferably 0.01 to 2 parts by mass, more preferably 0.05 to 1 part by mass with respect to 100 parts by mass of the monomer mixture.

Further, at the time of polymerization, a pH buffer may be further added from the viewpoint of pH adjustment.
The pH buffering agent is not particularly limited as long as it is a compound having a pH buffering action. For example, sodium bicarbonate, potassium bicarbonate, monosodium phosphate, monopotassium phosphate, disodium phosphate, trisodium phosphate, Examples include sodium acetate, ammonium acetate, sodium formate, and ammonium formate.

In the case of emulsion polymerization, the water used is preferably ion-exchanged water.
The amount of water used is preferably 30 to 400 parts by mass, more preferably 35 to 200 parts by mass, and still more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the monomer mixture.
If the usage-amount of water is 30 mass parts or more, the viscosity of the adhesive (A) containing a polymer (A1) can be made into an appropriate range. Moreover, the polymerization stability of the obtained polymer (A1) also becomes favorable.
On the other hand, if the amount of water used is 400 parts by mass or less, the active ingredient concentration of the obtained pressure-sensitive adhesive composition can be within an appropriate range, and the pressure-sensitive adhesive composition is applied onto a substrate or a release sheet. Therefore, the formability of the coating film when forming the coating film is improved.

As a method for synthesizing the polymer (A1), a method in which the monomer mixture is subjected to emulsion polymerization by adding a polymerization initiator in the presence of a surfactant is preferable.
Examples of the procedure for carrying out the emulsion polymerization include the following methods (1) to (3), and the method (2) or (3) is preferred from the viewpoint of easy control of the polymerization temperature. .
(1) The whole amount of monomer mixture, surfactant, water, etc. is charged, the temperature is raised, and the polymerization initiator dissolved in water is added dropwise or dividedly and polymerized.
(2) After charging water, a surfactant and a part of the monomer mixture in the reaction vessel and raising the temperature, a polymerization initiator dissolved in water is dropped or dividedly added to advance the polymerization reaction, The whole monomer mixture is dropped or added in portions, and polymerization is continued.
(3) A polymerization initiator dissolved in water is charged in the reaction vessel and the temperature is raised, and then the whole amount of the emulsion composed of the monomer mixture, the surfactant, and water is added dropwise or dividedly for polymerization.

The polymerization conditions in the polymerization method are not particularly limited.
For example, in the method (1), the temperature range is preferably 40 to 100 ° C., and the polymerization reaction is preferably performed in about 1 to 8 hours after the start of the temperature increase.
In the method (2), 1 to 50% by mass of the monomer mixture is polymerized at 40 to 90 ° C. for 0.1 to 4 hours, and then the remaining monomer mixture is dropped over about 1 to 5 hours. Alternatively, it is preferable to add in portions and then ripen at the same temperature for about 1 to 3 hours.
In the method (3), the temperature of the polymerization initiator dissolved in water is preferably raised to 40 to 90 ° C., and the emulsion comprising the monomer mixture, the surfactant, and water is taken for about 2 to 5 hours. It is preferable to add all of them dropwise or dividedly. Thereafter, aging is preferably performed at the same temperature for about 1 to 3 hours.

  In the above polymerization method, from the viewpoint of polymerization stability, the monomer mixture is prepared by dissolving a surfactant (or a part of the surfactant) in the monomer mixture, or in advance an O / W type. It is preferable to keep the state of the emulsion.

  The emulsion can be prepared by using a stirring device in which the components are mixed and a stirring blade such as a homodisper or paddle blade is attached. If the temperature at the time of emulsification is a temperature at which the mixture does not react during emulsification, there is no problem, and 5 to 60 ° C. is preferable.

Further, by adding an alkaline aqueous solution such as aqueous ammonia, various water-soluble amines, an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, and adjusting the pH to 5-9, preferably pH 6-8, an emulsion copolymer (A ) Is obtained.
The alkaline aqueous solution can be added during the polymerization or after the completion of the polymerization. From the viewpoint of the polymerization stability and the stability of the resulting emulsion over time, after cooling to room temperature (25 ° C.) in the aging stage during the polymerization, It is preferable to add a part or the whole amount.

The active ingredient concentration of the aqueous dispersion containing the emulsion of the polymer (A1) obtained as described above is preferably 10 to 80% by mass, more preferably 25 to 70% by mass, and still more preferably 45 to 65% by mass. It is.
Moreover, the average particle diameter of the emulsion of a polymer (A) becomes like this. Preferably it is 100-900 nm, More preferably, it is 200-600 nm, More preferably, it is 300-500 nm.
In addition, the active ingredient density | concentration of said aqueous dispersion and the average particle diameter of the emulsion of a polymer (A) mean the value measured by the method as described in an Example.

[Crosslinking agent]
In addition to the polymer (A1), the pressure-sensitive adhesive (A) may further contain a crosslinking agent.
The said crosslinking agent is a compound which bridge | crosslinks with the functional group which a polymer (A1) has, when a polymer (A1) has a structural unit (a2) derived from a functional group containing unsaturated monomer (monomer (a2)). is there.
Examples of the crosslinking agent include hydrazine such as epoxy compound, oxazoline compound, carbodiimide compound, aziridine compound, polyisocyanate compound, melamine compound, metal complex compound, amine compound, adipic acid dihydrazide, and sebacic acid dihydrazide. Derivatives and the like.
These crosslinking agents may be used alone or in combination of two or more.
In addition, it is preferable to add a crosslinking agent after obtaining a polymer (A1).

  The content of the crosslinking agent is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and further preferably 1 to 10 parts by mass with respect to 100 parts by mass of the active ingredient of the polymer (A1). Part.

[Tackifying resin]
In addition to the polymer (A1), the pressure-sensitive adhesive (A) preferably further contains a tackifier resin from the viewpoint of improving the adhesive strength.
Examples of tackifying resins include rosin resins such as rosin resins, rosin phenol resins, and rosin ester resins; hydrogenated rosin resins obtained by hydrogenating these rosin resins; terpene resins, terpene phenol resins, aromatic modifications Terpene resins such as terpene resins; hydrogenated terpene resins obtained by hydrogenating these terpene resins; copolymerization of C5 fractions such as pentene, isoprene, piperine and 1.3-pentadiene produced by thermal decomposition of petroleum naphtha C5 petroleum resin and hydrogenated petroleum resin of this C5 petroleum resin; C9 fractions such as indene, vinyltoluene, α-methylstyrene, β-methylstyrene, etc. produced by thermal decomposition of petroleum naphtha are copolymerized C9 petroleum resin obtained by hydrogenation and hydrogenated petroleum resin of this C9 petroleum resin; and the like.
These tackifying resins may be added after obtaining the polymer (A1), and may be blended together with the monomer mixture before the polymer (A1) to undergo a polymerization reaction. It is preferable to blend with the mixture.

The softening point of the tackifying resin is preferably 60 to 170 ° C, more preferably 75 to 150 ° C, still more preferably 85 to 140 ° C, and still more preferably 90 to 130, from the viewpoint of improving the adhesive strength before voltage application. ° C.
The value of the softening point of the tackifier resin is a value measured in accordance with JIS K2531.

  The content of the tackifier resin is preferably 1 to 40 parts by mass, more preferably 100 parts by mass of the active ingredient of the polymer (A1) or 100 parts by mass of the monomer mixture which is a raw material of the polymer (A1). Is 2-30 parts by mass, more preferably 3-20 parts by mass, and still more preferably 4-15 parts by mass.

[Other additives]
The pressure-sensitive adhesive (A) of the present invention may contain other additives other than those described above as long as the effects of the present invention are not impaired.
Other additives include plasticizers, wetting agents, thickeners, antifoaming agents, antioxidants, UV absorbers, softeners (plasticizers), fillers, rust inhibitors, pigments, dyes, and the like. .
In addition, it is preferable to add these other additives after obtaining a polymer (A1).

Examples of the plasticizer include adipic acid diesters, fumaric acid diesters, sebacic acid diesters, and the like.
Examples of the wetting agent include anionic surfactants, nonionic surfactants, acrylic compounds, silicone compounds, fluorine compounds, and water-soluble alcohols.
As the thickener, for example, polyacrylic acid thickener, polyvinyl thickener, polyether thickener, polyglycol thickener, polyamide thickener, polyester thickener, hydrophobized A cellulose ester type thickener, a urethane type thickener, a polycarboxylic acid type thickener, etc. are mentioned.
As an antifoamer, a silicone type antifoamer, a polyether type antifoamer, etc. are mentioned, for example.

  The content of the other additives is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.000 parts by mass with respect to 100 parts by mass of the active ingredient of the polymer (A1). 1 to 3 parts by mass.

<(B) component: (poly) alkylene polyol>
The pressure-sensitive adhesive composition of the present invention contains (poly) alkylene polyol (B) having a hydroxyl value of 70 to 1500 mgKOH / g.
When the hydroxyl value of the component (B) is less than 70 mgKOH / g or exceeds 1500 mgKOH / g, the adhesive strength after voltage application is not sufficiently reduced, and the releasability of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition is inferior. Result.
Therefore, the number average molecular weight of the component (B) is preferably 80 to 900 mgKOH / g, more preferably 95 to 500 mgKOH / g, from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesive strength after voltage application. More preferably, it is 105-460 mgKOH / g, More preferably, it is 115-410 mgKOH / g, More preferably, it is 125-380 mgKOH / g, More preferably, it is 135-340 mgKOH / g.
In addition, the hydroxyl value of (B) component is the value measured based on JISK0070.

The number average molecular weight (Mn) of the component (B) is preferably 2000 or less, more preferably 100 to 2000, more preferably from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesive strength after voltage application. It is 120-1600, More preferably, it is 140-1300, More preferably, it is 180-1000, More preferably, it is 250-900, More preferably, it is 320-760.
(B) If the number average molecular weight (Mn) of a component is 2000 or less, the adhesive force after voltage application can be reduced effectively, and the releasability of the adhesive sheet using the obtained adhesive composition is demonstrated. Can be good.
The number average molecular weight (Mn) of the component (B) is a polystyrene-equivalent value measured by a gel permeation chromatography (GPC) method, and specifically measured based on the method described in the examples. Value.

Examples of the (poly) alkylene polyol as component (B) include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, and polyethylene polypropylene glycol; ethylene glycol, propylene glycol, 1,3-propanediol, 1, 4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2, Diols such as 2,2-trimethylpentanediol, 3,3-dimethylolheptane, diethylene glycol and triethylene glycol; polyhydric alcohols such as glycerol and triol such as trimethylolpropane It is.
These (poly) alkylene polyols may be used alone or in combination of two or more.

Among these, polyalkylene glycol and diol are preferable, and polyethylene glycol, triethylene glycol, diethylene glycol, and ethylene glycol are more preferable from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesive strength after voltage application.
The content of the (poly) alkylene glycol in the component (B) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, from the same viewpoint as above. More preferably, it is 95-100 mass%.

  The (poly) alkylene glycol is preferably a compound represented by the following general formula (b-1) from the viewpoint of obtaining a pressure-sensitive adhesive composition capable of effectively reducing the adhesive strength after voltage application, and more preferably polyethylene glycol. preferable.

In the general formula (b-1), EO represents ethylene oxide and PO represents propylene oxide. p and q are real numbers that satisfy p ≧ 0, q ≧ 0, and p + q ≧ 1. In addition, as for the compound represented by general formula (b-1), EO and PO may be a compound formed by block copolymerization, and may be a compound formed by random copolymerization.
The values of p and q are preferably values adjusted so that the number average molecular weight of the compound represented by the general formula (b-1) belongs to the above range.

In this invention, content of (B) component with respect to 100 mass parts of active ingredients of (A) component is 3.5 mass parts or more. (B) When the content of the component is less than 3.5 parts by mass, the adhesive strength after voltage application is not sufficiently lowered, and the releasability of the pressure-sensitive adhesive sheet using the resulting pressure-sensitive adhesive composition is poor. Become.
Therefore, the content of the component (B) relative to 100 parts by mass of the active ingredient of the component (A) is preferably 3.5 to from the viewpoint of obtaining a pressure-sensitive adhesive composition that can effectively reduce the adhesive strength after voltage application. 50 parts by mass, more preferably 5 to 45 parts by mass, more preferably 7 to 40 parts by mass, still more preferably 9 to 37 parts by mass, still more preferably 15 to 35 parts by mass, and even more preferably 20 to 32 parts by mass. is there.
In the present invention, the term “active ingredient” means an ingredient excluding substances that do not directly or indirectly affect the reaction or physical properties such as water and organic solvent remaining in the pressure-sensitive adhesive composition, Specifically, it means components other than water and organic solvents.

[Electrically peelable adhesive sheet]
The electric peelable pressure-sensitive adhesive sheet of the present invention (hereinafter also simply referred to as “pressure-sensitive adhesive sheet”) has a pressure-sensitive adhesive layer formed from a material containing the above-described electric peelable pressure-sensitive adhesive composition of the present invention.
In the material which forms an adhesive layer, in the range which does not inhibit the effect of this invention other than the electropeelable adhesive composition of this invention, for example, it does not correspond to (B) component, and the hydroxyl value is less than 70 mgKOH / g (Poly) alkylene polyols of (1) and (poly) alkylene polyols having a hydroxyl value of more than 1500 mgKOH / g may be included.
The content of the electrodetachable pressure-sensitive adhesive composition of the present invention is preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and still more preferably 98%, based on the total amount excluding moisture of the material forming the pressure-sensitive adhesive layer. It is -100 mass%, More preferably, it is 100 mass%.

  If the adhesive sheet of this invention has an adhesive layer formed from the material containing the adhesive composition of this invention, the structure will not be specifically limited, It has an adhesive layer in the at least single side | surface of a base material. An adhesive sheet may be sufficient and the adhesive sheet which has the structure by which the adhesive layer was pinched | interposed with two peeling sheets may be sufficient.

FIG. 1 is a cross-sectional view of an electrically peelable pressure-sensitive adhesive sheet having a configuration of the electrically peelable adhesive sheet of the present invention.
As a specific configuration of the pressure-sensitive adhesive sheet of the present invention, for example, as shown in FIG. 1 (a), a base-equipped electro-peelable pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 3 on one surface of a base material 2 is provided. Can be mentioned.
Further, as shown in FIG. 1 (b), a base-equipped electro-peelable pressure-sensitive adhesive sheet 1b having a pressure-sensitive adhesive layer 3 and a pressure-sensitive adhesive layer 3 ′ on both sides of the base material 2, and FIG. 1 (c). Examples also include a base-attached electro-peelable pressure-sensitive adhesive sheet 1c in which a release sheet 4 is further laminated on the pressure-sensitive adhesive layer 3 formed on one side of the base material 2 as shown. In addition, the electrically peelable adhesive sheet 1b may be further provided with a release sheet on the adhesive layers 3 and 3 ′.

Further, as shown in FIG. 1 (d), a baseless electro-peelable pressure-sensitive adhesive sheet having a configuration in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4 ′ without using a base material. It may be 1d.
The material of the release sheets 4 and 4 ′ of the electric peelable adhesive sheet 1 d may be the same or different, but is a material adjusted so that the release force between the release sheet 4 and the release sheet 4 ′ is different. Preferably there is.
In addition, an electrically peelable pressure-sensitive adhesive sheet having a configuration in which a pressure-sensitive adhesive layer is provided on one surface of a release sheet whose surface has been subjected to a release treatment is rolled.

Further, the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive that is connected to the cathode side when a voltage is applied between two adherends, or between both surfaces of the pressure-sensitive adhesive layer sandwiched between the adherend and the substrate. Peeling occurs between the surface of the layer and the surface of the pressure-sensitive adhesive layer and the adherend or substrate to which it is attached.
That is, as shown in FIG. 2 (a), consider a case where the electro-peelable pressure-sensitive adhesive sheet 1a of the present invention is to be peeled from the adherend 11. In FIG. 2A, the pressure-sensitive adhesive layer 3 is sandwiched between the adherend 11 and the substrate 2a, the anode terminal 51 of the voltage application device 50 is connected to the substrate 2a, and the cathode terminal 52 is adhered. By connecting to the body 11, an electrode can be applied between the surfaces on both sides of the pressure-sensitive adhesive layer 3.
In addition, when using the base-less electrodetachable pressure-sensitive adhesive sheet 1d as shown in FIG. 1D, the structure of the “base material 2a” in FIG. The layer 3 is configured to be sandwiched between two adherends, and is connected to the anode terminal 51 and the cathode terminal 52 of the voltage application device 50 and the respective adherends, so that the layers 3 on both sides of the pressure-sensitive adhesive layer 3 are connected. An electrode can be applied between them.
When a voltage is applied in the state shown in FIG. 2 (a), as shown in FIG. 2 (b), the surface 3a of the adhesive layer connected to the cathode side and the adhesive connected to the cathode side. Adhesive strength is reduced between the surface 3a of the agent layer and the adherend 11 to which the adhesive layer is applied, and the electro-peelable pressure-sensitive adhesive sheet 1a can be easily peeled from the adherend.

  On the contrary, as shown in FIG. 3 (a), when the cathode terminal and the anode terminal are connected in reverse, the surface 3a ′ of the adhesive layer connected to the cathode side and the cathode side are connected to the cathode side. The adhesive force is reduced between the surface 3a of the adhesive layer and the pasted base material 2a, and the base material 2a is peeled off from the adhesive layer 3.

The applied voltage (applied voltage) is preferably 10 to 200 V, more preferably 40 to 140 V, still more preferably 70 to 120 V, and the time for applying the voltage in the range (application time) is preferably 1 to 180. Second, more preferably 5 to 120 seconds, still more preferably 10 to 90 seconds.
In general, the larger the applied voltage, the shorter the applied time, while the smaller the applied voltage, the longer the applied time. For example, when the applied voltage is 10 to 50 V, peeling can be performed in an application time of 30 to 300 seconds.

The moisture content calculated by the Karl Fischer method of the pressure-sensitive adhesive layer of the electro-releasable pressure-sensitive adhesive sheet of the present invention is preferably 0.53 to 15.0%, more preferably 0.54 to 6.50%, more preferably Is 0.55 to 2.50%, more preferably 0.60 to 2.20%, and still more preferably 0.70 to 1.90%.
If the moisture content is within the above range, the adhesive force of the adhesive layer can be effectively reduced by applying a voltage, and an adhesive sheet having excellent removability can be obtained.
The water content calculated by the Karl Fischer method of the pressure-sensitive adhesive layer means a value measured by the method described in the examples.

Although the thickness of the adhesive layer of the adhesive sheet of this invention is suitably adjusted according to a use etc., Preferably it is 0.5-120 micrometers, More preferably, it is 1-100 micrometers, More preferably, it is 3-60 micrometers.
When the thickness of the pressure-sensitive adhesive layer is 0.5 μm or more, good adhesive force can be expressed regardless of the type of adherend. On the other hand, when the thickness of the pressure-sensitive adhesive layer is 120 μm or less, there is an advantage in terms of productivity, and an electro-releasable pressure-sensitive adhesive sheet that is also favorable in terms of handleability can be obtained.

The base material of the pressure-sensitive adhesive sheet of the present invention is preferably a conductive base material in order to apply a voltage to the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet when it is desired to peel from the adherend.
Examples of the material constituting the conductive substrate include metals such as aluminum, tin-doped indium oxide, copper, iron, silver, platinum, and gold, and alloys of these metals.
Moreover, you may use the metal vapor deposition body formed by vapor-depositing the said metal on resin films, such as a polyethylene terephthalate, as a base material. When depositing a metal on the resin film, it is preferable to deposit the metal on the surface of the resin film in contact with the adhesive layer.

  The thickness of a base material becomes like this. Preferably it is 5-300 micrometers, More preferably, it is 10-150 micrometers, More preferably, it is 20-100 micrometers.

The release sheet used in the pressure-sensitive adhesive sheet of the present invention can be obtained by applying a release agent to one side or both sides of the release sheet substrate.
Examples of the base material for the release sheet include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polybutene, polybutadiene, polymethylpentene, polyvinyl chloride, vinyl chloride copolymer, polyurethane, ethylene- Vinyl acetate copolymer, ionomer resin, ethylene (meth) acrylic acid copolymer, polystyrene, polycarbonate, fluororesin, low density polyethylene, linear low density polyethylene, triacetyl cellulose resin film, fine paper, coated paper And paper base materials such as glassine paper, and laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper base materials.

  Examples of the release agent to be used include silicone resins, olefin resins, long chain alkyl resins, alkyd resins, fluorine resins, rubber elastomers such as isoprene resins and butadiene resins.

  Although there is no restriction | limiting in particular in the thickness of a peeling sheet, Preferably it is 5-300 micrometers, More preferably, it is 10-200 micrometers. In addition, when using a polyethylene terephthalate-type film as a base material for peeling sheets, it is preferably 10-100 micrometers.

[Method for producing electro-peelable adhesive sheet]
There is no restriction | limiting in particular as a manufacturing method of the electrically peelable adhesive sheet of this invention, The aqueous dispersion of the adhesive composition prepared by said method is apply | coated by the well-known coating method on the above-mentioned base material or a release sheet. Can be manufactured.

  As an active ingredient density | concentration of the aqueous dispersion of an adhesive composition, Preferably it is 10-80 mass%, More preferably, it is 25-70 mass%, More preferably, it is 45-65 mass%.

  Examples of the method for applying the aqueous dispersion of the pressure-sensitive adhesive composition onto a substrate or a release sheet include spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, and die coating. And gravure coating method.

In addition, after apply | coating the aqueous dispersion of an adhesive composition on a base material or a peeling sheet and forming a coating film, it is preferable to dry-process.
As drying conditions of the formed coating film, from the viewpoint of adjusting the moisture content calculated by the Karl Fischer method of the pressure-sensitive adhesive layer to be within the above range, the temperature is 80 ° C. to 150 ° C. for 30 seconds to 5 minutes. It is preferable to heat and dry (preferably 40 seconds to 3 minutes, more preferably 45 seconds to 2 minutes). Through this drying step, the pressure-sensitive adhesive layer can be formed on the substrate or the release sheet.

The following method is mentioned as a specific manufacturing method according to the structure of the electrically peelable pressure-sensitive adhesive sheet.
First, as shown in FIG. 1 (a), an electro-releasable pressure-sensitive adhesive sheet 1a having a pressure-sensitive adhesive layer 3 on one side of a base 2 is formed on one side of the base 2 with water of the above-mentioned pressure-sensitive adhesive composition. The dispersion can be directly applied to form the pressure-sensitive adhesive layer 3.
Moreover, after apply | coating the aqueous dispersion of the above-mentioned adhesive composition directly on the peeling process surface of a peeling sheet and forming the adhesive layer 3, the adhesive layer 3 and the base material 2 are bonded together, The release sheet may be removed for production.

An electro-releasable pressure-sensitive adhesive sheet 1 b having pressure-sensitive adhesive layers 3 and 3 ′ on both surfaces of a substrate 2 as shown in FIG. 1B is, for example, an aqueous dispersion of the above-mentioned pressure-sensitive adhesive composition on both surfaces of the substrate 2. Can be directly applied to form the pressure-sensitive adhesive layers 3 and 3 ′.
Moreover, on the release treatment surface of the release sheet, two sheets of the above-mentioned pressure-sensitive adhesive composition aqueous dispersion were directly applied to form a pressure-sensitive adhesive layer. It may be produced by attaching to both sides and removing the release sheet.

An electro-peelable pressure-sensitive adhesive sheet 1c having a pressure-sensitive adhesive layer 3 and a release sheet 4 in this order on a substrate 2 as shown in FIG. 1C is, for example, an electro-peelable pressure-sensitive adhesive sheet 1a obtained as described above. The release sheet 4 can be laminated on the surface of the pressure-sensitive adhesive layer 3.
Moreover, after apply | coating the aqueous dispersion of the above-mentioned adhesive composition directly on the peeling process surface of the peeling sheet 4 and forming the adhesive layer 3, the adhesive layer 3 and the base material 2 are bonded together. May be produced.

As shown in FIG. 1 (d), an electro-peelable pressure-sensitive adhesive sheet 1 d having a configuration in which the pressure-sensitive adhesive layer 3 is sandwiched between two release sheets 4 and 4 ′ without using a substrate is, for example, An aqueous dispersion of the above-mentioned pressure-sensitive adhesive composition is directly applied on the release-treated surface to form a pressure-sensitive adhesive layer 3, and another release sheet 4 'is laminated on the surface of the pressure-sensitive adhesive layer 3. Can be produced.
In addition, as above-mentioned, it is preferable to adjust so that peeling force may differ between peeling sheet 4 and peeling sheet 4 '.

[How to use an electro-peelable adhesive sheet]
The electric peelable pressure-sensitive adhesive sheet of the present invention can be used by being attached to an arbitrary adherend.
The adherend is not particularly limited, and may or may not have conductivity. However, from the viewpoint of easily applying a voltage to the pressure-sensitive adhesive surface, the adherend is directly used as an electrode. Thus, an adherend having conductivity is preferable.
Therefore, from the above viewpoint, as a method for using the electro-releasable pressure-sensitive adhesive sheet of the present invention, a method of using the pressure-sensitive adhesive sheet of the present invention after being attached to an adherend having conductivity is preferable.
Examples of the conductive adherend include metals such as aluminum, tin-doped indium oxide, copper, iron, silver, platinum, and gold, and alloys of these metals.

The present invention will be specifically described with reference to the following examples, but the present invention is not limited to the following examples.
Moreover, the value measured based on the method shown below was used about the following physical-property value of the component used by the following synthesis examples, Examples, and Comparative Examples.

<Average particle diameter of emulsion type acrylic copolymer>
A value obtained by measuring a volume-based median diameter at 25 ° C. using a dynamic light scattering particle size distribution analyzer (manufactured by Horiba, Ltd., product name “LB-550”) was used (unit: nm). .

<Effective component concentration of emulsion type acrylic adhesive>
In accordance with JIS K-6833, the emulsion type acrylic pressure-sensitive adhesive was dried at 107 ° C. for 3 hours, the residue was weighed, and the active ingredient concentration was calculated from the following formula.
Active ingredient concentration (mass%) = (mass of residue) / (mass of emulsion-type acrylic pressure-sensitive adhesive before drying) × 100

<Hydroxyl value of (poly) alkylene polyol>
A value (unit: mgKOH / g) measured based on JIS K0070 was used.

<Number average molecular weight (Mn) of (poly) alkylene polyol>
Using a gel permeation chromatograph device (product name “HLC-8020” manufactured by Tosoh Corporation), the value measured under the following conditions and measured in terms of standard polystyrene was used.
(Measurement condition)
・ Column: “TSK guard column HXL-L” “TSK gel G2500HXL” “TSK gel G2000HXL” “TSK gel G1000HXL” (all manufactured by Tosoh Corporation)
-Column temperature: 40 ° C
・ Developing solvent: Tetrahydrofuran ・ Flow rate: 1.0 mL / min

Synthesis example 1
(Preparation of emulsion-type acrylic pressure-sensitive adhesive (A-1))
In a reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen inlet tube and dropping funnel, as a monomer mixture, 75 parts by mass of 2-ethylhexyl acrylate, 15 parts by mass of methyl acrylate, 7.5 parts by mass of methyl methacrylate A mixture of 1.5 parts by mass of acrylic acid and 1.0 part by mass of diacetone acrylamide, and as a tackifier resin, rosin ester resin (manufactured by Arakawa Chemical Industry Co., Ltd., product name “Super Ester A-100”, softening (Point 100 ° C.) 8 parts by mass were added, and the mixture was stirred and dissolved for 30 minutes while maintaining the temperature at about 30 ° C.
After the above components are homogeneously dissolved, an anionic reactive emulsifier (manufactured by ADEKA Corporation, product name “ADEKA rear soap SR-10”, a compound represented by the above formula (10) (X Is a dispersion in which 2.0 parts by mass of SO ₃ NH ₄ )) is dispersed in 57 parts by mass of deionized water and stirred for 30 minutes to obtain an emulsion (1).

Separately, in a reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introducing tube and a dropping funnel, 40 parts by mass of deionized water and an anionic reactive emulsifier (manufactured by ADEKA Corporation, product name “ Adekaria soap SR-10 ") 0.2 parts by mass, nitrogen was introduced, the temperature in the reaction vessel was raised to 80 ° C, and 5 mass% of potassium persulfate aqueous solution was added to the reaction vessel. Part by mass was added.
And while maintaining the temperature in this reaction container at 80-83 degreeC, the emulsion (1) prepared as mentioned above and 4 mass parts of 5 mass% potassium persulfate aqueous solution were paralleled, and the said reaction container The solution was dropped into the reactor over 3 hours, and emulsion polymerization was carried out with stirring.

After completion of dropping, the mixture was aged for 3 hours at a temperature of 80 to 83 ° C., then cooled to room temperature (25 ° C.), added with 25% by mass of ammonia water, and adjusted to a pH of 7.5. An emulsion type acrylic copolymer (1) having a diameter of 180 nm was obtained.
Then, 8 parts by mass of adipic acid dihydrazide (manufactured by Nippon Finechem Co., Ltd., product name “ADH”) as a crosslinking agent with respect to 100 parts by mass of the active ingredient of the obtained emulsion type acrylic copolymer (1) ( 0.5% by weight of an anionic surfactant (ADEKA Co., Ltd., product name “ADEKA COAL EC-4500”) was added and mixed as a wetting agent, and the active ingredient concentration was 50.5. A solution of a mass% emulsion-type acrylic pressure-sensitive adhesive (A-1) was obtained.

Synthesis example 2
(Preparation of emulsion-type acrylic pressure-sensitive adhesive (A-2))
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 40 parts by mass of ion-exchanged water and an anionic reactive surfactant (“AQUALON KH-10” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 0.2 parts by mass of the compound represented by the formula (9) (X is SO ₃ NH ₄ ) was charged, and the temperature was raised to 80 ° C.
Next, 80 parts by mass of 2-ethylhexyl acrylate, 16 parts by mass of methyl methacrylate, 2 parts by mass of acrylic acid, 2 parts by mass of methacrylic acid, and γ-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) “Silicone KBM-503”) 0.2 parts by weight, as chain transfer agent 0.03 parts by weight of dodecyl mercaptan, and radical polymerizable surfactant (Daiichi Kogyo Seiyaku Co., Ltd., product name “AQUALON HS-”) 10 ") A mixture of 1.0 part by mass emulsified and dispersed in 49 parts by mass of ion-exchanged water and a polymerization initiator in which 0.3 part by mass of potassium persulfate was dissolved in 9.7 parts by mass of ion-exchanged water were mixed. And this mixed solution was supplied into the said reaction container from the dropping funnel over 3 hours, and emulsion polymerization was performed at 80 degreeC, and the emulsion (2) was obtained.

After completion of the dropwise addition, the mixture was aged at 80 ° C. for 2 hours, then cooled to room temperature (25 ° C.), added with 25% by mass of ammonia water, adjusted to pH 7.5, and an emulsion having an average particle size of 150 nm. Type acrylic copolymer (2) was obtained.
And with respect to 100 mass parts of active ingredients of the obtained emulsion-type acrylic copolymer (2), as a defoaming agent, a silicone-based defoaming agent (product name “BYK025” manufactured by Bic Chemie) is used. 2 parts by weight, as a thickener, 0.3 parts by weight of urethane thickener (Rohm & Haas, product name “EXP300”) is added and mixed to obtain an emulsion having an active ingredient concentration of 50.5% by weight. A solution of a type acrylic pressure-sensitive adhesive (A-2) was obtained.

Examples 1-12, Comparative Examples 1-7
For 100 parts by mass of the emulsion type acrylic pressure-sensitive adhesive (A-1) or (A-2) obtained in Synthesis Example 1 or 2, the types shown in Table 1, number average molecular weight (Mn), and blending amount (poly ) Alkylene polyol was added, and deionized water was further added to adjust the concentration to prepare a coating solution of an electrodetachable pressure-sensitive adhesive composition having an active ingredient concentration of 37% by mass.
Next, a coating liquid of the electropeelable pressure-sensitive adhesive composition prepared as described above was used as a release sheet (product name “SP-PET381130” manufactured by Lintec Corporation, thickness: 38 μm, polyethylene terephthalate film whose surface was subjected to silicone release treatment) ) Was applied so that the thickness after drying was 50 μm, and dried at 100 ° C. for 120 seconds to form an adhesive layer on the release sheet.
Then, on the surface of the formed pressure-sensitive adhesive layer, an aluminum foil base material (manufactured by Nippon Metal Foil Industry Co., Ltd., product name “Aluminum Tantai S Shin 50 Fukuoka”, thickness: 50 μm) is pasted as a base material, A base-attached type electro-releasable pressure-sensitive adhesive sheet having the same configuration as that of the electro-peelable pressure-sensitive adhesive sheet 1c shown in FIG.
Each physical property value was measured based on the following method using the produced electro-releasable pressure-sensitive adhesive sheet. The results are shown in Table 1.

(1) Moisture content of pressure-sensitive adhesive layer The electro-peelable pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut into a size of 50 mm × 20 mm, and the environment was 23 ° C. and 50% RH (relative humidity). Left for hours.
After leaving, the peeled release sheet of the pressure-sensitive adhesive sheet is peeled to form a pressure-sensitive adhesive sheet composed of an aluminum foil base material and a pressure-sensitive adhesive layer, and a Karl Fischer moisture meter (manufactured by Kyoto Electronics Industry Co., Ltd., apparatus name “MKC-510N”) is used. Using, the value of the moisture content of the pressure-sensitive adhesive sheet was measured. The set heating temperature at the time of measurement is 230 ° C., the reagent is “Curomat AG-Oven (produced by Riedel de Haan)” as a generating liquid, and the coagulant liquid is “Curomat CG (Ridel de Haan). Manufactured)).
Separately, after measuring the moisture content of the aluminum foil base material alone, the moisture content of the aluminum foil base material alone was removed from the measured moisture content of the pressure-sensitive adhesive sheet comprising the aluminum foil base material and the pressure-sensitive adhesive layer. The value is shown in Table 1 as the moisture content of the pressure-sensitive adhesive layer.

(2) Adhesive strength of pressure-sensitive adhesive sheet before voltage application The electrically peelable pressure-sensitive adhesive sheets prepared in Examples and Comparative Examples were cut into a size of 25 mm × 300 mm, and the environment was 23 ° C. and 50% RH (relative humidity). Then, the release sheet was peeled off, and the exposed pressure-sensitive adhesive layer was attached to an adherend aluminum plate (product name “A105OP”, 150 mm × 70 mm × 1 mm). When sticking, use a roller with a weight of 2 kg, reciprocate once, press on the adherend, and leave in an environment of 23 ° C. and 50% RH (relative humidity) for 24 hours after sticking. A sample was made.
Then, in an environment of 23 ° C. and 50% RH (relative humidity), using a tensile tester (product name “Tensilon”, manufactured by Orientec Co., Ltd.), the pressure is 300 mm / min and the peel angle is 180 °. The value (unit: N / 25 mm) measured when the sheet was peeled was defined as the adhesive strength of the adhesive sheet before voltage application.

(3) Adhesive strength of pressure-sensitive adhesive sheet after voltage application As shown in FIG. 2A, the voltage application device 50 (product name “KH-100H” manufactured by Takasago Seisakusho Co., Ltd.) The anode terminal 51 was connected to the aluminum foil substrate 2a, the cathode terminal 52 was connected to the adherend 11, and a voltage of 100 V was applied for 60 seconds.
After the voltage application, the sample was left for 30 seconds, and then peeled at 300 mm / min using a tensile tester (Orientec, trade name “Tensilon”) in the same environment of 23 ° C. and 50% RH (relative humidity). The value (unit: N / 25 mm) measured when the pressure-sensitive adhesive sheet was peeled off at a peeling angle of 180 ° was defined as the pressure-sensitive adhesive strength of the pressure-sensitive adhesive sheet after voltage application.
In addition, the adhesive force reduction rate in Table 1 is a value calculated by the following formula.
[Decrease rate of adhesive strength (%)] = 100− [Adhesive strength of adhesive sheet after voltage application] / [Adhesive strength of adhesive sheet before voltage application] × 100

According to Table 1, it can be seen that the electrically peelable pressure-sensitive adhesive sheets of Examples 1 to 16 have low adhesive strength after voltage application and a high rate of decrease in adhesive strength due to voltage application. In addition, as for the electrically peelable adhesive sheet of Examples 1-16, it was confirmed that an adhesive layer peels from a cathode side after a voltage application, as FIG.2 (b) shows.
On the other hand, since the electrically peelable pressure-sensitive adhesive sheets of Comparative Examples 1 to 4 have a small content of (poly) alkylene polyol in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer, for example, compared with the pressure-sensitive adhesive sheet of Example 5, The adhesive strength after voltage application was high, and the result showed that there was little decrease in adhesive strength before and after voltage application.
Moreover, since the value of the hydroxyl value of the (poly) alkylene polyol in the pressure-sensitive adhesive composition constituting the pressure-sensitive adhesive layer is less than 70 mgKOH / g, the electro-releasable pressure-sensitive adhesive sheets of Comparative Examples 5 to 7 Compared to the sheet, the adhesive strength after voltage application was high, and a decrease in the adhesive strength before and after voltage application was not seen much.

  The electrically peelable pressure-sensitive adhesive sheet of the present invention can achieve both excellent adhesive strength and removability. Therefore, for example, it is suitable for applications requiring removability such as a surface protective film, a coating or decorative masking tape, a removable memo, and a temporary fixing of industrial products.

DESCRIPTION OF SYMBOLS 1a, 1b, 1c, 1d Electrically peelable adhesive sheet 2 Base material 2a Aluminum foil base material 3, 3 'Adhesive layer 3a, 3a' Surface 4 of the adhesive layer connected to the cathode side, 4 'Release sheet 11 Adhesion Body 50 Voltage application device 51 Anode terminal 52 Cathode terminal

Claims (14)

  Emulsion-type acrylic pressure-sensitive adhesive (A) containing an emulsion-type acrylic polymer (A1) obtained by emulsion polymerization in the presence of a surfactant using a monomer mixture containing (meth) acrylic acid alkyl ester , And an electro-releasable pressure-sensitive adhesive composition comprising (poly) alkylene polyol (B) having a hydroxyl value of 70 to 1500 mgKOH / g, comprising (B) component with respect to 100 parts by mass of active component (A) An electrodetachable pressure-sensitive adhesive composition having an amount of 3.5 parts by mass or more.   The electroreleasable pressure-sensitive adhesive composition according to claim 1, wherein the content of the component (B) with respect to 100 parts by mass of the active ingredient (A) is 3.5 to 50 parts by mass.   The electroreleasable pressure-sensitive adhesive composition according to claim 1 or 2, wherein the component (B) comprises (poly) alkylene glycol. The electropeelable pressure-sensitive adhesive composition according to claim 3, wherein the (poly) alkylene glycol is a compound represented by the following general formula (b-1).
[In the formula (b-1), EO represents ethylene oxide, PO represents propylene oxide, and p and q are real numbers that satisfy p ≧ 0, q ≧ 0, and p + q ≧ 1. In addition, the compound represented by general formula (b-1) may be a compound formed by block copolymerization of EO and PO, or may be a compound formed by random copolymerization. ]   The number average molecular weight of (B) component is 2000 or less, The electrically peelable adhesive composition in any one of Claims 1-4.   The emulsion type acrylic polymer (A1) is composed of 60 to 99.9% by mass of the structural unit (a1) derived from the (meth) acrylic acid alkyl ester, and the structural unit (a2) derived from the functional group-containing unsaturated monomer. The electrodetachable pressure-sensitive adhesive composition according to any one of claims 1 to 5, which is a copolymer containing 0.1 to 40% by mass.   The electrodetachable pressure-sensitive adhesive composition according to any one of claims 1 to 6, wherein the surfactant is an anionic reactive emulsifier.   The electroreleasable pressure-sensitive adhesive composition according to claim 7, wherein the anionic reactive emulsifier is an ammonium salt.   An electro-peelable pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a material containing the electro-peelable pressure-sensitive adhesive composition according to claim 1.   The electrically peelable pressure-sensitive adhesive sheet according to claim 9, wherein the water content calculated by the Karl Fischer method of the pressure-sensitive adhesive layer is 0.53 to 15.0%.   The electroreleasable pressure-sensitive adhesive sheet according to claim 9 or 10, which has the pressure-sensitive adhesive layer on at least one surface of a conductive substrate.   The electrically peelable pressure-sensitive adhesive sheet according to claim 9 or 10, wherein the pressure-sensitive adhesive layer has a structure sandwiched between two release sheets.   When a voltage is applied between two adherends, or both sides of the pressure-sensitive adhesive layer sandwiched between the adherend and the substrate, the surface of the pressure-sensitive adhesive layer connected to the cathode side and the pressure-sensitive adhesive The electrically peelable pressure-sensitive adhesive sheet according to any one of claims 9 to 12, which peels between the surface of the agent layer and the adherend or the base material attached thereto.   A method for using an electro-releasable pressure-sensitive adhesive sheet, wherein the electro-releasable pressure-sensitive adhesive sheet according to claim 9 is attached to an adherend having conductivity.