JP7092251B1 - Adhesive for skin application and adhesive tape for skin application - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive for skin application capable of obtaining an adhesive tape for skin application having excellent adhesiveness and transparency. A polymer (A) having a reactive functional group, a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000, and a curing agent (C) are contained, and the urethane compound ( A pressure-sensitive adhesive for skin application, wherein the content of B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A). [Selection diagram] None

Description

Embodiments of the present invention relate to a skin-adhesive adhesive, a cured product of the skin-adhesive adhesive, and a skin-adhesive tape.

Adhesive tape for skin application is medical tape such as adhesive plasters and surgical tapes; pharmaceutical products such as paps and plasters; for eye makeup in the cosmetic field, for preventing wig slippage, for creating wrinkles in special makeup, etc. It is widely used (for example, Patent Document 1). Further, in low frequency treatment, electroencephalogram or electrocardiogram measurement, electrodes may be attached to the skin, and in this case as well, an adhesive tape for attaching to the skin is used.

The adhesive tape for skin application may be applied for a long period of one week or longer depending on the intended use. In that case, due to the influence of sebum, sweat, etc. absorbed by the pressure-sensitive adhesive over time, the adhesion between the base material and the pressure-sensitive adhesive may decrease, and adhesive residue may occur at the time of peeling. Further, in recent years, adhesives with reduced adhesive strength have been actively developed in order to suppress exfoliation of keratin at the time of tape exfoliation, and in the case of such adhesives, the adhesiveness between the base material and the adhesive is originally low. Similarly, the adhesive residue at the time of peeling was a problem. In order to improve the adhesion between the base material and the pressure-sensitive adhesive, complicated steps such as primer treatment, corona treatment, and heat laminating processing on the base material using dedicated equipment were required.

International Publication No. 2014/148582

An object of the present invention is to provide a skin-adhesive adhesive and a cured product capable of obtaining a skin-adhesive adhesive tape having excellent adhesion and transparency. Another object of the present invention is to provide an adhesive tape for skin application, which has excellent adhesion and transparency.

Examples of embodiments of the present invention are given below. The present invention is not limited to the following embodiments.
(1) The urethane compound (B) containing a polymer (A) having a reactive functional group, a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000, and a curing agent (C). ) Is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A).
(2) The polymer (A) contains at least one selected from the group consisting of a carboxyl group-containing acrylic polymer, a hydroxyl group-containing acrylic polymer, a hydroxyl group-containing urethane polymer, and a polyether polyol. The adhesive for skin application according to 1).
(3) The pressure-sensitive adhesive for skin application according to (1) or (2) above, wherein the urethane compound (B) contains a structure derived from an aromatic isocyanate.
(4) The pressure-sensitive adhesive for skin application according to any one of (1) to (3) above, wherein the urethane compound (B) contains a trifunctional or higher functional isocyanate-derived structure.
(5) Any of the above (1) to (4), wherein the urethane compound (B) contains a structure obtained by reacting an alcohol component containing a monoalcohol with a polyisocyanate component containing a trifunctional or higher functional isocyanate. Adhesive for skin application described in Crab.
(6) The pressure-sensitive adhesive for skin application according to any one of (1) to (5) above, wherein the urethane compound (B) has an amine value of 0.1 to 60 mgKOH / g.
(7) A cured product obtained by curing the adhesive for skin application according to any one of (1) to (6) above.
(8) The cured product according to (7) above, which has a gel fraction of 20 to 63%.
(9) The cured product according to (7) or (8) above, which has a permanent adhesive force against SUS of 0.3 N / 25 mm or more in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%.
(10) An adhesive tape for skin application, which has a base material and an adhesive layer containing the cured product according to any one of (7) to (9) above.

According to the embodiment of the present invention, it is possible to provide a skin-adhesive adhesive and a cured product capable of obtaining a skin-adhesive adhesive tape having excellent adhesion and transparency. Further, according to another embodiment of the present invention, it is possible to provide an adhesive tape for skin attachment having excellent adhesion and transparency.

An embodiment of the present invention will be described. The present invention is not limited to the following embodiments. The following embodiments can be implemented alone or in combination. A combination of a plurality of embodiments described below is also included in the present invention.

<Adhesive for skin application>
The pressure-sensitive adhesive for skin application according to the embodiment of the present invention has a mass average molecular weight of 1 with a polymer (A) having a reactive functional group (in the present specification, it may be simply referred to as “polymer (A)”). , 500 to 40,000 urethane compound (B) (in the present specification, it may be simply referred to as “urethane compound (B)”) and a curing agent (C). The content of the urethane compound (B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A).

[Polymer having a reactive functional group (A)]
The polymer (A) has at least one reactive functional group in the molecule. Examples of the reactive functional group include a carboxyl group, a hydroxyl group, an amide group (a group containing an amide bond), an epoxy group, an amino group and the like. The reactive functional group preferably comprises at least one selected from the group consisting of a hydroxyl group and a carboxyl group.

Examples of the polymer (A) include acrylic polymers, urethane polymers, and polyethers having reactive functional groups. The polymer (A) preferably contains at least one selected from the group consisting of an acrylic polymer having a reactive functional group, a urethane polymer having a reactive functional group, and a polyether having a reactive functional group. , At least one selected from the group consisting of a carboxyl group-containing acrylic polymer, a hydroxyl group-containing acrylic polymer, a hydroxyl group-containing urethane polymer, and a polyether polyol is more preferable. The polymer (A) may be used alone or in combination of two or more.

(Acrylic polymer with reactive functional groups)
Acrylic polymers having a reactive functional group (in the present specification, may be referred to as "reactive functional group-containing acrylic polymer") are a (meth) acrylic acid ester and a reactive functional group-containing monomer (b). It may be a copolymer of a monomer component containing and, preferably one or more selected from the group consisting of a (meth) acrylic acid ester having an alkyl group and a (meth) acrylic acid ester having an alicyclic structure. It is a copolymer of a monomer component containing the (meth) acrylic acid ester (a) and the reactive functional group-containing monomer (b). The reactive functional group-containing acrylic polymer preferably contains at least one selected from the group consisting of a carboxyl group-containing acrylic polymer and a hydroxyl group-containing acrylic polymer, and more preferably contains a carboxyl group-containing acrylic polymer. preferable. The reactive functional group-containing acrylic polymer may be used alone or in combination of two or more.

The (meth) acrylic acid ester (a) can improve the adhesive force and the cohesive force of the reactive functional group-containing acrylic polymer. When the (meth) acrylic acid ester (a) contains a (meth) acrylic acid ester having an alkyl group having 8 to 12 carbon atoms, the adhesive strength is further improved. When the (meth) acrylic acid ester (a) contains a (meth) acrylic acid ester having an alicyclic structure, the cohesive force is further improved. The (meth) acrylic acid ester (a) may be used alone or in combination of two or more.

The content of the (meth) acrylic acid ester (a) is preferably 70 to 99.7% by mass, more preferably 80 to 99.5% by mass, and 88 to 99.5% by mass in 100% by mass of the monomer component. It is more preferably 99% by mass, and particularly preferably 92 to 98% by mass. When it is 70 to 99.7% by mass, it becomes easier to achieve both adhesive strength and transparency.

When a (meth) acrylic acid ester having an alkyl group having 8 to 12 carbon atoms and a (meth) acrylic acid ester having an alicyclic structure are used in combination, the adhesive strength may be further improved. When used in combination, the mass ratio of the (meth) acrylic acid ester having an alkyl group having 8 to 12 carbon atoms to the (meth) acrylic acid ester having an alicyclic structure is 100/0 to 100% based on the balance between adhesive force and cohesive force. 50/50 is preferable, and 100/0 to 65/35 is more preferable.

Examples of the (meth) acrylic acid ester having an alkyl group having 8 to 12 carbon atoms include (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid octyl, (meth) acrylic acid isooctyl, and (meth) acrylic acid nonyl. , (Meta) isononyl acrylate, (meth) decyl acrylate, (meth) isodecyl acrylate, (meth) dodecyl acrylate and the like. Among these, 2-ethylhexyl (meth) acrylate can achieve both adhesive strength and transparency at a high level.

Examples of the (meth) acrylic acid ester having an alicyclic structure include (meth) acrylic acid cyclohexyl, (meth) acrylic acid dicyclopentenyl, (meth) acrylic acid dicyclopentenyl, and (meth) acrylic acid isobornyl. Can be mentioned. Among these, cyclohexyl (meth) acrylate can achieve both adhesive strength and transparency at a higher level.

The reactive functional group-containing monomer (b) can function as a cross-linking point for a cross-linking reaction with a curing agent. The content of the reactive functional group-containing monomer (b) is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass, and 1 to 1 to 20% by mass in 100% by mass of the monomer component. It is more preferably 12% by mass, and particularly preferably 2 to 8% by mass. When it is 0.3 to 30% by mass, it is easy to obtain a desired crosslink density, and it is easy to adjust the adhesive force and the cohesive force.

Examples of the reactive functional group-containing monomer (b) include a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an amide group-containing monomer, an epoxy group-containing monomer, and an amino group-containing monomer. Among these, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, and an amide group-containing monomer are preferable, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are more preferable, and a carboxyl group-containing monomer is further preferable. The reactive functional group-containing monomer (b) may be used alone or in combination of two or more.

Examples of the carboxyl group-containing monomer include (meth) acrylic acid, phthalic acid monohydroxyethyl acrylic acid ester, p-carboxybenzyl acrylic acid ester, and ethylene oxide-modified (ethylene oxide addition mole number is 2 to 18) phthalic acid acrylic acid. Examples thereof include esters, monohydroxyethyl succinic acid esters, β-carboxyethyl acrylate, and itaconic acid. Among these, (meth) acrylic acid is preferable.

The content of the carboxyl group-containing monomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in 100% by mass of the monomer component. By using an appropriate amount of a carboxyl group-containing monomer, both adhesive strength and cohesive strength can be achieved at a higher level.

Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. (Meta) Acrylic Acid Hydroxyalkyl Esters such as 3-Hydroxybutyl (meth) Acrylic Acid, 4-Hydroxybutyl (Meta) Acrylic Acid, 6-Hydroxyhexyl (Meta) Acrylic Acid, 8-Hydroxyoctyl (Meta) Acrylic Acid; Polyethylene Glycol mono (meth) acrylic acid esters such as glycol mono (meth) acrylic acid ester, polypropylene glycol mono (meth) acrylic acid ester, 1,4-cyclohexanedimethanol mono (meth) acrylic acid ester; caprolactone-modified (meth) acrylic Acid ester; N-hydroxyalkyl (meth) acrylamide such as N-hydroxymethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide can be mentioned. Among these, 2-hydroxyethyl (meth) acrylate is preferable.

The content of the hydroxyl group-containing monomer is preferably 0.01 to 7% by mass, more preferably 0.05 to 5% by mass in 100% by mass of the monomer component. By using an appropriate amount of a hydroxyl group-containing monomer, both adhesive strength and cohesive strength can be achieved at a higher level.

Examples of the amide group-containing monomer include heterocycles such as (meth) acrylamide-based compounds such as (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N- (butoxymethyl) acrylamide. Examples include compounds.

The content of the amide group-containing monomer is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in 100% by mass of the monomer component. By using an appropriate amount of the amide group-containing monomer, both adhesive strength and cohesive strength can be achieved at a higher level.

Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylate.

The content of the epoxy group-containing monomer is preferably 0.1 to 1 part by mass in 100% by mass of the monomer component.

Examples of the amino group-containing monomer include (meth) monomethylaminoethyl acrylate, (meth) monoethylaminoethyl acrylate, (meth) monomethylaminopropyl acrylate, and (meth) monoethylaminopropyl acrylate. ) Acrylic acid monoalkylamino ester and the like.

The content of the amino group-containing monomer is preferably 0.1 to 1 part by mass in 100% by mass of the monomer component.

The monomer component may contain other monomers in addition to the (meth) acrylic acid ester (a) and the reactive functional group-containing monomer (b). The other monomer may be a monomer that does not impair the adhesive strength and cohesive strength of the pressure-sensitive adhesive. Examples of other monomers include (meth) acrylic acid alkyl ester monomers having an alkyl group having 1 to 7 or 13 or more carbon atoms, aromatic ring-containing monomers, alkoxy (poly) alkylene oxide-containing monomers, and other vinyl monomers. Be done.

The reactive functional group-containing acrylic polymer can be synthesized by radical polymerization such as solution polymerization, bulk polymerization, and emulsion polymerization. Among these, solution polymerization is preferable because it is easy to adjust the mass average molecular weight of the reactive functional group-containing acrylic polymer. For radical polymerization, it is preferable to use a polymerization initiator. The polymerization initiator is generally an azo compound or an organic peroxide.

The mass average molecular weight (hereinafter, also referred to as Mw) of the reactive functional group-containing acrylic polymer is preferably 400,000 to 1.5 million, more preferably 500,000 to 1.4 million, and even more preferably 600,000 to 1.3 million. When Mw is in the range of 400,000 to 1.5 million, it becomes easier to achieve both adhesive physical properties and coatability. In the present specification, Mw is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). Specifically, Mw can be measured by the method described in Examples.

(Urethane polymer with reactive functional groups)
The urethane-based polymer having a reactive functional group (in the present specification, it may be referred to as “reactive functional group-containing urethane-based polymer”) is prepared by reacting, for example, a component containing a polyol component with a polyisocyanate component. The obtained polyurethane or a urethane prepolymer obtained by reacting a component containing a polyol component and a polyisocyanate component with an excess of isocyanate groups and a urethane prepolymer obtained by reacting an amine component with a urea reaction may be used. .. The former polyurethane has at least one selected from the group consisting of an isocyanate group and a hydroxyl group as a reactive functional group, depending on the type and amount of each component. The latter polyurethane urea has at least one selected from the group consisting of an isocyanate group, an amino group, and a hydroxyl group as a reactive functional group, depending on the type and amount of each component. The reactive functional group-containing urethane polymer may be used alone or in combination of two or more.

The mass average molecular weight of the reactive functional group-containing urethane polymer may be, for example, 10,000 to 500,000, 25,000 to 500,000, or 30,000 to 300,000. From the viewpoint of obtaining particularly excellent initial curability and adhesiveness, 45,000 to 500,000 is preferable, and 55,000 to 300,000 is even more preferable.

The content of the polymer (A) in the pressure-sensitive adhesive for skin application is preferably 40 to 99.9% by mass, more preferably 60 to 99.9% by mass, based on the mass of the pressure-sensitive adhesive for skin application. When the content of the polymer (A) is within the above range, the pressure-sensitive adhesive can exhibit better adhesive strength and cohesive strength.

(Polyurethane)
Polyurethane can be obtained, for example, by reacting a component containing a polyol component and a polyisocyanate component. The obtained polyurethane has at least one selected from the group consisting of an isocyanate group and a hydroxyl group as a reactive functional group. Polyurethane preferably has a hydroxyl group as a reactive functional group. The polyurethane may be, for example, a polyurethane polyol obtained by reacting a polyol component (a) containing a polyether polyol (a1) with a component containing a polyisocyanate component (b). The polyisocyanate component (b) preferably contains at least diisocyanate.

The hydroxyl value of the polyurethane polyol is preferably 2.0 to 45 mgKOH / g, more preferably 3.0 to 40 mgKOH / g. When the hydroxyl value is 2.0 mgKOH / g or more, there is a tendency that the adhesive residue can be suppressed by increasing the cohesive force of the pressure-sensitive adhesive, and good initial curability is likely to be exhibited by increasing the reaction points. When the hydroxyl value is 45 mgKOH / g or less, the adhesive becomes flexible, the exfoliation property of the keratin is improved, and the followability to the skin is improved, so that the adhesiveness to the skin tends to be improved. In the present specification, the hydroxyl value can be measured by the method described in Examples.

The mass average molecular weight of the polyurethane polyol is preferably 25,000 to 300,000, more preferably 30,000 to 300,000, still more preferably 45,000 to 300,000, and 55,000 to 20. 10,000 is particularly preferable. Within this range, excellent coatability and initial curability can be imparted.

The polyol component (a) contains at least the polyether polyol (a1). The polyol component (a) preferably has a hydroxyl group at the molecular terminal, has a primary hydroxyl group content of 40 mol% or more in all hydroxyl groups, and has an average number of hydroxyl groups of 2 or more (a1). -1) may be contained, and another polyol (a2) may be further contained. The average number of hydroxyl groups of the polyether polyol (a1-1) is preferably 3 or more. The polyol component (a) may be used alone or in combination of two or more.

By using the polyether polyol (a1-1), the initial curability is excellent due to the presence of the primary hydroxyl group, and the reaction is more likely to occur more uniformly than the normal polyol. Therefore, the oligomer normally produced due to insufficient curing is produced. As a result, there is a tendency to suppress the generation of adhesive residue.

The content of the polyether polyol (a1-1) contained in 100% by mass of the polyol component (a) is preferably 25 to 100% by mass, and particularly preferably 35 to 100% by mass. Within this range, since it exhibits high reactivity, it is easy to form an adhesive layer having excellent initial curability and less likely to cause adhesive residue.

The polyether polyol (a1-1) is not particularly limited, but can be obtained by the following known method.
In [Method 1], a compound having an active oxygen atom having two or more functional groups, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine, is used as an initiator to open rings of ethylene oxide, butylene oxide, tetrahydrofuran, and the like. It is obtained by polymerizing an oxylan compound that gives a terminal primary hydroxyl group. In this case, all the hydroxyl groups at the ends are primary hydroxyl groups. Commercially available products include Polyserine DC-3000E (manufactured by NOF Corporation), PTMG1000, PTMG2000 (manufactured by Mitsubishi Chemical Holdings), Adeka Polyether GM-30 (manufactured by ADEKA), Sanniks GE-800 (manufactured by Sanyo Chemical Industries, Ltd.), etc. Applies to.

In [Method 2], a compound having an active oxygen atom having two or more functional groups, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine, is used as an initiator to open rings of ethylene oxide, butylene oxide, tetrahydrofuran, and the like. It is obtained by randomly polymerizing an oxylan compound that gives a terminal primary hydroxyl group and an oxylan compound that gives a terminal secondary hydroxyl group by opening a ring of propylene oxide or the like. In this case, the content of the primary hydroxyl group can be controlled by the compounding ratio of the oxylan compound giving the terminal primary hydroxyl group and the oxylan compound giving the terminal secondary hydroxyl group. Commercially available products include Adeka Polyether PR-3007, Adeka Polyether PR-5007, Adeka Polyether GR-2505, and Adeka Polyether GR-3308 (manufactured by ADEKA).

In [Method 3], a compound having an active oxygen atom having 2 or more functional groups such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator to polymerize propylene oxide, and finally. This is a method for polymerizing an oxylan compound such as ethylene oxide, butylene oxide, or tetrahydrofuran. By this method, polypropylene glycol having a primary hydroxyl group content of 40 mol% or more can be obtained. In this case, the content of the primary hydroxyl group can be controlled by the amount of the oxylan compound that gives the terminal primary hydroxyl group by ring-opening such as ethylene oxide, butylene oxide, and tetrahydrofuran to be added last. Commercially available products include Pronon # 201, Pronon # 202B (manufactured by Nichiyu Co., Ltd.), Adeka Polyether BM-34, Adeka Polyether BM-54, Adeka Polyether AM-302, Adeka Polyether AM-502, Adeka Polyether AM- 702 (manufactured by ADEKA), PREMINOL7001K, PREMINOL7012 (manufactured by Asahi Glass Co., Ltd.), Sanniks GL-600, Sanniks GL-3000 (manufactured by Sanyo Kasei Kogyo Co., Ltd.) and the like are applicable.

In [Method 4], a compound having an active oxygen atom having 2 or more functional groups such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and ethylenediamine is used as an initiator, and propylene oxide is further prepared using a specific catalyst. It can be obtained by a method of alpha cleavage addition (for example, the method described in JP-A-2000-344881). By this method, polypropylene glycol having a primary hydroxyl group content of 40 mol% or more can be obtained. In this case, the primary hydroxyl group content can be controlled by the amount, type and the like of the catalyst used. Commercially available products include Prime Pole PX1000, Prime Pole FX2202, and Prime Pole 3550 (manufactured by Sanyo Chemical Industries, Ltd.).

Of the above methods, the polyether polyol (a1-1) is preferably a polyether polyol containing polypropylene glycol as a main component obtained in [Method 3] and [Method 4]. By using such polypropylene glycol, a polyurethane polyol having excellent flexibility and water resistance can be obtained, and more excellent skin adhesiveness, low keratin exfoliation property and water resistance can be exhibited.

The content of the primary hydroxyl group of the polyether polyol (a1-1) is 40 mol% or more, preferably 70 mol% or more and 100 mol% or less. When the primary hydroxyl group content is 40 mol% or more, the initial curability is excellent and the generation of adhesive residue can be suppressed. The primary hydroxyl group content can be determined by pretreating (esterifying) the sample in advance and then measuring by ¹ H-NMR method.

The number average molecular weight (hereinafter, also referred to as Mn) of the polyether polyol (a1-1) is not particularly limited, but is preferably 400 to 20,000, and particularly preferably 600 to 15,000. When the number average molecular weight is within the above range, it is possible to exhibit appropriate cohesive force and good initial curability. In this specification, Mn is a polystyrene-equivalent value measured by gel permeation chromatography (GPC). Specifically, Mn can be measured by the method described in Examples.

The average number of hydroxyl groups of the polyether polyol (a1-1) is not particularly limited as long as it is 2 or more, but 2 to 6 is preferable, and 3 to 4 is particularly preferable. When the average number of hydroxyl groups is within the above range, it has an appropriate crosslink density and can exhibit suitable adhesive properties. Here, the average number of hydroxyl groups refers to the number of active hydrogen atoms per molecule of the initiator used as a raw material in producing the polyol component (a), for example, ethylene glycol and propylene glycol are 2, glycerin and Trimethylol propane is 3.

(Other polyol (a2))
Examples of the other polyol (a2) include polyester polyols, polyether polyols other than polyether polyols (a1-1), low molecular weight polyols, polybutadiene-modified polyols, polycaprolactone polyols, polycarbonate polyols, polyacrylic polyols, or castor oil-based polyols. And so on. Among these, a polyester polyol, a polyether polyol other than the polyether polyol (a1-1), a polycaprolactone polyol, or a polycarbonate polyol is preferable, and since it has excellent wettability and excellent followability to the skin, it is a polyester polyol or a polyester polyol. Polyester polyols other than the polyether polyol (a1-1) are more preferable.

As the polyester polyol, a known polyester polyol is used. As the polyester polyol, for example, an acid component and a glycol component are indispensable, and if necessary, the polyester polyol can be synthesized by an esterification reaction using the polyol component. Examples of the acid component include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like. In addition, as glycol components, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexaneglycol, 3-methyl-1,5-pentanediol, 3,3'- Dimethylol heptane, butylethylpentanediol, polyoxyethylene glycol, polyoxypropylene glycol and the like can be mentioned, and examples of the polyol component include glycerin, trimethylolpropane, pentaerythritol and the like.

The number average molecular weight of the polyester polyol is not particularly limited, but is preferably 500 to 5,000. When a polyester polyol having a number average molecular weight of 500 to 5,000 is used, appropriate reactivity can be obtained, and a polyurethane polyol having better cohesive force can be easily obtained.
The content of the polyester polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).

As the polyether polyol other than the polyether polyol (a1-1), a known polyether polyol is used. As the polyether polyol, for example, water; a low molecular weight polyol such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane or the like is used as an initiator to polymerize an oxylan compound such as ethylene oxide, propylene oxide, butylene oxide or tetrahydrofuran. Obtained by As the polyether polyol other than the polyether polyol (a1-1), for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like having one or more hydroxyl groups are preferable, and polypropylene glycol is more preferable.

The number average molecular weight of the polyether polyol other than the polyether polyol (a1-1) is not particularly limited, but is preferably 500 to 10,000. When the number average molecular weight is 500 to 10,000, appropriate flexibility can be obtained, and a polyurethane polyol having good skin adhesion can be easily obtained.
The content of the polyether polyol other than the polyether polyol (a1-1) is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).

Low molecular weight polyols include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methylpentanediol, 1,6-hexanediol, butylethylpentanediol, 1,9. -A compound having a molecular weight of less than 500 and having two or more hydroxyl groups at the terminal, such as glycols such as nonanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, xylitol and mannitol. By using the low molecular weight polyol, the urethane bond in the pressure-sensitive adhesive is increased, and an appropriate cohesive force and good substrate adhesion can be imparted.

The content of the low molecular weight polyol is preferably 0 to 10% by mass, more preferably 0 to 6% by mass, based on 100% by mass of the polyol component (a). By keeping the content within the above range, it is possible to improve the adhesive residue and the adhesion to the base material.

Polybutadiene-modified polyols have, for example, two or more hydroxyl groups at the ends and have a 1,2-vinyl site, a 1,4-cis site, a 1,4-trans site or a structure in which they are hydrogenated. , Linear or branched polybutadiene.

The number average molecular weight (Mn) of the polybutadiene-modified polyol is preferably 500 to 6,000, more preferably 800 to 6,000. By setting the number average molecular weight within the above range, appropriate reactivity can be obtained, and a polyurethane polyol having good cohesive force can be easily obtained.
The content of the polybutadiene-modified polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).

To the extent that the polybutadiene-modified polyol is hydrogenated, it is preferable that all of the double bond sites existing before hydrogenation are hydrogenated, but in the embodiment of the present invention, some double bond sites remain. You may be doing it.

The polycaprolactone polyol is preferably, for example, a caprolactone-based polyester diol obtained by ring-opening polymerization of a cyclic ester monomer such as ε-caprolactone or σ-valerolactone.

The number average molecular weight of the polycaprolactone polyol is not particularly limited, but is preferably 500 to 5,000. When the number average molecular weight is within the above range, appropriate reactivity can be obtained, and skin adhesiveness and cohesive force can be further improved.
The content of the polycaprolactone polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).

Examples of the polycarbonate polyol include a polycarbonate polyol obtained by subjecting the above-mentioned polyol component and phosgen to a polycondensation reaction; the above-mentioned polyol component and dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, and the like. Polycarbonate polyol obtained by ester exchange condensation with carbonic acid diesters such as propylene carbonate, diphenyl carbonate, dibenzyl carbonate; copolymerized polycarbonate polyol obtained by using two or more of the above polyol components in combination; containing various polycarbonate polyols and a carboxyl group. Polycarbonate polyol obtained by esterifying a compound; Polycarbonate polyol obtained by etherifying a various polycarbonate polyols and a hydroxyl group-containing compound; Obtaining by an ester exchange reaction between various polycarbonate polyols and an ester compound. Polycarbonate polyol; Polycarbonate polyol obtained by performing an ester exchange reaction between the various polycarbonate polyols and a hydroxyl group-containing compound; Polycarbonate-based polycarbonate polyol obtained by a polycondensation reaction between the various polycarbonate polyols and a dicarboxylic acid compound; Examples thereof include a copolymerized polyether polycarbonate polyol obtained by copolymerizing and alkylene oxide.

The number average molecular weight of the polycarbonate polyol can be used without particular limitation, but the number average molecular weight is preferably 500 to 5,000. By setting the number average molecular weight within the above range, appropriate reactivity can be obtained, and a polyurethane polyol having good cohesive force can be easily obtained.
The polycarbonate polyol is preferably 0 to 75% by mass, more preferably 0 to 65% by mass, based on 100% by mass of the polyol component (a).

The other polyol (a2) is preferably a polyol having a hydroxyl group having 1 to 6 functional groups, and particularly preferably 1 to 4. By using the polyol (a2) within the above range, the crosslink density and the hydroxyl value of the polyurethane polyol can be appropriately controlled, and excellent skin adhesiveness and initial curability can be exhibited.

When the polyol component (a) contains two or more kinds of polyols, the polyol component (a) preferably contains a polyether polyol (a1-1) and another polyol (a2), and more preferably a polyether polyol. It contains (a1-1) and a polyester polyol. In this embodiment, the polyether polyol (a1-1) is preferably 70 to 95% by mass, more preferably 60 to 97% by mass, based on 100% by mass of the polyol component (a). The other polyol (a2) is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the polyol component (a).

As the polyisocyanate component (b), known ones can be used, and examples thereof include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. The polyisocyanate component (b) may be used alone or in combination of two or more.

Examples of the aromatic polyisocyanate include 1,3-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediocyanate, 4,4'-diphenylmethanediisocyanate, 2,4-tolylene diisocyanate, and 2,6-triisocyanate. Range isocyanate, 4,4'-toluidin diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, and 4,4', 4 "-Triphenylmethane triisocyanate, ω, ω'-diisocyanate-1,3-dimethylbenzene, ω, ω'-diisocyanate-1,4-dimethylbenzene, ω, ω'-diisocyanate-1,4-diethylbenzene, 1, , 4-Tetramethylxylylene diisocyanate, 1,3-Tetramethylxylylene diisocyanate, etc., and 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4 because the raw materials are easily available. '-Diphenylmethane diisocyanate is preferred.

Examples of the aliphatic polyisisis include trimethylene diisocyanis, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanis, 2,3-butylenedisisocyanis, 1,3-butylenedisisis, dodecamethylene diisocyanate, and 2 , 4,4-trimethylhexamethylene diisocyanate, and the like, hexamethylene diisocyanate and pentamethylene diisocyanate are preferable because the raw materials are easily available.

Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate, 1,3-cyclopentanediisocyanate, 1,3-cyclohexanediisocyanate, 1,4-cyclohexanediisocyanate, and methyl-2,4. -Cyclohexanediisocyanate, methyl-2,6-cyclohexanediisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane and the like can be mentioned. 3-Isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate and 1,4-cyclohexanediisocyanate are preferable because the raw materials are easily available.

The polyisocyanate exemplified above is a diisocyanate, but a triisocyanate modified from the above diisocyanate can also be used. Examples of the triisocyanate include a trimethylolpropane adduct form, a biuret form, and a trimer of the diisocyanate (the trimer contains an isocyanurate ring) and the like.

The polyisocyanate component (b) includes 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), and 3-isocyanatemethyl-3,5 because of its reactivity with the polyol and the availability of raw materials. , 5-trimethylcyclohexyl isocyanate (isophorone diisocyanate (IPDI)) and the like are particularly preferable.

The polyisocyanate component (b) preferably contains a diisocyanate. The diisocyanate is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, based on 100% by mass of the polyisocyanate component (b).

The amount of the polyisocyanate component (b) used is preferably 0.1 to 25 parts by mass with respect to 100 parts by mass of the polyol component (a). When the content is within the above range, it becomes easy to appropriately control the molecular weight and urethane bond concentration of the polyurethane polyol.

The polymerization method of the polyurethane polyol is not particularly limited, and known polymerization methods such as a bulk polymerization method and a solution polymerization method can be applied. Known catalysts and / or solvents can be used for the polymerization, if necessary. Various methods are possible, but they are roughly classified into the following two methods.
[Method 1] A method in which a polyol component (a), a polyisocyanate component (b), a catalyst, and / or a solvent and the like, if necessary, are collectively charged into a flask and copolymerized.
[Method 2] A method in which a polyol component (a), a catalyst, and / or a solvent or the like, if necessary, are charged in a flask, and the polyisocyanate component (b) is added dropwise thereto for polymerization.
[Method 2] is preferable because the reaction can be easily controlled.

(Polyurethane urea)
The polyurethane urea can be obtained, for example, by subjecting a urethane prepolymer obtained by reacting a component containing a polyol component and a polyisocyanate component with an excess of isocyanate groups to an amine component by a urea reaction. The obtained polyurethane urea has at least one selected from the group consisting of an isocyanate group, an amino group, and a hydroxyl group as a reactive functional group. The polyurethane urea preferably has a hydroxyl group as a reactive functional group. The polyurethane urea is, for example, a urethane prepolymer obtained by reacting a polyol component (a) containing a polyether polyol (a1) with a component containing a polyisocyanate component (b) in an excess of isocyanate groups, and an amine component. And may be a polyurethane urea polyol that has been subjected to a urea reaction. The polyisocyanate component (b) preferably contains at least diisocyanate.

The hydroxyl value of the polyurethane urea is preferably 5.0 mgKOH / g or more from the viewpoint of ensuring the cohesive force of the pressure-sensitive adhesive, and preferably 20.0 mgKOH / g or less from the viewpoint of ensuring the adhesive strength of the pressure-sensitive adhesive. More preferably, it is 7.0 mgKOH / g or more and 15.0 mgKOH / g or less.

The mass average molecular weight of the polyurethane urea is preferably 10,000 or more from the viewpoint of ensuring the cohesive force of the pressure-sensitive adhesive, and more preferably 500,000 or less from the viewpoint of ensuring the adhesive strength of the pressure-sensitive adhesive. Is 30,000 to 300,000, more preferably 45,000 to 300,000, and particularly preferably 55,000 to 200,000.

As the polyol component, a polyether polyol (a1-1) and / or another polyol (a2) can be used. The polyol component can be used alone or in combination of two or more. When using two or more kinds, it is preferable to use polypropylene glycol and / or polyethylene glycol, and polypropylene glycol alone or a combination of polypropylene glycol and polyethylene glycol is more advantageous from the viewpoint of flexibility and cohesive force. preferable. The description of the polyol component (a) in polyurethane can also be applied to polyurethane urea.

As the polyisocyanate component, the above-mentioned polyisocyanate component (b) can be used. Examples of the polyisocyanate component include the above-mentioned aromatic polyisocyanate, aliphatic polyisocyanate, aromatic aliphatic polyisocyanate, alicyclic polyisocyanate, and triisocyanate. The polyisocyanate component may be used alone or in combination of two or more. The description of the polyisocyanate component (b) in polyurethane can also be applied to polyurethane urea.

The amine component is preferably a monoamine, a diamine, a trifunctional or higher amine, more preferably a diamine or a trifunctional or higher amine, further preferably a diamine having a hydroxyl group or a trifunctional or higher amine, and two or more amino groups or 1 Compounds having one or more amino groups and one or more hydroxyl groups are particularly preferred. By using the amine component, the cohesive force can be improved by the urea bond regardless of the molecular weight of the polyurethane urea. In particular, when the polyurethane urea has a primary hydroxyl group, the reaction rate is high, so that the time to complete curing is short, and the productivity is further improved. The amine component may be used alone or in combination of two or more.

Examples of the amine component include ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, triaminopropane, 2,2,4-trimethylhexamethylenediamine and 2-hydroxyethyl. Ethylenediamine, diethanolamine, diisopropanolamine, 1-methylamino-2,3-propanediol, N- (2-hydroxyethyl) propylenediamine, N- (3-hydroxypropyl) ethylenediamine, (2-hydroxyethylpropylene) diamine, Aliper amine compounds such as (di-2-hydroxyethylethylene) diamine, (di-2-hydroxyethylpropylene) diamine, (2-hydroxypropylethylene) diamine, (di-2-hydroxypropylethylene) diamine, piperazine; Alicyclic amine compounds such as isophoronediamine, dicyclohexylmethane-4,4'-diamine; phenylenediamine, xylylenediamine, 2,4-tolylene diamine, 2,6-tolylenediamine, diethyltoluenediamine, 3,3 Aromatic diamines such as'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-bis- (sec-butyl) diphenylmethane; dimerdiamine converted from the carboxyl group of dimer acid to an amino group; and 1 at the end. Examples thereof include dendrimers having a secondary or secondary amino group.

Among these amine components, a compound having two or more secondary amino groups and one primary hydroxyl group is preferable from the viewpoint of controlling the urea reaction. As the compound, a known compound can be used without limitation. To give an example of a method for synthesizing a compound having two or more secondary amino groups and one primary hydroxyl group, a compound having two or more primary amino groups has at least one hydroxyl group and (meth) acryloyl group. A compound obtained by carrying out a Michael addition reaction of the individual compounds is preferable. The hydroxyl group contained in the compound is preferably a primary hydroxyl group. As a result, the time required to complete the curing of the polyurethane urea is short, and the coating speed can be increased, so that the productivity is further improved.

Examples of the compound having two or more primary amino groups include the compounds exemplified as the amine component. Among these, isophoronediamine, 2,2,4-trimethylhexamethylenediamine, and hexamethylenediamine are preferable because the Michael addition reaction can be easily controlled.

Examples of the compound having at least one hydroxyl group and (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate, 3-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate.

Further, for the purpose of adjusting the hydroxyl value, a Michael addition reaction can be carried out with other compounds having a (meth) acryloyl group. Other compounds having a (meth) acryloyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, and 2-ethylhexyl (meth). ) Acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate , Tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, octadecyl (meth) acrylate, nonadecyl (meth) acrylate, icocil (meth) acrylate, henicocil (meth) acrylate, docosyl Examples thereof include alkyl (meth) acrylates having 1 to 22 carbon atoms such as (meth) acrylate. For the purpose of adjusting the polarity, an alkyl group-containing acrylate having an alkyl group having 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, or a corresponding methacrylate can be mentioned.

In the Michael addition reaction between the diamine compound and the compound having a (meth) acryloyl group, 1 mol of the active hydrogen of the amino group in the diamine compound and 1 mol of the ethylenically unsaturated group in the compound having the (meth) acryloyl group were used. Reacts. Since the amino group in the diamine compound easily adds Michael to the ethylenically unsaturated group of the compound having an electron-withdrawing group, a (meth) acrylic compound is preferable as the ethylenically unsaturated compound, and an acrylate-based compound is particularly preferable. The compound is most preferred in terms of the efficiency of the Michael addition reaction.

Regarding the ratio of the compound having a (meth) acryloyl group to be added to the compound having two or more primary amino groups, at least two primary or secondary amino groups remain in the compound having a (meth) acryloyl group. As described above, the ratio is preferably 0.1 to 1.0 mol, more preferably 0.2 to 1.0 mol, with respect to 1 mol of the primary amino group contained in the compound having two or more primary amino groups. It is preferable to react the (meth) acryloyl group in the compound having the (meth) acryloyl group.

The amount of the polyol component (a) used is preferably 40% by mass or more in 100% by mass of the polyurethane urea from the viewpoint of maintaining the cohesive force of the adhesive and imparting durability, and reduces the flexibility of the polyurethane urea. From the viewpoint of preventing and ensuring sufficient adhesive strength, it is preferably 90% by mass or less, and more preferably 50 to 80% by mass. Here, "in 100% by mass of polyurethane urea" means "in 100% by mass of synthetic raw material of polyurethane urea", for example, a polyol component used for synthesis of polyurethane urea, a polyisocyanate component, and used as necessary. It means that the total amount of the amine component to be used and the reaction terminator used as needed is 100% by mass (the same applies in the following description).

The amount of the polyisocyanate component (b) used is preferably 5% by mass or more in 100% by mass of the polyurethane urea from the viewpoint of maintaining the cohesive force of the adhesive and imparting durability, and the flexibility of the polyurethane urea is increased. From the viewpoint of preventing deterioration and ensuring sufficient adhesive strength, it is preferably 50% by mass or less, and more preferably 10 to 30% by mass.

The amount of the amine component used is preferably 0.5% by mass or more in 100% by mass of the polyurethane urea from the viewpoint of maintaining the cohesive force of the adhesive and imparting durability, and reduces the flexibility of the polyurethane urea. From the viewpoint of preventing and ensuring sufficient adhesive strength, it is preferably 20% by mass or less, and more preferably 1 to 10% by mass.

The polymerization method of polyurethane urea is not particularly limited, and known polymerization methods such as a bulk polymerization method and a solution polymerization method can be applied. Known catalysts and / or solvents can be used for the polymerization, if necessary. Various methods are possible, but they are roughly classified into the following two methods.
[Method 1] A method in which all of a polyol component, a polyisocyanate component, and an amine component are charged and copolymerized. (Method of performing urethanization reaction and urea conversion reaction at once)
[Method 2] A urethane prepolymer having at least one isocyanate group is obtained by charging and copolymerizing a polyol component and a polyisocyanate component which are part of the raw materials, and then the obtained urethane prepolymer and an amine component are required. A method of further copolymerizing with a reaction terminator according to the above. (Method of ureaizing the obtained urethane prepolymer after performing a urethanization reaction)
[Method 2] is more preferable when the reaction is precisely controlled.

(Reaction inhibitor)
The urethane-based polymer having a reactive functional group can be obtained, for example, by copolymerizing a polyol component and a polyisocyanate component, or by copolymerizing a polyol component, a polyisocyanate component and an amine component. The obtained copolymer can be further copolymerized with a monoamine compound as a reaction terminator, if necessary. That is, when synthesizing a urethane-based polymer having a reactive functional group, the molecular weight is controlled, and the reaction activity of the polymer is stabilized by reacting with the unreacted isocyanate group at the terminal of the copolymer. A reaction terminator can be used.

Examples of the reaction terminator include dialkylamines such as diethylamine, di-n-butylamine, di-n-octylamine, dicyclohexylamine and diisononnylamine, as well as monoethanolamine, diethanolamine and 2-amino-2-methyl-. Monoamines having a hydroxyl group such as 1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol can be used.

Among the above reaction terminators, monoethanolamine, diethanolamine, 2-amino-2-methyl-1-propanol, tri (hydroxymethyl) aminomethane, 2-amino-2-ethyl-1,3-propanediol, etc. When a monoamine compound having a hydroxyl group as described above is used, a urethane-based polymer having a hydroxyl group at the terminal and having excellent storage stability can be obtained. Further, a urethane-based polymer having a hydroxyl group at the terminal is preferable because it can be used as a reaction point with the isocyanate curing agent described later. In the case of a monoamine having a hydroxyl group, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane-based prepolymer, but the reactivity of the amino group is higher, and the isocyanate group is preferentially used. Reacts with.

When the above reaction terminator is used, the amount used is 0.05% by mass or more from the viewpoint of ensuring the reaction stability of the urethane-based polymer in 100% by mass of the urethane-based polymer having a reactive functional group. It is preferably 5% by mass or less from the viewpoint of appropriately controlling the mass average molecular weight (Mw) of the urethane-based polymer to ensure the durability of the pressure-sensitive adhesive. "In 100% by mass of the urethane-based polymer having a reactive functional group" means "in 100% by mass of the synthetic raw material of the urethane-based polymer having a reactive functional group".

(Polyester with reactive functional group)
The polyether having a reactive functional group may be, for example, a polyether polyol, an ether ester polyol obtained by partially esterifying a polyether polyol, a polyalkylene (for example, ethylene and propylene) oxide diamine having an amino group, and the like. , Polyether polyols are preferred. The reactive functional group-containing polyether may be used alone or in combination of two or more.

The mass average molecular weight of the polyether having a reactive functional group is preferably used in order to secure the cohesive force of the pressure-sensitive adhesive and to prevent the mixture at the time of coating from becoming low in viscosity and deteriorating the coatability. It is 12,000 or more, more preferably 13,000 or more, and further preferably 14,000 or more. The mass average molecular weight of the polyether having a reactive functional group is preferable in order to prevent a decrease in cohesive force and to prevent a mixture at the time of coating from becoming highly viscous and a decrease in coatability. It is 30,000 or less, more preferably 20,000 or less, and even more preferably 18,000 or less.

The polyether polyol has an average number of hydroxyl groups of 2 or more, preferably 3 or more. As the polyether polyol, a polyether polyol other than the above-mentioned polyether polyol (a1-1) and the polyether polyol (a1-1) exemplified as the other polyol (a2) can be used.

Examples of the polyether polyol having an average number of hydroxyl groups of 3 include a polyether polyol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like, starting with one having three active hydrogen groups such as glycerin and trimethylolpropane. ..

A commercially available product may be used as the polyether polyol having an average number of hydroxyl groups of 3. Examples of commercial products are given below.
Preminol S3015: polyether polyol, polymer of propylene oxide (PO) unit starting with glycerin, mass average molecular weight 15,000, average number of functional groups (F) = 3, AGC preminol 3012: polyether polyol, Polymer of propylene oxide (PO) unit using glycerin as an initiator, mass average molecular weight 12,000, average number of functional groups (F) = 3, Preminol S3011: polyether polyol manufactured by AGC, propylene starting from glycerin Polymer of oxide (PO) unit, mass average molecular weight of 10,000, average number of functional groups (F) = 3, Preminol 7012 manufactured by AGC: polyether polyol, ethylene oxide (EO) unit and propylene oxide using glycerin as an initiator (PO) unit copolymer, mass average molecular weight 10,000, average number of functional groups (F) = 3, EO unit content = 10%, manufactured by AGC

[Urethane compound (B)]
The adhesive for skin application contains a urethane compound (B) having a mass average molecular weight of 1,500 to 40,000. The urethane compound (B) may be a compound that can function as an adhesion-imparting agent. When the mass average molecular weight of the urethane compound (B) is 1,500 or more, good adhesion can be obtained. Furthermore, it tends to suppress skin irritation. When the mass average molecular weight of the urethane compound (B) is 40,000 or less, good adhesion and transparency can be obtained. Furthermore, the compatibility with other components tends to be excellent. The mass average molecular weight may be 5,000 or more, or 10,000 or more. The mass average molecular weight may be 30,000 or less, or 20,000 or less. The urethane compound (B) may be used alone or in combination of two or more.

The content of the urethane compound (B) in the pressure-sensitive adhesive for skin application is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A). When the content of the urethane compound (B) is within the above range, good adhesion and transparency can be obtained. The content of the urethane compound (B) may be 0.06 parts by mass or more, 0.1 parts by mass or more, or 0.3 parts by mass or more from the viewpoint of obtaining better adhesion. The content of the urethane compound (B) may be 17 parts by mass or less, 15 parts by mass or less, 12 parts by mass or less, or 10 parts by mass or less from the viewpoint of obtaining better transparency.

The urethane compound (B) is a compound containing at least one urethane bond in the molecule. However, the polymer (A) is excluded from the urethane compound (B). That is, the urethane compound (B) is a compound other than the polymer (A). Examples of the urethane compound (B) include urethane-based oligomers and urethane branched compounds.

The urethane compound (B) preferably contains a structure derived from aromatic isocyanate in the molecule. When the urethane compound (B) contains a structure derived from an aromatic isocyanate, better adhesion can be easily obtained. The aromatic isocyanate preferably contains at least one selected from the group consisting of toluene diisocyanate (TDI), xylylene diisocyanate (XDI), and diphenylmethane diisocyanate (MDI), and more preferably contains toluene diisocyanate (TDI). preferable.

The urethane compound (B) preferably contains a trifunctional or higher functional isocyanate-derived structure in the molecule. When the urethane compound (B) contains a trifunctional or higher functional isocyanate-derived structure, better adhesion and compatibility can be easily obtained. The number of functional groups is, for example, 3 to 6, preferably 3 to 5. Examples of the trifunctional or higher functional isocyanate include the diisocyanate nurate, adduct, and biuret bodies exemplified in the description of the polyisocyanate component (b), the polyisocyanate exemplified by the structural formula below, and the curing agent (C) described later. Examples thereof include "a compound having three or more isocyanate groups in the molecule".

The urethane compound (B) may have an amino group. When the urethane compound (B) has an amino group, the amine value is preferably 0.1 to 60 mgKOH / g. When the amine value is 0.1 mgKOH / g or more, good adhesion tends to be obtained. When the amine value is 60 mgKOH / g or less, it tends to be possible to prevent the compatibility with other components from being lowered. The amine value may be 1 mgKOH / g or more, 5 mgKOH / g or more, or 10 mgKOH / g or more. The amine value may be 30 mgKOH / g or less, 25 mgKOH / g or less, or 20 mgKOH / g or less. The amine value of the urethane compound (B) can be measured by the method described in Examples.

(Urethane-based oligomer)
The urethane-based oligomer can be obtained, for example, by reacting a urethane oligomer obtained by reacting a component containing a polyol component and a polyisocyanate component, or by reacting a component containing a polyol component and a polyisocyanate component with an excess of isocyanate groups. It may be a urethane urea oligomer obtained by reacting a urethane pre-oligomer with an amine component with a urea reaction. The urethane-based oligomer is preferably a urethane oligomer. The urethane-based oligomer may be used alone or in combination of two or more.

The urethane-based oligomer can be obtained by the same method using the components exemplified in the above-mentioned description of the urethane-based polymer. However, the mass average molecular weight of the urethane-based oligomer is preferably 1,500 to 15,000, more preferably 1,500 to 10,000, and even more preferably 1,500 to 5,000. .. Within this range, it tends to be possible to impart excellent adhesiveness to the pressure-sensitive adhesive. The above description of urethane-based polymers can also be applied to urethane-based oligomers, except that the mass average molecular weights are different.

The polyol component preferably contains a polyol component having a functional group number of 2 (that is, a diol component), and examples thereof include a polyether polyol having a functional group number of 2 and a polyester polyol.

The polyisocyanate component preferably contains a polyisocyanate component having two functional groups (that is, a diisocyanate component), and for example, toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate ( HDI), isophorone diisocyanate (IPDI) and the like.

(Urethane branched compound)
The urethane branched compound contains, for example, a structure obtained by reacting a polyisocyanate component containing a trifunctional or higher functional isocyanate with an alcohol component containing a monoalcohol. The urethane branched compound may further contain any structure. The urethane branched compound can be obtained, for example, by reacting a polyisocyanate component containing a trifunctional or higher functional isocyanate with a component containing an alcohol component containing a monoalcohol. The urethane branched compound may be used alone or in combination of two or more.

The trifunctional or higher functional isocyanate is, for example, a nurate form, an adduct form, or a biuret form of diisocyanate, a polyisocyanate exemplified by the structural formula below, and "three or more in a molecule" mentioned in the description of the curing agent (C) described later. It may be a compound having an isocyanate group. A nurate form of diisocyanate can be obtained by a trimerization reaction of diisocyanate. The adduct can be obtained by reacting diisocyanate with a trifunctional or higher functional polyol. The biuret body can be obtained by forming a biuret bond with diisocyanate.

As the diisocyanate, the diisocyanate mentioned as an example of the polyisocyanate component (b) described above can be used. For example, toluene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), pentamethylene diisocyanate (PDI) and the like can be mentioned. The diisocyanate preferably contains an aromatic isocyanate. As the trifunctional or higher polyol used for the reaction with the diisocyanate, the trifunctional or higher polyol mentioned as an example of the above-mentioned low molecular weight polyol can be used.

Further examples of trifunctional or higher functional isocyanates are given below.

Polyisocyanate represented by the formula (1)

In the formula, R independently represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these groups. R may be independently a residue of the above-mentioned isocyanate component (b), and is specifically selected from the compounds exemplified as aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. It may be a residue of diisocyanate. R ¹ represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these groups.
Specific examples of R ¹ include the following trivalent groups.

Polyisocyanate represented by the formula (2)

In the formula, R independently represents a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or a group containing two or more selected from these groups. R may be independently a residue of the above-mentioned isocyanate component (b), and is specifically selected from the compounds exemplified as aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. It may be a residue of diisocyanate.

Polyisocyanate represented by the formula (3)

In the formula, R ¹ to R ⁵ each independently contain a substituted or unsubstituted aromatic hydrocarbon group, an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or two or more selected from these. Represents a group. n is an integer of 0 to 5. R may be independently a residue of the above-mentioned isocyanate component (b), and is specifically selected from the compounds exemplified as aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. It may be a residue of diisocyanate.

Specific examples of R and R ¹ to R ⁵ in the formulas (1) to (3) include the following.

In formula (d), n represents an integer of 5 or 6.

The compounds represented by the formulas (1) to (3) may be, for example, the following compounds.
In the formula (1), R ¹ is a group represented by the above formula (1-1), R is a group represented by the formula (d), and n in the formula (d) is 6. Polyisocyanate ・ In the formula (2), R is a group represented by the formula (d), and n in the formula (d) is 6. In the polyisocyanate formula (3), n is 1 and R. ¹ , R ² and R ⁴ are the groups represented by the formula (c), and R ³ and R ⁵ are the groups represented by the formula (d). In the polyisocyanate formula (3), n is 1. Yes, in the polyisocyanate formula (3) where R ¹ to R ⁵ are the groups represented by the formula (c), n is 2 and R ¹ to R ⁵ are the groups represented by the formula (c). In a certain polyisocyanate formula (3), n is 3, and in the polyisocyanate formula ( ³ ), where ^R1 to R5 are groups represented by the formula (c), n is 0 and ^R1 . , R ⁴ and R ⁵ are the groups represented by the formula (b).

Examples of commercially available products of trifunctional or higher functional isocyanates include the following.
Death Module ultra IL, TDI Nurate, Isocyanate 51%, NCO Content 8.0%, Sumika Cobestro Urethane Death Module N3300 HDI Nurate, Non-volatile Content 100%, NCO Content 21.8%, Sumika Co Bestro Urethane Death Module Z4470 IPDI Nurate, Non-volatile Content 70%, NCO Content 11.9%, Sumika Cobestro Urethane Death Module 44V70L Polymeric MDI, Non-volatile Content 100%, NCO Content 31.3%, Sumi Kacobestro Urethane Takenate D-110N XDI Adduct, Isocyanate 75%, NCO Content 11.5%, Mitsui Chemicals Death Module L75 TDI Adduct, Isocyanate 75%, NCO Content 13.3%, Sumi Made by Kacobestro Urethane

The amount of the trifunctional or higher functional isocyanate used is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, based on 100% by mass of the polyisocyanate component. Within the above range, there is a tendency that good adhesion can be imparted to the pressure-sensitive adhesive.

Examples of the monoalcohol include polyester monoalcohol, polyether monoalcohol, polyacrylic monoalcohol, polybutadiene-modified monoalcohol, polycarbonate monoalcohol, monoalcohol based on castor oil, and aliphatic alcohols having 1 to 20 carbon atoms. Can be mentioned. The monoalcohol preferably contains at least one selected from the group consisting of polyester monoalcohols, polyether monoalcohols, and polyacrylic monoalcohols.

The number average molecular weight of the monoalcohol is preferably 100 to 6,000, more preferably 150 to 5,000. Within the above range, excellent compatibility and substrate adhesion tend to be exhibited.

In the polyester monoalcohol, for example, a monohydric alcohol is used as a starting component, and a compound obtained by ring-opening polymerization of a lactone (ring-opening polymer) is subjected to an esterification reaction between a diol and an acid component in the presence of the monohydric alcohol. It may be a compound (esterified product) or the like. A ring-opening polymer can be preferably used as the polyester monoalcohol.

As the monohydric alcohol, an alcohol having 1 to 20 carbon atoms is preferable, and an alcohol having 3 to 10 carbon atoms is more preferable. For example, propyl alcohol, isopropur alcohol, butyl alcohol, isobutyl alcohol, pentyl alcohol, isopentyl alcohol, hexyl alcohol, isohexyl alcohol, heptyl alcohol, isoheptyl alcohol, octyl alcohol, isooctyl alcohol, nonyl alcohol, isononyl alcohol, Examples include decyl alcohol and isodecyl alcohol.

Examples of the lactone include β-butyrolactone, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, γ-caprolactone, γ-heptanolactone, and α-methyl-β-. Examples thereof include propiolactone.

Examples of the acid component include succinic acid, adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, isophthalic acid, trimellitic acid and the like.

The polyether monoalcohol may be, for example, a monoalkyl ether of a polyalkylene glycol compound. Specifically, polyethylene glycol monomethyl ether, polyethylene glycol monoethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, polyethylene glycol monohexyl ether, polypropylene glycol monomethyl ether, polypropylene glycol monoethyl ether, polypropylene glycol monopropyl ether, Examples thereof include polypropylene glycol monobutyl ether and polypropylene glycol monohexyl ether.

The polyacrylic monoalcohol may be a compound obtained by reacting a poly (meth) acrylic acid alkyl ester with a thiol compound having a hydroxyl group by a thiolene reaction.

Examples of (meth) acrylic acid alkyl esters that can be used in the synthesis of poly (meth) acrylic acid alkyl esters include (meth) acrylic acid methyl, (meth) acrylic acid ethyl, (meth) acrylic acid propyl, and (meth) acrylic acid. It has an alkyl group having 1 to 7 carbon atoms such as isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, and hexyl (meth) acrylate. Examples thereof include (meth) acrylic acid alkyl esters and the above-mentioned (meth) acrylic acid alkyl esters having an alkyl group having 8 to 12 carbon atoms.

Examples of the thiol compound having a hydroxyl group include 2-mercaptoethanol, 2-mercaptohexanol, 6-mercapto-1-hexanol, 3-mercapto-1-propanol, 7-mercapto-1-heptanol and the like.

The amount of monoalcohol used is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 85 to 100% by mass, out of 100% by mass of the alcohol component. Within the above range, there is a tendency that good adhesion can be imparted to the pressure-sensitive adhesive.

As an alcohol component, monoalcohol and a polyol can be used in combination. When used in combination, it is preferable to use a monoalcohol and a diol, and it is more preferable to use a monoalcohol and a polyester polyol. The description of the polyol component (a) in the polyurethane polyol can also be applied to the diol here. When used in combination, the monoalcohol is preferably 50 to 99% by mass, more preferably 70 to 98% by mass, and even more preferably 85 to 97% by mass in 100% by mass of the alcohol component. The polyol is preferably 1 to 50% by mass, more preferably 2 to 30% by mass, still more preferably 3 to 15% by mass, based on 100% by mass of the alcohol component.

A catalyst and / or a solvent can be used for the reaction between the polyisocyanate component containing trifunctional or higher functional isocyanate and the alcohol component containing monoalcohol, if necessary. The catalyst may be a catalyst generally used for synthesizing polyurethane such as, for example, a tertiary amine compound or an organometallic compound. Solvents are commonly used in the synthesis of polyurethanes such as methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone, benzene, dioxane, acetonitrile, tetrahydrofuran, diglyme, dimetholsulfoxide, N-methylpyrrolidone, dimethylformamide and the like. May be. The reaction temperature is, for example, 100 to 180 ° C, preferably 120 to 180 ° C.

The urethane branched compound can be obtained by reacting a polyisocyanate component containing trifunctional or higher functional isocyanate with an alcohol component containing a monoalcohol. The obtained reaction product can be further reacted with an amine component, if necessary, to introduce an amino group into the reaction product. As a result, a urethane branched compound having an amino group can be obtained. The amine component may be, for example, a hydroxyl group-containing dialkylamine compound, a viridyl group-containing amine compound, or the like.

Examples of hydroxyl group-containing dialkylamine compounds are dimethylaminomethanol, dimethylaminoethanol, dimethylaminopropanol, dimethylaminobutanol, diethylaminomethanol, diethylaminoethanol, diethylaminopropanol, diethylaminobutanol, dipropylaminomethanol, dipropylaminoethanol, dipropyl. Examples thereof include aminopropanol, dipropylaminobutanol, dibutylaminoethanol, dibutylaminopropanol, dibutylaminobutanol and the like. Of these, diethylaminoethanol, dimethylaminoethanol, dipropylaminoethanol, and dibutylaminobutanol are preferable.

Examples of viridyl group-containing amine compounds are 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-amino-3-methylpyridine, 2-aminomethylpyridine, 3-aminomethylpyridine, 4-aminomethylpyridine. , 2-Amino-4-methylpyridine, 2-amino-6-methylpyridine, 2-amino-4-ethylpyridine, 2-amino-4-propylpyridine and the like. 2-Aminomethylpyridine, 3-aminomethylpyridine, and 4-aminomethylpyridine are preferred.

The amount of the alcohol component used is preferably 20% by mass or more from the viewpoint of obtaining high transparency, and preferably 90% by mass or less from the viewpoint of obtaining high substrate adhesion in 100% by mass of the urethane branched compound. , More preferably 30 to 80% by mass. Here, "in 100% by mass of the urethane-branched compound" is "in 100% by mass of the synthetic raw material of the urethane-branched compound", and for example, an alcohol component, a polyisocyanate component, and necessary for synthesizing the urethane-branched compound. It means that the total amount of the amine components used accordingly is 100% by mass (the same applies to the following description).

The amount of the polyisocyanate component used is preferably 10% by mass or more from the viewpoint of obtaining high substrate adhesion, and is preferably 70% by mass or less from the viewpoint of obtaining high transparency in 100% by mass of the urethane branched compound. It is preferable, more preferably 20 to 55% by mass.

The amount of the amine component used is preferably 0.1% by mass or more from the viewpoint of obtaining high substrate adhesion, and 20% by mass or less from the viewpoint of obtaining high transparency in 100% by mass of the urethane branched compound. Is preferable, and more preferably 0.5 to 10% by mass.

Commercially available products can be used as the urethane branched compound. Commercially available products include, for example, DISPERBYK-110, DISPERBYK-111, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-167, DISPERBYK-170, DISPERBYK-170. DISPERBYK-174, DISPERBYK-182, DISPERBYK-183, DISPERBYK-184, DISPERBYK-185, DISPERBYK-2155, DISPERBYK-2163, DISPERBYK-2164 (all manufactured by Big Chemie (BYK));
Solspers 76500 (manufactured by Lubrizol Co., Ltd.); Azisper PB711 (manufactured by Ajinomoto Co., Inc.); EFKA-46, 47, 48, EFKA PU 4046, 4047 (manufactured by BASF); Borchi Gen 0451, 0755, 1051 (The above is manufactured by Borchers) and the like.

[Curing agent (C)]
The adhesive for skin application uses a curing agent to carry out a cross-linking reaction of the reactive functional group of the polymer (A). As the curing agent, for example, an isocyanate compound, an epoxy compound, a metal chelate compound, an amine compound, an aziridine compound and the like are preferable. Among these, an appropriate crosslink density can be easily obtained by using an isocyanate compound or a metal chelate. The curing agent may be used alone or in combination of two or more.

Examples of the isocyanate compound include tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate. , And an adduct of a diisocyanate such as polymethylene polyphenyl isocyanate and a polyol compound such as trimethylolpropane; its burette body; its isocyanurate body; and the diisocyanate and a polyether polyol, a polyester polyol, an acrylic polyol, a polybutadiene polyol. , And a compound having three or more isocyanate groups in the molecule such as an adduct with any of the polyols such as polyisoprene polyols; tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xyl Two diisocyanates such as range isocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, tetramethylxylylene diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, and polymethylenepolyphenyl isocyanate, and hexamethylene diisocyanate allophanate. Examples thereof include compounds having an isocyanate group of. Among these, the trimethylolpropane adduct body of tolylene diisocyanate and the trimethylolpropane adduct body of xylylene diisocyanate are preferable because the adhesive physical properties can be easily adjusted. In this specification, the number of isocyanate groups is an average number.

The content of the isocyanate compound is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymer (A). If it contains 0.05 to 10 parts by mass, both cohesive force and adhesive force can be highly compatible.

Examples of the epoxy compound include bisphenol A-epichlorohydrin type epoxy resin, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, trimethylolpropane triglycidyl ether, diglycidyl aniline, N, N, N', N'-tetraglycidyl-m-xylylene diamine, 1,3-bis (N, N'-diglycidylaminomethyl) cyclohexane, And N, N, N', N'-tetraglycidylaminophenylmethane and the like.

The content of the epoxy compound is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). If it contains 0.01 to 1 part by mass, both cohesive force and adhesive force can be highly compatible.

Examples of the metal chelate include a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium and zirconium, and a coordination compound of acetylacetone or ethyl acetoacetate. Be done.

The content of the metal chelate is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymer (A). If it contains 0.1 to 5 parts by mass, both cohesive force and adhesive force can be highly compatible.

Examples of the amine compound include hexamethylenediamine, triethyldiamine, polyethyleneimine, hexamethylenetetramine, diethylenetriamine, triethyltetramine, isophoronediamine, amino resin, methylene resin and the like.

The content of the amine compound is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). If it contains 0.01 to 1 part by mass, both cohesive force and adhesive force can be highly compatible.

Examples of the aziridine compound include N, N'-diphenylmethane-4,4'-bis (1-aziridinecarbokisite), N, N'-toluene-2,4-bis (1-aziridinecarbokisite), and bisiso. Phthalloyl-1- (2-methylaziridine), tri-1-aziridinylphosphine oxide, N, N'-hexamethylene-1,6-bis (1-aziridinecarbokisite), 2,2'-bishydroxy Methylbutanol-tris [3- (1-aziridinyl) propionate], trimethylpropantri-β-aziridinylpropionate, tetramethylolmethanetri-β-aziridinylpropionate, and tris-2,4 6- (1-aziridinyl) -1,3,5-triazine and the like can be mentioned. Of these, 2,2'-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] is preferable because of its high reactivity.

The blending amount of the aziridine curing agent is preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer (A). If it contains 0.01 to 1 part by mass, both cohesive force and adhesive force can be highly compatible.

[Any ingredient]
The adhesive for skin application may contain any component as long as the problem can be solved. Any component may be, for example, from the viewpoints of plasticizer, reduction of polymerization curing shrinkage rate, improvement of dimensional stability, improvement of elastic modulus, suppression of oxidation reduction, viscosity adjustment, improvement of thermal conductivity, improvement of strength, improvement of toughness, improvement of coloring and the like. , Organic or inorganic additives and fillers. The filler is appropriately composed of polymers, ceramics, metals, metal oxides, metal salts, dyes and pigments. The shape of the filler is preferably, for example, particulate or fibrous. Additives include antioxidants, flame retardants, storage stabilizers, UV absorbers, thixotropy-imparting agents, dispersion stabilizers, fluidity-imparting agents, thickeners, moisturizers, transdermal absorbers, and pH adjustments. Examples thereof include agents, leveling agents, hydrolysis inhibitors, antifoaming agents and the like.

Any one or more plasticizers can be used for the purpose of making the polymer (A) more flexible, reducing pain at the time of peeling the adhesive tape, and improving the keratin peeling property. The plasticizer to be used is not particularly limited, and examples thereof include a fatty acid ester-based plasticizer, a polyether ester-based plasticizer, a hydroxycarboxylic acid ester-based plasticizer, and a phosphoric acid ester-based plasticizer. The plasticizer is preferably a fatty acid ester-based plasticizer from the viewpoint of skin irritation and compatibility with the polymer (A).

As the fatty acid ester-based plasticizer, esters of phthalic acid, maleic acid, adipic acid, stearic acid, various fatty acids and alkyl alcohols, and esters of polyhydric alcohols such as ethylene glycol and glycerin can be used. More specifically, as the ester of the monohydric alcohol, dibutylphthalate, di2-ethylhexylphthalate, dibutyladipate, di2-ethylhexylsevacate, dibutylmaleate, ethyl myristate, isopropyl myristate, isopropyl palmitate, stearer To butyl acid, isopropyl isostearate, hexyl laurate, cetyl lactate, myristyl lactate, diethyl phthalate, bis phthalate (2-ethylhexyl), octyldodecyl myristate, octyldodecyl oleate, hexyldecyl dimethyloctanoate, 2-ethyl Examples thereof include cetyl oxalate, isocetyl 2-ethylhexanoate, stearyl 2-ethylhexanoate, and dioctyl succinate. Examples of the ester of the divalent or higher alcohol include propylene glycol dicaprylate, propylene glycol dicaprate, propylene glycol diisostearate, glyceryl monocaprylate, glyceryl tricaprylate, glyceryl tri-2-ethylhexanoate, glyceryl tricaprate, and trilaurin. Examples thereof include glyceryl acid, glyceryl triisostearate, glyceryl trioleate, and trimethylolpropane tri-2-ethylhexanoate.

Examples of the polyether ester-based plasticizer include polyethylene glycol dihexylate, polyethylene glycol di-2-ethylhexylate, polyethylene glycol dilaurylate, polyethylene glycol dioleate, and dipolyethylene glycol adipolyamethyl ether.

Examples of the hydroxycarboxylic acid ester-based plasticizer include butyl citrate, triethyl citrate, tripropyl citrate, and triethyl o-acetylcitrate.

Examples of the phosphoric acid ester-based plasticizer include tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate and the like.

Further, the plasticizer may be a compound containing a fatty acid ester structure and a polyether structure, such as polyoxyethylene ether of sorbitan fatty acid ester obtained by condensing ethylene oxide with sorbitan fatty acid ester. For example, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monooleate and the like can be mentioned.

The content of the plasticizer is not particularly limited, but is preferably 10 to 80 parts by mass, more preferably 15 to 50 parts by mass with respect to 100 parts by mass of the polymer (A). When the content of the plasticizer) is within this range, it is possible to further improve the exfoliation property of the keratin while ensuring the cohesive force to the extent that no adhesive residue is left, which is preferable. Further, since the adhesive strength can be significantly reduced, the adhesive tape using the adhesive can be suitably used for medical applications in which the tape is directly attached to the wound.

[Manufacturing method of adhesive for skin application]
As the adhesive for skin application, a polymer (A), a urethane compound (B), and a curing agent (C) are prepared; the polymer (A), the urethane compound (B), and the curing agent (C) are mixed. It can be manufactured by a manufacturing method including. By using the polymer (A) and the urethane compound (B) that can function as a tackifier in the production of a pressure-sensitive adhesive for skin application, a pressure-sensitive adhesive having excellent adhesion and transparency can be obtained. ..

<Curing product>
The cured product according to the embodiment of the present invention is obtained by curing the pressure-sensitive adhesive for skin application according to the embodiment. In the cured product, cross-linking is formed between the molecules of the polymer (A) by the cross-linking reaction with the curing agent (C). Curing of the skin-applying pressure-sensitive adhesive can be promoted, for example, by heating the skin-sticking pressure-sensitive adhesive.

The gel fraction of the cured product is preferably 20 to 63%. When the gel fraction is 20% or more, the cohesive force is high and the cohesive fracture at the time of peeling is suppressed, so that the re-peelability is good. Therefore, it is easy to obtain an adhesive having excellent initial peeling. When the gel fraction is 63% or less, sufficient cohesive force can be obtained, but sufficient adhesiveness tends to be easily obtained. In addition, since the cohesive force does not become too high, the followability to the skin is improved, and the amount of exfoliation of the keratin tends to be suppressed. The gel fraction may be 30% or more, or 35% or more. The gel fraction may be 55% or less, or 45% or less. The gel fraction of the cured product can be measured by the method described in Examples. The gel fraction can be adjusted by changing the contents of the polymer (A), the urethane compound (B), and the curing agent (C).

The cured product preferably has a permanent adhesive strength against SUS of 0.3 N / 25 mm or more in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%. When the permanent adhesive force against SUS of the cured product is 0.3 N / 25 mm or more, an adhesive layer having good adhesive force can be easily obtained. The permanent adhesive force against SUS may be 0.5 N / 25 mm or more, 1.0 N / 25 mm or more, or 2.0 N / 25 mm or more. The upper limit is not particularly limited, but the permanent adhesive strength against SUS is, for example, 30 N / 25 mm or less. Permanent adhesive strength to SUS can be measured by the method described in Examples.

<Adhesive tape for skin application>
The adhesive tape for skin application according to the embodiment of the present invention has a base material and an adhesive layer containing the cured product of the embodiment. The skin-adhesive tape can be manufactured, for example, by (1) applying a skin-adhesive adhesive on a release liner and drying it to form an adhesive layer, and then adhering a base material, or (2) a base material. A method of forming an adhesive layer by applying an adhesive for skin application on the surface and drying it, and attaching a peelable sheet to the adhesive layer is preferable.

The thickness of the adhesive layer is usually about 10 to 200 μm, preferably 25 μm to 100 μm.

The coating method is not particularly limited. Examples thereof include a Meyer bar, an applicator, a brush, a spray, a roller, a bar coater, a gravure coater, a die coater, a kiss coater, a lip coater, a comma coater, a blade coater, a knife coater, a reverse coater, a spin coater, a dip coater and the like. In addition, when coating, it is usually dried. The drying method is not particularly limited, and for example, hot air drying, infrared rays, decompression method and the like can be used. The drying temperature is usually preferably about 60 to 180 ° C, more preferably about 80 to 150 ° C.

As the base material, for example, non-woven fabric; wood material, processed paper product; woven fabric, non-woven fabric, or knitted fabric using rayon, polyurethane yarn, cotton, wool, polyolefin yarn, polyester yarn, etc .; plastic foam film having open cells. , Plastic film having pores formed by punching or the like, cellulose, cellulose acetate or the like. Further, the moisture permeable base material may be a single layer or a laminated body in which two or more layers of base materials are laminated. The base material is preferably a polyurethane-based film, a polyurethane-based non-woven fabric, or a polyester-based non-woven fabric from the viewpoint of obtaining high transparency.

The thickness of the base material is usually about 5 μm to 1,000 μm, preferably 15 μm to 500 μm.

In the release liner, for example, a release treatment layer such as a silicone treatment is formed on the surface of a base material such as paper or a plastic film. The base material may be a single layer or a laminated body in which two or more layers of base materials are laminated.

The adhesive tape for skin application can be used, for example, as a tape or bandage for covering a wound, a tape for fixing a medical device to the skin, an adhesive plaster, a dressing tape, a supporter, or the like. Further, when the adhesive layer contains a drug, a drug that can be stably dispersed is mixed with the medical adhesive and used as a sustained release sheet.

The embodiments of the present invention will be specifically described with reference to Examples. The embodiments of the present invention are not limited to the following examples.

In the following description, unless otherwise specified, "parts" means parts by mass, "%" means mass%, and "RH" means relative humidity. Unless otherwise specified, the unit of compounding amount in the table is "part by mass". Unless otherwise specified, the blending amount of the components other than the solvent described in the table is the amount of the non-volatile component.

<Synthesis of polymer (A)>
<Polymer (A-1): Carboxyl group-containing acrylic polymer>
In a reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a dropping device, and a nitrogen introduction tube (hereinafter, may be simply referred to as a “reaction vessel”), 95.0 parts of 2-ethylhexyl acrylate, acrylic. After adding 5.0 parts of acid, 70 parts of ethyl acetate, and 0.05 part of azobisisobutyronitrile (AIBN), the air in the reaction vessel was replaced with nitrogen gas. The mixture in the reaction vessel was then heated to 80 ° C. with stirring under a nitrogen atmosphere to initiate the reaction. Further, a mixture having the same composition and the same amount as the mixture in the reaction vessel (95.0 parts of 2-ethylhexyl acrylate, 5.0 parts of acrylic acid, 70 parts of ethyl acetate, 0.05 part of AIBN) is added to the dropping funnel. The mixture was added dropwise to the reaction vessel over 1 hour, and the polymerization reaction was carried out under a nitrogen atmosphere at a reflux temperature for 7 hours. After completion of the reaction, the mixture was cooled, and ethyl acetate was added to the polymerization reaction product to dilute it to obtain an acrylic copolymer solution having a non-volatile content of 40%. Moreover, when the mass average molecular weight (Mw) of the acrylic copolymer was measured using GPC, it was 630,000.

<Polymer (A-2): Acrylic polymer containing hydroxyl group>
After adding 97.0 parts of 2-ethylhexyl acrylate, 3.0 parts of 2-hydroxyethyl acrylate, 70 parts of ethyl acetate, and 0.05 part of azobisisobutyronitrile (AIBN) to the reaction vessel, the reaction was carried out. The air in the container was replaced with nitrogen gas. The mixture in the reaction vessel was then heated to 80 ° C. with stirring under a nitrogen atmosphere to initiate the reaction. Further, in the dropping funnel, the mixture having the same composition and the same amount as the mixture in the reaction vessel (97.0 parts of 2-ethylhexyl acrylate, 3.0 parts of 2-hydroxyethyl acrylate, 70 parts of ethyl acetate, AIBN 0.05) was added. Part) was added, and the mixture was added dropwise to the reaction vessel over 1 hour, and the polymerization reaction was carried out under a nitrogen atmosphere at a reflux temperature for 7 hours. After completion of the reaction, the mixture was cooled, and ethyl acetate was added to the polymerization reaction product to dilute it to obtain an acrylic copolymer solution having a non-volatile content of 40%. Moreover, when the mass average molecular weight (Mw) of the acrylic copolymer was measured using GPC, it was 580,000.

<Polymer (A-3): Polyurethane urea>
(Synthesis of diamine compound (a))
19.25 parts of isophorone diamine (IPDA) in a 4-necked flask (hereinafter, may be simply referred to as "4-necked flask") equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping funnel. , And 19.25 parts of toluene were added. A mixture of 16.25 parts of 4-hydroxybutyl acrylate and 14.5 parts of butyl acrylate was dropped from the dropping funnel into a 4-necked flask at room temperature. After completion of the dropping, the temperature of the mixture in the 4-necked flask was gradually raised to 80 ° C., and the mixture was reacted for 2 hours while maintaining 80 ° C., then 30.75 parts of toluene was added, and two secondary amino groups were added. And a solution of the diamine compound (a) having one primary hydroxyl group was obtained.

(Polymer (A-3): Synthesis of polyurethane urea)
Sannicks PP-2000 (polyoxypropylene glycol, Mn2,000, number of hydroxyl groups 2, manufactured by Sanyo Kasei Kogyo Co., Ltd.) 78.9 parts, isophorone diisocyanate 13.2 parts, toluene 23.6 parts, and catalyst in a 4-port flask. As a result, 0.01 part of dioctyltin dilaurate was added, and the obtained mixture was gradually heated to 100 ° C. and reacted for 2 hours. The mixture was cooled to 40 ° C., 76.4 parts of ethyl acetate and 0.3 parts of acetylacetone were added, and then 7.8 parts of the diamine compound (a) was added dropwise to the 4-necked flask over 2 hours. Then, the temperature was maintained at 40 ° C. and the reaction was continued for another 1 hour. After confirming the remaining amount of isocyanate group by titration, 0.2 part of 2-amino-2-methyl-propanol (AMP) was added, and the characteristic absorption of NCO group (2,270 cm ^-1 ) on the IR chart disappeared. After confirming that it was present, the reaction was terminated. The obtained polyurethane urea (A-3) had a mass average molecular weight (Mw) of 11,7000 and a hydroxyl value of 11.1 mgKOH / g.

<Polymer (A-4): Polyurethane>
In a 4-port flask, 84.0 parts of Adecapolyether AM-302 (terminal EO-modified polyether polyol, Mn 3,000, number of hydroxyl groups 3, manufactured by ADEKA), Claret polyol P-1010 (polyester polyol, Mn1,000, hydroxyl group) Number 2, 15 parts manufactured by Claret Co., Ltd.), 1 part of ethylene glycol, 70 parts of ethyl acetate, and 0.020 parts of dioctyltin dilaurate as a catalyst were added and mixed. Then, the mixture was gradually heated to 80 ° C. 8.8 parts of hexamethylene diisocyanate (manufactured by Sumika Covestro Urethane Co., Ltd.) and 24.5 parts of ethyl acetate were added to the dropping funnel and mixed, and the obtained mixture was dropped into a 4-necked flask over 1 hour. .. After the completion of the dropping, the reaction was carried out for 1 hour. It was confirmed that the characteristic absorption of the NCO group (2,270 cm ^-1 ) on the IR chart had disappeared, and the reaction was terminated. The obtained polyurethane (polymer A-4) had a mass average molecular weight (Mw) of 81,000 and a hydroxyl value of 25.1 mgKOH / g.

<Polymer (A-5): Polyether polyol>
As the polymer (A-5), Preminol S3015 (polymer of propylene oxide (PO) unit using glycerin as an initiator, Mw 15,000, average number of functional groups 3, manufactured by AGC) was used.

<Synthesis of urethane compound (B)>
<Urethane oligomer (B-1)>
To a 4-port flask, 100 parts of Kuraray polyol P-510 (polyester polyol, Mn500, number of hydroxyl groups 2, manufactured by Kuraray Co., Ltd.), 70 parts of ethyl acetate, and 0.020 parts of dioctyltin dilaurate as a catalyst were added and mixed. Then, the mixture was gradually heated to 78 ° C. 23.2 parts of toluene diisocyanate (TDI) and 53.2 parts of ethyl acetate were added to the dropping funnel and mixed, and the obtained mixture was dropped into a 4-necked flask over 1 hour. After the completion of the dropping, the reaction was carried out for 1 hour. It was confirmed that the characteristic absorption of the NCO group (2,270 cm ^-1 ) on the IR chart had disappeared, and the reaction was terminated. The mass average molecular weight (Mw) of the obtained urethane oligomer (B-1) was 3,900.

<Urethane oligomers (B-2), (B-3), and (B2-1)>
Urethane oligomers (B-2), (B-3), and (B2-1) were prepared in the same manner as in Production Example (B-1) except that the isocyanates and polyols were selected in the types and amounts shown in Table 1. Obtained. The mass average molecular weights (Mw) of the urethane oligomers (B-2), (B-3), and (B2-1) are shown in Table 1.

The abbreviations shown in Table 1 are as follows.
TDI: Toluene diisocyanate P-510: "Kurare polyol P-510", Mn500, number of hydroxyl groups 2, polyester polyol, Kurare PP200: "Sannicks PP-200", polyoxypropylene glycol, Mn200, number of hydroxyl groups 2, Sanyo Kasei Kogyo Co., Ltd. PP1000: "Sannicks PP-1000", polyoxypropylene glycol, Mn1000, number of hydroxyl groups 2, manufactured by Sanyo Kasei Kogyo Co., Ltd.

<Synthesis of urethane branched compounds (B-4) to (B-17) and (B2-2)>
(Synthesis of hydroxyl group-containing polycaprolactone b)
18.8 parts of 1-decanol, 100 parts of caprolactone, and 0.003 parts of dibutyltin dilaurate were homogenized under a nitrogen atmosphere and heated at 160 ° C. for 12 hours. Polycaprolactone b (number average molecular weight 1,000) containing a single-ended hydroxyl group, which is a colorless solid at room temperature, was obtained.

(Synthesis of hydroxyl group-containing polycaprolactone c)
8.6 parts of 1-decanol, 100 parts of caprolactone, and 0.003 parts of dibutyltin dilaurate were homogenized under a nitrogen atmosphere and heated at 160 ° C. for 12 hours. Polycaprolactone c (number average molecular weight 2,000) containing a single-ended hydroxyl group, which is a colorless solid at room temperature, was obtained.

(Synthesis of Polyester d Containing Hydroxy Group)
38 parts of adipic acid, 52.7 parts of dodecanediol, 9.3 parts of octanol, 0.01 part of p-toluenesulfonic acid, and 30 parts of toluene were homogenized and heated. The generated water was azeotropically distilled off within 5 to 6 hours. The temperature reached 140-150 ° C. The solvent was then carefully distilled under vacuum. Polyester d (number average molecular weight 1,400), which is a colorless solid at room temperature, was obtained.

(Synthesis of hydroxyl group-containing acrylic polymer e)
To the reaction vessel, 120 parts of butyl acrylate, 13 parts of 6-mercapto-1-hexanol, and 133 parts of methoxypropyl acetate were added, and the air in the reaction vessel was replaced with nitrogen gas. The inside of the reaction vessel was heated to 90 ° C., 0.50 part of AIBN was added, and then the mixture in the reaction vessel was reacted for 7 hours. After confirming that 95% or more of the monomers have reacted by measuring the non-volatile content, cool to room temperature and 50% of the non-volatile content of the vinyl polymer e (number average molecular weight 2,000) having one hydroxyl group in one terminal region. A solution was obtained.

<Urethane branch compound (B-4)>
In a 4-port flask, 100 parts of Death Module IL (51% in butyl acetate) as the first component (polyisocyanate component) and 244.8 caprolactone polyester b having an average molecular weight of 1,000 as the second component (alcohol component). And 300 parts of ethyl acetate cellosolve / xylene (1: 2) were added and mixed under a nitrogen atmosphere. Then, 0.02 part of dibutyltin dilaurate was added as a catalyst, and then an addition reaction was carried out at room temperature. After confirming that the OH group had disappeared, a mixture of 11.4 parts of dimethylaminoethanol and 110 parts of xylene as a third component (amine component) was added dropwise into the 4-necked flask. The mixture in the 4-necked flask was heated to 50 ° C. and stirred for 1 hour to obtain a slightly yellow urethane oligomer (B-4). The obtained urethane oligomer (B-4) had a mass average molecular weight (Mw) of 23,000 and an amine value of 20.1 mgKOH / g.

<Urethane branched compounds (B-5) to (B-17) and (B2-2)>
The urethane branched compounds (B-5) to (B) are operated in the same manner as the urethane branched compound (B-4) except that the first component, the second component and the third component are selected in the types and amounts shown in Table 2. -17) and (B2-2) were obtained. Table 2 shows the mass average molecular weight (Mw) and amine value of the urethane branched compounds (B-5) to (B-17) and (B2-2).

The components listed in Table 2 are as follows.
Death Module IL: Death Module ultra IL, TDI Nurate, Non-volatile Content 51%, NCO Content 8.0%, Sumika Cobestro Urethane Death Module N3300: HDI Nurate, Non-volatile Content 100%, NCO Content 21.8 %, Sumika Cobestro Urethane Death Module Z4470: IPDI Nurate, Non-volatile Content 70%, NCO Content 11.9%, Sumika Cobestro Urethane Death Module 44V70L: Polymeric MDI, Non-volatile Content 100%, NCO Containing Amount 31.3%, Sumika Cobestro Urethane Takenate D-110N: XDI Adduct, Non-volatile content 75%, NCO content 11.5%, Mitsui Chemicals Co., Ltd. Death Module L75: TDI Adduct, Non-volatile content 75%, NCO content 13.3%, Sumika Cobestro Urethane MPEG750: methoxypolyethylene glycol, Mn750, number of hydroxyl groups 1, Evermore Japan P-1010: Claret polyol P-1010, Mn1000, number of hydroxyl groups 2, polyester polyol , Made by Clare

<Measurement of mass average molecular weight (Mw) and number average molecular weight (Mn)>
The mass average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method. The measuring device and measuring conditions were basically based on the following measurement condition 1. However, depending on the polymer species, an appropriate carrier (eluent) and a column suitable for the carrier may be selected and used as appropriate. For other matters, refer to JISK7252-1 to 4: 2008. The measuring device and the measuring conditions for measuring the compound having an amino group are basically according to the following measuring condition 2. Both Mw and Mn are polystyrene-equivalent values.

[Measurement condition 1]
Equipment: SHIMADZU Prominence (manufactured by Shimadzu Corporation)
Column: SHODEX LF-804 (manufactured by Showa Denko KK) connected in series Detector: Differential refractive index detector Solvent: Tetrahydrofuran (THF)
Flow velocity: 0.5 mL / min Solvent temperature: 40 ° C
Sample concentration: 0.1% by mass
Sample injection amount: 100 μL

[Measurement condition 2]
Equipment: SHIMADZU Prominence (manufactured by Shimadzu Corporation)
Column: TOSOHTSKgelSuperAW4000, TOSOHTSKgelSuperAW3000, TOSOHTSKgelSuperAW2500 (manufactured by Tosoh Corporation) connected in series Detector: Differential refractometer Detector Solvent: N, N-dimethylformamide (1L), triethylamine (3.04g), LiBr Mixture flow rate: 0.5 mL / min Solvent temperature: 40 ° C
Sample concentration: 0.2% by mass
Sample injection amount: 100 μL

<Measurement of non-volatile content>
About 1 g of the sample was heat-dried at 120 ° C. for 20 minutes, and then determined from the mass change after drying with respect to before drying.

<Measurement of hydroxyl value (OHV)>
1 g of the sample was precisely weighed in an Erlenmeyer flask with a stopper, and 100 mL of pyridine was added to dissolve the sample. Further, exactly 5 mL of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 mL) was added, and the mixture was stirred for 1 hour and then titrated with a 0.5 N-alcoholic potassium hydroxide solution. The hydroxyl value (unit: mgKOH / g) was calculated by the following formula. The hydroxyl value was the value of the dried sample.
Hydroxy group value = [{(ba) × F × 28.05} / S] / (nonvolatile content concentration / 100) + D
S: Sample collection amount (g)
a: Consumption (mL) of 0.5N-alcoholic potassium hydroxide solution
b: Consumption (mL) of 0.5N-alcoholic potassium hydroxide solution in the blank experiment
F: Factor D of 0.5N-alcoholic potassium hydroxide solution: Acid value (mgKOH / g)

<Measurement of amine value>
Approximately 1 g of the sample was precisely weighed in an Erlenmeyer flask with a stopper, and 100 mL of cyclohexanone solvent was added to dissolve the sample. To this, add a few drops of an indicator prepared by separately mixing 0.20 g of Methyl Orange in 50 mL of distilled water and 0.28 g of Xylene Cyanol FF in 50 mL of methanol, and adding 30 drops. Held for seconds. Then, it was titrated with a 0.1N alcoholic hydrochloric acid solution until the solution became blue-gray. The amine value was calculated by the following formula (unit: mgKOH / g).
Amine value (mgKOH / g) = (5.611 × a × F) / S
S: Sample collection amount (g)
a: Consumption of 0.1N alcoholic hydrochloric acid solution (mL)
F: Titer of 0.1N alcoholic hydrochloric acid solution

<Example 1>
100 parts of polymer (A-1), 0.5 part of urethane branched compound (B-4), 0.6 part of aluminum chelate A as curing agent (C), 20 parts of ethyl acetate as solvent, and disperser. The mixture was stirred with a stirrer to obtain a uniform adhesive for skin application. A polyester separator (Super Stick SP-PET38, manufactured by Lintec Corporation) with a thickness of 38 μm is coated so that the thickness of the adhesive layer after drying is 30 μm, and the adhesive layer is dried at 100 ° C. for 2 minutes to form the adhesive layer. Formed.
Next, a total of three types of laminates obtained by laminating this adhesive layer with the following base material B, the following base material C, or a polyester film (thickness 25 μm) using a rubber roll were prepared, and the temperature was 23 ° C. to 50%. After curing with RH for 1 week, an adhesive tape for skin application with a separator was obtained.

<Examples 2-29, Comparative Examples 1-10>
In each of Examples 2 to 29 and Comparative Examples 1 to 10, the composition except that the composition of the pressure-sensitive adhesive, the amount (parts by mass), and the base material for adhesion evaluation were changed as shown in Table 3 was carried out. In the same manner as in Example 1, a skin-adhesive adhesive and a skin-adhesive tape using the same were produced.

The curing agents (C) shown in Table 3 are as follows.
C-1: Aluminum chelate A (manufactured by Kawaken Fine Chemical Co., Ltd.)
C-2: HDI adduct body (hexamethylene diisocyanate adduct body, isocyanato radix = 3, NCO value = 12.6%, non-volatile content = 75.0%)
C-3: TDI-TMP adduct (trimethylolpropane adduct of tolylene diisocyanate, isocyanato radix = 3, NCO value = 6.5%, non-volatile content = 37.5%)

The base materials A to C are as follows.
Base material A: Polyester urethane film (Silklon NES85, thickness 25 μm, manufactured by Okura Industrial Co., Ltd.)
Base material B: Urethane-based non-woven fabric (Espancione, UHO-100, thickness 0.37 mm, made by KB Seiren)
Base material C: Polyester-based non-woven fabric (Sontara # 8010, manufactured by DuPont, basis weight: 45 g / m ² )

[Physical characteristics of adhesives, cured products and adhesive tapes, evaluation items, and evaluation methods]
The adhesives, cured products, and adhesive tapes obtained in Examples and Comparative Examples were evaluated for gel fraction, permanent adhesive strength against SUS, skin adhesion, substrate adhesion, and transparency according to the methods described below. .. Unless otherwise specified, the test piece was produced by cutting an adhesive tape so that the flow direction of the original winding was the long side (MD direction).

<Gel fraction>
The gel fraction was measured by the following procedure.
(1) Prepare an adhesive tape whose base material is a PET film according to the procedure described in Examples.
(2) Prepare a wire mesh and weigh it. Let this weight be W1.
(3) Peel off the separator, attach adhesive tape to the wire mesh, and weigh the entire weight. Let this weight be W2.
(4) Immerse in ethyl acetate, seal tightly, and leave in an atmosphere of 50 ° C. for 24 hours.
(5) Take out, dry in an atmosphere of 100 ° C. for 20 minutes, and then weigh. Let this weight be W3.
(6) The wire mesh is removed, the adhesive layer is further removed from the PET film, and the weight of the PET film is weighed. Let this weight be W4.
(7) Calculate the gel fraction by the following formula.
Gel fraction (%) = (W3-W1-W4) / (W2-W1-W4) x 100

<Permanent adhesive strength against SUS>
An adhesive tape whose base material is a polyester film was cut into a size of 25 mm in width and 100 mm in length and used as a sample. Then, in a 23 ° C.-50% RH atmosphere, the separator was peeled off from the sample in accordance with JIS Z 0237, the exposed adhesive layer was attached to a polished stainless steel (SUS) plate, and then pressure-bonded once with a 2 kg roll. The adhesive strength (N / 25 mm) was measured 24 hours after the application using a tensile tester under the conditions of a peeling speed of 300 mm / min and a peeling angle of 180 °.

<Transparency>
The adhesive tape for skin application, whose base material was a polyester film, was visually observed for transparency and evaluated according to the following criteria.
[Evaluation criteria]
◯: Transparent, good.
△: Slightly cloudy, practically possible.
×: Cloudy, not practical.

<Adhesion to skin, adhesion to substrate>
The inside of the forearms of a total of 10 adult males and females was lightly wiped with ethanol under an atmosphere of 23 ° C.-50% RH, air-dried for 10 minutes, and a 12 mm wide test piece having a substrate A, B or C was attached thereto. Thirty-six hours after application, it was observed whether or not the adhesive layer adhered to the skin and the adhesive layer was peeled off from the substrate after peeling (transfer of the adhesive layer to the skin), and evaluated according to the following criteria.

<Adhesion to skin>
Adhesiveness to the skin; The adhesion state of the adhesive tape 36 hours after application was evaluated according to the following criteria.
[Evaluation criteria]
◯: 8 to 10 people adhered well to the entire surface of the test piece, which was good.
Δ: 3 to 7 people adhered well to the entire surface of the test piece, which is practical.
×: 0 to 2 people adhered well to the entire surface of the test piece, which is not practical.

<Substrate adhesion>
Adhesion to the substrate; The peeling of the adhesive layer from the substrate at the time of peeling the test piece was evaluated according to the following criteria.
[Evaluation criteria]
◯: There was no peeling in 9 to 10 people, which was good.
Δ: 4 to 8 people did not peel off, practically possible.
×: 0 to 3 people did not peel off, not practical.

Claims (10)

Polymer (A) having a reactive functional group and a mass average molecular weight of 1,500 to 40,000.
It contains the urethane compound (B) and the curing agent (C).
The content of the urethane compound (B) is 0.05 to 20 parts by mass with respect to 100 parts by mass of the polymer (A) .
The urethane compound (B) is a urethane branched compound having a structure obtained by reacting a polyisocyanate component containing a trifunctional or higher functional isocyanate with an alcohol component containing a monoalcohol, and has a mass average molecular weight of 1,500 to 15. A pressure-sensitive adhesive for skin application, which comprises at least one selected from the group consisting of 000 urethane-based oligomers . The first aspect of the present invention, wherein the polymer (A) contains at least one selected from the group consisting of a carboxyl group-containing acrylic polymer, a hydroxyl group-containing acrylic polymer, a hydroxyl group-containing urethane polymer, and a polyether polyol. Adhesive for skin application. The pressure-sensitive adhesive for skin application according to claim 1 or 2, wherein the urethane compound (B) contains a structure derived from an aromatic isocyanate. The urethane compound (B) contains the urethane branched compound, and the amount of the trifunctional or higher isocyanate used is 50 to 100% by mass in 100% by mass of the polyisocyanate component, and the amount of the monoalcohol used is The pressure-sensitive adhesive for skin application according to any one of claims 1 to 3 , wherein the alcohol component is 50 to 100% by mass in 100% by mass . The urethane compound (B) contains the urethane branched compound, and the urethane branched compound is a reaction product obtained by reacting a polyisocyanate component containing the trifunctional or higher functional isocyanate with an alcohol component containing the monoalcohol. The pressure-sensitive adhesive for skin application according to any one of claims 1 to 4, which comprises a urethane branched compound obtained by further reacting an amine component . The pressure-sensitive adhesive for skin application according to any one of claims 1 to 5, wherein the urethane compound (B) has an amine value of 0.1 to 60 mgKOH / g. A cured product obtained by curing the adhesive for skin application according to any one of claims 1 to 6. The cured product according to claim 7, wherein the gel fraction is 20 to 63%. In an atmosphere with a temperature of 23 ° C. and a relative humidity of 50%, the permanent adhesive strength against SUS is 0.
The cured product according to claim 7 or 8, which is 3N / 25 mm or more. An adhesive tape for skin application, which comprises a base material and an adhesive layer containing the cured product according to any one of claims 7 to 9.