JP2023082745A - Patch for skin-to-skin bonding, adhesive layer, and patch sheet for skin-to-skin bonding - Google Patents

Abstract

To provide a patch for skin-to-skin bonding and an adhesive layer that achieve bonding between skins with suppressed irritation and can exhibit excellent skin-to-skin bonding for a long period of time even under conditions where salt and oil coexist on the skin in abundance.SOLUTION: A patch for skin-to-skin bonding comprises fine resin particles (A) and an aqueous medium. The fine resin particles (A) have a glass transition temperature of -60°C to -10°C and an acid value of 3.0 to 40.0 mgKOH/g. The fine resin particles (A) are a polymer of an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated monomer (a-1) and an ethylenically unsaturated monomer (a-2). In 100 mass% of the ethylenically unsaturated monomer mixture, the content of the ethylenically unsaturated monomer (a-1) is 2.0 to 40.0 mass%, the content of the ethylenically unsaturated monomer (a-2) is 20.0 to 97.5 mass%, and the surface tension thereof at 25°C is 25.0 to 50.0 mN/m.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a patch and an adhesive layer that are directly attached to the skin and adhere between skins. It also relates to an inter-skin patch sheet used for forming an adhesive layer for bonding between skins.

Due to the recent corona wreck, the situation of wearing protective equipment such as masks, gloves, and goggles for a long time is increasing. Wearing such protective equipment causes a large amount of sweat containing salt and sebum containing oil to be secreted on the skin. ing. In particular, patches used for the purpose of bonding between skins, such as in medical care, beauty, and special makeup, secrete salt and oil from both sides of the skin, so in an environment where these are abundant, excellent adhesion is maintained for a long time. Difficult to maintain sexuality. In addition, these patches must be designed in consideration of less damage to the skin and less skin irritation.

Patent Document 1 discloses a patch for skin containing a mixture of rubber latex and acrylic resin emulsion. Patent Document 2 discloses a patch for skin characterized by containing an acrylic resin emulsion and modified corn starch. Patent Document 3 discloses a patch for skin containing an acrylic resin emulsion composed of 2-ethylhexyl acrylate and methacrylic acid.

Japanese Patent Application Laid-Open No. 2008-208076 JP 2014-024762 A JP 2015-199695 A

However, these conventional dermal patches have poor resistance to salt and oil, and the adhesiveness between the skins is reduced in a short period of time, especially under severe conditions where salt and oil coexist abundantly. In addition, there is a problem of skin irritation when it is applied for a long time because it is likely to cause an allergy to the skin.

The present invention achieves both adhesion between skins and suppression of skin irritation, and exhibits excellent adhesion between skins for a long period of time even under harsher conditions where salt and oil coexist on the skin. An object of the present invention is to provide an adhesive patch for indirect skin application and an adhesive layer.

The present invention includes resin fine particles (A) and an aqueous medium,
The fine resin particles (A) have a glass transition temperature of −60 to −10° C. and an acid value of 3.0 to 40.0 mgKOH/g. a-1), and a polymer of an ethylenically unsaturated monomer mixture containing the following ethylenically unsaturated monomer (a-2), in 100% by mass of the ethylenically unsaturated monomer mixture, ethylene The content of the ethylenically unsaturated monomer (a-1) is 2.0 to 40.0% by mass, and the content of the ethylenically unsaturated monomer (a-2) is 20.0 to 97.5% by mass. and has a surface tension of 25.0 to 50.0 mN/m at 25°C.
(a-1); a nonionic ethylenically unsaturated monomer (a-2) having an octanol/water partition coefficient logarithm (Log Kow) at 25°C of 0.4 or more and less than 2.0; at 25°C An ethylenically unsaturated monomer having an octanol/water partition coefficient log Kow of 2.0 or more and less than 2.5

Further, in the present invention, the total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) in 100% by mass of the ethylenically unsaturated monomer mixture is , 40.0 to 99.5% by mass.

Further, according to the present invention, the adhesive layer formed from the adhesive patch for indirect contact with the skin is
The patch for interdermal application has an elution rate of 50.0 to 100.0% by mass when immersed in ethyl acetate at 50° C. for 24 hours.

Further, in the present invention, the ethylenically unsaturated monomer (a-1) contains at least one ethylenically unsaturated monomer selected from the group consisting of methoxyethyl acrylate, methyl acrylate, and methyl methacrylate, It relates to an adhesive patch for indirect skin application.

The present invention also relates to the above-mentioned patch for interdermal application, wherein the ethylenically unsaturated monomer (a-2) contains at least one of n-butyl acrylate and phenoxyethyl acrylate.

The present invention also relates to an adhesive layer formed from the adhesive patch for indirect contact with the skin.

The present invention also relates to an interskin patch sheet comprising a peelable substrate and the adhesive layer.

The present invention achieves both adhesion between skins and suppression of skin irritation, and exhibits excellent adhesion between skins for a long period of time even under harsher conditions where salt and oil coexist on the skin. An interskin patch and an adhesive layer can be provided.

Embodiments of the present invention will be described below.
In the present specification, a nonionic ethylenically unsaturated monomer (a-1) having an octanol/water partition coefficient logarithm (Log Kow) at 25°C of 0.4 or more and less than 2.0, octanol/ An ethylenically unsaturated monomer (a-2) having a water partition coefficient logarithm (Log Kow) of 2.0 or more and less than 2.5 is referred to as an ethylenically unsaturated monomer (a-1) and an ethylenically unsaturated monomer (a-1), respectively. Sometimes abbreviated as saturated monomer (a-2).

Further, the octanol/water partition coefficient (Log Kow) is represented by the following (Formula 1) and is used as an index showing whether a certain compound X is likely to be partitioned into an aqueous phase or an oil phase (octanol). The Log Kow of each ethylenically unsaturated monomer can be calculated from experiments such as the flask shaking method and HPLC method, and can also be calculated from chemical structure simulations such as the YMB method (physical property estimation function) of the Hansen solubility parameter software HSPiP. It is also possible to
(Formula 1)
Log Kow = Log (concentration of compound X in octanol phase/concentration of compound X in water phase)
The various components appearing in this specification are not limited only to such examples, and unless otherwise noted, they may be independently used alone or in combination of two or more.

《Patches for indirect skin application》
The indirect skin patch of the present invention is directly applied to the skin and used for adhesion between skins.
The patch for indirect contact with the skin contains fine resin particles (A) and an aqueous medium, and has a surface tension of 25.0 to 50.0 mN/m at 25°C.
Further, the resin fine particles (A) have a glass transition temperature of −60 to −10° C. and an acid value of 3.0 to 40.0 mgKOH/g, and the following ethylenically unsaturated monomer (a-1), And a polymer of an ethylenically unsaturated monomer mixture containing the following ethylenically unsaturated monomer (a-2), in 100% by mass of the ethylenically unsaturated monomer mixture, the ethylenically unsaturated monomer The content of (a-1) is 2.0 to 40.0% by mass, and the content of the ethylenically unsaturated monomer (a-2) is 20.0 to 97.5% by mass.
(a-1); a nonionic ethylenically unsaturated monomer (a-2) having an octanol/water partition coefficient logarithm (Log Kow) at 25°C of 0.4 or more and less than 2.0; at 25°C An ethylenically unsaturated monomer having an octanol/water partition coefficient Log Kow of 2.0 or more and less than 2.5. Excellent adhesiveness between skins can be exhibited for a long time even under harsher conditions where salt and oil coexist abundantly.

The patch for indirect application has a surface tension of 25.0 to 50.0 mN/m, preferably 28.0 to 40.0 mN/m at 25°C. When the surface tension is within the above range, the wettability and permeation of the interskin patch to the skin are improved, and the film-forming properties between the resins are also improved. Therefore, it exhibits excellent adhesiveness between skins, and is also excellent in salt water resistance, oil resistance, and durability under conditions where salt water and oil coexist. Also, skin irritation can be reduced.
The surface tension value can be determined by the plate method (Wilhelmy method).

The elution rate of the adhesive layer formed from the patch for indirect application is preferably 50.0 to 100.0% by mass, more preferably 60.0 to 100%, when immersed in ethyl acetate at 50°C for 24 hours. 0% by mass is more preferable. When the elution rate is within the above range, the anchoring property to the skin is improved, the adhesion between the skin is further improved, and the resistance to salt water and oil, as well as the durability under conditions where salt water and oil coexist. will be excellent. There is also less skin irritation.

The content of the fine resin particles (A) contained in the patch for indirect skin application is preferably 20.0 to 60.0% by mass, more preferably 30.0 to 58.0%, based on 100% by mass of the patch for indirect skin application. A weight percent range is more preferred. By containing it in the above range, unevenness of the applied adhesive layer is reduced, and more excellent adhesion between skins can be exhibited.

<Aqueous medium>
An aqueous medium refers to an aqueous dispersion medium or an aqueous solvent.
As the aqueous medium, it is preferable to use water, but if necessary, a water-soluble solvent can also be used. Examples of water-soluble solvents include alcohols, glycols, cellosolves, aminoalcohols, amines, ketones, carboxylic acid amides, phosphoric acid amides, sulfoxides, carboxylic acid esters, and phosphoric acid esters. , ethers, nitriles and the like.

<Resin fine particles (A)>
The fine resin particles (A) have a glass transition temperature of −60 to −10° C. and an acid value of 3.0 to 40.0 mgKOH/g.
Further, it is a polymer of an ethylenically unsaturated monomer mixture containing the following ethylenically unsaturated monomers (a-1) and (a-2), and in 100% by mass of the ethylenically unsaturated monomer mixture , the content of the ethylenically unsaturated monomer (a-1) is 2.0 to 40.0% by mass, and the content of the ethylenically unsaturated monomer (a-2) is 20.0 to 97.5 % by mass.

The ethylenically unsaturated monomers constituting the resin fine particles (A) are classified into the following ethylenically unsaturated monomers (a-1) to (a-3). In addition to the saturated monomers (a-1) and (a-2), if necessary, other ethylenically unsaturated monomers (a-3) may be used.
(a-1); a nonionic ethylenically unsaturated monomer (a-2) having an octanol/water partition coefficient logarithm (Log Kow) at 25°C of 0.4 or more and less than 2.0; at 25°C An ethylenically unsaturated monomer (a-3) having an octanol/water partition coefficient log Kow of 2.0 or more and less than 2.5; other ethylenically unsaturated monomers

The glass transition temperature (Tg) of the fine resin particles (A) is in the range of -60 to -10°C, more preferably in the range of -40 to -15°C. By having a Tg within the above range, the interskin patch can be sufficiently wetted and anchored on the skin surface, and can exhibit excellent adhesiveness.

The acid value of the fine resin particles (A) is in the range of 3.0-40.0 mgKOH/g, preferably in the range of 5.0-30.0 mgKOH/g. By having an acid value within the above range, the carboxyl groups in the fine resin particles (A) interact sufficiently with the functional groups on the skin surface to improve adhesion between the particles and the skin. Furthermore, since the carboxyl groups between particles also interact to improve the strength of the coating, it exhibits excellent adhesiveness between skins, and has excellent resistance to salt water and oil, as well as durability under conditions where salt water and oil coexist. .

[Ethylenically unsaturated monomer (a-1)]
The ethylenically unsaturated monomer (a-1) is a nonionic ethylenically unsaturated monomer having an octanol/water partition coefficient Log Kow at 25°C of 0.4 or more and less than 2.0. . Log Kow is preferably 0.45 or more and less than 1.3. When the Log Kow is within the above range, the patch exhibits good adhesiveness to the skin, and is also excellent in salt water resistance and oil resistance.
The nonionic ethylenically unsaturated monomer is an ethylenically unsaturated monomer that does not have a charged functionality when in an aqueous medium. and an ethylenically unsaturated monomer having no sulfonyl group or the like.

The content of the ethylenically unsaturated monomer (a-1) is 2.0 to 40.0% by mass, more preferably 10.0% by mass, based on the total mass of 100% by mass of the ethylenically unsaturated monomer mixture. 0 to 30.0% by mass. Due to the above range, the copolymerization with the ethylenically unsaturated monomer (a-2) and other ethylenically unsaturated monomers (a-3) is excellent, and the patch is good for the skin. While exhibiting excellent adhesiveness, it has excellent resistance to salt water and oil, and durability under conditions where salt water and oil coexist. In addition, it is less irritating to the skin.

Examples of the ethylenically unsaturated monomer (a-1) include methoxyethyl acrylate (Log Kow = 0.45), methyl acrylate (Log Kow = 0.65), methoxyethyl methacrylate (Log Kow = 1.15 ), 2-hydroxyethyl methacrylate (Log Kow = 0.7), 4-hydroxybutyl acrylate (Log Kow = 0.56), isopropylacrylamide (Log Kow = 0.54), diacetone acrylamide (Log Kow = 0.54). 84), 2-acetoacetoxyethyl methacrylate (Log Kow = 0.61), glycidyl methacrylate (Log Kow = 0.95), 3,4-epoxycyclohexyl acrylate (Log Kow = 1.78), vinyl acetate (Log Kow = 0.65), methyl methacrylate (Log Kow = 1.13), ethyl acrylate (Log Kow = 1.16), ethyl methacrylate (Log Kow = 1.78), trifluoroethyl acrylate (Log Kow = 1.57 ), trifluoromethacrylate (Log Kow=1.95), ethylene glycol dimethacrylate (Log Kow=1.90), and the like. Among them, at least one selected from the group consisting of methoxyethyl acrylate, methyl acrylate, and methyl methacrylate from the viewpoint of exhibiting less irritation to the skin surface, better adhesion, and excellent resistance to salt water and oil. It preferably contains an ethylenically unsaturated monomer.
The content of methoxyethyl acrylate, methyl acrylate, and methyl methacrylate is the ethylenically unsaturated monomer (a-1) 100 from the viewpoint of excellent salt water resistance, oil resistance, and durability against a mixture of salt water and oil. Among the mass %, 50 to 100 mass % is preferable, and 80 to 100 mass % is more preferable.

[Ethylenically unsaturated monomer (a-2)]
The ethylenically unsaturated monomer (a-2) is an ethylenically unsaturated monomer having an octanol/water partition coefficient (Log Kow) at 25°C of 2.0 or more and less than 2.5. Log Kow is preferably 2.2 or more and less than 2.5. When the Log Kow is within the above range, the patch exhibits good adhesiveness to the skin even in the coexistence of salt water and oil.

The content of the ethylenically unsaturated monomer (a-2) is 20.0 to 97.5% by mass, more preferably 40.5% by mass, based on 100% by mass of the total ethylenically unsaturated monomer mixture. 0 to 90.0% by mass. Due to the above range, the copolymerization with the ethylenically unsaturated monomer (a-1) and other ethylenically unsaturated monomers (a-3) is excellent, and the patch is good for the skin. While exhibiting excellent adhesiveness, it is also excellent in salt water resistance, oil resistance, and durability under conditions where salt water and oil coexist.

The total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) is 40.0 in 100% by mass of the total ethylenically unsaturated monomer mixture. It is preferably up to 99.5% by mass, more preferably 50.0 to 96.5% by mass. When the content is within the above range, the adhesiveness between skins is further improved, and salt water resistance and oil resistance are also improved.

Examples of ethylenically unsaturated monomers (a-2) include t-butyl acrylate (Log Kow = 2.06), n-butyl acrylate (Log Kow = 2.23), n-propyl methacrylate (Log Kow = 2.28), benzyl acrylate (Log Kow = 2.32), phenoxyethyl acrylate (Log Kow = 2.44), phenoxydiethylene glycol acrylate (Log Kow = 2.12), 3-(methacryloyloxy)propyltrimethoxy silane (Log Kow=2.42) and the like. Among them, from the viewpoint of exhibiting high affinity with the skin surface, better adhesiveness, excellent salt water resistance, oil resistance, and durability under conditions where salt water and oil coexist, n-butyl acrylate, and phenoxy It preferably contains at least one of ethyl acrylate.
The content of n-butyl acrylate or phenoxyethyl acrylate is an ethylenically unsaturated monomer from the viewpoint of adhesion between skins, salt water resistance, oil resistance, and durability under conditions where salt water and oil coexist. (a-2) is preferably 50 to 100% by mass, more preferably 80 to 100% by mass in 100% by mass.

[Ethylenically unsaturated monomer (a-3)]
The ethylenically unsaturated monomer (a-3) is the ethylenically unsaturated monomer (a-1) described above, and other ethylenically unsaturated monomers polymerizable with the ethylenically unsaturated monomer (a-2). an ethylenically unsaturated monomer that is a saturated monomer and has an octanol/water partition coefficient at 25°C that is less than 0.4 or 2.5 or more; It is an ionic ethylenically unsaturated monomer having a logarithm (Log Kow) of 0.4 or more and less than 2.0.

Examples of ethylenically unsaturated monomers (a-3) include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, vinylnaphthalene, benzyl methacrylate, phenoxyethyl methacrylate, and the like. aromatic ethylenically unsaturated monomer;
hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, Linear or branched alkyl groups such as tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, behenyl (meth)acrylate, etc. an ethylenically unsaturated monomer having
Ethylenically unsaturated monomers having an alicyclic group such as cyclohexyl methacrylate and isobornyl (meth)acrylate;
Ethylenically unsaturated monomers having a fluorinated alkyl group such as heptadecafluorodecyl (meth)acrylate;
(meth) an ethylenically unsaturated monomer having a nitrile group such as acrylonitrile;
(anhydrous) maleic acid, fumaric acid, itaconic acid, citraconic acid, or their alkyl or alkenyl monoesters, β-(meth)acryloxyethyl succinate monoester, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid Ethylenically unsaturated monomers having a carboxy group such as;
Ethylenically unsaturated sulfonic acid groups such as sodium 2-acrylamide 2-methylpropanesulfonate, methallylsulfonic acid, sodium methallylsulfonate, allylsulfonic acid, sodium allylsulfonate, ammonium allylsulfonate, and vinylsulfonic acid monomer;
(meth)acrylamide, N-methoxymethyl-(meth)acrylamide,
Ethylenically unsaturated monomers having an amide group such as N-ethoxymethyl-(meth)acrylamide;
ethylenically unsaturated monomers having a hydroxyl group such as 2-hydroxyethyl acrylate;
Ethylenically unsaturated monomers having a polyoxyethylene group such as methoxypolyethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate;
Ethylenically unsaturated monomers having an amino group such as dimethylaminostyrene, diethylaminostyrene, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and methylethylaminoethyl (meth)acrylate;
etc.

As the ethylenically unsaturated monomer (a-3), the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) are polymerized in an aqueous medium. And, in view of good physical property expression, it is preferably n-octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, isodecyl acrylate, methacrylic acid, acrylic acid, acrylamide, or 2-hydroxyethyl acrylate, more preferably 2 - ethylhexyl acrylate, methacrylic acid, or acrylic acid.

When the ethylenically unsaturated monomer (a-3) is used in combination, the content of the ethylenically unsaturated monomer (a-3) is within the range that does not impair the effects of the present invention. It is preferably 0.4 to 60.0% by mass, more preferably 1.0 to 20.0% by mass, based on 100% by mass of the total mass of the solid mixture. Within the above range, more excellent adhesiveness, resistance to salt water and oil, and durability under conditions where salt water and oil coexist can be exhibited.

[Method for Synthesizing Resin Fine Particles (A)]
Methods for synthesizing the fine resin particles (A) include solution polymerization, emulsion polymerization, bulk polymerization, and the like. Emulsion polymerization is preferred from the viewpoints of controllability of reaction heat and avoiding the use of organic solvents that may cause skin irritation. preferable.

Emulsion polymerization is preferably carried out in the presence of at least a surfactant. Examples of surfactants include anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants. Among these, anionic surfactants, cationic surfactants, and nonionic surfactants are preferred, and anionic surfactants and nonionic surfactants are more preferred. Surfactants may be reactive surfactants or non-reactive surfactants.

Examples of non-reactive anionic surfactants include higher fatty acid salts such as sodium oleate, alkylarylsulfonates such as dodecylbenzenesulfonic acid, alkylsulfuric acid ester salts such as sodium laurylsulfate, and polyoxyethylene lauryl ether sulfate. Polyoxyethylene alkyl ether sulfate salts such as sodium, alkyl sulfosuccinate salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof, polyoxyethylene distyrenated phenyl ether sulfate and ester salts.

Non-reactive nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; polyoxyethylenes such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; Alkylphenyl ether, sorbitan higher fatty acid esters such as sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, poly Polyoxyethylene higher fatty acid esters such as oxyethylene monolaurate and polyoxyethylene monostearate, glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride, polyoxyethylene/polyoxypropylene block copolymers, polyoxyethylene di styrenated phenyl ether and the like.

Further, the reactive surfactant is an anionic surfactant or nonionic surfactant having one or more unsaturated double bonds capable of radical polymerization.
The reactive anionic surfactant preferably has, for example, a sulfosuccinic acid ester, an alkyl ether, an alkylphenyl ether, an alkylphenyl ester, a (meth)acrylate sulfate, or a phosphate as a main skeleton.
The reactive nonionic surfactant preferably has, for example, an alkyl ether, alkylphenyl ether, alkylphenyl ester or the like as the main skeleton.

The surfactant is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the ethylenically unsaturated monomer mixture. By using an appropriate amount of surfactant, the polymerization stability is improved and the skin is less likely to be adversely affected.

For emulsion polymerization, it is preferable to use a radical polymerization initiator (hereinafter also simply referred to as "polymerization initiator"). As the polymerization initiator, a known oil-soluble polymerization initiator or water-soluble polymerization initiator can be used.
Examples of oil-soluble initiators include benzoyl peroxide, tert-butyloxybenzoate, tert-butyl hydroperoxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxy-3,5,5 -trimethylhexanoate, di-tert-butyl peroxide, cumene hydroperoxide, organic peroxides such as p-menthane hydroperoxide, 2,2'-azobis isobutyronitrile, 2,2'-azobis -2,4-dimethylvaleronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1'-azobis-cyclohexane-1-carbonitrile and other azo compounds.
Examples of water-soluble polymerization initiators include ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2′-azobis(2-methylpropionamidine) dihydrochloride and the like.

A reducing agent and a transition metal salt can be used in combination with the polymerization initiator when carrying out the polymerization. The combined use of these accelerates the decomposition of the polymerization initiator.
Examples of reducing agents include ascorbic acid, erythorbic acid, tartaric acid, citric acid, glucose, reducing agent organic compounds such as metal salts such as formaldehyde sulfoxylate, sodium sulfite, sodium bisulfite, sodium metabisulfite, and sodium hyposulfite. and reducing inorganic compounds such as
Examples of transition metal salts include ferrous chloride, ferrous sulfate, and copper sulfate.

It is preferable to use a water-soluble polymerization initiator for emulsion polymerization in the present invention. It is preferable to use 0.03 to 5 parts by mass of the polymerization initiator with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture. It is preferable to use 0.01 to 2.5 parts by mass of the reducing agent with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture. The transition metal salt is preferably used in an amount of 0.0001 to 0.002 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture. Examples of the method of adding the polymerization initiator include initial batch charging, divided charging, and continuous dropwise addition, but are not particularly limited. From the viewpoint of accelerating the end point of the polymerization reaction, part of the polymerization initiator may be added to the reaction system before or after the completion of adding the monomers to the reaction system.

A buffer, a chain transfer agent, a basic compound, and the like may be used as necessary during the emulsion polymerization.
Buffers include, for example, sodium acetate, sodium citrate, sodium bicarbonate and the like.
Chain transfer agents include, for example, n-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, stearyl mercaptan, 3-mercaptopropionic acid, n-octyl 3-mercaptopropionic acid, 3-mercaptopropionic acid 2 -ethylhexyl, n-octyl thioglycolate, 2-ethylhexyl thioglycolate, and the like. Among these, 2-ethylhexyl 3-mercaptopropionate and 2-ethylhexyl thioglycolate are preferred, and 2-ethylhexyl thioglycolate is more preferred.
The chain transfer agent is preferably used in an amount of 0.01 to 0.1 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture.
Basic compounds are used for neutralization, for example alkylamines such as trimethylamine, triethylamine, n-butylamine, alcoholamines such as 2-dimethylaminoethanol, diethylaminoethanol, diethanolamine, triethanolamine, aminomethylpropanol, morpholine, and ammonia.
The basic compound is preferably ammonia from the viewpoint of volatility when drying the adhesive.

Emulsion polymerization methods include, for example, a batch reaction in which an ethylenically unsaturated monomer, a surfactant, and water are all charged into a reaction tank and reacted, a dropping reaction in which the monomers are gradually added dropwise to the reaction tank and reacted, and the like. are mentioned. Among these, the dropping reaction is preferable from the viewpoint of easy control of the heat generation of the polymerization reaction. In addition, in order to further improve the polymerization stability, the dropping reaction is preferably carried out by mixing and stirring the monomers, water, and surfactant to form a pre-emulsion in an emulsified state before dropping.

The average particle size of the fine resin particles (A) obtained by emulsion polymerization is preferably 50 to 400 nm, more preferably 50 to 400 nm, from the viewpoint of stably coating and exhibiting excellent adhesiveness, salt water resistance, and oil resistance. It ranges from 150 to 300 nm.
The average particle size is the _D50 average particle size using a dynamic light scattering measurement method. , can be measured with Nanotrac (manufactured by Nikkiso Co., Ltd.) using about 5 mL of the diluted solution.

<Optional component>
The patch for indirect application of the present invention may contain optional additives such as extender pigments, thickeners, moisturizers, preservatives, solvents, antifoaming agents, and wetting agents, as long as the problems can be solved. can be done.
Examples of extender pigments include talc, silica, calcium carbonate, barium sulfate, titanium oxide, and diatomaceous earth.
Examples of thickeners include alkali-swelling thickeners, associative polyurethanes, carboxyvinyl polymers, thickening polysaccharides, and clay minerals.
Examples of moisturizing agents include sorbitol, xylitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glycerin, diglycerin, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, and DL-pyrrolidone carboxylate. etc.
Examples of solvents include ethyl alcohol, isopropyl alcohol, n-butyl alcohol and the like.
Examples of antiseptics include methyl parahydroxybenzoate, ethyl parahydroxybenzoate, propyl parahydroxybenzoate, butyl parahydroxybenzoate, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol, 4-hydroxyacetophenone, dehydroacetic acid. , caprylyl glycol, pentylene glycol, and the like.
Antifoaming agents include, for example, silicone antifoaming agents and mineral oil antifoaming agents.
Examples of the wetting agent include the surfactants exemplified in the synthesis of the fine resin particles (A).

≪Adhesive layer≫
The adhesive layer is formed by evaporating volatile components such as water and solvent from the patch for indirect application of the present invention.
The patch for direct and indirect application to the skin can be applied on the skin and allowed to dry naturally to form an adhesive layer, or the patch for indirect and indirect application is once applied to a peelable base material and dried to form an adhesive layer. It can also be used by transferring it onto the skin after producing a skin patch sheet.
Any base material can be used as the peelable base material as long as it does not leave an adhesive layer on the base material during transfer. Examples of the release substrate include substrates such as silicone-coated polyethylene terephthalate, release polyethylene terephthalate, and release polyolefin.

The coating amount per unit area of the adhesive layer is not particularly limited, but it is preferably in the range of 5 to 50 g/m ² in terms of solid content, more preferably 10 to 40 g/m 2 from the viewpoint of expressing excellent adhesiveness. ^m2 .

As a method of attaching the skin with an indirect skin patch, there is a method in which the indirect skin patch is applied to one side of the skin and then the other side of the skin is attached and then dried, and an indirect skin patch is applied to one side of the skin. After applying, once dry and then pasting the other skin, the above-mentioned skin patch sheet is pasted on one side of the skin, the adhesive layer is transferred onto the skin, and the other skin is pasted. It can be pasted together by arbitrary methods, such as the method of pasting together. When the patch for indirect skin application is applied directly to the skin, the drying temperature is preferably in the range of 25 to 50° C. in consideration of less damage to the skin.

The patch for indirect application to the skin and the sheet for skin patch of the present invention can be applied to various uses such as medical care, beauty care, special makeup, etc., for the purpose of sticking the skin together.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the examples below do not limit the scope of the present invention. In the examples, "part" means "mass part" and "%" means "mass %". Numerical values in the table are the mass of the solid content, and blanks indicate that they are not used.
Methods for measuring the octanol/water partition coefficient (Log Kow) of the ethylenically unsaturated monomer, the acid value, the glass transition temperature (Tg) and the average particle size of the fine resin particles (A) are as follows.

<Octanol/water partition coefficient (Log Kow)>
The octanol/water partition coefficient (Log Kow) at 25° C. of the ethylenically unsaturated monomer is obtained by the YMB method (physical property estimation function) of the software HSPiP (Ver.5.02.5). It was calculated by converting the structural formula of the body into Smiles notation and inputting it.
(Formula 1)
Log Kow = Log (concentration of compound X in octanol phase/concentration of compound X in water phase)

<Acid value>
The acid value of the fine resin particles (A) is the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the dried resin. According to the method described in JIS K2501, it was calculated by performing potentiometric titration using an automatic titrator (“COM” manufactured by HIRANUMA) with a potassium hydroxide/ethanol solution.

<Glass transition temperature>
The glass transition temperature of the fine resin particles (A) was measured using a DSC (Differential Scanning Calorimeter, manufactured by TA Instruments). Specifically, an aluminum pan in which about 3 mg of dried resin was precisely weighed and an empty aluminum pan as a reference were set in a DSC measurement holder, and the temperature was increased at 10 ° C./min. The temperature at the intersection of the baseline on the low temperature side of the endothermic phenomenon in the obtained DSC curve and the tangent line at the point of inflection was defined as the glass transition temperature (Tg).

<Average particle size>
The average particle diameter of the resin fine particles (A) is obtained by diluting the aqueous dispersion of the resin fine particles (A) 1000 times, and measuring about 5 ml of the diluted solution by a dynamic light scattering measurement method (measured by Nanotrac UPA Co., Ltd.). Microtrack Bell Co.) was used for measurement. The peak of the obtained volume particle size distribution data (histogram) was taken as the average particle size.

<Production of patch for indirect skin application>
[Example 1]
19.0 parts of ion-exchanged water was charged into a flask (reaction vessel) equipped with a reflux condenser, a dropping funnel, a stirrer, a thermometer, a nitrogen gas inlet tube, and a raw material inlet, and stirred while introducing nitrogen gas. The liquid temperature was heated to 80°C.
As the ethylenically unsaturated monomer (a-1), 6.0 parts of methoxyethyl acrylate, 25.0 parts of methyl methacrylate, as the ethylenically unsaturated monomer (a-2), n-butyl acrylate 49.0 parts, as other ethylenically unsaturated monomers (a-3), 10.0 parts of 2-ethylhexyl acrylate, 7.0 parts of n-lauryl acrylate, 1.0 parts of 2-hydroxyethyl acrylate, 1.5 parts of methacrylic acid part, 0.5 part of acrylic acid, 11.9 parts of 10% aqueous solution of Emal 0 (manufactured by Kao Corporation, sodium lauryl sulfate), 0.04 part of 2-ethylhexyl thioglycolate as a chain transfer agent, and ion exchange 19.6 parts of water were stirred and mixed to prepare a pre-emulsion (an emulsion of an ethylenically unsaturated monomer), which was charged into a dropping funnel (dropping tank).
Into the flask, 0.12 parts of a 10% aqueous solution of Emal 0 and 6.6 parts of 5.0% pre-emulsion were added. Then, after adding 10.0 parts of a 5% aqueous solution of potassium persulfate as a polymerization initiator into the flask, the remainder of the pre-emulsion was continuously added dropwise from the dropping funnel over 180 minutes, and emulsion polymerization was performed while maintaining the temperature at 80°C. did After the dropwise addition, stirring was continued for 5 hours while maintaining the temperature at 80° C. to obtain an aqueous dispersion of fine resin particles (A). After the reaction, 25% aqueous ammonia was added to neutralize the acid value of the resin by 100%. 0%. Thereafter, 0.5 part of phenoxyethanol was added as an additive component to obtain an interdermal patch.

[Examples 2 to 24, Comparative Examples 1 to 10]
An inter-skin patch was obtained in the same manner as in Example 1, except that the composition and amount (parts by mass) shown in Tables 1 to 3 were used. In Examples 9, 20, 21 and Comparative Example 8, the 10% aqueous solution charged in the flask was changed to 0.08, 1.33, 0.01, and 0.08 parts in order to obtain fine resin particles (A). was synthesized. In addition, in Example 11 and Comparative Example 10, the surfactant was changed from Emal 0 to Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene-1-(allyloxymethyl)aalkyl ether sulfate ammonium), and flask The 10% aqueous solution of KH-10 charged inside was changed to 0.05 parts and 0.03 parts, and the 10% aqueous solution of KH-10 charged to the dropping tank was changed to 12.3 parts and 12.1 parts, respectively.

[Surface tension γ]
The surface tension γ of the patch for indirect skin application prepared above was measured by the plate method (Wilhelmy method) at 25° C. using a surface tensiometer manufactured by Kyowa Kaimen Co., Ltd. (automatic surface tensiometer DY-300). .

<Elution rate>
The resulting patch for indirect application was poured into a frame mold of a silicone container and dried at 40° C. for 96 hours (48 hours on one side). A test piece of the obtained resin coating film was wrapped with a metal mesh and immersed in ethyl acetate at 50° C. for 72 hours, and the amount of elution from the resin coating film was measured. The elution amount was calculated from the following formula.
Elution rate (%) = (coating film mass before immersion - coating mass after immersion) / coating mass after immersion × 100

<Preparation of skin attachment sheet>
[Example 25]
The patch for indirect application of Example 22 was coated on a peelable PET base material with a bar coater so that the dry conversion was 30 g/m ² , and then dried in an oven at 100°C for 5 minutes to prepare a skin patch sheet. bottom.

<<Evaluation of Indirect Skin Patches>>
Adhesiveness, resistance to salt water, resistance to oil, resistance to a mixed solution of salt water and oil, and skin irritation were evaluated using the patch for indirect application to the skin and the sheet for skin application prepared above. The results are shown in Tables 1-3.

<Adhesion evaluation>
The resulting patch for interdermal application was applied to the Suprale artificial skin with an applicator so as to have a dry weight of 30 g/m ² . After coating, it was dried under conditions of 25° C. and 5 minutes to prepare a test piece of 10 mm long and 20 mm wide. Two test pieces were prepared for each, and the coated surfaces were bonded together, pressure-bonded under conditions of 0.5 Mpa, and further cured under conditions of 23° C. and 50% humidity.
After curing, one end of the test piece was pulled in the direction of 180°, and the peel strength was measured with a tensile tester ("AGS-X" manufactured by Shimadzu Corporation). (Peeling speed: 300 mm/min, unit: N/20 mm width).
For the patch sheet of Example 25, the adhesive layer was transferred to a supplementary artificial skin to prepare a coated product.
[Evaluation criteria]
S: The peel strength is 10 N/20 mm or more. Very good.
A: The peel strength is 5 N/20 mm or more and less than 10 N/20 mm. Good.
B: The peel strength is 3 N/20 mm or more and less than 5 N/20 mm. Usable for practical use.
C: The peel strength is less than 3N/20mm. There is a problem in practical use.

<Evaluation of salt water resistance>
After preparing 300 parts of 0.4% by mass aqueous sodium chloride solution in a 500 ml glass bottle so that the salt concentration is the same as that of sweat, a test piece was prepared in the same manner as in the evaluation of adhesiveness, and then bonded together at 37 ° C. for 24 hours. soaked. After the immersion, the salt water adhering to the test piece was lightly wiped off, and then the peel strength was measured in the same manner as the adhesion evaluation. From the obtained peel strength, the rate of change in peel strength before and after immersion was calculated.
Rate of change [%] = (Peel strength before immersion in salt water - Peel strength after immersion in salt water) / Peel strength before immersion in salt water x 100
[Evaluation criteria]
S: Less than 1% change in peel strength. Very good.
A: Change rate of peel strength is 1% or more and less than 5%. Good.
B: Change rate of peel strength is 5% or more and less than 10%. Usable for practical use.
C: Change rate of peel strength is 10% or more. There is a problem in practical use.

<Oil resistance evaluation>
After putting 300 ml of jojoba oil as a component close to sebum into a 500 ml glass bottle, the bonded test piece prepared above was immersed at 37° C. for 24 hours. After immersion, the oil adhering to the test piece was lightly wiped off, and the peel strength was measured in the same manner as above. From the obtained peel strength, the rate of change in peel strength before and after immersion was calculated.
Change rate [%] = (peel strength before oil immersion - peel strength after oil immersion) / peel strength before oil immersion x 100
[Evaluation criteria]
S: Less than 1% change in peel strength. Very good.
A: Change rate of peel strength is 1% or more and less than 5%. Good.
B: Change rate of peel strength is 5% or more and less than 10%. Usable for practical use.
C: Change rate of peel strength is 10% or more. There is a problem in practical use.

<Resistance to mixture of salt water and oil>
After putting 150 parts of 0.4% sodium chloride aqueous solution and 150 parts of jojoba oil in a 500 ml glass bottle, the bonded test piece prepared above was immersed, covered and shaken at 37 ° C. for 24 hours. was shaken with After shaking, salt water and oil adhering to the test piece taken out were lightly wiped off, and the peel strength was measured in the same manner as above. From the obtained peel strength, the rate of change in peel strength before and after immersion was calculated.
Rate of change [%] = (Peel strength before immersion in mixed solution - Peel strength after immersion in mixed solution) / Peel strength before immersion in mixed solution x 100
[Evaluation criteria]
S: Less than 1% change in peel strength. Very good.
A: Change rate of peel strength is 1% or more and less than 5%. Good.
B: Change rate of peel strength is 5% or more and less than 10%. Usable for practical use.
C: Change rate of peel strength is 10% or more. There is a problem in practical use.

<Skin irritation>
The patch for indirect skin application was applied to the inside of the arm of 10 test subjects, and the test was observed for 24 hours to evaluate whether or not abnormalities such as itching and rash occurred. The patch sheet of Example 23 was attached to the skin to transfer the adhesive layer.
[Evaluation criteria]
A: No subject felt abnormal. Good.
B: One subject felt abnormal. Usable for practical use.
C: Two or more subjects felt abnormal. There is a problem in practical use.

Abbreviations in the table are as follows.
Emulgen TW-O320: Polyoxyethylene sorbitan trioleate manufactured by Kao Corporation Emulgen 409P: Polyoxyethylene oleyl ether manufactured by Kao Corporation

As can be seen from Tables 1 to 3, the indirect adhesive patches of Examples 1 to 24 and the skin patch sheet of Example 25 were very excellent in adhesiveness, salt water resistance, and oil resistance. Furthermore, it has excellent durability even under harsher conditions where salt water and oil coexist, and has very little skin irritation. On the other hand, the adhesive patches for indirect application of Comparative Examples 1 to 10 were remarkably inferior in one of various performances and did not meet the practical level.

Claims (7)

containing resin fine particles (A) and an aqueous medium,
The resin fine particles (A) have a glass transition temperature of −60 to −10° C. and an acid value of 3.0 to 40.0 mgKOH/g,
The fine resin particles (A) are polymers of an ethylenically unsaturated monomer mixture containing the following ethylenically unsaturated monomer (a-1) and the following ethylenically unsaturated monomer (a-2). ,
In 100% by mass of the ethylenically unsaturated monomer mixture, the content of the ethylenically unsaturated monomer (a-1) is 2.0 to 40.0% by mass, and the ethylenically unsaturated monomer (a- The content of 2) is 20.0 to 97.5% by mass,
An interdermal patch having a surface tension of 25.0 to 50.0 mN/m at 25°C.

(a-1); a nonionic ethylenically unsaturated monomer (a-2) having an octanol/water partition coefficient logarithm (Log Kow) at 25°C of 0.4 or more and less than 2.0; at 25°C An ethylenically unsaturated monomer having an octanol/water partition coefficient log Kow of 2.0 or more and less than 2.5 The total content of the ethylenically unsaturated monomer (a-1) and the ethylenically unsaturated monomer (a-2) in 100% by mass of the ethylenically unsaturated monomer mixture is 40.0 to 99. The patch for indirect application according to claim 1, wherein the content is 0.5% by mass. The adhesive layer formed from the patch for indirect skin application,
3. The patch for interdermal application according to claim 1, wherein the elution rate when immersed in ethyl acetate at 50° C. for 24 hours is 50.0 to 100.0% by mass. Any one of claims 1 to 3, wherein the ethylenically unsaturated monomer (a-1) comprises at least one ethylenically unsaturated monomer selected from the group consisting of methoxyethyl acrylate, methyl acrylate, and methyl methacrylate. 1. The patch for indirect skin application according to 1 or 2 above. The interdermal patch according to any one of claims 1 to 4, wherein the ethylenically unsaturated monomer (a-2) contains at least one of n-butyl acrylate and phenoxyethyl acrylate. An adhesive layer formed from the interskin patch according to any one of claims 1 to 5. An inter-skin patch sheet comprising a peelable substrate and the adhesive layer according to claim 6.