JP4715232B2 - Active energy ray-curable composition for skin patch and skin patch - Google Patents

Description

  The present invention relates to a composition for active energy ray-curable skin patch comprising a compound having two or more specific maleimide groups, and a skin patch having an adhesive layer formed from the composition. Can be used in a technical field.

  The patch is used for the purpose of protecting the damaged part of the skin surface, transdermally absorbing a medicinal component for treating a disease and administering it to a living body. Specifically, emergency bonds, magnetic bonds, surgical tapes, accelerated wound dressings (dressing materials), sports taping tapes, tape preparations, plasters, and poultices are known.

  The performance required of the patch is excellent in adhesion to the skin, does not cause pain and exfoliation of the stratum corneum at the time of peeling, and has low skin irritation and high safety to be applied directly to the skin Etc.

As the adhesive component used in the patch, a solvent-based adhesive obtained by dissolving an acrylic polymer or rubber resin in an organic solvent is usually used (for example, Patent Documents 1 and 2).
However, solvent-based adhesives do not use organic solvents because there are concerns about the environmental impact of organic solvents that diverge when processing into patches, and the safety of residual solvents in adhesive coatings. In recent years, pressure-sensitive adhesives have been required.

  As an alternative to solvent-based adhesives, it has low viscosity, is easy to handle, is easy to apply solvent-based coating equipment, has excellent water resistance, and is cured with active energy rays such as ultraviolet rays and visible light. Energy ray-curable pressure-sensitive adhesives are being studied.

Active energy ray-curable adhesives and other active energy ray-curable pressure-sensitive adhesive compositions are not usually crosslinked or cured by the raw material components alone, so photopolymerization initiators or photosensitizers (hereinafter collectively referred to as photopolymerization). It is necessary to add an initiator).
When the addition amount of the photopolymerization initiator or the like is increased, the curing proceeds quickly, so that the addition amount tends to increase. However, since photopolymerization initiators and the like use a compound having an aromatic ring to efficiently absorb light, this causes a problem that the resulting cured coating film turns yellow. It is.
As the photopolymerization initiator, a low molecular weight compound is usually used in order to efficiently initiate the polymerization reaction. However, when the composition is irradiated with active energy, the temperature rises due to the heat of polymerization.However, the low molecular weight photopolymerization initiator has a high vapor pressure, so that a bad odor is generated at the time of curing, resulting in a problem of working environment. It has the problem of generating or contaminating the resulting product. In addition, since a decomposition product such as an unreacted photopolymerization initiator remains in the cured coating film, when the cured coating film is subjected to light or heat, the cured coating film turns yellow or has a bad odor. There was a problem of generating.
In addition, when used in patches, if the cured coating film gets wet with water or touches sweat that the human body diverges, unreacted photopolymerization initiators bleed in large quantities, which is also safe and hygienic. There was a problem.
In order to improve the disadvantages of the active energy ray curable composition containing these photopolymerization initiators, etc., compositions that do not contain photopolymerization initiators and can be cured by irradiation with active energy rays have been studied. (For example, Patent Documents 3 to 6).

JP-A-7-69870 (Claims) JP-A-11-12163 (Claims) JP 11-124403 A (Claims) JP-A-11-124404 (Claims) JP 2001-219508 A (Claims) JP 2001-220567 A (Claims)

However, although Patent Documents 3 and 4 disclose a pressure-sensitive adhesive as a use of a composition containing a compound having a maleimide group, the list of twenty or more kinds of uses is listed. It is merely disclosed, and naturally the use of the skin patch is not disclosed at all.
On the other hand, the composition containing the compound having a maleimide group disclosed in Patent Documents 5 and 6 is an adhesive, and the cured coating film has no tackiness or poor tackiness, It was difficult to use as an adhesive. Further, the compound having a maleimide group described in Patent Document 6 has crystallinity, a melting point of 40 ° C. or higher, and is not liquid at room temperature, and therefore has particularly poor adhesiveness and is difficult to use as an adhesive. Met.
The present inventors are liquid at room temperature, and have a practical crosslinkability or curability in the absence of a photopolymerization initiator even when irradiated with visible light or ultraviolet light, and a cured coating film obtained is obtained. Active energy that is not colored, has excellent adhesive properties, has moderate adhesiveness that does not damage the pain or stratum corneum even after repeated application to the skin and peeling, and also has excellent water resistance As a result of intensive studies to find a composition for a line curable skin patch, a composition for a skin patch containing a compound having two or more maleimide groups and an oil component or water or a water-soluble compound is effective. (Patent document 7).

The composition is excellent in solving the above problems, but may be insufficient in the following cases. That is, in order to further suppress skin irritation, it is necessary to have excellent water vapor permeability that efficiently transmits water vapor emitted from the human body. In addition, when actually applying a skin patch to the skin, it should be lightly applied to the skin, and it must have an appropriate degree of tackiness that does not easily peel off immediately after that. It is required that the tack is high and the adhesion to the skin is higher than before. The composition was insufficient especially when these performances were required at the same time.
In addition to the above-mentioned performance, the present inventors have intensively studied to find a composition having excellent water vapor permeability, tack and adhesion to skin.

PCT / JP2004 / 012358 specification (Claims)

As a result of various investigations to solve the above problems, the present inventors are a composition for skin patches containing a compound having two or more maleimide groups and an oily component or water or a water-soluble compound, As a compound having two or more maleimide groups, a composition using a polyether compound containing a propylene oxide unit and a random copolycondensation product of an aliphatic dicarboxylic acid and an aliphatic diol is found to solve the above-mentioned problems. The present invention has been completed.
Hereinafter, the present invention will be described in detail.

1. (A) Compound having two or more maleimide groups The active energy ray-curable skin patch composition of the present invention essentially comprises a compound having two or more maleimide groups (hereinafter also referred to as a maleimide compound). Furthermore, the component (A) of the present invention is a combination of (A1) a polyether compound containing a propylene oxide unit and (A2) a random copolycondensation product of an aliphatic dicarboxylic acid and an aliphatic diol. It is.
As the maleimide group in the component (A), various functional groups can be used, and those represented by the following formulas (1) to (4) are used.

[In the formula (1), R ¹ represents an alkyl group, an aryl group, an arylalkyl group or a halogen atom. ]

[In the formula (3), R ² and R ³ represent an alkyl group, an aryl group, an arylalkyl group, or a halogen atom. ]

[However, in Equation (4), R ⁴ represents a propylene group or a butylene group may also have as a substituent an alkyl group. ]

In the above formulas (1) and (3), the alkyl group of R ^{1 to} R ³ is preferably an alkyl group having 4 or less carbon atoms, particularly preferably a methyl group. A phenyl group etc. can be mentioned as an aryl group. Examples of the arylalkyl group include a benzyl group.
Among these, as R ^{1 to} R ³ , an alkyl group is preferable, an alkyl group having 4 or less carbon atoms is more preferable, and a methyl group is particularly preferable.
In the formula (4), the propylene group or butylene group that may have the alkyl group of R ⁴ as a substituent is preferably a butylene group in terms of easy availability and excellent adhesive performance. In the case of a propylene group or butylene group having a substituent, the substituent is preferably an alkyl group, and more preferably a methyl group. Specific examples of the propylene or butylene group having a _{substituent, -CH 2 CH (CH 3)} CH 2 CH 2 - and the like.

As the component (A), the following component (A) or component (A) is used because it is excellent in cross-linking or curing (hereinafter collectively referred to as “curing”) performance and the cured film obtained is excellent in water resistance. A maleimide compound selected from is essential.
(A): A compound having two or more maleimide groups represented by the formula (1) (hereinafter referred to as Compound 1).
(A): (a) a compound having two or more maleimide groups represented by the formula (2) (hereinafter referred to as compound 2) and (b) having two or more maleimide groups represented by the formula (3) A compound (hereinafter referred to as Compound 3) or / and a compound having two or more maleimide groups represented by the above formula (4) (hereinafter referred to as Compound 4).

  Since the component (A) used in the present invention has a maleimide group, the maleimide group is dimerized by irradiation with active energy rays to cross-link the molecules of the compound. In addition, even when the maleimide group is cured with ultraviolet rays or visible light, it can cause a dimerization reaction by irradiation with ultraviolet rays or visible light with or without a photopolymerization initiator.

  In addition, the component (A) in the present invention is preferably liquid at room temperature. Thereby, handling of coating work etc. becomes easy. On the other hand, those that are solid at room temperature are difficult to handle, and the cured coating film has a high elastic modulus and may have insufficient adhesive performance. In the present invention, normal temperature means 25 ° C.

(A) As a molecular weight of a component, 1,000-20,000 are preferable at a number average molecular weight, More preferably, it is 2,000-10,000, More preferably, it is 2,000-8,000. If the number average molecular weight is less than 1,000, the adhesive strength and tack of the cured coating film may decrease. On the other hand, if the number average molecular weight exceeds 20,000, the viscosity of the composition becomes too high, and the coatability decreases. Even if it mix | blends (B) component, it may not become a liquid composition at normal temperature.
In the present invention, the number average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography (hereinafter abbreviated as GPC) using tetrahydrofuran as a solvent based on the molecular weight of polystyrene.
Further, when the component (A) is a water-soluble polymer, the number average molecular weight is a value obtained by converting a molecular weight measured by GPC using a phosphate buffer as a solvent based on the molecular weight of polyethylene oxide. It is.

The component (A) used in the present invention has a maleimide group, and the (A1) component is a polyether compound containing a propylene oxide unit, and the (A2) component is a random co-condensation of an aliphatic dicarboxylic acid and an aliphatic diol. As long as it is a polymer, various compounds can be used. (A) Although what was manufactured by the various method can be used for a component, the following three types of compounds are preferable at the point which manufacture is easy.

[1] An addition reaction product of a prepolymer having two or more isocyanate groups at a terminal and a compound having a maleimide group and an active hydrogen group (hereinafter referred to as compound [1]).

[2] An esterification reaction product of a prepolymer having two or more carboxyl groups at the terminal and a compound having a maleimide group and an active hydrogen group (hereinafter referred to as compound [2]).

[3] An esterification reaction product of a prepolymer having two or more hydroxyl groups at a terminal and a carboxylic acid having a maleimide group (hereinafter referred to as compound [3]).
Hereinafter, the compounds [1] to [3] will be described.

1-1. Compound [1]
Compound [1] is an addition reaction product of a prepolymer having two or more isocyanate groups at the terminal (hereinafter simply referred to as a urethane prepolymer) and a compound having a maleimide group and an active hydrogen group (hereinafter simply referred to as a maleimide active hydrogen compound). It is produced by reacting 2 moles or more of maleimide active hydrogen compound with respect to 1 mole of urethane prepolymer.
Hereinafter, the urethane prepolymer and the maleimide active hydrogen compound will be described.

A) Urethane prepolymer As the urethane prepolymer, various compounds can be used as long as they have two or more isocyanate groups at the molecular ends.
Examples of the urethane prepolymer include a reaction product of a polyol having two or more hydroxyl groups (hereinafter simply referred to as polyol) and a polyisocyanate having two or more isocyanate groups (hereinafter simply referred to as polyisocyanate).

As the a1) polyol polyol, a polyether polyol is used when the component (A1) is produced, and a polyester polyol is used when the component (A2) is produced.
As a polyol, 2 or more types can be used together as needed.

a1-1) Polyether polyol As the polyether polyol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, Ethylene oxide modified products, propylene oxide modified products, butylene oxide modified products and tetrahydrofuran modified products of alkylene glycols such as hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane and dipentaerythritol; Copolymer of ethylene oxide and propylene oxide, propylene glycol Copolymer of ethylene and tetrahydrofuran; copolymer of ethylene glycol and tetrahydrofuran; hydrocarbon polyols such as polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol; and polytetramethylene hexaglyceryl ether ( And the like, and the like.

Of these, preferred are polyether polyols that essentially require propylene oxide units. Thereby, the obtained maleimide compound can be made into a liquid thing.
Moreover, as a polyether polyol which requires a propylene oxide unit as an essential component, it has an ethylene oxide unit in addition to a propylene oxide unit depending on whether an oil component or water or a water-soluble compound is blended as the component (B). A thing can be used and the ratio of a propylene oxide unit can be adjusted and used.
In the case of using a polyether polyol having a propylene oxide unit and an ethylene oxide unit, the proportion of the propylene oxide unit is preferably a high proportion of the propylene oxide unit when the oil component is blended. Based on the total amount of propylene oxide units and ethylene oxide units, those having 30 to 100% by mass of propylene oxide units are preferred, and those having 60 to 100% by mass are more preferred. When water or a water-soluble compound (hereinafter collectively referred to as “aqueous component”) is blended, specifically, the propylene oxide unit is preferably 1 to 90% by mass, and preferably 15 to 90% by mass. Those are more preferred.

a1-2) Polyester polyol The polyester polyol is a random copolycondensation product of a polyvalent carboxylic acid and a polyhydric alcohol. Among these, aliphatic polyester polyols are preferable because they are excellent in curability by active energy rays of the composition.

Here, various polycarboxylic acids can be used as long as they have two or more carboxyl groups in the molecule. Specifically, succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, eicoic acid diacid, 2,6-naphthalenedicarboxylic acid, trimellitic acid, glutaric acid, 1,9 -Nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, malonic acid, fumaric acid, 2,2-dimethylglutaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Examples include acids, itaconic acid, maleic acid, 2,5-norbornane dicarboxylic acid, 1,4-terephthalic acid, 1,3-terephthalic acid, dimer acid, and paraoxybenzoic acid.
Among these, aliphatic dicarboxylic acids are preferable, and adipic acid and sebacic acid are more preferable.
Two or more polycarboxylic acids can be used in combination as required.

Any polyhydric alcohol can be used as long as it has two or more hydroxyl groups in the molecule. Specifically, butylethylpropanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol and polyethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,2-octanediol, 1,8-octanediol, 1,9-nonanediol, 1,2, decanediol, 1,10-decanediol, 2 , 2-Dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,6 Hexanediol, 1,3-cyclohexanedimethanol and 1,4-cyclohexane dimethanol, etc. diol dimer acid and 2-methyl-1,8-octanediol and the like.
Among these, aliphatic diols are preferable, and 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, Dimer acid diol and 2-methyl-1,8-octanediol are more preferable because the resulting composition has low viscosity and excellent adhesiveness and water resistance.
Two or more polyhydric alcohols can be used in combination as required.

  As a method for producing the polyester polyol, a general esterification reaction may be followed, and examples thereof include a method in which a polyvalent carboxylic acid and a polyhydric alcohol are heated with stirring in the presence of a catalyst.

  As said catalyst, the catalyst normally used by esterification reaction can be used, A base catalyst, an acid catalyst, a metal alkoxide, etc. are mentioned. Examples of the base catalyst include metal hydroxides such as sodium hydroxide and potassium hydroxide, and amines such as triethylamine, N, N-dimethylbenzylamine and triphenylamine. Examples of the acid catalyst include sulfuric acid and paratoluenesulfonic acid. As the metal alkoxide, an alkoxide of titanium, tin or zirconium is preferable. Specific examples of these metal alkoxides include tetraalkyl titanates such as tetrabutyl titanate; tin alkoxides such as dibutyltin oxide and monobutyltin oxide; and zirconium alkoxides such as zirconium tetrabutoxide and zirconium isopropoxide.

  What is necessary is just to set suitably as reaction temperature and time in esterification reaction according to the objective. As reaction temperature, 80-220 degreeC is preferable.

  As the aliphatic polyester polyol, commercially available products can be used. For example, “Kuraray polyol P-5010” and “Kuraray polyol P-5050” manufactured by Kuraray Co., Ltd., manufactured by Kyowa Hakko Kogyo Co., Ltd. “Kyowapol 5000PA”, “Kyowapol 3000PA”, “Dynacoll 7250” manufactured by Degussa Japan Co., Ltd., and the like.

a2) Various polyisocyanates can be used as long as they have two or more isocyanate groups in the molecule, and diisocyanates are preferred. Specifically, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 4,4′-diphenylene diisocyanate, 1,5-octylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexa Methylene diisocyanate, pentamethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl 2,4-cyclohexane diisocyanate, methyl 2,6-cyclohexane diisocyanate, diphenylmethane Diisocyanate, 1,4-bis (isocyanatemethyl) cyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, Examples include sophorone diisocyanate and carbodiimide-modified 4,4′-diphenylmethane diisocyanate.
Among these, alicyclic or aliphatic isocyanates are preferable in that they are excellent in curability by active energy rays of the composition and weather resistance of the cured product. As the alicyclic or aliphatic isocyanate, hexamethylene diisocyanate and isophorone diisocyanate are preferable.
Polyisocyanate can use 2 or more types together as needed.
In the present invention, the amount of the polyisocyanate with respect to the polyol in producing the urethane prepolymer is preferably in a range in which the equivalent ratio of group-NCO / group-OH is 1 to 3, more preferably 1.5 to 2.5. And particularly preferably 1.8 to 2.2.

a3) Method for Producing Urethane Prepolymer The urethane prepolymer may be produced by a conventional method. For example, a method of heating a polyol and a polyisocyanate in the presence of a catalyst can be mentioned.
As a catalyst, the catalyst used by a general urethanation reaction can be used, for example, a metal compound, an amine, etc. are mentioned. As metal compounds, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate; lead-based catalysts such as lead dioctylate; zirconium-based compounds such as K-KAT XC-4025 and K-KAT XC-6212 (manufactured by KING INDUSTRIES, INC) Catalysts: Aluminum catalysts such as K-KAT XC-5217 (manufactured by KING INDUSTRIES, INC); and titanate catalysts such as tetra 2-ethylhexyl titanate. Examples of the amine include triethylamine, N, N-dimethylbenzylamine, triphenylamine, and triethylenediamine.
As a usage ratio of the urethanization reaction catalyst, it is preferable to use a small amount as much as possible so as not to adversely affect the skin.
In the production of the urethane prepolymer, a general radical polymerization inhibitor such as hydroquinone and triethylamine can be used as necessary for the purpose of preventing gelation during the reaction.

  Furthermore, a phosphorus compound can be blended during the production of the urethane prepolymer. By blending the phosphorus compound, the action of the catalyst used during esterification and ring-opening polyaddition can be stopped. If the activity of the catalyst is not deactivated, when the obtained urethane prepolymer is stored in the presence of moisture or heated in the presence of moisture in the next reaction, or the cured film of the resulting maleimide compound and composition, When stored in the presence of moisture, a transesterification reaction may occur and the physical properties of the composition may be significantly reduced.

  As a phosphorus compound, the inorganic or organic phosphorus compound etc. which are mentioned by following (i)-(e) are mentioned.

(I) Phosphoric acid and its alkyl esters Examples of phosphoric acid alkyl esters include trialkyl phosphates such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, trinonyl phosphate, and triphenyl phosphate.

(B) Phosphonic acid organic esters Dibutylbutylphosphonate and the like.

(C) Phosphorous acid Used alone or in combination with other phosphorus compounds, it has the most powerful hue stabilizing effect and oxidative degradation preventing effect.

(D) Organic esters of phosphorous acid Examples include dibutyl hydrogen phosphite and triphenyl phosphite. However, triphenyl phosphite may deteriorate the properties of the polyester skeleton in the maleimide compound, and it is necessary to pay attention to the amount of triphenyl phosphite added.

(E) Other inorganic phosphorus compounds Polyphosphoric acid etc. are mentioned.

  The amount of the phosphorus compound used may be appropriately set according to the molecular weight of the phosphorus compound (phosphorus atom content), and is generally preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of the polyester polyol. More preferably, it is 0.01-1 mass part. When the amount of the phosphorus compound used is less than 0.001 part by mass, the effect of addition is not recognized, and when it is more than 3 parts by mass, the effect does not increase.

B) Maleimide active hydrogen compound As the maleimide active hydrogen compound, an alcohol having a maleimide group (hereinafter referred to as maleimide alcohol) is preferable. Examples of maleimide alcohols include maleimide alkyl alcohols represented by the following formulas (5-1) to (5-4).

In formulas (5-1) to (5-4), R ⁵ represents an alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms. In formulas (5-1), (5-3) and (5-4), R ^{1 to} R ⁴ are the same groups as described above.

C) Method for producing component (A) As a method for producing component (A), a urethane prepolymer and a maleimide active hydrogen compound may be produced in accordance with a general urethanization reaction. Specific examples of the urethanization reaction include the same methods as described above.
In the production of the component (A), it is preferable to react in the presence of an antioxidant in order to prevent discoloration of the resulting maleimide compound.
Examples of antioxidants include phenolic, phosphite triester and amine antioxidants which are generally used. Examples of the antioxidant include JP-B 36-13738, JP-B 36-20041, and JP-B. Examples thereof include compounds described in Japanese Patent Publication No. 36-20042 and Japanese Patent Publication No. 36-20043.
Various phenolic antioxidants can be used, such as butylhydroxytoluene, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate is particularly preferred.
The phenolic antioxidant can be used in combination with an acid value zinc in order to enhance the effect.
The mixing ratio of the antioxidant is preferably 0.01 to 2 parts by mass per 100 parts by mass of the urethane prepolymer. If this proportion is less than 0.01 parts by weight, the sufficient effect due to the blending of the antioxidant may not be exhibited, and even if blended more than 2 parts by weight, no further effect is expected and the cost is reduced. Disadvantageous.
Moreover, you may mix | blend the above-mentioned phosphorus compound at the time of maleimide compound manufacture.
(A) In manufacture of a component, in order to remove the trace amount impurity contained in the maleimide compound obtained and to improve safety | security further, it can refine | purify. There is no restriction | limiting in particular regarding a purification method, What is necessary is just to follow a well-known method. For example, a method of adding a washing solvent to the obtained maleimide compound, separating the impurities after extraction using the difference in solubility between the maleimide compound and the impurities to be removed, and then removing the solvent, and the like.

1-2. Compound [2]
Compound [2] is an esterification reaction product of a prepolymer having two or more carboxyl groups at its terminal (hereinafter simply referred to as carboxylic acid prepolymer) and a maleimide active hydrogen compound.
Examples of the carboxylic acid prepolymer include those produced using the same polycarboxylic acid and polyol or polyhydric alcohol as described above. In this case, when the component (A1) is produced, a polyether polyol is used, and when the component (A2) is produced, a polyester polyol is used.
Examples of the maleimide active hydrogen compound include those described above.
The esterification reaction method of the carboxylic acid prepolymer and the maleimide active hydrogen compound may follow the same method as described above.
Compound [2] can be preferably used when a lower viscosity is required as a maleimide compound.

1-3. Compound [3]
Compound [3] is an esterification reaction product of a prepolymer having two or more hydroxyl groups at its terminal (hereinafter simply referred to as polyol prepolymer) and a carboxylic acid having a maleimide group (hereinafter referred to as maleimide carboxylic acid).
Examples of the polyol prepolymer include the same polyols. In this case, when the component (A1) is produced, a polyether polyol is used, and when the component (A2) is produced, a polyester polyol is used.
As the maleimide carboxylic acid, various compounds can be used, and compounds represented by the following formulas (6-1) to (6-4) are preferable.

In formulas (6-1) to (6-4), R ⁶ represents an alkylene group and is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. In formulas (6-1), (6-3) and (6-4), R ^{1 to} R ⁴ are the same groups as described above.
The esterification reaction method of the polyol prepolymer and maleimide carboxylic acid may follow the same method as described above.
Compound [3] can be preferably used when a lower viscosity is required as a maleimide compound.

1-4. Preferred maleimide compounds As the above-mentioned compounds [1] to [3], the compound [1] has a higher reaction rate than the compounds [2] and [3], a high yield, can be easily produced, and is cured. Most preferable in terms of excellent adhesive strength of the film. This is considered that the flexible polyol part and the hard polyisocyanate part have a micro phase separation structure, and the adhesiveness is improved by the difference in the cohesive force associated with van der Waals force and hydrogen bonding force in each micro domain. . For applications where a low viscosity maleimide compound is required, compounds [2] and [3] are preferred.
The maleimide compound is obtained by changing the copolymer composition according to the purpose, thereby allowing the viscosity and flowability of the composition, the adhesive strength of the cured coating film, the holding power and tack, the blendability of the component (B) and the medicinal component, and the skin. The feeling of use and peelability when the patch is applied to the skin can be adjusted.

In the present invention, as the component (A), the component (A1) having a polyether skeleton and the component (A2) having a polyester skeleton are used in combination.
These (A) components are preferable in that they are excellent in curability by active energy rays, excellent in various adhesive properties, and excellent in water resistance of the cured coating film. Furthermore, the combined use of the components (A1) and (A2) is preferable because water vapor permeability, tack and adhesiveness to the skin can be improved at the same time.
As the component (A1), those having a propylene oxide unit as essential among the polyether skeleton are preferable.
As a maleimide compound having a polyether skeleton that essentially includes a propylene oxide unit, a compound having an ethylene oxide unit in addition to a propylene oxide unit is used depending on whether an oily component or an aqueous component is blended. The ratio of the oxide unit can be adjusted and used, and the specific preferable ratio is as described in the section of the polyether polyol.
As the component (A2), a random copolycondensation product of an aliphatic dicarboxylic acid and an aliphatic diol is preferable among polyester skeletons. Particularly preferred aliphatic dicarboxylic acids are adipic acid and sebacic acid, and particularly preferred aliphatic diols are 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol. 3-methyl-1,5-pentanediol, dimer acid diol and 2-methyl-1,8-octanediol.

  Moreover, as (A) component, since the compound which has two maleimide groups is excellent in the adhesive force and tack of the cured coating film of a composition, it is preferable.

2. (B) Oily component or water or water-soluble compound The composition of the present invention is blended with the oily component of component (B) or water or a water-soluble compound. This improves skin adhesion, prevents skin damage when the skin patch is peeled off, and promotes solubilization of the medicinal ingredients in the composition when compounding medicinal ingredients described below. It acts as a carrier for ingredients and can further improve skin absorbability.
The choice of blending an oily component or water or a water-soluble compound as the component (B) depends on the intended use of the skin patch, the hydrophilicity and lipophilicity of the component (A) to be used, and the hydrophilicity of the medicinal component May be selected according to the property and lipophilicity.

2-1. The oily component oily component, various materials can be used as long as it exhibits an oily.
Specifically, fatty acids such as myristic acid, palmitic acid, stearic acid, lauric acid, oleic acid, isostearic acid, neodecanoic acid, trimethylhexanoic acid and neoheptanoic acid; esters of the fatty acids such as isopropyl myristate; adipic acid Esters of aliphatic dicarboxylic acids such as diisopropyl and diethyl sebacate; aliphatic alcohols such as myristyl alcohol, cetyl alcohol, oleyl alcohol and lauryl alcohol; aliphatic pyrrolidones such as N-lauryl-2-pyrrolidone, l-menthol, d- Acts as a solubilizer and transdermal absorption enhancer of terpenes such as limonene and α-terpineol; alkanes such as heptane, octane, nonane and decane; and medicinal components such as crotamiton and α-, β-, γ-cyclodextrin material And the like. In addition to these, L-menthol, camphor, thymol, peppermint oil, castor oil, fennel oil, daikyo oil, cinnamon oil, clove oil, thiamine oil, terpylene oil, eucalyptus oil, lavender oil, lemon oil, orange Examples include substances used as perfumes and refreshing agents such as oil, bergamot oil and rose oil.

2-2. As water or a water-soluble compound, various compounds can be used as long as they exhibit water solubility.
Specifically, alcohols such as ethanol, propanol and butanol, polyols such as propylene glycol, ethylene glycol, polyethylene glycol and glycerin, amines such as diethanolamine and triethanolamine, and N-methyl-2-pyrrolidone and 2-pyrrolidone Pyrrolidone and the like.
Further, an aqueous solution in which a water-soluble compound is dissolved can be used as necessary. In this case, the proportion of the water-soluble compound in the aqueous solution is preferably 3 to 95% by mass.
As water or a water-soluble compound, it is preferable to use water alone or an aqueous solution of a water-soluble compound.

As the component (B), one having an absorbance at a wavelength of 365 nm of 1.0 or less is preferable in that the composition has excellent curability. Examples of such component (B) include isopropyl myristate, N-methyl-2-pyrrolidone, water and ethanol.
In addition, when compounding a medicinal component described later, it promotes solubilization of the medicinal component in the composition, acts as a carrier of the medicinal component, can further improve skin absorbability, and when peeling the skin patch It is more preferable to use two or more kinds of compounds in combination as the component (B) from the viewpoint of satisfying prevention of skin damage. The selection of the compound in this case may be appropriately selected according to the individual purpose based on the solubility of the medicinal component, the action on the stratum corneum and the ability to adjust the adhesiveness appropriately. For example, there is an example of using a compound that easily dissolves a medicinal component and a compound for exerting appropriate adhesiveness to the skin, specifically, an example of using N-methyl-2-pyrrolidone and isopropyl myristate in combination. Etc.

3. Composition for active energy ray-curable skin patch The composition of the present invention is essentially a liquid composition at room temperature, essentially comprising the component (A) and the component (B).
(A) A component functions as an adhesive component.
In the component (A), the proportion of the components (A1) and (A2) is 20 to 95 parts by mass of the component (A1) and (A2) based on 100 parts by mass of the total amount of the components (A1) and (A2). ) The component is preferably 80 to 5 parts by mass. More preferably, the component (A1) is 50 to 95 parts by mass and the component (A2) is 50 to 5 parts by mass, most preferably 70 to 90 parts by mass and the component (A2) is 30 to 10 parts by mass. When the proportion of the component (A1) is less than 20 parts by mass or the component (A2) exceeds 80 parts by mass, the water vapor permeability may be lowered. On the other hand, if the proportion of the component (A1) exceeds 95 parts by mass or the proportion of the component (A2) is less than 5 parts by mass, tackiness and adhesiveness to the skin may be lowered.
The component (A) must be selected from the compound 1 as the component (a) or the component (a) (a) the compound 2 and (b) the compound 3 or / and the compound 4.
When the component (A) is selected as the component (A), the ratio of the component (a) and the component (b) is as follows: (a) The component is preferably 20 to 40 parts by mass and the component (b) is preferably 80 to 60 parts by mass, and more preferably the component (a) is 25 to 35 parts by mass and the component (b) is 75 to 65 parts by mass. When the proportion of the component (a) is less than 20 parts by mass, the curability of the composition may be reduced, and the cohesive force of the cured coating film may be reduced. On the other hand, when the proportion of the component (a) exceeds 40 parts by mass, the tackiness and water resistance of the cured coating film may be lowered.
When the compound 3 and the compound 4 are used in combination as the component (b), the compound 3 is 10 to 90 parts by mass and the compound 4 is 90 to 10 parts by mass with respect to 100 parts by mass of the total amount of the compound 3 and the compound 4. preferable.

  What is necessary is just to set suitably as a compounding ratio of (A) component and (B) component according to the objective. (B) When mix | blending an oily component as a component, 0.1-50 mass% of an oily component is preferable with respect to the total amount of (A) component and (B) component, More preferably, it is 1-30 mass%. It is. Moreover, when mix | blending an aqueous component, 0.1-80 mass% of an aqueous component is preferable with respect to the total amount of (A) component and (B) component, More preferably, it is 0.3-40 mass%. .

  The composition of the present invention must be liquid at room temperature. Thereby, handling of coating work etc. becomes easy. On the other hand, those that are solid at room temperature are difficult to handle, and the cured coating film has a high elastic modulus, resulting in insufficient adhesive performance.

  In addition to the essential components, various components can be blended in the composition of the present invention as necessary. Each component will be described below.

3-1. As described above, the composition of the present invention, such as a photopolymerization initiator , is easily cured by active energy rays, and further contains no photopolymerization initiator or a small amount of photopolymerization even when cured by ultraviolet rays or visible light. Although it has excellent curability by blending an initiator or the like, a photopolymerization initiator or the like can be blended as necessary.
In the case of blending a photopolymerization initiator, benzoin and its alkyl ethers, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, xanthones, acylphosphine oxides, α- And diketones.
Moreover, in order to improve the sensitivity by an active energy ray, a photosensitizer can also be used together.
Examples of the photosensitizer include benzoic acid and amine photosensitizers. These can also be used in combination of two or more. As these compounding ratios, 0.01-10 mass parts is preferable with respect to 100 mass parts of (A) component.
As the photopolymerization initiator, benzophenones and thioxanthones are preferable because they have a high effect of improving the curing rate of the composition.

3-2. Compound having a reactive unsaturated group The composition of the present invention has a (meth) acrylic monomer, a (meth) acrylic oligomer, etc. in order to enhance the adhesive performance of the cured coating film or to adjust the sensitivity of the composition. You may mix | blend the compound which has these reactive unsaturated groups.
Examples of the (meth) acrylic monomer include alkyl acrylate or alkyl methacrylate (hereinafter, acrylate or methacrylate is referred to as (meth) acrylate), hydroxyalkyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, mono or glycol Examples include di (meth) acrylate, polyol poly (meth) acrylate, and poly (meth) acrylate of a polyol alkylene oxide adduct.
Examples of (meth) acrylic oligomers include urethane (meth) acrylate oligomers, polyester (meth) acrylate oligomers, and epoxy (meth) acrylate oligomers.
As a compounding ratio of the compound which has a reactive unsaturated group, 50 mass parts or less are preferable with respect to 100 mass parts of (A) component, More preferably, it is 20 mass parts or less.

3-3. Polymer A polymer may be added to the composition of the present invention in order to adjust the viscosity before curing and the adhesive performance after curing. Although it does not specifically limit as the said polymer, (meth) acrylate type polymer, polystyrene, polyolefin, etc. are mentioned. Among these, a (meth) acrylate polymer having a maleimide group is preferable because it is crosslinked with the component (A) of the present invention in curing.

3-4. Other Maleimide Compound In the composition of the present invention, a compound having one maleimide group can be used in combination as long as the curability by active energy irradiation and the performance of the cured coating film are not impaired.
Examples of the compound include a compound having one maleimide group in the same skeleton as described above and a compound having a maleimide group and an ethylenically unsaturated group.
When the component (A) of the present invention is a polymer polyol produced from the above-mentioned radical polymerizable monomer, the polymer polyol has two or more hydroxyl groups in one molecule and one molecule. A mixture with one having one hydroxyl group may be used. In this case, the resulting compound is a mixture of a compound having two or more maleimide groups and a compound having one maleimide group, which can be used as it is.
The blending ratio of the compound having one maleimide group is preferably 80 parts by mass or less, more preferably 50 parts by mass or less, with respect to 100 parts by mass of the component (A).

3-5. Tackifying agent In the composition of the present invention, a tackifying agent may be blended in order to lower the glass transition temperature (hereinafter abbreviated as Tg) of the cured coating film or to increase the adhesive performance.
Various tackifiers can be used, and examples thereof include natural resins such as rosin resins and terpene resins and derivatives thereof, and synthetic resins such as petroleum resins. Among these, those having no double bond or having a small ratio of double bonds are preferable because the inhibition of curing by active energy rays of the composition is small.
As a compounding ratio of the tackifier, the ratio of the tackifier is preferably 50 parts by mass or less, more preferably 10-30 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the tackifier. Part. When the compounding amount of the tackifier exceeds 50 parts, the viscosity of the composition becomes too high, and the coating property is lowered.

3-6. Crosslinking agent In order to increase cohesion, the composition of the present invention may be used by adding a crosslinking agent that reacts quickly at normal temperature for the purpose of crosslinking between molecules of the polymer. Examples of the crosslinking agent include polyvalent isocyanate compounds, polyoxazoline compounds, epoxy resins, aziridine compounds, polycarbodiimide resins, and coupling agents.

3-7. As an acid mask agent (A2) component, when polyester is used as a raw material, an acid mask agent may be blended into the composition.
Polyester is generally known to hydrolyze and lower its molecular weight when used under severe conditions such as high temperature and humidity for a long time. Adhesive strength decreases depending on the storage conditions even for skin patches. Or may leave a plaster residue when peeled from the skin.
In this case, if an acid mask agent is blended, a carboxyl group generated by hydrolysis can be trapped and further hydrolysis can be prevented.
Examples of the acid masking agent include carbodiimide compounds, oxazoline compounds, and epoxy compounds.
As a compounding ratio of an acid mask agent, 0.01-2 mass parts is preferable per 100 mass parts of (A2) component.

3-8. Medicinal components When the composition of the present invention is used for medical purposes, a medicinal component may be blended.
Examples of medicinal ingredients include salicylic acid and derivatives, indomethacin, ketoprofen, flurbiprofen, ibuprofen, thiaprofenic acid, zaltoprofen, pranoprofen, loxoprofen sodium, ampiroxicam, piroxicam, meloxicam, lornoxicam, thiaramide hydrochloride, diclofenac sodium, felbinac Antibacterial agents such as nitroglycerin, isosorbite nitrate and pindolol; antisickness agents such as scopolamine; cancer pain agents such as fentanyl; hormone supplements such as estradiol; clonidine hydrochloride; Methyldopa, hydralazine hydrochloride, rescinamine, doxazosin mesylate, bunazosin hydrochloride, prazosin hydrochloride, carvedilol, arotinolol hydrochloride, Acid labetalol, tilisolol hydrochloride, betaxolol hydrochloride, metoprolol tartrate, delapril hydrochloride, temocapril hydrochloride, captopril, alacepril, benazepril hydrochloride, imidapril hydrochloride, enalapril maleate, lisinopril, nifedipine, manidipine hydrochloride, nididipine hydrochloride, nicardipine hydrochloride, nicardipine hydrochloride Smoking cessation aid such as nicotine; Asthma therapeutic agents such as oxatomide and tranilast are listed.
What is necessary is just to set the compounding ratio of a medicinal ingredient suitably according to the objective, and 0.05-20 mass% is preferable in a composition.

3-9. In addition , a filler may be added to the composition of the present invention in order to enhance coloring and adhesion performance. Specific examples of the filler include various silicas, dyes, calcium carbonate, magnesium carbonate, titanium oxide, iron oxide, and glass fiber.
Moreover, you may mix | blend radical polymerization inhibitors, such as hydroquinone and hydroquinone monomethyl ether, according to a use.
In addition to these, antifoaming agents, dyes and pigments, thickeners, lubricants, film forming aids, fillers, plasticizers, antistatic agents, fiber auxiliaries, cleaning agents, antistatic agents, leveling agents, General additives used in adhesives and pressure-sensitive adhesives such as dispersion stabilizers, hydrophilic resins, latexes, wetting agents, and leveling improvers can be used in a commonly used proportion. In addition, antioxidants such as dibutylhydroxytoluene and butylhydroxyanisole; preservatives such as methyl paraoxybenzoate and propyl paraoxybenzoate; and general additives used in skin patches such as emulsifiers are usually used. Can be used in combination.
Moreover, in order to adjust a viscosity, an organic solvent can also be mix | blended as needed.
Furthermore, the above-mentioned phosphorus compound and antioxidant can also be mix | blended.

4). Method for Producing Skin Patch The composition of the present invention can be used as a skin patch in various forms such as a tape, a plaster and a poultice.

As a method for producing a skin patch using the composition of the present invention, a conventional method may be followed. Preferable methods include, for example, a method of applying the composition of the present invention to a support and irradiating the coating film with an active energy ray to cure.
The obtained cured coating film has adhesiveness and forms a plaster layer when it is a plaster or a poultice.

  Examples of the support include paper, cloth and plastic, and combinations thereof. Examples of the cloth include woven cloth, non-woven cloth, and knitted cloth. Examples of the plastic include polyester, nylon, polyethylene and polypropylene, polyurethane, polyvinyl chloride, polyacrylate, polycarbonate, polyethylene terephthalate, and acrylonitrile butadiene styrene copolymer.

  Examples of the coating method of the composition include roll coating, die coating, knife coating and the like.

What is necessary is just to select the coating amount of the composition with respect to a support body suitably according to the use to be used.
A preferable coating amount is 5 to 200 g / m ² , more preferably 10 to 100 g / m ² . If it is less than 5 g / m ² , the adhesive strength may be insufficient, and if it exceeds 200 g / m ² , the target energy may not be obtained because the active energy ray is difficult to reach the deep part.

After completion of the coating treatment, active energy rays are irradiated to crosslink the maleimide groups of the component (A) to increase the molecular weight, thereby improving the cohesive force and adhesive force of the resulting cured coating film.
The irradiation method of the active energy ray in this case may follow the method conventionally performed with the active energy ray-curable adhesive. Examples of active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, and it is preferable to use ultraviolet rays because inexpensive devices can be used. Examples of the light source in the case of using ultraviolet light include ultrahigh pressure, high pressure, medium pressure or low pressure mercury lamp, metal halide lamp, xenon lamp, electrodeless discharge lamp, and carbon arc lamp, and the irradiation may be performed for several seconds to several minutes.

  Moreover, as Tg of the cured coating film of the composition of this invention, -10 degrees C or less is preferable, More preferably, it is -30 degrees C or less. In the present invention, Tg means the peak temperature of tan δ obtained by measuring temperature dependence using a dynamic viscoelasticity measuring apparatus.

The adhesive strength of the patch of the present invention is preferably 10 to 2200 g / 25 mm, more preferably 50 to 1500 g / 25 mm, and most preferably 100 to 1200 g / 25 mm. When the adhesive strength is less than 10 g / 25 mm, the adhesiveness to the skin may be insufficient. On the other hand, when it exceeds 2200 g / 25 mm, the adhesiveness to the skin is too strong and the stratum corneum is damaged. There is.
The tack of the patch of the present invention is preferably 8 or more, more preferably 9 to 25 in the ball rolling method of JIS Z-0237. If the tack is less than 8, there may be cases where sufficient adhesion to the skin cannot be obtained simply by lightly sticking to the skin.
The water vapor permeability of the patch of the present invention is preferably 400 g / m ² or more under the conditions of 40 ° C. and 30% RH. If the water vapor permeability is less than 400 g / m ² , it may cause skin irritation when the skin is applied to the skin for a long period of time.

5. Use The skin patch obtained from the composition of the present invention has high safety and can be used for various uses.
As described above, the skin patch of the present invention can be used in various forms such as a tape, a plaster and a poultice.
Specific examples include emergency bonds, magnetic bonds, surgical tapes, accelerated wound dressings, sports taping tapes and transdermal patches.
The surgical tape is used when the catheter is fixed to the body. The accelerated wound dressing is also called a dressing material and is used for healing by covering the wound tightly to prevent external infection and relieve pain and keep the wound in a moist environment. The sports taping tape protects and strengthens the injured part of joints and muscles by preventing injury during exercise, first aid and preventing relapse (rehabilitation).
The composition of the present invention is useful as a transdermal absorption patch, plaster and cataplasm, and these uses will be described in detail below.

5-1. Transdermal absorption patch The transdermal absorption patch is a tape preparation used in a percutaneous absorption treatment system (hereinafter referred to as TTS) in which a medicinal component is absorbed from the skin and guided into the body.
The composition of the present invention can be used as a raw material for adhesive components used in transdermal patches.
Examples of the medicinal component of the transdermal absorption patch include, for example, an anti-inflammatory agent, an angina pectoris agent, an antisickness agent, a cancer pain agent, a hormone replacement agent, an antihypertensive agent, an anti-smoking agent, and an asthma treatment in the medicinal component described above. And the like having an agent as an active ingredient.
It is preferable to mix an absorption enhancer with the transdermal absorption patch in order to promote absorption of the medicinal component. Examples of absorption accelerators that act on lipids of the stratum corneum as a medicinal component include, for example, sulfoxides such as dimethyl sulfoxide, amides such as urea and dimethylacetamide, amines, terpenes, and surfactants. Can be mentioned. Examples of the absorption promoter that acts as a carrier of a medicinal component include those mentioned for the oil component and water-soluble compounds.
The composition of the present invention can be used for any transdermal patch used in reservoir-type TTS, matrix-type TTS and adhesive-type TTS.
A production example of a transdermal absorption patch will be described taking an adhesive type TTS as an example. For example, a composition containing a medicinal ingredient and an absorption accelerator is applied to a substrate and irradiated with active energy rays. Examples include a method of curing and cutting the composition of the invention.

5-2. Plaster plaster is an external preparation that is used by spreading a normal solid plaster on a support such as paper, cloth, or plastic and bringing it into close contact with the skin.
The composition of the present invention can be used as an adhesive component of a plaster used in plaster.
Examples of the plaster component include fat, fatty oil, fatty acid salt, wax, resin, purified lanolin and rubber. Examples of the medicinal component include the aforementioned medicinal components.

5-3. A poultice is a topical agent used for a poultice, which contains a medicinal component powder and an essential oil component, and is stretch-formed on a support such as a cloth.
The composition of the present invention can be used as an adhesive component of a plaster base used in a poultice.
An example of the preparation of a poultice is described by taking a molded poultice as an example. For example, a medicinal component, an essential oil component and a paste base are kneaded to form a paste, which is spread on a support, and an active energy ray is produced. The composition of the present invention is cured by irradiation, coated with a liner, and cut.
Examples of the medicinal component include the above-mentioned medicinal components, mainly salicylic acid derivatives and the like. Examples of the plaster base include sodium polyacrylate, gelatin, methylcellulose, polyvinyl alcohol, purified water and the like in addition to the composition of the present invention. Examples of the liner include polyester, polyethylene, and polypropylene.

According to the composition of the present invention, since it is liquid at room temperature, it is easy to handle and has excellent coatability. Further, even when irradiated with visible light or ultraviolet light, it has a practical crosslinkability or curability in the absence of a photopolymerization initiator, so that it is safe with little odor and toxicity. Furthermore, the resulting cured coating is not colored, has excellent adhesive properties, and does not hurt the pain or stratum corneum even when it is repeatedly applied to and peeled off from the skin, and has excellent water resistance. .
Furthermore, since it has a high water vapor permeability, it does not irritate the skin even if it is applied to the skin for a long time and does not irritate the skin. In addition, since it can easily improve the adhesive strength against tack and skin, it can be immediately applied to the skin just by lightly adhering to it. .

The composition of the present invention essentially comprises the component (A) and the component (B). As the component (A), the following are preferable.
That is, the component (A) is preferably liquid at room temperature. Furthermore, as the component (A), the component (a) or the component (a) is preferable. Furthermore, the number average molecular weight is preferably 1,000 to 20,000.
Furthermore, what contains a medicinal component in a composition is preferable.
The present invention also provides a skin patch prepared by applying the above composition to a support and then curing it by irradiation with active energy rays.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples.
In the following, “%” means mass%.

○ Production Example 1
A flask equipped with a stirrer, a thermometer and a cooler was charged with 270 g of polyether polyol Adeka polyether P-3000 [polypropylene glycol, manufactured by Asahi Denka Kogyo Co., Ltd., hereinafter referred to as P-3000] at room temperature while stirring. The temperature was raised to 120 ° C. and dehydrated under reduced pressure for 1 hour.
After dehydration, the mixture was cooled to 60 ° C., and 40.4 g of isophorone diisocyanate (hereinafter referred to as IPDI) and 0.050 g of di-n-butyltin dilaurate (hereinafter referred to as DBTL) were charged and reacted for 2 hours. Thereafter, the temperature was raised to 80 ° C. and the reaction was continued for another 30 minutes, and then 2-hydroxyethyl citracimide [compound of the following formula (7). Hereinafter referred to as CM-ETA. 28.5 g was charged and reacted for 2 hours to obtain a maleimide compound.
The viscosity of this compound at 25 ° C. was 26,000 mPa · s, and the number average molecular weight (hereinafter abbreviated as Mn) was about 3,800. This compound is referred to as A1-1.

○ Production Examples 2-8
In Production Example 1, a maleimide compound was produced under the same conditions as in Production Example 1, except that the components and amounts shown in the following table were used.
Table 1 shows the viscosity and Mn of the obtained compound.

The abbreviations in Table 1 mean the following.
1) CM-381: Polyether polyol, Adeka Polyether CM-381 manufactured by Asahi Denka Kogyo Co., Ltd.
2) CM-294: Polyether polyol, Adeka Polyether CM-294 manufactured by Asahi Denka Kogyo Co., Ltd.
3) 5000 PA: polyester polyol, Kyowa Hakko Kogyo Kyowapol 5000 PA
4) PES-2: Polyester polyol, random copolycondensation product of MPD / BEPG = 50/50 and adipic acid, Mn = 5000
5) PPG: Polypropylene glycol, EO: Ethylene oxide unit, PO: Propylene oxide unit, DEPD: 2,4-diethyl-1,5-pentanediol, MPD: 3-methyl-1,5-pentanediol, BEPG: 2-Butyl-2-ethyl-1,3-propanediol 6) Unit: mPa · s
7) ML-ETA: Compound represented by the following formula (8)

8) DM-ETA: compound represented by the following formula (9)

9) HT-ETA: Compound represented by the following formula (10)

○ Examples 1-7, Comparative Examples 1-4
The maleimide compounds produced in the above production examples and comparative production examples were used, mixed thoroughly with the formulation of Table 2 until uniform, and then defoamed to prepare a composition for skin patches.
The composition obtained so as to have a film thickness of 50 μm is applied to the surface of a polyester film having a thickness of 50 μm, which is a support sheet, and a 120 W / cm condensing type high-pressure using an ultraviolet irradiation device having a belt conveyor. Passes 4 passes under a mercury lamp (1 light, height 10 cm) at a conveyor speed of 10 m / min and irradiates with ultraviolet rays from the application surface side (integrated light quantity = 1200 mJ / cm ² ) to cure the composition and produce a patch. did.
In Comparative Examples 2 and 4, the composition was heated to 80 ° C. and applied.
The obtained patch was cut into a length direction of 200 mm and a width direction of 25 mm to obtain a test specimen.

The following evaluation was performed about the obtained test body. The results are shown in Table 3.
[1] Adhesive strength With respect to the 180 degree peel strength of the test specimen, a bakelite plate was used as a test plate under the conditions of 23 ° C. and 65% RH, and the others were baked on a bakelite plate according to JIS Z-0237. Was attached and pressure-bonded with a roller having a load of 2 kg, and the peel strength was measured after standing for 30 minutes (adhesive strength 1) and after standing for 24 hours (adhesive strength 2).

[2] Tack According to the ball rolling method of JIS Z-0237, it was measured in an atmosphere of 23 ° C. and 65% RH.

[3] Water vapor permeability The composition for skin patch prepared above was applied to a release paper having a silicon treatment on the surface, and the composition was cured by irradiating with ultraviolet rays in the same manner as described above, and then the fine quality of 90 μm in thickness. A test specimen for evaluating water vapor permeability was prepared by transferring to paper.
Regarding the water vapor permeability of this specimen, the mass (g) of water vapor passing through the specimen for 24 hours in accordance with JIS Z-0208 under the conditions of 40 ° C. and 30% RH, is 1 m ^{2 of the} specimen. It was determined as per the value P _C. Further, the water vapor permeability P _B of the support itself was determined without transferring the cured product to the support (90 μm fine paper) under the same conditions, and the water vapor permeability P _A of the adhesive layer was determined by the following equation (1). .

[Formula 1]
1 / P _A = 1 / P _C − 1 / P _B (1)

[4] Remaining paste The paste layer remains on the bakelite plate when the peel strength is measured after 24 hours of standing (1) Were observed visually and touched with fingers, and evaluated in the following three stages.
○: None, △: Slightly, ×: Available

[5] Sensation of skin adhesion Adhesion to the skin when the test specimen is affixed to the back of 5 hands and peeled immediately, adhesion that does not peel off when the skin is moved by gently opening and closing the palm while it is affixed to the back of the hand The force and the feeling of use at that time were evaluated in the following four stages.
A: Moderate adhesiveness, sufficient adhesive strength that does not peel off even when moving the skin,
In particular, it has excellent usability.
○: Moderate adhesiveness, sufficient adhesive strength that does not peel off even when moving the skin,
Excellent usability.
Δ: Adhesive strength is slightly strong or too strong, and the feeling of use when moving the skin is poor.
X: A part peeled slightly when the skin is moved, and the adhesive strength is insufficient.

[6] Skin peelability The test specimen was affixed to the back of five hands, and the presence or absence of exfoliated horny substance (destructive state of the stratum corneum) adhered on the glue surface when peeled off slowly after standing for 30 minutes was visually observed. The following four levels were evaluated.
◎: No destruction, ○: Almost no destruction, △: Destruction, x: Remarkable destruction

The abbreviations in Table 2 have the following meanings.
1) IPM: isopropyl myristate 2) DIA: diisopropyl adipate 3) DES: diethyl sebacate 4) OLA: oleic acid

Examples 8 to 14 (Patch compositions containing medicinal ingredients)
Using the maleimide compound produced in the above production example, it was thoroughly mixed until it became uniform according to the formulation shown in Table 4, and then defoamed to prepare a skin patch composition.
On the surface of a polyester film having a thickness of 50 μm as a support sheet, the composition obtained so as to have a thickness shown in Table 4 was applied, and using an ultraviolet irradiation device having a belt conveyor, 120 W / Passed under a 10 cm / min conveyor speed of 10 m / min under a concentrating high-pressure mercury lamp (1 light, height 10 cm), and irradiated with ultraviolet rays from the coated surface side (total light quantity per pass is 300 mJ / cm ² ). Irradiation was repeated until the accumulated light amount shown was reached, and the composition was cured to produce a patch.
The obtained patch was cut into a length direction of 200 mm and a width direction of 25 mm to obtain a test specimen. About the obtained test body, the same evaluation as the above was performed. The results are shown in Table 5.

The abbreviations in Table 4 mean the following. Otherwise, it has the same meaning as described above.
1) NMP: N-methyl-2-pyrrolidone

  The composition for active energy ray-curable skin patch of the present invention can be used for applications in which a skin patch is used.

Claims (5)

(A) A compound having two or more maleimide groups, comprising the following components (A1) and (A2), and (B) a composition comprising an oil component or water or a water-soluble compound. The composition for active energy ray-curable skin patches wherein the component (A) is a liquid at 25 ° C., which is a compound selected from the following components (A) or (A):
(A): A compound having two or more maleimide groups represented by the following formula (1).

[In the formula (1), R ¹ represents an alkyl group, an aryl group, an arylalkyl group or a halogen atom. ]
(A): (a) a compound having two or more maleimide groups represented by the following formula (2) and (b) a compound having two or more maleimide groups represented by the following formula (3) or / and the following formula A compound having two or more maleimide groups represented by (4).

[In the formula (3), R ² and R ³ represent an alkyl group, an aryl group, an arylalkyl group, or a halogen atom. ]

[In the formula (4), R ⁴ represents a propylene group or a butylene group which may have an alkyl group as a substituent. ]

(A1): a polyether compound containing propylene oxide units (A2): a random copolymer polycondensate of an aliphatic dicarboxylic acid and an aliphatic diol The composition for active energy ray-curable skin patch according to claim 1, wherein the component (A) is a compound that is liquid at 25 ° C. The composition for active energy ray-curable skin patches according to claim 1 or 2, wherein the component (A) has a number average molecular weight of 1,000 to 20,000. Furthermore, the composition for active energy ray hardening-type skin patches in any one of Claims 1-3 containing a medicinal component. A skin patch prepared by applying the composition according to any one of claims 1 to 4 to a support and then curing the composition by irradiation with active energy rays.