JP2001253819A - Adhesive tape for medical use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare an adhesive tape for medical use containing a urethane resin adhesive layer applicable to the human body, having simultaneously solved such problems as bleeding of the low-molecular fraction in a rubber-based adhesive, lack in the re-releasability of an acrylic resin-based adhesive and in moisture permeability, skin irritancy, or the like, thereby free from skin irritancy and excellent in moisture permeability and re-releasability. SOLUTION: This adhesive tape comprises (A) a sheet substrate >=1,500 g/(m2.24 h) in moisture permeability and (B) a urethane-urea adhesive layer >=1,500 g/(m2.24 h) in moisture permeability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive adhesive tape for medical use, and more particularly, to a plaster, a salicylic acid plaster, an anti-inflammatory analgesic plaster, a cataplasm, a surgical dressing,
The present invention relates to a medical adhesive tape used as a surgical drape, a suture tape, an electrode terminal tape, a steroid tape, a percutaneous absorption tape, a sports tape, an adhesive sheet for hair removal, and the like.

[0002]

2. Description of the Related Art The constituent components of an adhesive layer of a medical adhesive tape are roughly classified into an acrylic resin type and a rubber type, but both have drawbacks in performance. Acrylic resin-based adhesives have excellent adhesive properties, but the crosslinking is strong, the elastic loss rate at room temperature is high, the adhesive cannot follow the movement of the skin, and various chemical components are mixed in the adhesive, There are problems that higher safety is required and that it has an odor peculiar to acrylic. On the other hand, rubber-based pressure-sensitive adhesives can not secure adhesive properties unless low-molecular-weight substances are contained, so the addition of low-molecular-weight substances such as plasticizers is indispensable. Causes a significant reduction in the adhesive properties.

[0003] In addition, if a medical adhesive tape does not have an appropriate moisture permeability, the site where the adhesive tape is applied becomes a favorable culture area having an appropriate temperature and humidity, and bacteria groups can be propagated. May cause skin irritation. Moisture permeability suitable as a medical adhesive tape is demonstrated by various references to have an average body water loss of 250 (g) from the skin excluding visible sweat.
/ (M ² · 24h)). However, parts such as the palms and soles of the feet are 500 (g / (m ² · 24
h)) High water loss near.

Japanese Patent Publication No. 7-83760 discloses a pressure-sensitive adhesive member having high moisture permeability using a polyurethane resin. However, the pressure-sensitive adhesive layer of the present invention is not a polyurethane resin but an acrylic resin (Chrisbon 7367). -SL,
Dainippon Ink), synthetic rubber (Kraton Thermoplastic Bar, Ciel) and natural rosin (KE
707, manufactured by Yasuhara Yushi Co., Ltd.), so that the above-mentioned problems peculiar to the conventional pressure-sensitive adhesive have not been solved.

[0005] Also, studies have been made on the use of urethane resins having good moisture permeability and non-skin irritation for the pressure-sensitive adhesive layer. Was limited to If the amount of the curing agent is reduced to increase the adhesive strength of the urethane-based adhesive, the cross-linking structure is reduced and the cohesive strength is insufficient, so that good removability is not developed. It was difficult to use as an adhesive layer.

[0006]

DISCLOSURE OF THE INVENTION The present invention is intended to alleviate problems such as bleeding of low molecular weight rubber-based pressure-sensitive adhesives, removability of acrylic resin-based pressure-sensitive adhesives, insufficient moisture permeability, and skin irritation. Further, the present invention provides a medical pressure-sensitive adhesive tape having a urethane resin pressure-sensitive adhesive layer which has no skin irritation, is excellent in moisture permeability and removability, and can be applied to a human body.

[0007]

Means for Solving the Problems The present inventors have developed a urethane urea resin having a moisture permeability of at least 1,500 (g / (m ² · 24 h)) and a high molecular weight urethane urea resin into which a urea bond has been introduced. It has been found that a medical pressure-sensitive adhesive tape excellent in moisture permeability, skin irritation, and removability can be obtained by using the pressure-sensitive adhesive layer.

That is, according to the present invention, the moisture permeability is 1,500.
(G / (m ² · 24h)) or more sheet base material (A)
When, a medical adhesive tape comprising a moisture permeability is ^{1,500 (g / (m 2 ·} 24h)) or the pressure-sensitive adhesive layer, the adhesive layer is, the polyol (a) and polyisocyanate (b ) Is reacted in the presence of a catalyst (c) with a urethane prepolymer (B) to give a compound (f) obtained by subjecting a polyamine (d) and a compound (e) having an unsaturated double bond to a Michael addition reaction. For medical use, comprising a urethane resin (C) having an isocyanato group at the end obtained by chain extension and a compound (g) having an active hydrogen capable of reacting with the isocyanate group, and a urethane resin adhesive (D). Related to adhesive tape.

The present invention also relates to the above medical pressure-sensitive adhesive tape, wherein the pressure-sensitive adhesive layer has a skin irritation (PII) of 0.

The present invention also provides a first step of synthesizing a urethane prepolymer (B) by reacting a polyol (a) and a polyisocyanate (b) in the presence of a catalyst (c). The polymer (B) is chain-extended with a compound (f) obtained by subjecting a polyamine (d) and a compound (e) having an unsaturated double bond to a Michael addition reaction to obtain a urethane resin (C) having an isocyanato group at a terminal. In the second step of the synthesis, the urethane resin (C) having an isocyanato group at the terminal is reacted with a compound (g) having an active hydrogen capable of reacting with the isocyanato group to synthesize a urethane resin adhesive (D). In the third step, the urethane resin pressure-sensitive adhesive (D) contains the curing agent (E) in an amount of 0.5 to 10% by weight based on the urethane resin pressure-sensitive adhesive (D) to obtain a urethane resin pressure-sensitive adhesive (F). No. Step, the urethane resin adhesive agent (F), moisture permeability ^{1,500 (g / (m 2 ·} 24
h)) The present invention relates to a method for producing a medical pressure-sensitive adhesive tape including a fifth step of laminating on one surface of the sheet substrate (A) described above.

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The sheet substrate used in the present invention is not particularly limited as long as it has a moisture permeability of 1,500 ((m ² · 24 h)) or more. Such sheet substrates are broadly classified into cloth, paper, nonwoven fabric and polymer film. The moisture permeability used in the present invention means that the moisture permeability of the moisture-proof packaging material is measured according to the moisture permeability test method (cup method) (JIS Z0208).

[0012] The material fibers of the cloth include cotton, rayon, polyester, and acetate.

As for paper, manila hemp, mainly pulp,
A material obtained by mixing a synthetic fiber or the like to improve the strength of the support may be used.

As the nonwoven fabric, fibers such as rayon, polyester, nylon and the like can be mentioned.

As for the polymer film, flexible PVC, polyethylene, a copolymer of polyethylene and vinyl acetate,
Examples include polypropylene and urethane.

The urethane prepolymer (B) used in the present invention is obtained by a urethanization reaction between the polyol (a) and the polyisocyanate (b).

Examples of the polyol (a) used in the present invention include polyester polyols, polyether polyols, polyester polyols and / or polyurethane polyols which are reactants of polyether polyols and diisocyanates, and polyether adducts of polyhydric alcohols. Used.

Known polyester polyols can be used as the polyester polyol used in the present invention. Terephthalic acid, adipic acid, azelaic acid, sebacic acid, phthalic anhydride, isophthalic acid,
Trimellitic acid and the like, and glycol components such as ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol,
3,3′-dimethylol heptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4
-Butanediol, neopentyl glycol, butylethylpentanediol, and glycerin, trimethylolpropane, pentaerythritol and the like as polyol components. In addition, polycaprolactone, poly (β
-Methyl-γ-valerolactone), and polyester polyols obtained by ring-opening polymerization of lactones such as polyvalerolactone. The molecular weight of the polyester polyol can be used from a low molecular weight to a high molecular weight, preferably a polyester polyol having a molecular weight of 1,000 to 5,000 and bifunctional or more, more preferably a molecular weight of 1,
A polyester polyol having a bifunctionality of 500 to 3,500 or more is used. The use amount thereof is preferably 0 to 50 mol% in the polyol constituting the urethane prepolymer (B).

As the polyether polyol used in the present invention, a known polyether polyol can be used. For example, water, propylene glycol, ethylene glycol, glycerin, using a low molecular weight polyol such as trimethylolpropane as an initiator, ethylene oxide, propylene oxide, butylene oxide, polyether polyol obtained by polymerizing an oxirane compound such as tetrahydrofuran Specifically, those having two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol, can be used. The molecular weight of the polyether polyol can be used from a low molecular weight to a high molecular weight, but is preferably a polyether polyol having a molecular weight of 1,000 to 5,000 and difunctional or higher, more preferably a molecular weight of 1,500 to 4,000. Is used. The use amount thereof is preferably 50 to 100 mol% in the polyol constituting the urethane prepolymer (B).

The polyurethane polyol which is a reaction product of the polyester polyol and / or polyether polyol and the polyisocyanate (b) used in the present invention includes a urethane reaction product of the polyester polyol and the polyisocyanate (b), and a polyether polyol and a polyether polyol. The urethanization reaction product of isocyanate (b), polyester polyol and polyether polyol and urethanization reaction of polyisocyanate (b) are included.
In the polyurethane polyol of the present invention, both terminal components consist of polyester polyol or polyether polyol, and both terminals are hydroxyl groups. The polyester polyol and polyether polyol used here are the compounds described above. The polyisocyanate (b) is a polyisocyanate (b) described later. The molecular weight of the polyurethane polyol can be used from a low molecular weight to a high molecular weight, but is preferably 1,000 to 5,
A 2,000 bifunctional or more functional polyurethane polyol, more preferably, a 2,000 to 4,000 bifunctional or more functional polyurethane polyol is used.

The polyether adduct of the polyhydric alcohol used in the present invention includes glycerin, sorbitol, trimethylolpropane, trimethylolbutane, 1,2,6-
It is obtained by adding a polyether polyol to a polyhydric alcohol such as hexanetriol or pentaerythritol. Adducts of partially esterified polyhydric alcohols and polyether polyols can also be used. In this case, the polyether moiety may be a block polymer or a random polymer. The terminal to which the polyether polyol is added is a hydroxyl group, but may be partially blocked with an alkyl group or an aromatic hydrocarbon group.

In the present invention, glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane and pentaerythritol, ethylenediamine, N- Polyvalent amines such as aminoethylethanolamine, isophoronediamine and xylylenediamine can also be used in combination.

The polyisocyanate (b) used in the present invention includes aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, alicyclic polyisocyanate and the like.

Examples of the aromatic polyisocyanate include 1,
3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,
Examples thereof include 3,5-triisocyanatebenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, and 4,4 ', 4 "-triphenylmethane triisocyanate.

Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-
Butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate and the like can be mentioned.

As the araliphatic polyisocyanate,
ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate And 1,3-tetramethylxylylene diisocyanate.

As the alicyclic polyisocyanate, 3-
Isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-
2,6-cyclohexane diisocyanate, 4,4'-
Methylene bis (cyclohexyl isocyanate), 1,
4-bis (isocyanatomethyl) cyclohexane,
1,4-bis (isocyanatomethyl) cyclohexane and the like can be mentioned.

Further, a trimethylolpropane adduct of the above-mentioned polyisocyanate (b), a burette which has been reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination. A reaction product of the above-mentioned polyhydric alcohol polyether adduct and diisocyanate can also be used as the polyisocyanate (b).

As the polyisocyanate (b) used in the present invention, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) and the like are preferable.

The compound (f) obtained by subjecting the polyamine (d) used in the present invention to a Michael addition reaction with the compound (e) having at least one unsaturated double bond includes a known polyamine (d) and at least one compound. An amine compound obtained by subjecting a compound (e) having two unsaturated double bonds to a Michael addition reaction can be used. Compound (e) having polyamine (d) and at least one unsaturated double bond
The use of a polyamine compound obtained by subjecting the compound to a Michael addition reaction is preferable because the chain elongation becomes a mild reaction and the control becomes much easier as compared with the case of using the polyamine (d) alone.

The known polyamine (d) used in the present invention includes ethylenediamine, isophoronediamine, phenylenediamine, 2,2,4-trimethylhexamethylenediamine, tolylenediamine, hydrazine, piperazine, hexamethylenediamine, propylenediamine, Diamines such as dicyclohexylmethane-4,4-diamine, 2-hydroxyethylethylenediamine, di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, and di-2-hydroxypropylethylenediamine are exemplified. be able to. Isophorone diamine,
2,2,4-Trimethylhexamethylenediamine is preferable because the reaction can be easily controlled and the hygiene is excellent.

The compound (e) having at least an unsaturated double bond used in the present invention is not particularly limited as long as it is a substance having two or more functional groups containing an unsaturated double bond capable of Michael addition with an amine. is not. Specific examples thereof include (meth) acrylate monomers, compounds having a vinyl group and an ethynyl group, and the like. As the (meth) acrylate monomer used in the present invention, butyl (meth) acrylate, 2-ethylhexyl (meth)
Acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3
-Hydroxypropyl (meth) acrylate, tetraethylene glycol (meth) acrylate, tetrapropylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylate monomers.
These can be used alone or in combination of two or more.

Comparing the acrylate monomer and the methacrylate monomer, the acrylate monomer is preferred because it has a higher efficiency of the Michael addition reaction. It is preferable to use a (meth) acrylate monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, or 3-hydroxypropyl (meth) acrylate since the Michael addition reaction is accelerated.
(Meth) having a long-chain alkyl group such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate
The use of an acrylate monomer is preferred because the adhesion is improved, and the product after the Michael addition reaction is one in which an average of one active hydrogen of the amino group has reacted with (meth) acrylate.

In the Michael addition reaction between the polyamine (d) and the (meth) acrylate monomer, 1 mol of active hydrogen of the amino group of the polyamine (d) reacts with 1 mol of the double bond group of the (meth) acrylate monomer. Although the reaction proceeds even without a catalyst, the reaction proceeds at 60 to 100 ° C. while heating under a nitrogen atmosphere.
When the reaction is carried out at a suitable rate, an appropriate reaction rate is obtained. It is preferred that the polyamine (d) and the (meth) acrylate are reacted in substantially equimolar amounts. As the compound having a vinyl group or an ethynyl group used in the present invention, vinyl acetate,
Vinyl butyrate, vinyl propionate, vinyl hexanoate,
Fatty acid vinyl compounds such as vinyl caprylate, vinyl laurate, vinyl palmitate and vinyl stearate, alkyl vinyl ether compounds such as butyl vinyl ether and ethyl vinyl ether, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1- Tetradecene, 1
Α-olefin compounds such as hexadecene, allyl compounds such as allyl acetate, allyl alcohol, allyl benzene and allyl cyanide, vinyl compounds such as styrene, vinyl cyanide, vinyl cyclohexane and vinyl methyl ketone, acetylene, ethynyl benzene and ethynyl toluene And ethynyl compounds such as 1-ethynyl-1-cyclohexanol, dialkyl ether, divinylbenzene, diallyl terephthalate and diallyl phthalate. These can be used alone or in combination of two or more.

In the Michael addition reaction between the polyamine (d) and the compound having a vinyl group or an ethynyl group, 1 mol of active hydrogen of the amino group of the polyamine (d) reacts with 1 mol of a vinyl group or an ethynyl group. Polyamine (d) is preferably a compound having a vinyl group or an ethynyl group because vinyl cyanide easily adds Michael to a vinyl group or an ethynyl group of a compound having an electron-withdrawing group.
Even a compound having no electron-withdrawing group can react in the presence of a metal catalyst. 60 to 10 with heating in the presence of a catalyst
The reaction at 0 ° C. is preferable because the reaction rate becomes appropriate. The polyamine (d) and the compound having a vinyl group or an ethynyl group are preferably reacted in substantially equimolar amounts.

As the compound (g) having an active hydrogen used in the present invention, a monoamine compound having a hydroxyl group is preferable, and 2-amino-2-methyl-propanol, 2-amino-2-methyl-propanol,
Aminopropanol, 3-aminopropanol and the like.

Urethane resin (C) prepared by chain extension reaction
Comprises mixing a urethane prepolymer (B) having an isocyanato group at the end with a compound (f) obtained by subjecting a polyamine (d) to a compound (e) having at least one unsaturated double bond by a Michael addition reaction. The compound (g) having an active hydrogen further reacts with the unreacted isocyanate group at the end of the urethane resin (C) to form a urethane resin pressure sensitive adhesive (D), and the reaction activity of the pressure sensitive adhesive (D) Stabilize. Compound (g) having active hydrogen is 2-amino-
In the case of 2-methyl-propanol, both the amino group and the hydroxyl group can react with the terminal isocyanate group of the urethane resin (C), but the amino group has higher reactivity and reacts preferentially with the isocyanate group.

As the catalyst (c) used in the present invention, a known catalyst can be used. For example, tertiary amine compounds, organometallic compounds and the like can be mentioned.

Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, DBU and the like.

The organometallic compounds include tin compounds and non-tin compounds. Examples of the tin compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, Examples include triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

Examples of the non-tin compounds include titanium compounds such as dibutyl titanium dichloride, tetrabutyl titanate and butoxy titanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate and lead naphthenate. Iron, such as iron, 2-ethylhexanoate and iron acetylacetonate; cobalt, such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc, such as zinc naphthenate and zinc 2-ethylhexanoate; zirconium naphthenate And the like.

The catalyst (c) used in the present invention includes:
Dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate and the like are preferable, and depending on the case, they can be used alone or in combination.

As the solvent used in the synthesis of the urethane prepolymer (B) of the present invention, known solvents can be used. Examples include methyl ethyl ketone, ethyl acetate, toluene, xylene, acetone and the like. Ethyl acetate and toluene are particularly preferred from the viewpoint of the solubility of the polyurethane urea resin and the boiling point of the solvent.

The urethane-forming reaction for producing the urethane prepolymer (B) by reacting the polyol (a) with the polyisocyanate (b) can be carried out by various methods. The reaction is roughly classified into 1) the case where the reaction is carried out by charging the whole amount, and 2) the method where the polyol (a) and the catalyst (c) are charged into a flask and the polyisocyanate (b) is added dropwise. 2) is preferred. The reaction temperature for obtaining the urethane prepolymer (B) is preferably 120 ° C. or lower. More preferably, it is 70 to 110 ° C. When the temperature exceeds 120 ° C., the allohanate reaction proceeds, and the urethane prepolymer (B) having a predetermined molecular weight and structure cannot be obtained. Further, it becomes difficult to control the reaction rate. The urethanization reaction is
The reaction is preferably performed at 70 to 110 ° C for 2 to 20 hours in the presence of the catalyst (c).

The mixing ratio of the polyol (a) and the polyisocyanate (b) is such that the molar equivalent of the isocyano group of the polyisocyanate (b) is 1 relative to the molar equivalent of the hydroxyl group of the polyol (a) of 1 so that the isocyanate group remains at the terminal. It must be greater than one. An appropriate compounding ratio largely depends on the reactivity of the compound, the abundance ratio of a compound having three or more valences, and the like.

A chain extension for obtaining a urethane resin (C) from a compound (f) obtained by subjecting a urethane prepolymer (B), a polyamine (d) and a compound (e) having at least one unsaturated double bond to a Michael addition reaction, In the reaction, 1) a method in which a urethane prepolymer (B) solution is charged into a flask, and a compound (f) obtained by subjecting a polyamine (d) to a compound (e) having an unsaturated double bond to undergo a Michael addition reaction,
2) A method in which a compound (f) solution obtained by subjecting a polyamine (d) to a compound (e) having at least one unsaturated double bond to undergo a Michael addition reaction is charged into a flask, and a urethane prepolymer (B) solution is dropped. It is roughly divided. Synthesis is performed in a stable reaction, but if there is no problem with the reaction,
The method 1) which is easy to operate is preferred. The temperature of the chain extension reaction of the present invention is preferably 100 ° C. or lower. If it exceeds 100 ° C., a urethane prepolymer (B) having a predetermined molecular weight and structure cannot be obtained. More preferably, it is 70 ° C. or lower. The reaction rate is high even at 70 ° C., and if it cannot be controlled, the temperature is more preferably 50 ° C. or lower.

When the compound (g) having active hydrogen is added, the mixture is heated at 70 ° C. or lower after the completion of the chain extension reaction. 70
When the temperature exceeds ℃, the urethane prepolymer (B) having a predetermined molecular weight and structure cannot be obtained. The end point of the reaction is determined based on isocyanate% measurement and disappearance of the isocyanate peak by IR measurement.

The weight average molecular weight of the urethane resin (C) and the urethane resin pressure-sensitive adhesive (D) is preferably 10,000 or more in terms of standard polystyrene equivalent molecular weight by GPC. More preferably, it is 30,000 or more. If the weight-average molecular weight is less than 10,000, the adhesive properties, particularly the holding power, decrease remarkably, which is not preferable.

Urethane resin pressure-sensitive adhesive (D) according to the present invention
Means that the curing agent (E) is 0.5 to 10 with respect to the pressure-sensitive adhesive (D).
% By weight to form an adhesive (F). Adhesive (F)
If necessary, another resin such as an acrylic resin, a polyester resin, an amino resin, an epoxy resin, or a polyurethane resin can be used in combination. In addition, depending on the application, a filler such as a tackifier, talc, calcium carbonate, titanium oxide, a coloring agent, an ultraviolet absorber, an antioxidant, an antifoaming agent, and an additive such as a light stabilizer may be blended. good.

The curing agent (E) used in the present invention includes a polyfunctional isocyanate compound. As the polyfunctional isocyanate compound, the above-mentioned polyisocyanate compounds and their trimethylolpropane adducts,
A buret body reacted with water, a trimer having an isocyanurate ring, or the like is used.

The following shows a synthesis example.

Synthesis Example 1 (Synthesis Example of Compound (f)) 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
300 g of toluene was charged, 184 g of 2-hydroxyethyl acrylate, and 3-ethylhexyl acrylate 3
24 g are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and the mixture obtained by adding 508 g of toluene was designated as compound (1).

Synthesis Example 2 (Synthesis Example of Compound (f)) 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
300 g of toluene is charged, and 184 g of 2-hydroxyethyl acrylate and 176 g of ethyl acrylate are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and 360 g of toluene was added thereto to obtain a compound (2).

Synthesis Example 3 (Synthesis Example of Compound (f)) 300 g of 2,2,4-trimethylhexamethylenediamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel. 300 g of toluene is charged, and 198 g of 2-hydroxyethyl acrylate and 190 g of ethyl acrylate are added dropwise at room temperature. After the completion of the dropwise addition, the mixture was reacted at 80 ° C. for 1 hour, and then added with 388 g of toluene to obtain compound (3).

Synthesis Example 4 (Synthesis Example of Compound (f)) 300 g of isophorone diamine was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
300 g of toluene and 0.2 g of copper acetate are charged, and 438 g of 1-ethynyl-1-hexanol is added dropwise. After the completion of the dropwise addition, the reaction was carried out at 80 ° C. for 1 hour, and the compound obtained by adding 438 g of toluene was designated as compound (4).

Synthesis Example 5 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and gradually heated to 100 ° C.
The reaction is performed for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 229 g of ethyl acetate was added, and 44 g of compound (1) was added dropwise over 1 hour.
After aging for 2 hours, 2.1 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) is added to terminate the reaction. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 3
The number average molecular weight MN was 22,000, and the weight average molecular weight MW was 87,000.

Synthesis Example 6 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and gradually heated to 100 ° C.
The reaction is performed for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 229 g of ethyl acetate was added, and 37 g of compound (2) was added dropwise over 1 hour.
After aging for 2 hours, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) is added to terminate the reaction. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 3
000 cps, number average molecular weight MN 27,000, and weight average molecular weight MW 94,000.

Synthesis Example 7 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and gradually heated to 100 ° C.
The reaction is performed for 2 hours. After confirming the remaining amount of isocyanate group by titration, the mixture was cooled to 40 ° C., 229 g of ethyl acetate was added, and 35 g of compound (3) was added dropwise over 1 hour.
After aging for 2 hours, 2.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) is added to terminate the reaction. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 3
The number average molecular weight MN was 31,000 and the weight average molecular weight MW was 102,000.

Synthesis Example 8 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., and 43 of isophorone diisocyanate (manufactured by Huls Japan KK)
g, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and gradually heated to 100 ° C.
The reaction is performed for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 229 g of ethyl acetate was added, and 40 g of compound (4) was added dropwise over 1 hour.
After aging for 2 hours, 2.0 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) is added to terminate the reaction. The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 2
The number average molecular weight MN was 26,000 and the weight average molecular weight MW was 100,000.

Synthesis Example 9 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 129 g of polyester polyol P-2010 (bifunctional polyester polyol, OH value 56, manufactured by Kuraray Co., Ltd.) 128 g, isophorone diisocyanate (manufactured by Huls Japan KK)
43 g, toluene 75 g, and dibutyltin dilaurate 0.05 g as a catalyst are charged, and the temperature is gradually raised to 100 ° C., and the reaction is carried out for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., 229 g of ethyl acetate was added, 36 g of the compound (2) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.0 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). This reaction solution was colorless and transparent, had a solid content of 50%, a viscosity of 2800 cps, a number average molecular weight MN of 24,000 and a weight average molecular weight MW of 81,000.

Synthesis Example 10 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 266 g, manufactured by Sanyo Chemical Industries, Ltd.), 34 g of hexamethylene diisocyanate, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and 100
The temperature was gradually raised to 0 ° C., and the reaction was carried out for 2 hours. After confirming the remaining amount of the isocyanate group by titration, the mixture was cooled to 40 ° C., and 229 g of ethyl acetate was added.
After dropping for 2 hours and aging for 1 hour, 2-amino-
1. 2-methyl-propanol (manufactured by Nagase & Co., Ltd.)
The reaction is terminated by adding 2 g. The reaction solution was colorless and transparent, the solid content was 50%, the viscosity was 3700 cps, and the number average molecular weight was M.
N28,000 and a weight average molecular weight MW of 110,000.

Synthesis Example 11 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
237 g, 4,4′-diphenylmethane diisocyanate 63 g, toluene 75
g, 0.05 g of dibutyltin dilaurate as a catalyst, gradually raise the temperature to 100 ° C., and carry out a reaction for 2 hours. After confirming the remaining amount of isocyanate groups by titration,
After cooling to 227 g of ethyl acetate, 32 g of compound (2) was added dropwise over 1 hour, and after aging for 1 hour, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) Is added to terminate the reaction. This reaction solution is colorless and transparent, has a solid content of 50%, and has a viscosity of 3000 cp.
s, number average molecular weight MN 24,000, weight average molecular weight M
W83,000.

Synthesis Example 12 (Synthesis Example of Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, 257 g of Sanyo Kasei Kogyo Co., Ltd., 44 of isophorone diisocyanate (Hurth Japan K.K.)
g, 75 g of toluene, 0.05 g of dibutyltin dilaurate as a catalyst, and gradually heated to 100 ° C.
The reaction is performed for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, and 35 g of compound (2) was added dropwise over 1 hour.
After aging for 2 hours, 2.2 g of 2-amino-2-methyl-propanol (manufactured by Nagase & Co., Ltd.) is added to terminate the reaction. The reaction solution was colorless and transparent, had a solid content of 50%, and had a viscosity of 4%.
000 cps, number average molecular weight MN 30,000 and weight average molecular weight MW 84,000.

Synthesis Example 13 (Synthesis Example of Pressure-Sensitive Adhesive (D)) Polyether polyol PP- was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping funnel.
2000 (bifunctional polyether polyol, OH value 5
6, manufactured by Sanyo Chemical Industries, Ltd.) 259 g, 2,2,4-
41 g of trimethylhexamethylene diisocyanate, 76 g of toluene, and dibutyltin dilaurate 0.1 g as a catalyst.
After adding 05 g, the temperature was gradually raised to 100 ° C., and the reaction was carried out for 2 hours. After confirming the remaining amount of isocyanate groups by titration, the mixture was cooled to 40 ° C., 227 g of ethyl acetate was added, 36 g of compound (2) was added dropwise over 1 hour, and the mixture was aged for 1 hour. The reaction is terminated by adding 2.2 g of methyl-propanol (manufactured by Nagase Sangyo Co., Ltd.). The reaction solution was colorless and transparent, the solid content was 50%, and the viscosity was 28.
The number average molecular weight MN was 27,000 and the weight average molecular weight MW was 90,000.

Synthesis Example 14 (Synthesis Example of Adhesive (D)) 75 g of butyl acrylate, 5 g of 2-ethylhexyl acrylate, 135 g of ethyl acetate, and 135 g of toluene were placed in a four-necked flask equipped with a stirrer, a nitrogen inlet tube, a thermometer, and a dropping funnel. A solution containing 15 g of benzoyl peroxide and 0.2 g of benzoyl peroxide was placed in a reactor equipped with a reflux condenser, and was placed under a stream of nitrogen gas at 80 to 8 g.
The reaction is performed at 5 ° C. for 8 hours. This solution was colorless and transparent, had a solid content of 40%, and had a viscosity of 5,200 cps.

[0066]

EXAMPLE 1 2 g of a curing agent (E) was added to 100 g of the urethane resin solution (D) synthesized in Synthesis Example 5, 0.5 g of an antioxidant (i), and an ultraviolet absorber ( 0.5 g of the light stabilizer (k) and 0.5 g of the light stabilizer (k) were blended, and a moisture permeability test was performed by the following method. However, as the curing agent (E), a hexamethylene diisocyanate trimethylolpropane adduct 75% ethyl acetate solution was used. Antioxidant (i)
Is IRGANOX L 135 (Chiba Special
Chemicals, Inc.) was used. As the ultraviolet absorber (j), TINUVIN 571 (Ciba Specialty Chemicals Co., Ltd.) was used. Light stabilizer (k) is TINU
VIN 765 (Ciba Specialty Chemicals Co., Ltd.) was used.

The urethane resin solution was applied to a release paper with an applicator so as to have a dry coating film thickness of 30 μm.
The adhesive sheet obtained by applying a urethane resin solution to release paper is dried with a moisture-permeable urethane film (thickness: 30 μm).
To make a medical adhesive tape. After one week at room temperature, it was used for the following measurements.

The test method is as follows. <Coating method> The urethane resin solution was coated on a release paper with an applicator so as to have a dry coating film thickness of 25 μm.
For 2 minutes to produce a coating. After one week at room temperature, it was used for the following measurements. <Adhesive force> A pressure-sensitive adhesive sheet obtained by coating a release paper with a urethane resin solution is applied to a polyethylene terephthalate film (film thickness 2).
5 μm) and a 0.4 mm thick stainless steel plate (S
US304) at 23 ° C. and 65% RH,
After 20 minutes of roll pressure bonding according to JIS, the peel strength (180 degree peel, tensile speed 300 mm / min; unit g / 25 mm width) was measured by a shopper type peel tester. However, in the measurement of the adhesive strength, in order to ensure the strength of the substrate, instead of the moisture-permeable urethane film, a polyethylene terephthalate moisture permeability is less than ^{1,500 (g / m (m 2} · 24h)) A film (film thickness 25 μm) was used. <Removability> An adhesive sheet obtained by coating a release paper with a urethane resin solution was transferred to a polyethylene terephthalate film (25 μm in thickness), and transferred to a 0.4 mm thick stainless steel plate (SUS304) at 23 ° C. and 65% RH. After sticking under the conditions, roll-pressing according to JIS (SUS304), sticking to a glass plate, leaving it to stand at 40 ° C under the condition of 80% RH, and cooling at 23 ° C under the condition of 65% RH. After peeling, the adhesive residue was visually evaluated. After peeling, there was no adhesive transfer to the adherend at all. ご Very slight thing ○ Partially present △ Completely transferred × However, in the measurement of removability,
In order to ensure the strength of the substrate, a polyethylene terephthalate film (25 μm in thickness) was used instead of the moisture-permeable urethane film. <Moisture permeability> The above-mentioned urethane resin solution is applied to a moisture-permeable urethane film having a moisture permeability of 3,000 to 4,000 with an applicator so that a dry coating film has a thickness of 30 μm.
C. for 2 minutes to prepare a coating. After one week at room temperature, it was used for the following measurements. The moisture permeability test is performed by the moisture permeability test method (cup method) of the moisture-proof packaging material (JIS Z02).
08). <Skin irritation> The hair on the back of the trunk of each test animal was shaved about 24 hours before the test.

After measuring the body weight, about 6 c
Four areas were set with an area of m ² , of which 18
Using a gauge needle, a horny layer was cut into the keratin layer so as not to reach the dermis (injured skin), and the other two portions were left untreated (intact skin).

An adhesive sheet obtained by coating a release paper with a urethane resin solution was transferred to a moisture-permeable urethane film, and was transferred to about 2 cm ×
The specimen cut to 3 cm was attached to each of the intact and injured skin such that the adhesive surface was in contact with the skin, and then fixed with an adhesive plaster (JP). In addition, the specimen was held with Blender Arm Surgical Tape [3M Healthcare Co., Ltd.] so that the specimen was in contact with the skin. The remaining intact and intact skin served as controls.

The exposure time was 4 hours, after which the specimen was removed and the exposed surface was wiped with purified water. 1, 24, 4 after removal
Observations were made at 8 and 72 hours, and stimulus responses were scored according to Table-1. If a stimulus response was observed 72 hours after removal, observation was continued up to 14 days until the response disappeared.

Also, the Federal Register
According to (1972), 1, 24 and 48 after sample removal
The time scores were summed and divided by 6, and the average of each test animal was calculated to determine the primary irritation index (PII).
Based on the standard of ISO10993-10 shown in Table-2, the evaluation of the irritation of the sample was performed. Table 1 Evaluation of skin reaction Erythema and scab formation No erythema ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0 Very mild erythema ( Barely identifiable) ... 1 clear erythema ... 2 moderate to high Erythema ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 3 Slight eschar formation from advanced erythema (up to deep damage) ・ ・ ・ ・ ・ ・ ・ ・ ・ 4 * [Maximum Point 4] * Bleeding, ulceration, and necrosis were classified as deep injuries with a score of 4. Edema formation No edema ... 0 Very mild edema (barely identifiable) ... ·········· 1 mild edema (clear edges can be identified by clear bulge) · · · 2 moderate edema (approximately 1 mm bulge) · · ·・ ・ ・ ・ ・ ・ ・ ・ 3 Severe edema (bulge of 1 mm or more and spread beyond exposure range) ・ ・ ・ ・ ・ ・ ・ 4 [Highest point 4] Table-2 Primary stimulus response category in rabbits Response category P. I. I. Non-irritant 0-0.4 Weak irritant 0.5-1.9 Moderate irritant 2-4.9 Strong irritant 5-8 I. I. When the value is 0 I. I. A value other than 0 was evaluated as x.

Examples 2 to 9 Comparative Examples 1 to 4 The urethane resin pressure-sensitive adhesive (D) was changed to that shown in Table 3,
The same operation as in Example 1 was performed, and Examples 2 to 9 and Comparative Examples 1 to 9 were performed.
And 4.

The results of the tests of the adhesive strength, removability (weather resistance), moisture permeability and skin irritation of the medical adhesive tapes of Examples 1 to 9 and Comparative Examples 1 to 4 are also shown in Table 3. Table 3

[0075]

[Table 1]

The moisture permeability of the present invention is 1500 (g / (m ²⁾
24h)) A medical adhesive tape having excellent moisture permeability, skin irritation, and removability is obtained from the above base material and a urethane resin adhesive layer having a high molecular weight by introducing a urea bond into the resin composition. I found what I could get. On the other hand, the adhesive tapes shown in Comparative Examples 1 to 4 are irritating to the skin, have insufficient moisture permeability of 1500 (g / (m ² · 24 h)), and have poor removability.

[0077]

As described above, the moisture permeability is 1,500 (g / g).
And (m ² · 24h)) or in a substrate, by using the introducing urea bonds in the resin composition high molecular weight urethane resin pressure-sensitive adhesive layer, moisture permeability, skin irritation, excellent in removability Medical adhesive tape was obtained.

Continued on the front page F term (reference) 4C076 AA72 BB31 DD60 EE22A FF36 FF56 GG11 4J004 AA02 AA14 CA02 CA03 CA04 CA06 CB01 CB03 EA01 FA09 4J040 EF051 EF061 EF111 EF131 EF281 JA09 JB09 KA14 LA07 MA09 MA10 MA10

Claims (3)

[Claims] 1. A water vapor transmission rate of 1,500 (g / (m ² · 24)
h)) The above-mentioned sheet base material (A) and a moisture permeability of 1,5
A pressure-sensitive adhesive tape for medical use comprising a pressure-sensitive adhesive layer having a pressure of at least 00 (g / (m ² · 24h)), wherein the pressure-sensitive adhesive layer comprises a catalyst (c) comprising a polyol (a) and a polyisocyanate (b). Compound (f) obtained by subjecting a urethane prepolymer (B) obtained by the reaction in the presence of a compound to a Michael addition reaction of a polyamine (d) and a compound (e) having an unsaturated double bond.
For medical use, comprising a urethane resin (C) having an isocyanato group at the end obtained by chain extension and a compound (g) having an active hydrogen capable of reacting with the isocyanate group, and a urethane resin adhesive (D). Adhesive tape. 2. The pressure-sensitive adhesive layer has a skin irritating property (PII).
The medical pressure-sensitive adhesive tape according to claim 1, wherein 3. A first step of synthesizing a urethane prepolymer (B) by reacting a polyol (a) and a polyisocyanate (b) in the presence of a catalyst (c), wherein the urethane prepolymer (B) is used. Is extended with a compound (f) obtained by subjecting a polyamine (d) and a compound (e) having an unsaturated double bond to a Michael addition reaction to synthesize a urethane resin (C) having an isocyanate group at a terminal. A urethane resin (C) having an isocyanato group at the terminal,
A third step of synthesizing the urethane resin adhesive (D) by reacting the isocyanate group with a compound (g) having an active hydrogen capable of reacting, wherein a curing agent (E) is added to the urethane resin adhesive (D); 0.5 to resin adhesive (D)
A fourth step in which the urethane resin pressure-sensitive adhesive (F) is contained by adding 10% by weight, and the urethane resin pressure-sensitive adhesive (F) has a moisture permeability of 1,500 (g / (m ² · 24 h)) or more. A method for producing a medical pressure-sensitive adhesive tape, comprising a fifth step of laminating on one surface of a sheet substrate (A).