JPH1088093A - Self-adhesive composition and medical self-adhesive tape or sheet prepared therefrom - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impact moisture permeability to a rubber-base self-adhesive without detriment to its self-adhesiveness and thereby to obtain a lowly irritant self-adhesive compsn., a self-adhesive tape, etc., by compounding a specific self-adhesive, a water-soluble polymer, and a fatty acid ester of a polyhydric alcohol. SOLUTION: This compsn. contains 5-25wt.% ethylene-arom. vinyl compd. copolymer (A) which contains 1-55mol% units derived from an arom. vinyl compd. monomer and of which the stereoregularity of phenyl groups in the alternating structure of ethylene and an arom. vinyl compd. represented by formula II (wherein Ph is an arom. group; and x'>2) contained in a structure represented by formula I (wherein Ph is an arom. group; x is 2 or higher; y is 1 or higher; and z is 0 or 1) is 0.75 or higher in terms of isotactic diad fraction m, 75-95wt.% self-adhesive comprising a 10-30C paraffinic and/or a 10-30C naphthenic hydrocarbon and a tackfier, 2-30wt.% water-soluble polymer, and 2-30wt.% fatty acid ester of a polyhydric alcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pressure-sensitive adhesive composition and a medical pressure-sensitive adhesive tape and sheet having a support provided with a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition on one surface.

[0002] More specifically, it has a low irritating property that imparts moisture permeability at the time of sticking and hardly causes physical irritation such as scalping and exfoliation of the skin at the time of peeling. The present invention relates to a medical adhesive tape and sheet which are not damaged.

[0003]

2. Description of the Related Art In general, medical pressure-sensitive adhesive tapes and sheets are used as medical plasters, plasters, surgical dressings, surgical drapes, and the like, and as an adhesive, a rubber elastic material such as natural rubber or polyisoprene rubber is used. It uses a rubber-based pressure-sensitive adhesive obtained by blending an application resin and a softening agent. However, medical pressure-sensitive adhesive tapes and sheets provided with a pressure-sensitive adhesive layer mainly composed of such a rubber elastic body have excellent adhesiveness at the time of application, but have a horny layer of skin due to their strong adhesive strength at the time of peeling. In some cases, the skin peeled off, resulting in scalp of the body hair and, due to lack of moisture permeability, rash on the skin and inflammation.

Accordingly, as a method for reducing irritation to the skin, a medical adhesive tape or sheet as shown below has been proposed.

[0005] For example, Japanese Patent Publication No. 54-44688 discloses a water-soluble polyol such as propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol having a molecular weight of 1,000 or less, glycerin, and sorbitol; It has been proposed to mix molecules with a rubber-based pressure-sensitive adhesive.
Japanese Patent No. 97069 discloses a water-absorbing polymer (eg, a crosslinked product of a water-soluble polymer, specifically, Sunwet IM-300, manufactured by Sanyo Chemical Co., Ltd.) , Sunwet IM-1000MPS) in a rubber-based pressure-sensitive adhesive.

However, when a water-soluble polyol is added to a rubber-based pressure-sensitive adhesive as described above, there is a disadvantage that the polyol bleeds from the rubber-based pressure-sensitive adhesive due to poor compatibility between the two. Furthermore, when a water-absorbing polymer is added to the rubber-based adhesive, there is a problem that the water-absorbing polymer absorbs water during application and does not repel water. Was.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a low pressure-sensitive adhesive which relieves skin irritation by imparting moisture permeability to the rubber pressure-sensitive adhesive without impairing the tackiness of the rubber pressure-sensitive adhesive. An object of the present invention is to provide an agent composition, a moisture-permeable medical pressure-sensitive adhesive tape and sheet.

[0008]

Means for Solving the Problems The present inventors have developed a pressure-sensitive adhesive composition containing an ethylene-aromatic vinyl compound copolymer having a specific composition and structure, and a pressure-sensitive adhesive on one side of a support using the same. The present inventors have found that the above problems can be solved by using a medical pressure-sensitive adhesive tape and sheet provided with a layer, and completed the present invention.

That is, the present invention provides the following (A) an ethylene-aromatic vinyl compound copolymer;
(I) comprising a paraffinic and / or naphthenic hydrocarbon having 10 to 30 carbon atoms and a tackifying resin
And (II) a water-soluble polymer and (III) a fatty acid ester of a polyhydric alcohol.
(A) has an aromatic vinyl compound monomer unit content of 1 to 55;
Mole-% of an ethylene-aromatic vinyl compound copolymer, mainly having a structure represented by the following general formula (1),
The stereoregularity of the phenyl group of the alternating structure of ethylene and the aromatic vinyl compound represented by the following general formula (2) contained in the structure is 0.1 in isotactic dyad fraction m.
It is an ethylene-aromatic vinyl compound copolymer having a molecular weight of 75 or more. Further, the present invention relates to 5 to 25% by weight of the ethylene-aromatic vinyl compound copolymer (A) and (B)
To 30 paraffins and / or 10 to 30 carbon atoms
75 to 9 in total of naphthenic hydrocarbon and tackifier resin
5% by weight of the pressure-sensitive adhesive (I) and (II) a water-soluble polymer in 2 to 30% by weight of the whole pressure-sensitive adhesive composition and (II)
I) A pressure-sensitive adhesive composition containing 2 to 30% by weight of a fatty acid ester of a polyhydric alcohol based on the entire pressure-sensitive adhesive composition. Furthermore, the present invention provides a pressure-sensitive adhesive tape and sheet using the above-mentioned pressure-sensitive adhesive composition for a pressure-sensitive adhesive layer provided on one surface of a support.

[0010]

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Wherein Ph is an aromatic group such as a phenyl group;
x is an integer of 2 or more indicating the number of repeating units, and y is an integer of 1 or more, and may be the same or different in each repeating unit. z is 0 or 1, and may be the same or different in each repeating unit. )

[0012]

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(Wherein Ph is an aromatic group such as a phenyl group,
x 'represents the number of repeating units and represents an integer of 2 or more. )

Further, the present invention provides a method for producing a composition comprising the component (A) comprising ethylene and an aromatic vinyl compound monomer by using a transition metal compound represented by the above general formula (3) or (4) and a co-catalyst. The pressure-sensitive adhesive composition, the medical pressure-sensitive adhesive tape and the sheet, which is an ethylene-aromatic vinyl compound copolymer produced by polymerization.

Hereinafter, the contents of the present invention will be described in detail. In the following description, Ph in the chemical formula represents an aromatic group such as a phenyl group, and Me represents a methyl group. The (A) ethylene-aromatic vinyl compound copolymer of the present invention refers to a copolymer having mainly the structure represented by the above general formula (1), and ethylene and aromatic represented by the above general formula (2). The stereoregularity of the phenyl group of the alternating structure of the aromatic vinyl compound is 0.75 or more in isotactic dyad fraction m,
The aromatic vinyl compound monomer unit content of the copolymer is 1 to 5
It is a copolymer characterized by being 5 mol%. Its structure is determined by nuclear magnetic resonance (NMR).

Hereinafter, the component (A) will be described in more detail by taking an ethylene-styrene copolymer as a typical example of the component (A) of the present invention as an example. Styrene content is 1 to 55
The 13C-NMR spectrum of this copolymer, which is mol%, mainly shows peaks at the following positions. That is, the peaks derived from the main chain methylene and methine carbon are located at around 25 ppm, around 27 ppm, around 30 ppm, around 36 ppm, and around 45 ppm, and also from the five carbons of the phenyl group that are not bonded to the polymer main chain. Peaks near 126 ppm and 128 ppm, and a peak derived from one carbon atom of the phenyl group bonded to the main chain of the copolymer near 146 ppm. JP-A-3-
13C of copolymer described in JP 163088 A
By comparison with the NMR spectrum, this is a so-called pseudo-random copolymer having no styrene chains in the head-tail structure.

The general formula (1) which is the component (A) of the present invention
Is an index θ given by the following formula (i):
Is greater than 70 when the styrene content is less than 1 to 45 mol% and greater than 30 when the styrene content is 45 to 55 mol%. θ = Al / A2 × 100 Formula (i) Here, Al is found in the range of 25 to 50 ppm by 13 C-NMR based on TMS, and methine and methylene of α to ε in the following general formula (1 ′) It is the sum of the peak areas attributed to carbon. A2 is the total sum of the peak areas in the range of 25 to 50 ppm by 13C-NMR based on TMS.

[0018]

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(In the formula, x is an integer of 2 or more representing the number of repeating units, y is an integer of 1 or more, and may be the same or different in each repeating unit. Z is 0 or 1. The repeating unit may be the same or different from each other.When z is 0, the bonding direction of styrene to ethylene is uniform in the polymer, and when z is 1, the bonding direction of styrene to ethylene is Is non-uniform, that is, a case including a heterogeneous bond.)

An index λ indicating the ratio of the ethylene-styrene alternating structure contained in the copolymer represented by the general formula (1) is defined by the following formula (ii). λ = A3 / A2 × 100 Formula (ii) Here, A3 is ethylene- found in the range of 25 to 50 ppm by 13C-NMR based on TMS.
It is the total sum of the peak areas attributed to three types of a, b, and c methines and methylene carbon in the following general formula (2 ′) derived from the styrene alternating structure. A2 is the total sum of the peak areas in the range of 25 to 50 ppm by 13C-NMR based on TMS.

[0021]

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(In the formula, x ′ represents the number of repeating units and represents an integer of 2 or more.)

The ethylene-styrene copolymer as the component (A) of the present invention has an alternating structure index λ of less than 70 and 0.1.
It is characterized by being greater than 1, preferably less than 70 and greater than 5, particularly preferably less than 70 and greater than 10. Further, the ethylene-styrene copolymer of the present invention may include a heterogeneous bond structure derived from styrene represented by the following general formula (5) depending on polymerization conditions and the like.

[0024]

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(In the formula, n represents 0 or an integer of 1 or more.)

When the styrene content is 30 mol% or more, a limited styrene chain structure represented by the following general formula (6) can be contained.

[0027]

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However, in any case, the ethylene-styrene copolymer which is the component (A) of the present invention has 13C-NM based on TMS at any styrene content.
In the R spectrum, 40.8 to 41.0 ppm of syndiotactic polystyrene, 40.5 to 41.0 p
No clear peaks of pm atactic polystyrene and isotactic polystyrene are seen. That is, as shown by the following general formula (7), which is characterized by these peaks, there is substantially no chain of atactic, syndiotactic, or isotactic polystyrene having a head-tail structure. It is.

[0029]

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(In the formula, q represents an integer of 3 or more.)

In the ethylene-styrene copolymer of the present invention, the isotactic structure in which the stereoregularity of the phenyl group in the alternating copolymer structure of ethylene and styrene is the isotactic structure means that the isotactic dyad fraction m is 0.75 or more. , Preferably 0.85 or more, more preferably 0.95 or more. Here, the isotactic diad fraction m
Is a methylene carbon peak appearing around 25 ppm, which is derived from a racemic dyad structure.
The peak area Ar around 5 ppm and the peak area Am around 25.2 to 25.3 ppm derived from the meso diad structure can be determined by the following formula (iii). In addition, the 13C-NMR spectrum was determined based on TMS using heavy chloroform as a solvent. m = Am / (Ar + Am) Formula (iii)

Taking styrene as a typical example of the aromatic vinyl compound monomer, the ethylene-aromatic vinyl compound copolymer as the component (A) of the present invention has been described.
Specific examples of the aromatic vinyl compound monomer used for the component include styrene, various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene,
ot-butylstyrene, mt-butylstyrene, p
-T-butylstyrene, p-chlorostyrene, o-chlorostyrene, α-methylstyrene, etc., and a monomer having a plurality of vinyl groups in one molecule such as divinylbenzene. Or a combination of two or more.

The component (A) of the present invention has a weight average molecular weight of 10
It is at least 00, but is preferably at least 10,000, particularly preferably at least 30,000, in order to satisfy the required properties as an adhesive tape or sheet.

The component (A) of the present invention does not necessarily need to be a pure copolymer, and may contain other structures as long as the structure and stereoregularity fall within the scope of the present invention. Also, other monomers may be copolymerized. Other monomers to be copolymerized include propylene, 1
Α-olefins having 3 or more carbon atoms such as -hexene and 1-octene; conjugated diene monomers such as butadiene and isoprene; and cyclic olefins such as cyclopentene, cyclopentadiene and cyclohexene.

Depending on the polymerization conditions and the like, a small amount of an atactic homopolymer obtained by thermally or radically polymerizing an aromatic vinyl compound monomer may be contained, but the amount is not more than 10% by weight of the whole. Is preferred. Such a homopolymer can be removed by a means such as solvent extraction. However, if there is no particular problem in physical properties, it can be used while containing it.

The method for producing the component (A) of the present invention is not particularly limited, but preferably, a transition metal containing at least one unsubstituted or substituted indenyl group is prepared by mixing ethylene and an aromatic vinyl compound monomer. It is produced by polymerizing a compound or a transition metal compound containing an unsubstituted or substituted cyclopentadienyl group and an unsubstituted or substituted indenyl group and a promoter. The transition metal compound is a transition metal compound represented by the following general formula (3) or (4).

[0037]

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(Where Ind1 and Ind2 are unsubstituted
Or Ind1 is a substituted indenyl group, and Ind1 and Ind2 are
They may be the same or different. Y is In
a carbon having a bond with d1 and Ind2 and having another substituent
Element, silicon, germanium or boron, other substitution
The group may be hydrogen, halogen, alkyl group, preferably carbon
An alkyl group of the formulas 1 to 15, or an aryl group,
An aryl group having 6 to 10 carbon atoms and an alkylaryl group are preferred.
Or an alkylaryl group having 7 to 40 carbon atoms. Place
The substituents may be different or identical to each other, but may be cyclohexyl.
And a cyclic structure such as a cyclopentyl group.
No. Illustrating the structure of Y, -CH_Two-, -CMe
_Two-, -CPh_Two-, -SiH _Two-, -SiMe_Two−,
-SiPh_Two-And so on.

X1 and X2 each represent a halogen such as hydrogen, chlorine or bromine, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a silyl group such as a trimethylsilyl group, a methoxy group, an ethoxy group or an isopropoxy group. And the like. X1 and X2 may be the same or different from each other. M is a Group IV metal such as Zr, Hf, and Ti. )

Examples of Ind1 and / or Ind2 include 1-indenyl, 2-alkyl-1-indenyl,
2-alkyl-4-aryl-1-indenyl, 2,4
-Dialkyl-1-indenyl, 2,4-diaryl-
1-indenyl, 2,4,6-trialkyl-1-indenyl, 1-alkyl-4,5-benzo-1-indenyl, 2,5-dialkyl-1-indenyl, 2,5,6
-Trialkyl-1-indenyl, 2,4,5-trialkyl-1-indenyl, 2-aryl-1-indenyl, 2,6-dialkyl-4-aryl-1-indenyl, 2-alkyl-5-aryl -1-indenyl, 2
-Alkyl-5,6-diaryl-1-indenyl, 2
-Alkyl-4,5-diaryl-1-indenyl, 2
-Alkyl-4,6-diaryl-1-indenyl and the like.

[0041]

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(Where Ind is an unsubstituted or substituted
It is a benzyl group. Cp is an unsubstituted or substituted cyclopen
Tadienyl group. Y has a bond with Ind and Cp
And carbon having other substituents, silicon, germanium or
Is boron, and other substituents include hydrogen, halogen,
An alkyl group, preferably an alkyl group having 1 to 15 carbon atoms, or
Or an aryl group, preferably an aryl group having 6 to 10 carbon atoms
Group, an alkylaryl group, preferably an alkyl group having 7 to 40 carbon atoms.
There are alkaryl groups. The substituents are different from each other
Are the same, a cyclohexyl group, a cyclopentyl group, etc.
It may have a ring structure. To illustrate the structure of Y,
-CH_Two-, -CMe_Two-, -CPh_Two-, -SiH _Two
-, -SiMe_Two-, -SiPh_Two-And so on.

X1 and X2 each represent a halogen such as hydrogen, chlorine or bromine, an alkyl group such as a methyl group or an ethyl group, an aryl group such as a phenyl group, a silyl group such as a trimethylsilyl group, a methoxy group, an ethoxy group or an isopropoxy group. And the like. X1 and X2 may be the same or different from each other. M is a Group IV metal such as Zr, Hf, and Ti. )

Ind is Ind1, Ind of the general formula (3)
2 can be used. As an example of Cp,
Cyclopentadienyl, 2-alkyl-1-cyclopentadienyl, 2,4-dialkyl-1-cyclopentadienyl, 2,4,5-trialkyl-1-cyclopentadienyl, 2-trialkylsilyl -1-cyclopentadienyl, 2-trialkylsilyl-4-alkyl-1
-Cyclopentadienyl, 2-trialkylsilyl-
4,5-dialkyl-1-cyclopentadienyl, 2-
Alkyl-4-aryl-1-cyclopentadienyl,
2-alkyl-4,5-diaryl-1-cyclopentadienyl, 2,5-dialkyl-4-aryl-1-cyclopentadienyl, 2,4-dialkyl-5-aryl-1-cyclopentadienyl , 2-aryl-1-cyclopentadienyl, 2-aryl-4-alkyl-1
-Cyclopentadienyl, 2-aryl-4,5-dialkyl-1-cyclopentadienyl, 2,3,4,5-
Tetraalkylcyclopentadienyl, 2,3,4,5
-Tetraarylcyclopentadienyl and the like.

In producing the component (A) of the present invention, it is preferable to use an organoaluminum compound and / or a boron compound as a promoter together with the above-mentioned transition metal complex. As the organoaluminum compound used as the co-catalyst, alumoxanes such as methylalumoxane, ethylalumoxane and triisobutylalumoxane are preferably used, and methylalumoxane is particularly preferred. If necessary, a mixture of these different alumoxanes may be used. These alumoxanes may be used in combination with alkylaluminums, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, and alkylaluminums containing halogen, for example, dimethylaluminum chloride.

The boron compound used as a cocatalyst is N,
N-dimethylanilinium tetra (pentafluorophenyl) borate, trityltetra (pentafluorophenyl) borate, lithium tetra (pentafluorophenyl) borate, tri (pentafluorophenyl) borate and the like. Further, these boron compounds and the above-mentioned organoaluminum compounds may be used at the same time. In particular, when a boron compound is used as a co-catalyst, the addition of an alkyl aluminum compound such as triisobutyl aluminum is effective for removing impurities such as water contained in the polymerization system and adversely affecting the polymerization.

In the production of the component (A) of the present invention, a desired monomer can be mixed with a transition metal complex and a cocatalyst and polymerized in the presence or absence of a suitable solvent.
Examples of the solvent used include aliphatic hydrocarbons such as pentane, hexane, heptane, and cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, chloro-substituted benzene, and chloro-substituted toluene; and halogenated hydrocarbons such as methylene chloride and chloroform. And can be used alone or as a mixed solvent.

In producing the component (A), the polymerization temperature is as follows:
-78 ° C to 200 ° C is appropriate, preferably 0 ° C to
160 ° C. A polymerization temperature lower than -78 ° C is industrially disadvantageous, and a temperature higher than 200 ° C is not suitable because decomposition of the metal complex occurs. When an organoaluminum compound is used as the cocatalyst, the ratio of aluminum atom to complex metal atom is preferably 0.1 to 10 with respect to the transition metal of the complex.
0000, particularly preferably in the range of 10 to 10,000. If it is less than 0.1, the activation of the transition metal complex is insufficient, and if it exceeds 100,000, it is economically disadvantageous. When a boron compound is used as a co-catalyst, it is suitable to use a boron atom / complex metal atom ratio in the range of 0.01 to 100, preferably 0.1 to 10, particularly preferably 1. Used. If it is less than 0.01, the activation of the transition metal complex is insufficient, and if it exceeds 100, it is economically disadvantageous. The Group IV metal complex and the cocatalyst may be mixed and prepared outside the polymerization tank, or may be mixed in the tank during polymerization.

The carbon number 1 used as the component (B) of the present invention
0-30 paraffinic and / or 10-3 carbon atoms
0 naphthenic hydrocarbons include light liquid paraffin, heavy liquid paraffin, hexamethyltetracosane,
Hexamethyltetracosahexane, α-olefin oligomers and the like are exemplified, and these are used alone or in combination of two or more.

The paraffinic and / or naphthenic hydrocarbons having 31 or more carbon atoms are solid at room temperature and are sufficiently mixed with the tackifier resin and the ethylene-aromatic vinyl compound copolymer (A). Since there is no softening property, a patch having good adhesive strength cannot be obtained. Those having 9 or less carbon atoms are not preferred because the softening property becomes high and the pressure-sensitive adhesive becomes too soft.

Examples of the tackifying resin used in the present invention include rosin resins such as rosin, hydrogenated rosin, and esters thereof, polyterpene resins, cumarone-indene resins, and petroleum resins such as aliphatic and alicyclic resins. Resin, terpene
Softening point 50-1 selected from the group such as phenolic resin
Those at 30 ° C. are exemplified, and these are used alone or in combination of two or more. Above all, softening point 65
Alicyclic saturated hydrocarbon resin of petroleum resin at ~ 130 ° C, glycerin ester of hydrogenated rosin having softening point of 80-130 ° C,
Polyterpene resins having a softening point of 80 to 130 ° C. are preferred.

The mixing ratio of the tackifier resin is appropriately determined so that the adhesive force at the time of application and the scalping at the time of peeling do not occur.

The (II) water-soluble polymer of the present invention includes:
Water-soluble cellulose derivatives such as methylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose and sodium carboxymethylcellulose, starch, pregelatinized starch, dextrin, cyclodextrin, pullulan, hydroxypropyl starch , Water-soluble synthetic polymers such as sodium carboxymethyl starch, gum arabic, sodium alginate, propylene glycol alginate,
Examples include water-soluble natural polymers such as xanthan gum and gelatin.

The amount of the water-soluble polymer (II) is 2 to 30% by weight of the whole pressure-sensitive adhesive composition. If the amount is less than 2% by weight, the patch may not have sufficient moisture permeability,
If it exceeds 0% by weight, it is difficult to mix it with the adhesive,
Problems such as poor sticking properties occur. In order to ensure appropriate moisture permeability and sticking property, the amount of the water-soluble polymer is preferably 4 to 25% by weight.

The polyhydric alcohol fatty acid ester (III) of the present invention is compatible with the pressure-sensitive adhesive (I).
Specific examples thereof include sorbitan fatty acid esters such as sorbitanca plate, sorbitan laurate, sorbitan palmylate, sorbitan monostearate, and sorbitan monooleate, and monoesters, diesters, triesters, and mixtures thereof can be used. In addition, glycerin plate, glycerin myristate,
Glycerin monostearate, glycerin monooleate, decaglycerin laurate, decaglycerin myristate, decaglycerin stearate, decaglycerin oleate, diglycerin stearate, diglycerin oleate, tetraglycerin stearate, tetraglycerin oleate, Hexaglycerin stearate,
Hexaglycerin oleate, hexaglycerin myristate, glycerin fatty acid esters such as hexaglycerin laurate monoesters, diesters,
Triesters and the like and mixtures thereof can be used. Furthermore, propylene glycol fatty acid esters such as propylene glycol stearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan stearate, polyoxyethylene glycerin fatty acid esters such as polyoxyethylene glycerin oleate, and polyethylene such as polyethylene glycol stearate. Glycol fatty acid esters.

(III) The compounding amount of the fatty acid ester of the polyhydric alcohol is 2 to 30% by weight of the whole pressure-sensitive adhesive composition. If the amount is less than 2% by weight, the patch will not have sufficient moisture permeability, and if the amount exceeds 30% by weight, it will bleed from the pressure-sensitive adhesive layer or have poor sticking properties. Occurs. In order to ensure appropriate moisture permeability and sticking property, the compounding amount of the fatty acid ester of the polyhydric alcohol is preferably 4 to 25% by weight. As described above, by including the water-soluble polymer and the fatty acid ester of polyhydric alcohol in the pressure-sensitive adhesive layer, sufficient adhesiveness can be obtained for the patch. Moisture permeability, is less than 60g / m ² · 24 hours, so feel stuffy as feeling stuck, 60g / m ² · ²
It is desirable that the time be 4 hours or more.

The adhesive tape and sheet for medical use according to the present invention can be used as a plaster, a surgical drape, a surgical dressing, a taping tape, etc. without containing a drug. It may be.

As the drug to be used, those which can penetrate a biological membrane by transdermal or transmucosal administration can be applied without any particular limitation. Examples thereof include antipyretic and antiphlogistic analgesics, steroidal anti-inflammatory drugs, vasodilators, and hypertension. Antiarrhythmic, antihypertensive, antitussive, antitumor, local anesthetic, hormonal,
Asthma treatment, allergic rhinitis treatment, antihistamine, anticoagulant, antispasmodic, cerebral circulation and metabolism improving agent, antidepressant / anxiolytic, vitamin preparation, oral hypoglycemic agent, anti-ulcer agent, sleeping pill, antibiotic , Skin irritants and the like.

The pressure-sensitive adhesive layer of the pressure-sensitive adhesive composition, medical pressure-sensitive adhesive tape or sheet according to the present invention contains, in addition to the above-mentioned drugs, a liquid polymer such as polybutene, an antioxidant, a filler and the like. As long as the action and effect are not impaired, they may be appropriately added.

Examples of the material of the support used for the medical adhesive tape and sheet of the present invention include nonwoven fabric, woven fabric, polyester, polyethylene, polyvinyl chloride, polyvinylidene chloride, ethylene-vinyl acetate copolymer, polyurethane, and polyurethane. Examples thereof include a perforated aluminum foil and a laminate film thereof. Among these, materials having low moisture permeability are preferably subjected to physicochemical processing to impart moisture permeability. This treatment is to prevent rash due to excessive stuffiness of the skin. In addition, the support preferably has a function of expanding and contracting in at least one direction, and a material having no such function may be subjected to appropriate expansion and contraction processing. This is because if the support has a stretching function, it can follow the stretching of the skin surface when the medical adhesive tape and sheet are applied to the body. The thickness of the support is preferably 5 to 2,000 μm.
m.

Examples of the release paper described later used in the present invention include polyester, polypropylene, polyethylene-coated high-quality paper, polyethylene-coated glassine paper, etc., which have been subjected to a silicon treatment on the upper surface. The thickness of the release paper is preferably 20 to 200 μm.

Representative examples of the method for producing the medical pressure-sensitive adhesive tape and sheet according to the present invention include a solvent method and a hot melt method.

In the solvent method, a water-soluble polymer (II) and a fatty acid ester of a polyhydric alcohol (I) are added to the pressure-sensitive adhesive (I).
II), and if necessary, a drug component and / or a liquid polymer component, and other additives, and uniformly dissolve or disperse them. Examples of the solvent used include those that are compatible with the adhesive, the drug, and the like, for example, tetrahydrofuran, chloroform, and methylene chloride. However, among the water-soluble polymers, polyvinylpyrrolidone is difficult to dissolve unless it is an alcohol-based solvent. Therefore, it is advisable to first dissolve this in methanol or the like and then mix it with other components. The solution or dispersion thus obtained is spread on a release paper or a support, dried to remove the solvent, and the support or the release paper is laminated on the obtained pressure-sensitive adhesive layer.

When the hot melt method is applied,
Adhesive (I), water-soluble polymer (II) and fatty acid ester of polyhydric alcohol (III), if necessary, liquid polymer component and other additives are blended in predetermined amounts little by little,
The mixture is heated and mixed at a temperature of 120 to 150 ° C. under nitrogen replacement to melt. After melting, the temperature of the adhesive is set to 100 to 120
The temperature is lowered to 0 ° C., and a drug component is added, if necessary, and mixed uniformly to obtain a solution in a molten state. Next, this solution is spread on a release paper or a support using a hot melt coater, and the support or the release paper is laminated on the obtained pressure-sensitive adhesive layer.

[0065]

EXAMPLES The present invention will be described below with reference to examples, but these examples do not limit the present invention. In addition,
In the following description, the amount added is shown on a weight basis. The analysis of the polymer used was performed by the following means. 13C-N
The MR measurement was performed using JNMGX-270 or α-500 manufactured by JEOL Ltd., using deuterated chloroform or deuterated 1,1,2,2-tetrachloroethane as a solvent, and using TMS as a reference. Determination of the styrene content in the polymer was performed by 1H-NMR, and the apparatus was JNMG manufactured by JEOL Ltd.
Using X-270 or α-500, the solvent is deuterated chloroform or 1,1,2,2-tetrachloroethane, and the intensity of the peak derived from the phenyl group proton and the intensity of the proton derived from the alkyl group are determined based on TMS. went. The molecular weight was determined by using GPC (gel permeation chromatography) in terms of standard polystyrene. The solvent used was THF or 1,2,4-trichlorobenzene, and the column used was HLC-8020 manufactured by Tosoh Corporation or GPC-7100 manufactured by Senshu Kagaku.

The performance of the medical pressure-sensitive adhesive tapes and sheets was evaluated by the following test methods.

<Paste test> Medical adhesive tape for test (3
× 4 cm) was subjected to a sticking test on human skin as follows. That is, a medical adhesive tape was applied to the upper arms of seven (healthy, male) subjects, and after 12 hours, the adhesive property and the feeling of application were evaluated. Each medical adhesive tape was evaluated for pain and irritation at the time. The evaluation criteria are as follows.

The sticking property was evaluated by observing the ratio of the area to which the medical adhesive tape was adhered to the area at the start of the test after adhering for 12 hours. Good: The remaining adhesive area of the adhesive was 95% or more. Residual adhesive area is less than 75% to less than 95% Poor: Residual adhesive area of patch is less than 75%

The adhesive residue was evaluated as to whether or not the adhesive remained on the skin after peeling, and expressed as follows. -: No adhesive remained on skin after peeling +: Adhesive remained on skin after peeling

The pain at the time of peeling was evaluated by a sensory test and expressed as follows. -: No particular pain ±: Slightly painful +: Extremely painful

The irritation was evaluated by visual inspection of the condition of the skin at the application site about one hour after peeling, and expressed as follows. -: No change ±: Slight erythema is observed +: Erythema is observed

The feeling of sticking was evaluated by a sensory test and expressed as follows. -: No humidity ±: Slightly humid +: Slightly humid

<Moisture Permeability Test> The moisture permeability test was performed according to JIS Z
0208 “Moisture permeability test method for moisture-proof packaging material (cup method)”
It went according to. That is, about 12 g of anhydrous calcium chloride is put in a cup, and the mouth of the cup is sealed with a medical adhesive tape. The test cup was placed in a thermo-hygrostat at 40 ° C. and a relative humidity of 90%, left to stand for 24 hours, and the increase in the mass of calcium chloride was measured to determine the moisture permeability (g / m ² · 24 hours).

Reference Example 1 After replacing with nitrogen, 20 ml of styrene and 60 ml of toluene were added to a 300 ml-volume autoclave with a stirrer replaced with ethylene, and methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd.) was added on the basis of Al atoms. 8.4m
mol. Then, ethylene was introduced at room temperature to 9 k
g / cm ² G and then heating the autoclave,
The internal temperature was stabilized at 50 ° C. Racemic isopropylidenebis (1-indenyl) zirconium dichloride 8.4 μm from a pressure tank placed above the autoclave
was dissolved in 40 ml of toluene and poured into an autoclave. Next, the ethylene pressure was increased to 10 kg / c.
Polymerization was carried out for 1 hour while maintaining the m ² G. After completion of the polymerization, the content liquid was poured into a large excess of a diluted hydrochloric acid / methanol mixture to recover the polymer. This was dried at 60 ° C. under reduced pressure for 10 hours to obtain 18.2 g of an ethylene-styrene copolymer (P1).

Reference Example 2 After replacing with nitrogen, 340 ml of styrene and 4 parts of toluene were placed in a 1-liter autoclave equipped with a stirrer and replaced with ethylene.
0 ml was added, and methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd.) was added at 25 mmol based on Al atoms.
l was added. Then, ethylene was introduced at room temperature to obtain 9 kg /
After the pressure was raised to cm ² G, the autoclave was heated and the internal temperature was stabilized at 50 ° C. Racemic isopropylidenebis (1) is removed from the pressure tank installed at the top of the autoclave.
A catalyst solution obtained by dissolving 25 μmol of (indenyl) zirconium dichloride in 100 ml of toluene was injected into an autoclave. The polymerization was carried out for 1 hour while maintaining the ethylene pressure at 2 kg / cm ² G. After completion of the polymerization, the content liquid was poured into a large excess of hydrochloric acid-acidic methanol solution to recover the polymer. When this was dried at 60 ° C. for 10 hours or more under reduced pressure, 64 g of an ethylene-styrene copolymer (P2) was obtained.
I got

Reference Example 3 After replacing with nitrogen, 80 ml of styrene and 36 parts of toluene were placed in a 1-liter autoclave equipped with a stirrer and replaced with ethylene.
0 ml, and further added methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd.) to 8.4 mmol based on Al atoms.
l was added. Then, ethylene was introduced at room temperature to obtain 9 kg /
After the pressure was raised to cm ² G, the autoclave was heated and the internal temperature was stabilized at 50 ° C. Racemic isopropylidenebis (1) is removed from the pressure tank installed at the top of the autoclave.
-Indenyl) zirconium dichloride 8.4 μmol
Was dissolved in 40 ml of toluene and poured into an autoclave. Then, the ethylene pressure was increased to 10 kg / cm ²
While maintaining at G, polymerization was carried out for 1 hour. As a result of collecting the polymer in the same manner as in Reference Example 1, 97 g of an ethylene-styrene copolymer (P3) was obtained.

Reference Example 4 After purging with nitrogen, 80 ml of styrene and 36
0 ml, and further added methylalumoxane (MMAO-3A, manufactured by Tosoh Akzo Co., Ltd.) to 8.4 mmol based on Al atoms.
l was added. Then, ethylene was introduced at room temperature to obtain 9 kg /
After the pressure was raised to cm ² G, the autoclave was heated and the internal temperature was stabilized at 50 ° C. Racemic isopropylidenebis (1) is removed from the pressure tank installed at the top of the autoclave.
-Indenyl) zirconium dichloride 2.1 μmol
Was dissolved in 40 ml of toluene and poured into an autoclave. Polymerization was carried out for 1 hour while maintaining the ethylene pressure at 10 kg / cm ² G. After completion of the polymerization, the content liquid was poured into a large excess of hydrochloric acid-acidic methanol solution to recover the polymer. When this was dried under reduced pressure at 60 ° C. for 10 hours or more, 58 g of an ethylene-styrene copolymer (P4) was obtained.
I got The obtained ethylene-styrene copolymers P1 to P
Table 1 shows the analysis values of No. 4.

[0078]

[Table 1]

In Examples 1 to 12 and Comparative Examples 1 to 3, components other than the drug were blended in the proportions shown in Tables 2 to 4 and Table 5, respectively.
The mixture was heated and stirred at a temperature of 60 ° C. and melted. After melting, the temperature was lowered to 100 to 120 ° C., the drug was added, and a solution was obtained by uniform mixing. In addition, in Example 1, since no drug was contained, a solution was obtained by melting the compound after the above-mentioned heating and stirring.

Next, using a hot melt coater, the solution in a molten state is spread on a release paper made of polyethylene-coated high-quality paper so as to have a thickness after cooling of about 200 μm. Was laminated with a polyurethane film having a thickness of 30 μm. Thus, the medical adhesive tapes of Examples 1 to 12 and Comparative Examples 1 to 3 were produced.

[0081]

[Table 2]

[0082]

[Table 3]

[0083]

[Table 4]

[0084]

[Table 5]

In Tables 2 to 5, details of components other than the ethylene-styrene copolymer (P1 to P4) used are as follows.

Heavy liquid paraffin: (Nikko Pharmaceutical Co., Ltd.) Alicyclic saturated hydrocarbon resin: Trade name Alcon P-90
(Softening point 90 ° C, manufactured by Arakawa Chemical Industry Co., Ltd.) Polybutene: trade name Nisseki polybutene (average molecular weight 13
50, manufactured by Nippon Petrochemical Company)
(Manufactured by Shin-Etsu Chemical Co., Ltd.) Glycerin monostearate: trade name Glycerin monostearate MGS-B (manufactured by Nikko Chemicals) Polyvinylpyrrolidone: trade name Kollidon K90 (BA
Sorbitan monostearate: Sorbitan monostearate SS-10 (Nikko Chemicals) Polyethylene glycol monostearate: Trade name
POE (2) Monostearate YMS-2 (manufactured by Nikko Chemicals Co., Ltd.) SIS (styrene-isobutylene-styrene block copolymer): trade name CARIFLEX TR1107 (solution viscosity about 1600 cP 25% by weight toluene solution, styrene / rubber weight ratio) 14/86, manufactured by Shell Chemical Company)

In Tables 2 to 5, ethylene-styrene copolymer, SIS, heavy liquid paraffin, alicyclic saturated hydrocarbon resin and polybutene are represented by weight% based on the total of these components.
Indicated by Further, the contents of the water-soluble polymer, the fatty acid ester of polyhydric alcohol and the drug were shown by weight% with respect to the whole pressure-sensitive adhesive layer.

<Performance Test> The results of performance tests performed on the medical pressure-sensitive adhesive tapes obtained in Examples and Comparative Examples are shown in Tables 6 to 9.

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

As is clear from Tables 6 to 9, it is recognized that the medical pressure-sensitive adhesive tapes of the examples are excellent in any of the test items.

On the other hand, in Comparative Example 2, since the addition amount of glyceryl monostearate as the fatty acid ester of the polyhydric alcohol exceeded 30% by weight, glycerin monostearate bleeded out of the adhesive, resulting in poor sticking properties. There was also adhesive residue.

Comparative Example 3 is a medical pressure-sensitive adhesive tape described in Japanese Patent Publication No. 54-44688, in which glycerin bleeds from the pressure-sensitive adhesive layer, and the adhesive property was poor.

[0096]

According to the present invention, as described above, the rubber-based pressure-sensitive adhesive is provided with moisture permeability at the time of application without impairing the adhesiveness of the rubber-based pressure-sensitive adhesive. A low-irritating medical adhesive tape and sheet with little irritation can be obtained.

Claims (5)

[Claims] 1. An ethylene-aromatic vinyl compound copolymer (A), (B) a naphthenic hydrocarbon having 10 to 30 carbon atoms and / or a paraffinic hydrocarbon having 10 to 30 carbon atoms, and a tackifier resin. A pressure-sensitive adhesive composition comprising: a pressure-sensitive adhesive (I); (II) a water-soluble polymer; and (III) a fatty acid ester of polyhydric alcohol.
(A) has an aromatic vinyl compound monomer unit content of 1 to 55;
Mole-% of an ethylene-aromatic vinyl compound copolymer, mainly having a structure represented by the following general formula (1),
The stereoregularity of the phenyl group of the alternating structure of ethylene and the aromatic vinyl compound represented by the following general formula (2) contained in the structure is 0.1 in isotactic dyad fraction m.
It is an ethylene-aromatic vinyl compound copolymer characterized by being 75 or more. Embedded image (In the formula, Ph is an aromatic group such as a phenyl group, x is an integer of 2 or more representing the number of repeating units, y is an integer of 1 or more, and may be the same or different in each repeating unit. 0 or 1 and may be the same or different in each repeating unit.) (In the formula, Ph represents an aromatic group such as a phenyl group, and x ′ represents the number of repeating units and represents an integer of 2 or more.) 2. An ethylene-aromatic vinyl compound copolymer (A) of 5 to 25% by weight and (B) a paraffinic and / or naphthenic hydrocarbon having 10 to 30 carbon atoms. 75 to 95% by weight in total with tackifying resin
And (II) a water-soluble polymer in 2 to 30% by weight of the whole pressure-sensitive adhesive composition and (III) a fatty acid ester of a polyhydric alcohol in 2 to 3% by weight of the whole pressure-sensitive adhesive composition.
The pressure-sensitive adhesive composition according to claim 1, which contains 0% by weight. 3. The ethylene-aromatic vinyl compound copolymer of the component (A) is a copolymer of ethylene and an aromatic vinyl compound monomer with a transition metal compound represented by the following general formula (3) or (4). The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition is produced by polymerization using a co-catalyst. Embedded image (Where Ind1 and Ind2 are unsubstituted or substituted indenyl groups, and Ind1 and Ind2 may be the same or different from each other. Y is Ind1, Ind
Carbon, silicon, germanium or boron having a bond with 2 and having another substituent; examples of the other substituent include hydrogen, a halogen, an alkyl group, an aryl group, and an alkylaryl group; The substituents may be different or the same, or may have a cyclic structure such as a cyclohexyl group and a cyclopentyl group. X1 and X2 are hydrogen or chlorine,
Halogen such as bromine; alkyl group such as methyl group and ethyl group; aryl group such as phenyl group; silyl group such as trimethylsilyl group; alkoxy group such as methoxy group, ethoxy group and isopropoxy group. X1 and X2 may be the same or different from each other. M is Zr, Hf, T
Group IV metals such as i. ) (In the formula, Ind is an unsubstituted or substituted indenyl group. Cp is an unsubstituted or substituted cyclopentadienyl group. Y is a carbon atom having a bond with Ind and Cp and having another substituent. , Silicon, germanium or boron, and other substituents include hydrogen, halogen, an alkyl group,
Or an aryl group or an alkylaryl group. Even if the substituents are different or the same, a cyclohexyl group,
It may have a cyclic structure such as a cyclopentyl group. X
1, X2 represents a halogen such as hydrogen, chlorine, or bromine; an alkyl group such as a methyl group or an ethyl group; an aryl group such as a phenyl group; a silyl group such as a trimethylsilyl group; an alkoxy group such as a methoxy group, an ethoxy group, or an isopropoxy group. And the like. X1 and X2 may be the same or different from each other. M is a Group IV metal such as Zr, Hf, and Ti. ) 4. A medical pressure-sensitive adhesive tape comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of claims 1 to 3. 5. A medical pressure-sensitive adhesive sheet comprising a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition according to any one of claims 1 to 3.