JPH01297069A - Tacky adhesive agent composition - Google Patents

Abstract

PURPOSE:To obtain an ideal sticking agent for external use which is free from contact with air by forming the tacky adhesive agent compsn. consisting of an A-B-A type block copolymer, softener, water absorptive polymer, and alicyclic petroleum resin. CONSTITUTION:The A-B-A type block copolymer refers to a block copolymer of a monovinyl substd. arom. compd. A and conjugate, diolefin copolymer B and the compounding ratio thereof is specified to 10-30 pts.wt. in the tacky adhesive agent compsn. The water absorptive polymer refers to the polymer which gelatinizes and swells by absorbing water of >=10 times its own weight and is prepd. by properly mixing 1 or >=2 kinds of the water absorptive polymers introduced with a light crosslinking bond with, for example, a water soluble polymer. The ratio of said polymer to be compounded is 1-10 pts.wt. in the tacky adhesive agent compsn. The alicyclic petroleum resin refers to a petroleum resin having cyclic skeleton and the ratio of said resin to be compounded is 10-50 pts.wt. Higher fatty acid, liquefied rubber, mineral oil, etc., are used for the softener and the ratio of the softener to be compounded is 10-50 pts.wt. The base is selected from stretchable or non-stretchable bases consisting of, for example, polyethylene, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The object of the present invention is to provide a novel adhesive composition that overcomes the drawbacks of conventional medical adhesives.

[Conventional technology]

BACKGROUND ART Adhesives have heretofore been used in adhesive tapes such as surgical dressings, adhesive plasters, and tapings, as well as plasters, tapes, patches, poultices, etc. as means for transdermally administering drugs. However, when using these adhesives, there are problems such as hair pulling when peeled off, pressure on the skin due to the hardness of the adhesive, abrasion due to movement of the skin and slippage of the adhesive, and lack of breathability and moisture permeability. When applied to the skin, it causes a blockage of the skin surface, stopping the diffusion of moisture, and causing irritation due to the irritating components contained in sweat and secretions.

On the other hand, various attempts have been made to solve these problems.

For example, Japanese Patent Publication No. 58-52251 proposes a method of making ventilation holes in plaster. Also, Japanese Patent Publication No. 58-4721
No., JP-A-60-56911, JP-A-60-2331
No. 2 etc. shows drug combinations to prevent exposure or reduce skin irritation. JP-A-60-75428 discloses the use of a specific adhesive on a stretchable base fabric.

Japanese Patent Publication No. 59-19528 proposes a method of reducing skin irritation by subjecting the base material to special treatment. However, in either case, there are problems in practicality, the manufacturing process is complicated, and the effects are insufficient. In addition, methods have been attempted in which sweat and secretions, which are the main cause of skin irritation, are absorbed or adsorbed into the base.For example, in Japanese Patent Publication No. 54-44688, a method of blending PVA and Lt loins, Jitsukai 55-1925
No. 8 contains multi-tidal gum, Special Publication No. 58-23846
No. 60-41968 discloses a method of blending an acrylic copolymer. Also, JP-A-60-1
No. 23416 and JP-A-60-123417 attempt to reduce skin irritation by imparting sweat absorption or water permeability to patches by incorporating water-soluble polymers and polysaccharides.

However, in reality, since it is water-soluble, the plaster may dissolve with sweat, and in any case, the water and sweat absorption ability is insufficient, at most 1.
Since it has a water absorption capacity of only about 1.0%, it does not completely adsorb sweat or secretions, and therefore, the current situation is that sweat and secretions that are not adsorbed cause a feeling of discomfort.

Despite the various methods described above being attempted, they are far from practical, and at present no ideal external patch that does not cause discomfort has yet appeared.

[Means for solving problems]

In view of these circumstances, the inventors of the present invention have developed the following solutions: ■ Elimination of hair tension during peeling ■ Flexible adhesive that can follow the movement of the skin ■ Prevention of skin irritation due to physiological effects such as stuffiness and sweating due to long-term application. In order to eliminate the side effects of medical adhesives, such as dehydration, we have developed an A-B-A type block copolymer, a softening agent,
The adhesive composition composed of a water-absorbing polymer and an alicyclic petroleum resin has flexible adhesive properties that can sufficiently follow the movements of the skin, and soft adhesive properties that do not put pressure on the skin. The present inventors have discovered that by absorbing and adsorbing the sweat and secretions of the skin, side effects such as hair pulling, stuffiness, or feeling when peeled can be significantly reduced, and the present invention has been completed.

The four elements constituting the present invention will be described, but the present invention does not exist even if any one is missing, and each specific component is an essential element of the present invention.

1) A-B-A type block copolymer This is the main polymer of the adhesive component of the present invention and has shape retention properties.

2) Water-absorbing polymer The adhesive composition of the present invention absorbs and adsorbs sweat and secretions from the skin.

3) It is a ring-based petroleum resin tackifier, and optimal adhesive properties can only be obtained by combining it with an ABA type block copolymer.

4) Softener This is a material that dissolves and softens the A-B-A type block copolymer, and is a combination of the A-B-A type block copolymer, the alicyclic petroleum resin that is the tackifying resin, and the softener. This combination brings about the characteristics of the present invention: soft physical properties that follow the skin and soft adhesion that does not cause hair to pull when peeled off.

Next, each component will be explained in detail.

The A-B-A type block copolymer is a block copolymer of monovinyl-substituted aromatic compound A and conjugated diolefin copolymer B, and specifically, Cariflex TR-1
101, Kaliflex TR-1107, Kaliflex 7x TR-1111, Kaliflex TR-1112, Kaliflex TR-1117 (Shell chemical type), etc., Turprene 418 manufactured by Philip Petroleum, etc.
The amount incorporated in the adhesive composition is 10 to 30 parts by weight, preferably 15 to 25 parts by weight.

A water-absorbing polymer is one that absorbs more than 10 times its own weight of water and gels and swells. For example, a water-absorbing polymer that has a mild crosslinking bond introduced into a water-soluble polymer can be used alone or as a mixture of two or more. It is prescribed. Specifically, Sunwet IM-300, Sunwet IM-300MPS,
Sunwet IM-1000, Sunwet IM-10
00MPS (manufactured by Sanyo Chemical Co., Ltd.), Aqua Keep 4S, Aqua Keep 4SH (manufactured by Steel Chemical Co., Ltd.), etc., Sumikagel 5P-5
20, Sumikagel N-100, Sumikagel NP-102
0, Sumikagel NP-1040 (manufactured by Sumika Kagaku), etc., Kl
Gel 201-, KI Gel-201, -F2 (manufactured by Kuraray), Arasorb 800, Arasorb 800F (manufactured by Arayo Kagaku), etc. Among them, Sunwet IM-300
Particularly preferred are MPS, Sunwet IM-1000MPS, Sumikagel NP-1020, Sumikagel NP-1040, KI Gel-201-F2, Arasorb 800F, and the like. The blending amount is 1 to 10 parts by weight, preferably 2 to 8 parts by weight, in the pressure-sensitive adhesive composition.

Alicyclic petroleum resin is a petroleum resin with a cyclic skeleton, specifically Alcon P-85, Alcon P-10.
0, Alcon P-125 (manufactured by Arayo Kagaku), etc., Escoretz 3000 (manufactured by Exxon), Finton (Nippon Zeon), etc., and the blending amount is 10 to 50 parts by weight, preferably 25 to 45 parts by weight. Parts by weight.

As the softening agent, higher fatty acids, liquid rubber, mineral oil, etc. are used, and the amount thereof is 10 to 50 parts by weight, preferably 25 to 45 parts by weight.

In addition, conventionally known anti-aging agents, inorganic fillers, antioxidants, etc. can be added in appropriate amounts depending on the purpose of use.

As described above, the adhesive composition of the present invention obtained can be used for Kyocera bandages, surgical dressings for the purpose of protecting wounds after surgery, tapes for reinforcing and fixing incisions and sutures, and even tapings used during sports. It is also available.

Furthermore, it can be used as a medical patch by containing a drug for transdermal absorption. For example, as skin irritants and analgesic anti-inflammatory agents, salicylic acid, methyl salicylate, glycol salicylate, l-menthol, camphor, pepper oil, thymol, nicotinic acid benzyl ester, capsicum extract,
Kabsaicin, nonylic acid vanialamide, flubinac,
butyl flufenamate, piroxicam, indomethacin, ketoprofen, pranoprofen, fueprazone,
Loxobrofen, anzenaf sodium, oxaprozin, emorfazone, fentiazac, diclozenaf sodium, diflunisal, ibuprofenpiconol, pendazac, and subrofen, and their ester derivatives, or buprenorphine hydrochloride, pentazocine, butorphanol tartrate, etc.

Central nervous system acting agents (sedative sleep agents, anti-epileptic agents, psychiatric agents) include fluphenazine, thioridazine, diazepam, chlorpromazine, nitrazepam, estazolam, triazolam, nimetazepam, fludiazepam, halosexacillam, flurazepam, clonazepam, proberidiazine, prochlor. Perazine, albrasulam, oxazepam, oxazolam, cloxazolam, prazepam, flutazolam, mexazolam, lorazepam, fludiazepam, promazebam, prazepam, etc.

Diuretics include hydrothiazide, pendroflumethiazide, ethiazide, cyclopenthiazide, hydrochlorothiazide, penflutide, methyclothiazide, furosemide, metolazone, polythiazide, pendroflumethiazide, etc.

As antihypertensive agents, clonidine, altheroxirone,
Resinamine, dihydroergotoxin mesylate, Resel, pinprazosin, captopril, pindolol, enalapril maleate, etc.

Coronary vasodilators include nitroglycerin, nitroglycol, isosorbite cinitrate, bapaperine hydrochloride,
Diviridamol, efloxate, trimetacin, nicorandil, cinnarizine, nyridone, molsidomine nifedipine, etc.

As an antitussive expectorant: codeine phosphate, dihydrocodeine phosphate, ephedrine hydrochloride, chlorprenaline hydrochloride, phenotyrol hydrobromide, salbutamol sulfate, dimemorphan phosphate, azelastine hydrochloride, clenbuterol hydrochloride, tulobuterol hydrochloride, trimethoquinol hydrochloride, procaterol hydrochloride, Bromhexine hydrochloride, tranilast,
Tipevidine hibenzate, ketotifen fumarate, formotyol fumarate, pensproperine phosphate, glycyrrhetinic acid, etc.

Antihistamines include diphenhydramine hydrochloride, triprolidine hydrochloride, isotibenzyl hydrochloride, promethacin hydrochloride, chlorpheniramine maleate, cyprohebutadine hydrochloride, talemastine fumarate, carbinoxamine maleate, dimethindene maleate, etc.

Arrhythmia agents include alprenolol, oxprenolol, bucumolol, bupranolol, pindolol, indenolol, carteolol, bucumolol, propranolol, timolol, etc.

Cardiotropes include digitalis, ubidecarenone, digoxin, methyldigoxin, and destranoside.

Estradiol enanthate, estradiol cipinate, levonorgestrel, estradiol, etc. as sex hormones.

Adrenal skin hormones include hydrocortisone acetate, hydrocortisone, prednisolone, doriamcinolone acetonide, dexamethacin phosphate, methylprednisolone, gychlorine acetonide, dexamethacin acetate, dexamethacin, fluorometholone, betamethacin sodium phosphate, betamethacin, Betamethacin valerate, beclomethasone propionate, fludroxycortide, hydrocortisone butyrate, betamethacin dipropionate, fluocinonide, clobetapur propionate,
Diflucortolone valerate, haldinonide, amcinonide, prednisolone valerate, etc.

lidocaine, ethyl aminobenzoate, as a local anesthetic;
Examples include procytoin hydrochloride, dibucaine, procytoin, and the like.

These medicinal ingredients may be used alone or in combination of two or more if necessary.

Examples of the support include films or sheets of polyethylene, polypropylene, polybutadiene, ethylene vinyl acetate copolymer, polyvinyl chloride, polyester, nylon, polyurethane, or porous bodies and foams thereof, as well as paper, cloth, nonwoven fabric, etc. Selected from stretchable or non-stretchable supports.

Next, as a manufacturing method, a conventionally known method may be used, for example, using a kneader such as a kneader or a mixer,
It is manufactured by kneading it at a temperature of about 0°C and spreading it directly onto a tape or sheet substrate, or by spreading it onto paper, film, etc. that has been subjected to a release treatment, and then press-printing it onto the substrate to be used. You can also do that.

[Effect]

As mentioned above, the pressure-sensitive adhesive composition of the present invention described above, as described in the following test examples and examples, includes: 1) 10 parts by weight to 30 parts by weight of an A-B-A type block copolymer 2) 1 weight part of a water-absorbing polymer Parts to 10 parts by weight 3) Alicyclic petroleum resin 10 to 50 parts by weight 4) A combination with 10 to 50 parts by weight of a softening agent is essential, and this specific formulation allows ■ Softness that conforms to the skin. Adhesive properties - Absorbs sweat and secretions, and has adsorption properties, so it always adheres softly to the skin, does not pull the hair when peeled off, and also suppresses the appearance of stuffiness and sweating. Ta. This is truly an ideal pressure-sensitive adhesive composition.

Next, the above-mentioned functions and effects will be explained in more detail using Examples and Test Examples.

Example I 25 parts of Cauliflex TR-1107 (manufactured by Shell Chemical Co., Ltd.) as an A-B-A type block copolymer, 40 parts of Alcon (manufactured by Arayo Chemical Co., Ltd.) as an alicyclic petroleum resin, and fluidized as a softener. 30 parts of paraffin was kneaded in a kneader at 150°C, and then mixed with Sunwet IM-30 as a water-absorbing polymer.
A pressure-sensitive adhesive composition of the present invention was obtained by adding and mixing 5 parts of 0MPS (manufactured by Sanyo Chemical).

Example 2 22 parts of Cauliflex TR-1107 (manufactured by Shell Chemical Co., Ltd.) as an A-B-A type block copolymer, 42 parts of Al, Con (manufactured by Arayo Chemical Co., Ltd.) as an alicyclic petroleum resin, and a softening agent. 33 parts of liquid paraffin was kneaded at 160°C in a Nigu machine, and then Arasorb 800F was mixed as a water-absorbing polymer.
(manufactured by Arayo Kagaku Co., Ltd.) by adding and mixing 3 parts to obtain the adhesive composition of the present invention.

Example 3 20 parts of Cauliflex TR-1111 (manufactured by Shell Chemical Co., Ltd.) as an A-B-A type block copolymer, 31 parts of Alcon (manufactured by Arayo Chemical Co., Ltd.) as an alicyclic petroleum resin, and fluid as a softener. The pressure-sensitive adhesive composition of the present invention is prepared by kneading 40 parts of paraffin at 160°C in a Nigu machine, and then adding and mixing 3 parts of titanium oxide and 6 parts of Sunwet IM-300MPS (manufactured by Sanyo Chemical) as a water-absorbing polymer. Obtained.

Reference Example 1 One portion of the adhesive composition obtained in Example 1 was applied in the direction of both wheels.
It was spread on a 20% elongated polyester nonwoven fabric to a film thickness of 200 μ'' to make a medical taping tape.

Reference Example 2 The adhesive composition obtained in Example 2 was spread on silicone-treated release paper to a thickness of 60μ, and then the film thickness was 40/7.
This was transferred to a urethane film of 100 mm and used as a medical surgical dressing.

Reference Example 3 The adhesive composition obtained in Example 3 was spread on a release paper treated with silicone to a thickness of 100 mm, and then pressure-transferred onto a foamed polybutadiene sheet to obtain a medical surgical tape.

Reference Example 4 To 100 parts of the adhesive composition obtained in Example 1, 4.8 parts of l-menthol, 2.4 parts of methyl salicylate, and 1.0 parts of peppermint oil were added.
Add 5 parts and apply 1 part to a thickness of silicone-treated release paper.
It was spread to a thickness of 50 μm and then transferred to a polyvinyl chloride sheet by pressure to prepare a medical patch.

Reference Example 5 To 100 parts of the adhesive composition obtained in Example 1, 5.4 parts of 2-menthol and 5.0 parts of glycol salicylate were added,
It was spread on a nonwoven fabric to a thickness of 200 μm to prepare a medical patch.

Reference Example 6 3.5 parts of indomethacin was added to 100 parts of the adhesive composition obtained in Example 1, and a polyvinyl chloride sheet was coated with a thickness of 10 parts.
It was spread to a thickness of 0μ and used as a medical patch.

Reference Example 7 2 parts of ketoprofen was added to 100 parts of the adhesive composition obtained in Example 2, and the mixture was spread on a silicone-treated polyester film to a thickness of 100 μm, and then pressure-transferred onto a polyethylene film. It was made into a medical patch.

Reference Example 8 2.5 parts of ketoprofen dissolved in 5 parts of glycol salicylate was added to 100 parts of the adhesive composition obtained in Example 3, and the mixture was spread on a polyester film to a thickness of 100 nm and applied to a medical patch. It was used as a drug.

Comparative Example I 25 parts of Cauliflex TR-1307 (manufactured by Shell Chemical Co., Ltd.) as an A-B-A type block copolymer, 40 parts of Alcon (manufactured by Arayo Chemical Co., Ltd.) as an alicyclic petroleum resin, and fluid as a softener. 30 parts of paraffin were kneaded at 150 DEG C. in a Nigu machine, and then 4.5 parts of l-menthol, 2.3 parts of methyl salicylate, and 1.4 parts of peppermint oil were added, and the mixture was treated in the same manner as in Reference Example 4.

Comparative Example 2 25 parts of Cauliflex TR-1107 (manufactured by Shell Chemical) as an A-B-A type block copolymer, 40 parts of rosin resin, and 30 parts of liquid paraffin as a softener were mixed in a kneader at 140°C. Knead and then! -Menthol 4.5
After adding 2.3 parts of methyl salicylate and 1.4 parts of peppermint oil, the mixture was treated in the same manner as in Reference Example 4.

Test Example 1 (Patch Test) Reference Example 4 obtained from Example 1 of the present invention, Reference Example 5, and Comparative Example 1.2 were each applied to the upper backs of 35 healthy male adults in a size of 4 x 6-. was applied for 24 hours.

The results are shown in Table 1.

Table 1 ■) Skin irritation After application for 24 hours, the sample was peeled off, and the condition of the skin was observed 1 hour and 24 hours later, and the skin irritation was scored. (The evaluation criteria are as follows.) Judgment No change in score 0 Slight change ± 0.5 Clear change + 1.0 Severe redness +1 2.0 2) Pain when peeling off after 24 hours of application The tension of the skin and hair when the sample was peeled off was evaluated based on the pain during peeling. (The evaluation criteria are as follows.) Not painful ○ Slightly painful △ Painful when pulling skin and hair Compared to Comparative Example 1 in which no resin was added and Comparative Example 2 in which another resin was added, there was no pain during peeling and skin irritation was very low.

Test Example 2 (Water Absorption Power Test) As Example 1.2 of the present invention and Comparative Example, a test was conducted using 10-blocks of Comparative Example 3 in which the water-absorbing polymer was removed from Example 1, respectively.

Each block was immersed in water, taken out after 8 hours, weighed, divided by the increased weight, and the amount of water absorbed is shown in Table 2.

Table 2 As is clear from the results, the adhesive composition of the present invention exhibited remarkable water absorption power compared to the comparative example.

[Effects of the Invention] As shown in the above-mentioned Examples and Test Examples, the adhesive composition of the present invention comprises: 1) A-B-A type block copolymer 2) Water-absorbing polymer 3) Alicyclic petroleum resin 4) Due to a specific combination with an emollient, ■ Soft adhesive properties that follow the skin ■ Absorption of sweat and secretions, as well as adsorption properties, making it suitable for use as adhesive plasters, surgical dressings, surgical tapes, and medical patches. It can be used without worrying about problems, and its functions can be fully demonstrated, making it very useful industrially.

Procedural Amendment,. From, 1. Indication of the case 1988 Patent Separate Section No. 129387 2, Title of the invention Adhesive composition 3, Person making the amendment 4, Date of amendment order Voluntary action 5, Subject of amendment (1) In the specification, "3. Insert "Arasorb S-100J" next to "Arasorb 800 FJ" in the 7th line from the top of the "Detailed Description" column.

(2) In the same book, in the 13th line from the top of page 8, "transdermal drug" is corrected to "transdermal drug j."

(3) In the same book, after the 7th line from the top of the 14th line, it says, ``In addition,
In the use of each component in Examples 1 to 4 and Comparative Examples 1 to 2 below, parts refer to parts by weight. Insert j.

(4) In the same book, "Arcon" in the 11th line from just above the 14th line is corrected to "Arcon P 1001."

(5) “Archon” in the second line from the top of No. 15 in the same book
"Corrected to "Arcon P 100J.

(6) In the same book, "Arcon" in the 11th line from just above the 15th line is corrected to "Arcon P-85J."

(7) In the same book, the following "Example 4" is newly inserted after the third line from the bottom of page 15.

"Example 4 24 parts of Cauliflex TR-1107 (Shell chemical type) as an A-B-A type block copolymer, 35 parts of Alcon P-85 (manufactured by Arayo Kagaku) as an alicyclic petroleum resin,
Add 35 parts of liquid paraffin as a softener to 15 parts in a kneader.
Knead at 0°C, then add 3 parts of titanium oxide and Sanwet IM-1000MPS (manufactured by Sanyo Chemical) as a water-absorbing polymer.
By adding and mixing 3 parts, a pressure-sensitive adhesive composition of the present invention was obtained. ”

Claims (1)

[Claims] 1. 10 to 30 parts by weight of A-B-A type block copolymer, 10 to 50 parts by weight of alicyclic petroleum resin, 10 to 50 parts by weight of softener, and 1 part by weight of water-absorbing polymer ~1
An adhesive composition composed of 0 parts by weight.