JP2009233316A - Pressure-sensitive adhesive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pressure-sensitive adhesive composition, favorably usable for medical purposes, especially for application on skin. <P>SOLUTION: Polyoxyalkylene polymer having siloxane couplings, and one or more kinds of water-soluble or water-swelling hydrophilic colloids are used to provide the pressure-sensitive adhesive composition, achieving moisture permeability, familiarity with skin, low irritativeness, and high water absorption performance to be suitable for wound covering material, adhesive tape, and skin protective material. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a pressure sensitive adhesive composition, and more particularly to a pressure sensitive adhesive composition suitable for various medical applications, particularly to the skin dressing field.

  Adhesive compositions containing water-soluble or water-swellable hydrophilic colloids have been used for many years, but various problems remain.

  For example, US Pat. No. 3,339,546 discloses an adhesive composition containing a water-soluble or water-swellable hydrophilic colloid such as a powdered mixture of a rubber elastomer such as polyisobutylene and pectin, gelatin and carboxymethylcellulose. ing.

  In this hydrophilic colloid-containing adhesive composition, the rubber elastomer and the tackifier provide adhesion, and the hydrophilic loid powder provides a function of absorbing exudate and body fluid from the wound.

  Such hydrophilic colloid-containing adhesive compositions have the advantage of providing the desired adhesion to the skin while at the same time absorbing other body fluids including transepidermal water loss (i.e. sweating) or wound exudates. can do. As applications of the hydrophilic colloid-containing adhesive composition, ostomy devices and wound dressings are known. However, existing hydrophilic colloid-containing adhesive compositions have certain limitations in that they are opaque, do not have a rapid initial tack, and tend to disintegrate upon excessive moisture absorption. Further, the hydrophilic colloid-containing adhesive composition has no familiarity with the skin such as flexibility and followability on the skin. In addition, the adhesive composition often leaves an undesirable residue on the skin.

  For example, when the hydrophilic colloid-containing adhesive composition absorbs a large amount of water, the adhesive composition collapses. For example, when the adhesive is peeled from the skin, the residue remains on the skin. . Therefore, a method of incorporating a plurality of hydrophilic colloids (Patent Document 1) or mixing a metal salt has been selected (Patent Document 2).

  In addition, the hydrophilic colloid-containing adhesive composition is made of a rubber elastomer and prevents moisture from evaporating due to sweating from the skin. Therefore, moisture is often trapped under the cover region, causing skin maceration and skin damage.

Special table 2002-528620 Japanese Patent No. 3195420

  An object of the present invention is to provide a pressure-sensitive adhesive composition for application to the skin, which is well-adapted to the skin and has excellent water absorption and water vapor permeability.

  As a result of intensive studies based on the above problems, the present inventors have completed the following invention.

  That is, the present invention relates to a pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive composed of a polyoxyalkylene polymer having a siloxane bond and one or more water-soluble or water-swellable hydrophilic colloids.

  In the present invention, the polyoxyalkylene polymer having a siloxane bond is (A) a polyoxyalkylene polymer having at least one alkenyl group in one molecule, and (B) an average of two or more in one molecule. The present invention relates to a pressure-sensitive adhesive composition which is a pressure-sensitive adhesive formed by curing a mixture comprising a compound containing a hydrosilyl group and (C) a hydrosilylation catalyst.

  The present invention also relates to a pressure-sensitive adhesive composition, wherein the main chain of the polyoxyalkylene polymer (A) is polyoxypropylene.

  The present invention also relates to a pressure-sensitive adhesive composition, wherein the hydrosilylation catalyst (C) is a platinum-vinylsiloxane complex.

  The present invention is also characterized in that the total amount of hydrosilyl groups in the compound (B) containing a hydrosilyl group is 0.3 to 2.0 mol per mol of the total amount of alkenyl groups in the polyoxyalkylene polymer (A). And a pressure-sensitive adhesive composition.

  The present invention also provides a pressure-sensitive adhesive in which the water-soluble or water-swellable hydrophilic colloid is selected from guar gum, locust bean gum, pectin, alginate, gelatin, xanthan, cellulose derivatives, polyacrylic acid, polyvinyl alcohol, and polyethylene glycol. The present invention relates to a sex composition.

  The present invention also relates to a pressure-sensitive adhesive composition, wherein the water-soluble or water-swellable hydrophilic colloid is carboxymethyl cellulose or a salt thereof.

  The present invention also relates to a pressure-sensitive adhesive composition comprising 5 to 50% of a water-soluble or water-swellable hydrophilic colloid.

The present invention also relates to a pressure-sensitive adhesive composition having a moisture permeability of 100 g / m ² · 24 hours or more when measured under conditions of a thickness of 400 μm, a temperature of 40 ° C., and a relative humidity of 30%.

The present invention, the water absorption of physiological saline was measured by a thickness 400μm is about pressure-sensitive adhesive composition which is a 250g / ^m 2 · 24 hours ~3000g / ^m 2 · 24 hours.

  In addition, the present invention has a moisture permeability of 0.1 to 0.1% with respect to the amount of physiological saline measured under conditions of a thickness of 400 μm. The pressure-sensitive adhesive composition is 2.0.

  The present invention also relates to a pressure-sensitive adhesive composition having an Asker C hardness of 10 ° to 50 °.

  The present invention also relates to a wound dressing, a bandage or a skin protective material, characterized by using a pressure-sensitive adhesive composition.

  The pressure-sensitive adhesive composition of the present invention is well-adapted to the skin and exhibits sufficient adhesive performance for skin application. In addition, it exhibits water absorption, high water vapor permeability, low skin irritation, and can be suitably used as a pressure-sensitive adhesive composition for wound dressings, bandages and skin protection materials.

  The present invention will be described in detail below.

  The best mode for carrying out the present invention is from a pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive comprising a polyoxyalkylene polymer having a siloxane bond and one or more water-soluble or water-swellable hydrophilic colloids. Become.

  The pressure-sensitive adhesive used in the present invention is (A) a polyoxyalkylene polymer having at least one alkenyl group in one molecule, (B) a compound containing an average of two or more hydrosilyl groups in one molecule, (C ) A mixture of hydrosilylation catalyst is cured.

  The polymer (A) is a polyoxyalkylene polymer having at least one alkenyl group at the terminal. The alkenyl group is not particularly limited as long as it is a group containing a carbon-carbon double bond that is active for hydrosilylation reaction. The alkenyl group is preferably an aliphatic unsaturated hydrocarbon group having 2 to 20 carbon atoms, more preferably 2 to 4 carbon atoms (eg, vinyl group, allyl group, methylvinyl group, propenyl group, butenyl group, pentenyl group). Group, hexenyl group, etc.), preferably a cyclic unsaturated hydrocarbon group having 3 to 20 carbon atoms, more preferably 3 to 6 carbon atoms (eg, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc.) ), A methacryl group and the like.

From the viewpoint of easy synthesis reaction, preferred alkenyl groups include the following (1), (2)
Is mentioned. In the following formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or a methyl group.
(1) H ₂ C═C (R ¹ ) −
(2) HC (R ¹ ) = CH−

  The polymer (A) has an average of at least 1, preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2 alkenyl groups per molecule. Polymer (A) If the average number of alkenyl groups in one molecule is less than 1, the curability becomes insufficient, and if the number of alkenyl groups contained in one molecule is too large, the network structure becomes dense. For this reason, the adhesive properties tend to decrease.

A typical example of the polyoxyalkylene polymer which is the basic skeleton of the polymer (A) is a polyoxyalkylene polymer composed of a repeating unit represented by the general formula (—R ² —O—). Here, -R ² - is a divalent alkylene group. Adhesive properties, skin irritation, the wettability to the skin, the main chain of the preferred polymer (A) is a polyoxypropylene (i.e., the -R ² - is _-CH 2 CH (CH ₃₎ - is a) . Further, it is preferable from the viewpoint of workability in terms of availability. The polyoxyalkylene polymer may be composed of one type of repeating unit or may be composed of a plurality of repeating units. The polyoxyalkylene polymer may be a linear polymer or a branched polymer. Moreover, a polymer (A) may be used independently and may be used together 2 or more types.

  All the parts other than the alkenyl group of the polymer (A) preferably comprise a polyoxyalkylene skeleton, but may contain other structural units. In that case, the total of oxyalkylene units in the polymer (A) is preferably 80% by weight or more, more preferably 90% by weight or more.

  The molecular weight of the polymer (A) is preferably 3,000 to 50,000, more preferably 6,000 to 50,000, and particularly preferably 6,000 to 30,000 from the viewpoint of good workability at room temperature and obtaining good adhesive properties. When the number average molecular weight is less than 3,000, the obtained cured product tends to be brittle. Conversely, when the number average molecular weight exceeds 50,000, the viscosity tends to be high and workability tends to be lowered. The molecular weight is a polystyrene equivalent number average molecular weight measured by size exclusion chromatography. The bonding mode of the alkenyl group to the polyoxyalkylene polymer is not particularly limited, and examples thereof include a direct bond of an alkenyl group, an ether bond, an ester bond, a carbonate bond, a urethane bond, and a urea bond.

  The production method of the polymer (A) is not particularly limited, and examples thereof include a method of introducing an alkenyl group after obtaining a polyoxyalkylene polymer. In this case, various known production methods can be applied to the polyoxyalkylene polymer, and a commercially available polyoxyalkylene polymer may be used. In addition, a method of introducing an alkenyl group into a polyoxyalkylene polymer is also known. For example, a monomer having an alkenyl group (eg, allyl glycidyl ether) and a monomer for synthesizing a polyoxyalkylene polymer are copolymerized. Or a functional group having reactivity to the functional group in a polyoxyalkylene polymer in which a functional group (eg, hydroxyl group, alkoxide group) has been introduced into a desired portion (end of main chain, etc.) in advance. And a method of reacting a compound having both a group and an alkenyl group (eg, acrylic acid, methacrylic acid, vinyl acetate, acrylic acid chloride, etc.).

  Compound (B) is a compound containing an average of two or more hydrosilyl groups in one molecule. The hydrosilyl group means a group having a Si—H bond. In the present invention, when two hydrogen atoms (H) are bonded to the same silicon atom (Si), it is calculated as two hydrosilyl groups. The chemical structure of the compound (B) other than the hydrosilyl group is not particularly limited. The number average molecular weight of the compound (B) calculated from the SiH value obtained by titration is preferably 400 to 3000, more preferably 500 to 1000. This is because if the number average molecular weight is too low, it tends to volatilize at the time of heat-curing, and it tends to be difficult to obtain a sufficient cured product, and if it is too high, the curing rate tends to be slow.

  If the number of hydrosilyl groups contained in the compound (B) is two or more, a plurality of polymer (A) molecules can be cross-linked during curing, and a preferable adhesive force and cohesive force are expressed, and the skin is prolonged. Adhesive residue or the like is less likely to occur when affixed or applied to the skin and peeled off. However, when the number of hydrosilyl groups is too large, the cross-linking becomes too dense, and the adhesive properties such as skin adhesiveness and tackiness are easily lowered as an adhesive for skin application, and the stability of the compound (B) is further improved. In addition, a large amount of hydrosilyl groups remain in the cured product after curing, which is likely to cause skin irritation and voids. Note that the density of the cross-linking affects the density between the polyether parts as the main chain of the polymer (A), and further affects the moisture permeability of the entire pressure-sensitive adhesive composition. Therefore, the number of hydrosilyl groups in the compound (B) should be selected in consideration of the balance with the adhesive properties. Moreover, a compound (B) may be used independently and may be used together 2 or more types. The compound (B) is preferably compatible with the polymer (A). From the viewpoint of easy availability of raw materials and compatibility with the polymer (A), examples of suitable compounds (B) include organohydrogensiloxanes modified with organic groups. A typical example of the organohydrogensiloxane is a compound represented by the following (3).

The value of a in the above (3) matches the number of hydrosilyl groups in the molecule. The value of a + b is not particularly limited but is preferably 2-50. R ³ is a hydrocarbon group having 2 to 20 carbon atoms in the main chain. The compound of (3) can be obtained by modifying an unmodified methyl hydrogen silicone and introducing R ³ . Unmodified methylhydrogen silicone corresponds to the compound in which R ³ is all H in the above (3), and “Silicon Market Outlook-Maker Strategy and Application” issued by CMC Co., Ltd. (1990.1.31). As described in "Development-", it is used as a raw material for various modified silicones. Examples of the organic compound for introducing R ³ include α-olefin, styrene, α-methylstyrene, allyl alkyl ether, allyl alkyl ester, allyl phenyl ether, allyl phenyl ester, and the like. The number of hydrosilyl groups in the molecule after modification can be adjusted by the amount of the organic compound added for modification.

  The pressure-sensitive adhesive composition of the present invention is mainly formed by curing the above-described polymer (A) and compound (B). Here, the curing means that a hydrosilylation reaction is performed between the polymer (A) and the compound (B) by heating. Examples of the curing conditions include leaving at 40 to 180 ° C. for 1 to 60 minutes. If it is desired to complete the curing, it may be further left at 40 to 80 ° C. for several days.

  The ratio of the amount of the polymer (A) and the compound (B) in the pressure-sensitive adhesive forming the pressure-sensitive adhesive composition layer is derived from the compound (B) with respect to the total amount of alkenyl groups derived from the polymer (A). Expressed by the total amount of hydrosilyl groups. Depending on the total amount of hydrosilyl groups per mole of the total amount of alkenyl groups in the pressure-sensitive adhesive, the degree of crosslinking density after curing is determined. Considering the balance between imparting appropriate tackiness and reducing the adhesive residue, etc., the total amount of hydrosilyl groups per 1 mol of the total amount of alkenyl groups is preferably 0.3 to 2.0 mol, more preferably 0. 3 to 1.5 mol.

  It does not specifically limit as a hydrosilylation catalyst which is a catalyst (C) component, Arbitrary things can be used if a hydrosilylation reaction is accelerated | stimulated. Specifically, chloroplatinic acid, a platinum-vinylsiloxane complex (for example, platinum-1,3-divinyl-1,1,3,3, -tetramethyldisiloxane complex or platinum-1,3,5,7- Tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex), platinum-olefin complex (for example, Ptx (ViMe2SiOSiMe2Vi) y, Pt [(MeViSiO) 4] z (where x, y, and z are positive) )) And the like are exemplified. Among these, from the viewpoint of the activity of the catalyst, a platinum complex catalyst not containing a strong acid conjugate base as a ligand is preferable, a platinum-vinylsiloxane complex is more preferable, and platinum-1,3-divinyl-1,1 is preferable. 3,3, -tetramethyldisiloxane complex or platinum-1,3,5,7-tetravinyl-1,3,5,7-tetramethylcyclotetrasiloxane complex is particularly preferred.

The amount of the catalyst (C) is not particularly limited, but is preferably 10 ⁻⁸ to 10 ⁻¹ mol, more preferably 10 ⁻⁶ to 10 ⁻¹⁰ mol, based on 1 mol of the total amount of alkenyl groups by the polymer (A). ^-2 moles. If it is in the said range, it will become easy to achieve appropriate hardening rate, stable sclerosis | hardenability, ensuring of a required pot life, etc.

  The physical form of the water-soluble or water-swellable hydrophilic colloid used in the present invention is a relatively coarse and irregular particle, typically about 10 to 100 μm, and is usually supplied in the form of a dry powder. The

  Suitable hydrophilic colloids for incorporation into the pressure sensitive adhesive compositions of the present invention are selected from naturally occurring hydrophilic colloids, semi-synthetic hydrophilic colloids and synthetic hydrophilic colloids. Various hydrophilic colloids within the scope of the present invention include synthetic polymers prepared from single or multiple monomers, naturally occurring hydrophilic polymers, or chemically modified naturally occurring hydrophilic polymers. It is. The hydrophilic polymer may be linear or cross-linked.

  More particularly, guar gum, chitosan, locust bean gum (LBG), pectin, alginate, gelatin, xanthan and / or gum karaya, cellulose derivatives (eg carboxymethylcellulose or salts thereof such as sodium carboxymethylcellulose, methylcellulose, hydroxypropylmethylcellulose ) And / or starch glycolate sodium and / or polyvinyl alcohol and / or polyethylene glycol, polyhydroxyalkyl acrylate and methacrylate, polyacrylamide, polyacrylic acid, polystyrene sulfonate. Among these, carboxymethylcellulose or a salt thereof such as sodium carboxymethylcellulose is more preferable from the viewpoint of availability and water absorption performance.

  The content of the water-soluble or water-swellable hydrophilic colloid in the pressure-sensitive adhesive composition of the present invention is preferably 5 to 50%. When the amount of the hydrophilic colloid contained is less than 5%, it is difficult to achieve good water absorption performance, and when it exceeds 50%, there is a concern that the workability may be deteriorated or the pressure-sensitive adhesive composition may collapse due to water absorption. There is.

  The pressure-sensitive adhesive composition of the present invention may contain components other than the above (A) to (C) and water-soluble or water-swellable hydrophilic colloid. These components include tackifiers, storage stabilizers for compound (B), plasticizers, and other components.

  Tackifiers include phenol resin, modified phenol resin, terpene phenol resin, xylene phenol resin, cyclopentadiene-phenol resin, xylene resin, petroleum resin, phenol-modified petroleum resin, rosin ester resin, low molecular weight polystyrene resin, terpene Resin etc. are mentioned. When these are used to improve the adhesive properties, they may be used alone or in combination of two or more. The amount used in the case of using these tackifiers is preferably 10 to 150 parts by weight, more preferably 15 to 100 parts by weight with respect to 100 parts by weight of the total amount of the polymer (A) and the compound (B). . If the amount used is too large, the moisture permeability of the pressure-sensitive adhesive composition decreases, which is not preferable.

Examples of the storage stabilizer for the compound (B) include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, and organic peroxides. Specifically, 2-benzothiazolyl sulfide, benzothiazole, thiazole, dimethylacetylene dicarboxylate, diethylacetylene dicarboxylate, 2,6-di-t-butyl-4-methylphenol, butylhydroxyanisole, vitamin E, 2- (4-morphodinyldithio) benzothiazole, 3-methyl-1-buten-3-ol, acetylenically unsaturated group-containing organosiloxane, acetylene alcohol, 3-methyl-1-butyn-3-ol , 2-methyl-3-butyn-2-ol, diallyl fumarate, diallyl maleate, diethyl fumarate, diethyl maleate, dimethyl maleate, 2-pentenenitrile, 2,3-dichloropropene, and the like. It is not limited to these. The storage stabilizer suppresses the conversion of the hydrosilyl group (Si—H group) to the Si—OH group in the compound (B) and the compound (C) (due to standing for a long time or mixing of moisture). The pot life of the craft can be improved. The blending amount of the storage stabilizer is preferably 10 ⁻⁶ to 10 ⁻¹ mol with respect to 1 mol of the total amount of hydrosilyl groups contained in the pressure-sensitive adhesive due to the compound (B) and the compound (C).

  Although it does not specifically limit as a plasticizer, What has compatibility with each component and can melt and disperse | distribute uniformly in an adhesive is preferable. Specifically, mineral oil, cetostearyl alcohol, cetyl alcohol, coconut oil, olive oil, camellia oil, soybean oil, castor oil, lanolin, and other oils, oleyl alcohol, stearyl alcohol, ethylene glycol, diethylene glycol, dipropylene glycol, propylene Polyols such as glycol, polyethylene glycol, polypropylene glycol, butanediol, triethylene glycol, glycerin, hydrocarbons such as liquid paraffin, squalane, squalene, isopropyl myristate, isopropyl palmitate, dibutyl phthalate, diisooctyl phthalate, adipine And fatty acid esters such as dibutyl acid and dibutyl sebacate. When these are used to improve the adhesive properties, they may be used alone or in combination of two or more. The amount of the plasticizer used is preferably 1 to 50 parts by weight, more preferably 5 to 30 parts by weight, with respect to 100 parts by weight of the total amount of the polymer (A) and the compound (B). If the amount used is too large, the cohesiveness of the pressure-sensitive adhesive composition is lowered, which is not preferable.

  In addition, the pressure-sensitive adhesive composition of the present invention may contain other fillers, pigments, surfactants, ultraviolet absorbers, antioxidants, antibacterial agents, antibiotics, and the like.

  The pressure-sensitive adhesive composition of the present invention is used by being applied to an application site of a human body such as a wound site. In that case, it is preferable to use it laminated | stacked on a suitable support body from the surface of workability | operativity and the shape maintenance of a pressure sensitive adhesive composition.

  The material of the support is not particularly limited, and usual materials used for wound dressings and the like are used. Specifically, urethane polymers such as polyether urethane, amides such as polyether amide, etc. Polymers, acrylic polymers such as polyacrylates, olefin polymers such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymers, ester polymers such as polyether polyester, polyesters, nylon, polyethylene, polypropylene, and ethylene-vinyl acetate Examples include polymers, ethylene-ethyl acrylate copolymers, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene, polyurethane, polyamide, polyvinyl alcohol films, nonwoven fabrics, metal foils, and the like. These may be used singly or in combination of two or more, and moisture-permeable polyurethane films and nonwoven fabrics are preferably used. The thickness of the support is preferably 5 to 200 μm, more preferably 5 to 100 μm, from the viewpoint of skin irritation and durability. When the thickness of the support is more than 200 μm, the followability to the skin is lowered and it is easy to peel off, or physical stimulation to the skin is not preferable. If the thickness of the support is less than 5 μm, it is not preferable from the viewpoint of durability.

  The method for laminating the pressure-sensitive adhesive composition layer on the support is not particularly limited, for example, a method of applying the pressure-sensitive adhesive composition on one side of the support and then curing it under the above conditions, Examples include a method in which the pressure-sensitive adhesive composition is applied to a sheet (release sheet) that has been previously provided with a release agent and cured, and then the support is bonded. As the release agent, various release agents such as silicone, olefin and fluorine are known and can be used as appropriate. Of these, olefin-based and solvent-free addition-curable silicone-based release agents are preferable from the viewpoint of ensuring cost and releasability.

  The thickness of the pressure-sensitive adhesive composition layer is not particularly limited, and may be 10 to 5000 μm, for example.

The moisture permeability when the pressure-sensitive adhesive composition of the present invention is measured under conditions of a thickness conversion of 400 μm, a temperature of 40 ° C., and a relative humidity of 30% is preferably 50 to 2000 g / m ² · 24 hours or more, More preferably, it is 100-1500 g / m < ² > * 24 hours. This is because, if the moisture permeability of the pressure-sensitive adhesive composition is within this range, it is possible to prevent stuffiness and rash even when applied to the skin for a long time. A specific procedure for measuring the moisture permeability will be described later. The moisture permeability of the skin adhesive adhesive product such as a wound dressing naturally depends on the material and structure of the support, but the above preferred moisture permeability can be obtained by using the pressure-sensitive adhesive composition described above. The range of support choices is expanded.

  The pressure-sensitive adhesive composition of the present invention can absorb moisture. The amount of physiological saline absorbed in the pressure-sensitive adhesive composition of the present invention is defined as when the pressure-sensitive adhesive composition that has been applied to a certain thickness and heated and cured is immersed in physiological saline at 37 ° C. for 24 hours. The amount of physiological saline absorbed. Specifically, one side of a pressure-sensitive adhesive composition that has been coated to a certain thickness and heat-cured is covered with a moisture-impermeable film, and is cut into a 2 cm square and is 37 ° C in physiological saline. Is measured by the change in weight when immersed for 24 hours, and is represented by the following formula (1).

Formula (1)
Water absorption = (weight of pressure-sensitive adhesive composition after immersion−weight of pressure-sensitive adhesive composition before immersion) × 2500

The water absorption amount of the pressure-sensitive adhesive composition of the present invention depends on its thickness, but is preferably 250 to 3000 g / m ² · 24 hours under the condition of a thickness of 400 μm. When it is 250 g / m ² · 24 hours or less, for example, when used as a wound dressing, it is not sufficient to absorb exudate from the wound. Moreover, when it is 3000 g / m < ² > * 24 hours or more, there exists a possibility that a shape may deform | transform or destroy by excessive absorption of a water | moisture content.

  In the pressure-sensitive adhesive composition of the present invention, the moisture permeability measured under the conditions of a thickness of 400 μm, a temperature of 40 ° C., and a relative humidity of 30% is 0 with respect to the water absorption of physiological saline at the same thickness. 0.05 to 2.0, more preferably 0.1 to 2.0. If the ratio of moisture permeability and water absorption is in the range of 0.05 to 2.0, the exudate from the wound can be absorbed sufficiently, and even if it is applied to the skin for a long period of time, it can prevent stuffiness and fogging. Because it can. If it is 0.05 or less, there is a risk that the evaporation of moisture due to perspiration from the skin is prevented, and moisture is trapped under the cover area, causing skin maceration and skin damage. Moreover, at 2.0 or more, since a water | moisture content permeate | transmits too much, a coating | covering material may become inadequate to absorb the exudate from a wound, and there exists a possibility that a wound may dry, and use as a wound dressing use is possible. It becomes difficult.

  The Asker C hardness of the pressure-sensitive adhesive composition used in the present invention is preferably 10 ° or more and 50 ° or less. An Asker C hardness of 10 ° or less is not preferable because the compression strain becomes too large. Moreover, when the Asker C hardness is 50 ° or more, the composition becomes hard, the followability to the skin is lowered, and the tension feeling is affected, which is not preferable. Here, the Asker C hardness was measured by a method according to JIS K6301 in an environment of a temperature of 23 ° C. and a relative humidity of 55% using a sample having a thickness of 4 mm.

  The pressure-sensitive adhesive composition of the present invention can be used as a skin patch application without any particular limitation, but is preferably suitably used as a wound dressing, a bandage, a skin protective adhesive sheet, a wound protective material, and a wound prevention material. Can be used.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples, and various applications are possible without departing from the technical idea of the present invention. is there.
A: Polyoxyalkylene polymer having at least one alkenyl group at the terminal A-1: Allyl group-terminated polyoxyalkylene (see Synthesis Example below, containing alkenyl group 0.12 mmol / g)
B: Compound B-1 containing an average of 2 or more hydrosilyl groups in the molecule: Silicon oil (see structure below, containing 3.2 mmol / g hydrosilyl group)
C: Hydrosilylation catalyst C-1: Platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (3 wt% platinum isopropanol solution)
D: Hydrophilic colloid D-1: Sodium carboxymethyl cellulose (Nippon Paper Chemicals MAC10H)

(Synthesis of polymer (A-1))
An oxypropylene polymer glycol having a number average molecular weight of 3000 was obtained by a polymerization method using caustic alkali. According to the method of Synthesis Example 1 of JP-A-5-117521, propylene oxide is polymerized using a double metal cyanide complex catalyst (zinc hexacyanocobaltate) using the oxypropylene polymer glycol as an initiator, and the number average molecular weight 28,000 polymers were obtained. The polymer is converted to an allyl group using 28% methanol solution of sodium methylate and allyl chloride, and then desalted and purified to have approximately two allyl group ends in one molecule. A polyoxyalkylene polymer (polymer (A)) was obtained. The allyl terminal group amount of the obtained polymer was 0.12 mmol / g.

(Synthesis of Compound (B-1))
In the presence of a platinum catalyst, 0.5 equivalent of α-methylstyrene of the total hydrosilyl group amount is added to methyl hydrogen silicone represented by the following formula (4) (wherein x is an average of 5), and 1 molecule A compound (compound (B)) having an average of 2.5 hydrosilyl groups therein was obtained. The hydrosilyl group content of this compound was 3.2 mmol / g.

Example 1
2.2 parts by weight of compound (B-1), 0.1 parts by weight of hydrosilylation catalyst (C-1), 2-methyl-3-butyne-2 with respect to 100 parts by weight of polymer (A-1) -0.03 weight part of all was fully mixed and the adhesive was obtained. 30 parts by weight of sodium carboxymethylcellulose (D-1) was mixed with this pressure-sensitive adhesive, and coated on the treated surface of the release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing would be 400 μm. The pressure sensitive adhesive composition of the present invention was formed by curing at 130 ° C. for 3 minutes.

(Example 2)
2.2 parts by weight of compound (B-1), 0.1 parts by weight of hydrosilylation catalyst (C-1), 2-methyl-3-butyne-2 with respect to 100 parts by weight of polymer (A-1) -0.03 weight part of all was fully mixed and the adhesive was obtained. 50 parts by weight of sodium carboxymethyl cellulose (D-1) was mixed with this pressure-sensitive adhesive, and coated on the treated surface of the release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing would be 400 μm. The pressure sensitive adhesive composition of the present invention was formed by curing at 130 ° C. for 3 minutes.

(Example 3)
2.9 parts by weight of compound (B-1), 0.1 part by weight of hydrosilylation catalyst (C-1), 2-methyl-3-butyne-2 with respect to 100 parts by weight of polymer (A-1) -0.03 weight part of all was fully mixed and the adhesive was obtained. 50 parts by weight of sodium carboxymethylcellulose (D-1) was mixed with this pressure-sensitive adhesive, and applied to the treated surface of the release paper that had been subjected to silicone release treatment at room temperature so that the thickness after curing was 400 μm. The pressure sensitive adhesive composition of the present invention was formed by curing at 130 ° C. for 3 minutes.

(Comparative Example 1)
2.2 parts by weight of compound (B-1), 0.1 parts by weight of hydrosilylation catalyst (C-1), 2-methyl-3-butyne-2 with respect to 100 parts by weight of polymer (A-1) -0.03 weight part of all was fully mixed and the adhesive was obtained. This pressure-sensitive adhesive is coated on the treated surface of a release paper that has been subjected to silicone release treatment at room temperature so that the thickness after curing is 400 μm, and cured at 130 ° C. for 3 minutes. An adhesive composition was formed.

(Comparative Example 2)
A conotec duoactive ET was used.

(Comparative Example 3)
Tegasorbite manufactured by 3M was used.

(Adhesive force)
The pressure-sensitive adhesive composition obtained in the above examples was laminated with a polyester film (tolerant mirror film thickness 25 μm) as a support using a rubber roller weighing 2 kg at a speed of 2 m / min, and an adhesive sheet. Got. Cut into a width of 25 mm, a rubber roller weighing 2 kg was attached to a SUS304 plate at a speed of 2 m / min and left for 1 hour. The stress at the time of peeling off each tape from the SUS304 plate at an angle of 180 ° at a speed of 300 mm / min was used as a measured value of adhesive force.

(Water absorption)
The pressure-sensitive adhesive composition obtained in the above examples was laminated with a polyester film (tolerant mirror film thickness 25 μm) as a support using a rubber roller weighing 2 kg at a speed of 2 m / min, and an adhesive sheet. Got. A 2 cm square was cut and the weight (w ₁ ) was measured. The weight (w ₂ ) after immersing this test piece in 100 ml of physiological saline having the following composition for 24 hours was measured. The water absorption was determined from the following formula.

Saline composition NaCl 8.298 g CaCl ₂ 0.323 g / l Ion-exchange water Water absorption (g / m ² · 24 hours) = (w ₂ −w ₁ ) × 2500

(Moisture permeability)
10 ml of distilled water was put into a cylindrical glass container having an inner diameter of 35 mm, and the pressure-sensitive adhesive composition obtained in the above example cut into a circle was attached to the mouth of this container, and the total weight (W ₁ ) was measured. It was measured. This was placed in a constant temperature and humidity chamber at 40 ° C. and a relative humidity of 30% and left for 24 hours. The weight (W ₂ ) after 24 hours was measured, and the moisture permeability was calculated by the following formula.

Moisture permeability (g / m ² · 24 hours) = (W ₁ −W ₂ ) / (0.0175 × 0.0175 × 3.14)

(Asker C hardness)
The test pieces prepared according to the above examples were stacked to prepare a test piece having a thickness of about 4 mm, and measured by a method according to JIS K6301 using an Asker C hardness meter.

(Skin irritation)
A rubber roller having a weight of 2 kg under the conditions of a moisture-permeable polyurethane film (DSU-214-CDB, manufactured by Seadam Co., Ltd., 30 μm) as a support, and the pressure-sensitive adhesive composition obtained in the above examples. Was laminated to obtain an adhesive sheet. After cutting to 1.5 cm × 4 cm and repeating the application to the skin of the upper arm of 4 volunteers for 3 hours for 24 hours, the skin surface was visually observed and evaluated.

Evaluation criteria: Yes; No redness
Δ: Slightly red immediately after peeling, but disappeared after 1 hour
X: Redness was observed 24 hours after peeling (skin adhesion)

  A rubber roller having a weight of 2 kg under the conditions of a moisture-permeable polyurethane film (DSU-214-CDB, manufactured by Seadam Co., Ltd., 30 μm) as a support, and the pressure-sensitive adhesive composition obtained in the above examples. Was laminated to obtain an adhesive sheet. It was cut into 1.5 cm × 4 cm and applied to the skin of the upper arm of 4 volunteers for 24 hours, and then evaluated.

Evaluation criteria: Yes; no problem
△: There is some peeling, but there is no problem in sticking
×: Peeled

(Skin itching)
For the pressure-sensitive adhesive compositions obtained in the above examples, a 2 kg rubber with a moisture permeable polyurethane film (DSU-214-CDB, manufactured by Seadam Co., Ltd., 30 μm) as a support at a speed of 2 m / min. Lamination was performed using a roller to obtain an adhesive sheet. It cut | judged to 1.5 cm x 4 cm, it affixed on the skin inside the upper arm of four volunteers, and the sticking comfort was evaluated.

Evaluation criteria: ○;
Δ: Feeling uncomfortable
×: I feel a strong sense of incongruity such as pulling

  From the above results, the present invention is well-adapted to the skin, exhibits sufficient adhesive performance for skin sticking, exhibits water absorption and high water vapor permeability, and feels good for wound dressings, bandages and skin protection materials. It is clear that it can be suitably used as a pressure-bonding composition.

Claims (13)

  A pressure-sensitive adhesive composition comprising a pressure-sensitive adhesive comprising a polyoxyalkylene polymer having a siloxane bond and one or more water-soluble or water-swellable hydrophilic colloids.   The polyoxyalkylene polymer having a siloxane bond includes (A) a polyoxyalkylene polymer having at least one alkenyl group in one molecule, and (B) an average of two or more hydrosilyl groups in one molecule. The pressure-sensitive adhesive composition according to claim 1, which is a pressure-sensitive adhesive obtained by curing a mixture comprising a compound and (C) a hydrosilylation catalyst.   The pressure-sensitive adhesive composition according to claim 2, wherein the main chain of the polyoxyalkylene polymer (A) is polyoxypropylene.   The pressure-sensitive adhesive composition according to claim 2, wherein the hydrosilylation catalyst (C) is a platinum-vinylsiloxane complex.   3. The total amount of hydrosilyl groups in the compound (B) containing a hydrosilyl group is 0.3 to 2.0 mol per mol of the total amount of alkenyl groups in the polyoxyalkylene polymer (A). The pressure-sensitive adhesive composition according to -4.   The water-soluble or water-swellable hydrophilic colloid is selected from guar gum, locust bean gum, pectin, alginate, gelatin, xanthan, cellulose derivatives, polyacrylic acid, polyvinyl alcohol, and polyethylene glycol. Pressure sensitive adhesive composition.   The pressure-sensitive adhesive composition according to claim 1, wherein the water-soluble or water-swellable hydrophilic colloid is carboxymethyl cellulose or a salt thereof.   The pressure-sensitive adhesive composition according to claim 1, comprising 5 to 50% of a water-soluble or water-swellable hydrophilic colloid. The pressure-sensitive adhesive composition according to claim 1, wherein the moisture permeability when measured under conditions of a thickness of 400 μm, a temperature of 40 ° C., and a relative humidity of 30% is 100 g / m ² · 24 hours or more. The water absorption of physiological saline was measured by a thickness 400μm is, pressure sensitive adhesive composition according to claims 1-9, characterized in that a 250g / ^m 2 · 24 hours ~3000g / ^m 2 · 24 hours.   The water vapor transmission rate when measured under conditions of a thickness of 400 μm, a temperature of 40 ° C., and a relative humidity of 30% is 0.1 to 2.0 with respect to the water absorption of physiological saline measured under the condition of a thickness of 400 μm. The pressure-sensitive adhesive composition according to claim 1.   The pressure-sensitive adhesive composition according to claim 1, wherein the pressure-sensitive adhesive composition has an Asker C hardness of 10 ° or more and 50 ° or less.   A wound dressing, a bandage or a skin protecting material, wherein the pressure-sensitive adhesive composition according to claim 1 is used.